CA2221565A1 - Novel colorants and colorant modifiers - Google Patents

Novel colorants and colorant modifiers Download PDF

Info

Publication number
CA2221565A1
CA2221565A1 CA002221565A CA2221565A CA2221565A1 CA 2221565 A1 CA2221565 A1 CA 2221565A1 CA 002221565 A CA002221565 A CA 002221565A CA 2221565 A CA2221565 A CA 2221565A CA 2221565 A1 CA2221565 A1 CA 2221565A1
Authority
CA
Canada
Prior art keywords
colorant
cyclodextrin
compound
group
composition
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Abandoned
Application number
CA002221565A
Other languages
French (fr)
Inventor
Ronald Sinclair Nohr
John Gavin Macdonald
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kimberly Clark Worldwide Inc
Original Assignee
Individual
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Individual filed Critical Individual
Publication of CA2221565A1 publication Critical patent/CA2221565A1/en
Abandoned legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09BORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/0071Process features in the making of dyestuff preparations; Dehydrating agents; Dispersing agents; Dustfree compositions
    • C09B67/0075Preparations with cationic dyes
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B41PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41MPRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B41PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41MPRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/28Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using thermochromic compounds or layers containing liquid crystals, microcapsules, bleachable dyes or heat- decomposable compounds, e.g. gas- liberating
    • B41M5/282Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using thermochromic compounds or layers containing liquid crystals, microcapsules, bleachable dyes or heat- decomposable compounds, e.g. gas- liberating using thermochromic compounds
    • B41M5/284Organic thermochromic compounds
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B41PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41MPRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/40Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography
    • B41M5/46Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography characterised by the light-to-heat converting means; characterised by the heat or radiation filtering or absorbing means or layers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B41PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41MPRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M7/00After-treatment of prints, e.g. heating, irradiating, setting of the ink, protection of the printed stock
    • B41M7/0009Obliterating the printed matter; Non-destructive removal of the ink pattern, e.g. for repetitive use of the support
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B43WRITING OR DRAWING IMPLEMENTS; BUREAU ACCESSORIES
    • B43MBUREAU ACCESSORIES NOT OTHERWISE PROVIDED FOR
    • B43M11/00Hand or desk devices of the office or personal type for applying liquid, other than ink, by contact to surfaces, e.g. for applying adhesive
    • B43M11/06Hand-held devices
    • B43M11/08Hand-held devices of the fountain-pen type
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/61Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/67Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
    • C07C45/68Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
    • C07C45/70Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction with functional groups containing oxygen only in singly bound form
    • C07C45/71Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction with functional groups containing oxygen only in singly bound form being hydroxy groups
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C49/00Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/20Unsaturated compounds containing keto groups bound to acyclic carbon atoms
    • C07C49/213Unsaturated compounds containing keto groups bound to acyclic carbon atoms containing six-membered aromatic rings
    • C07C49/217Unsaturated compounds containing keto groups bound to acyclic carbon atoms containing six-membered aromatic rings having unsaturation outside the aromatic rings
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C49/00Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/76Ketones containing a keto group bound to a six-membered aromatic ring
    • C07C49/794Ketones containing a keto group bound to a six-membered aromatic ring having unsaturation outside an aromatic ring
    • C07C49/796Ketones containing a keto group bound to a six-membered aromatic ring having unsaturation outside an aromatic ring polycyclic
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C49/00Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/76Ketones containing a keto group bound to a six-membered aromatic ring
    • C07C49/84Ketones containing a keto group bound to a six-membered aromatic ring containing ether groups, groups, groups, or groups
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/347Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/58Preparation of carboxylic acid halides
    • C07C51/60Preparation of carboxylic acid halides by conversion of carboxylic acids or their anhydrides or esters, lactones, salts into halides with the same carboxylic acid part
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C65/00Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
    • C07C65/32Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups containing keto groups
    • C07C65/38Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups containing keto groups having unsaturation outside the aromatic rings
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/76Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/76Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring
    • C07C69/94Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring of polycyclic hydroxy carboxylic acids, the hydroxy groups and the carboxyl groups of which are bound to carbon atoms of six-membered aromatic rings
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08BPOLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B37/00Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
    • C08B37/0006Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
    • C08B37/0009Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid alpha-D-Glucans, e.g. polydextrose, alternan, glycogen; (alpha-1,4)(alpha-1,6)-D-Glucans; (alpha-1,3)(alpha-1,4)-D-Glucans, e.g. isolichenan or nigeran; (alpha-1,4)-D-Glucans; (alpha-1,3)-D-Glucans, e.g. pseudonigeran; Derivatives thereof
    • C08B37/0012Cyclodextrin [CD], e.g. cycle with 6 units (alpha), with 7 units (beta) and with 8 units (gamma), large-ring cyclodextrin or cycloamylose with 9 units or more; Derivatives thereof
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08BPOLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B37/00Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
    • C08B37/0006Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
    • C08B37/0009Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid alpha-D-Glucans, e.g. polydextrose, alternan, glycogen; (alpha-1,4)(alpha-1,6)-D-Glucans; (alpha-1,3)(alpha-1,4)-D-Glucans, e.g. isolichenan or nigeran; (alpha-1,4)-D-Glucans; (alpha-1,3)-D-Glucans, e.g. pseudonigeran; Derivatives thereof
    • C08B37/0012Cyclodextrin [CD], e.g. cycle with 6 units (alpha), with 7 units (beta) and with 8 units (gamma), large-ring cyclodextrin or cycloamylose with 9 units or more; Derivatives thereof
    • C08B37/0015Inclusion compounds, i.e. host-guest compounds, e.g. polyrotaxanes
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09BORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/0071Process features in the making of dyestuff preparations; Dehydrating agents; Dispersing agents; Dustfree compositions
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09BORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/0071Process features in the making of dyestuff preparations; Dehydrating agents; Dispersing agents; Dustfree compositions
    • C09B67/0092Dyes in solid form
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D105/00Coating compositions based on polysaccharides or on their derivatives, not provided for in groups C09D101/00 or C09D103/00
    • C09D105/16Cyclodextrin; Derivatives thereof
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00Inks
    • C09D11/16Writing inks
    • C09D11/17Writing inks characterised by colouring agents
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00Inks
    • C09D11/30Inkjet printing inks
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00Inks
    • C09D11/30Inkjet printing inks
    • C09D11/32Inkjet printing inks characterised by colouring agents
    • C09D11/328Inkjet printing inks characterised by colouring agents characterised by dyes
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00Inks
    • C09D11/30Inkjet printing inks
    • C09D11/36Inkjet printing inks based on non-aqueous solvents
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03GELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00Developers
    • G03G9/08Developers with toner particles
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03GELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00Developers
    • G03G9/08Developers with toner particles
    • G03G9/0825Developers with toner particles characterised by their structure; characterised by non-homogenuous distribution of components
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03GELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00Developers
    • G03G9/08Developers with toner particles
    • G03G9/087Binders for toner particles
    • G03G9/08775Natural macromolecular compounds or derivatives thereof
    • G03G9/08777Cellulose or derivatives thereof
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03GELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00Developers
    • G03G9/08Developers with toner particles
    • G03G9/09Colouring agents for toner particles
    • G03G9/0906Organic dyes
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03GELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00Developers
    • G03G9/08Developers with toner particles
    • G03G9/09Colouring agents for toner particles
    • G03G9/0926Colouring agents for toner particles characterised by physical or chemical properties
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03GELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00Developers
    • G03G9/08Developers with toner particles
    • G03G9/097Plasticisers; Charge controlling agents
    • G03G9/09708Inorganic compounds
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03GELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00Developers
    • G03G9/08Developers with toner particles
    • G03G9/097Plasticisers; Charge controlling agents
    • G03G9/09733Organic compounds
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03GELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00Developers
    • G03G9/08Developers with toner particles
    • G03G9/097Plasticisers; Charge controlling agents
    • G03G9/09733Organic compounds
    • G03G9/09741Organic compounds cationic
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03GELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00Developers
    • G03G9/08Developers with toner particles
    • G03G9/097Plasticisers; Charge controlling agents
    • G03G9/09733Organic compounds
    • G03G9/0975Organic compounds anionic
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03GELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00Developers
    • G03G9/08Developers with toner particles
    • G03G9/097Plasticisers; Charge controlling agents
    • G03G9/09733Organic compounds
    • G03G9/09758Organic compounds comprising a heterocyclic ring
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03GELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00Developers
    • G03G9/08Developers with toner particles
    • G03G9/097Plasticisers; Charge controlling agents
    • G03G9/09733Organic compounds
    • G03G9/09775Organic compounds containing atoms other than carbon, hydrogen or oxygen
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03GELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00Developers
    • G03G9/08Developers with toner particles
    • G03G9/097Plasticisers; Charge controlling agents
    • G03G9/09783Organo-metallic compounds
    • G03G9/09791Metallic soaps of higher carboxylic acids
    • GPHYSICS
    • G06COMPUTING; CALCULATING OR COUNTING
    • G06KGRAPHICAL DATA READING; PRESENTATION OF DATA; RECORD CARRIERS; HANDLING RECORD CARRIERS
    • G06K1/00Methods or arrangements for marking the record carrier in digital fashion
    • G06K1/12Methods or arrangements for marking the record carrier in digital fashion otherwise than by punching
    • G06K1/121Methods or arrangements for marking the record carrier in digital fashion otherwise than by punching by printing code marks
    • GPHYSICS
    • G06COMPUTING; CALCULATING OR COUNTING
    • G06KGRAPHICAL DATA READING; PRESENTATION OF DATA; RECORD CARRIERS; HANDLING RECORD CARRIERS
    • G06K19/00Record carriers for use with machines and with at least a part designed to carry digital markings
    • G06K19/06Record carriers for use with machines and with at least a part designed to carry digital markings characterised by the kind of the digital marking, e.g. shape, nature, code
    • G06K19/06009Record carriers for use with machines and with at least a part designed to carry digital markings characterised by the kind of the digital marking, e.g. shape, nature, code with optically detectable marking
    • G06K19/06046Constructional details
    • GPHYSICS
    • G09EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09FDISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F3/00Labels, tag tickets, or similar identification or indication means; Seals; Postage or like stamps
    • G09F3/02Forms or constructions
    • G09F3/0291Labels or tickets undergoing a change under particular conditions, e.g. heat, radiation, passage of time
    • G09F3/0294Labels or tickets undergoing a change under particular conditions, e.g. heat, radiation, passage of time where the change is not permanent, e.g. labels only readable under a special light, temperature indicating labels and the like
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B41PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41MPRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M3/00Printing processes to produce particular kinds of printed work, e.g. patterns
    • B41M3/14Security printing
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/31504Composite [nonstructural laminate]
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/31504Composite [nonstructural laminate]
    • Y10T428/31971Of carbohydrate
    • Y10T428/31993Of paper
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/20Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
    • Y10T442/2582Coating or impregnation contains an optical bleach or brightener or functions as an optical bleach or brightener [e.g., it masks fabric yellowing, etc.]
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/20Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
    • Y10T442/259Coating or impregnation provides protection from radiation [e.g., U.V., visible light, I.R., micscheme-change-itemave, high energy particle, etc.] or heat retention thru radiation absorption

Abstract

A light-stable colored composition which includes a colorant and a radiation transorber. The colorant, in the presence of the radiation transorber, is adapted, upon exposure of the transorber to specific, narrow bandwidth radiation, to be mutable. The radiation transorber also imparts light-stability to the colorant so that the colorant does not fade when exposed to sunlight or artificial light.

Description

CA 02221~6~ 1997-12-0~

NOVEL COLORANTS AND COLORANT MODIFIERS

Technical Field The present invention relates to a family of colorants and colorant modifiers. The colorant modifiers, according to the present invention, are capable of stabilizing a color to ordinary light and/or rendering the colorant mutable when exposed to specific wavelengths of electromagnetic radiation.

Background of the Invention A major problem with colorants is that they tend to fade when exposed to sllnli~ht or artificial light. It is believed that most of the fading of colorants when exposed to light is due to photodegradation mech~ni.~m.s. These degradation mech~ni~m.s include oxidation or reduction of the colorants depending upon the environmental conditions in which the colorant is placed.
Fading of a colorant also depends upon the substrate upon which they reside.
Product analysis of stable photoproducts and intermediates has revealed several important modes of photodecomposition.
These include electron ejection from the colorant, reaction with ground-state or excited singlet state oxygen, cleavage of the central carbon-phenyl ring bonds to form amino substituted benzophenones, such as triphenylmethane dyes, reduction to form the colorless leuco dyes and electron or hydrogen atom abstraction to form radical intermediates.

CA 0222l~6~ l997-l2-0~

WO 97/01605 PCTtUS96/04689 Various factors such as temperature, humidity, gaseous reactants, including ~2~ ~3~ S~2, and NO2, and water soluble, nonvolatile photodegradation products have been shown to influence fading of colorants. The factors that effect colorant fading appear to exhibit a certain amount of interdependence. It is due to this complex behavior that observations for the fading of a particular colorant on a particular substrate cannot be applied to colorants and substrates in general.
Under conditions of constant temperature it has been observed that an increase in the relative humidity of the atmosphere increases the fading of a colorant for a variety of colorant-substrate systems (e.g., McLaren, K., ~. Soc. Dyers Colour, 1956, 72, 527). For example, as the relative humidity of the atmosphere increases, a fiber may swell because the moisture content of the fiber increases. This aids diffusion of gaseous reactants through the substrate structure.
The ability of a light source to cause photochemical change in a colorant is also dependent upon the spectral distribution of the light source, in particular the proportion of radiation of wavelengths most effective in c~llcing a ch~nge in the colorant and the qll~nfllm yield of colorant degradation as a function of wavelength. On the basis of photochemical principles, it would be expected that light of higher energy (short wavelengths) would be more effective at causing fading than light of lower energy (long wavelengths). Studies have revealed that this is not always the case. Over 100 colorants of different classes were studied and found that generally the most unstable were faded more efficiently by visible light while those of higher lightfastness were degraded mainly by ultraviolet light (McLaren, K., J. Soc. Dyers Colour, 1956, 72, 86).
The influence of a substrate on colorant stability can be extremely important. Colorant fading may be retarded o r promoted by some chemical group within the substrate. Such a group can be a ground-state species or an excited-state species.
The porosity of the substrate is also an important ~actor in CA 0222l~6~ l997-l2-0~

WO 97/01605 ~ PCT/US96/04689 colorant stability. A high porosity can promote fading of a colorant by facilitating penetration of moisture and gaseous reactants into the substrate. A substrate may also act as a protective agent by screening the colorant from light of S wavelengths capable of c~llcing degradation.
The purity of the substrate is also an important consideration whenever the photochemistry of dyed technical polymers is considered. For example, technical-grade cotton, viscose rayon, polyethylene, polypropylene, and polyisoprene are known to contain carbonyl group impurities. These impurities absorb light of wavelengths greater than 300 nm, which are present in sunlight, and so, excitation of these ilnpuliLies may lead to reactive species capable of c~ in~; colorant fading (van Beek, H.C.A., Col. Res. Appl., 1983, 8(3), 176).
Therefore, there exists a great need for methods and compositions which are capable of stabilizing a wide variety of colorants from the effects of both sunlight and artificial light.
There is also a need for colorants that can be mllt~te~l, preferably from a colored to a colorless form, when exposed to a specific predetermined wavelength of electromagnetic radiation.
For certain uses, the ideal colorant would be one that is stable in ordinary light and can be mutated to a colorless form when exposed to a specific predetermined wavelength of electromagnetic radiation.
S~mm~ry of the Invention The present invention addresses the needs described above by providing compositions and methods for stabilizing colorants against radiation including radiation in the visible wavelength range. In addition, the present invention provides certain embodiments in which the light-stable colorant system is mutable by exposure to certain narrow bandwidths of radiation. In certain embodiments, the colorant system is stable in ordinary visible light and is mutable when exposed to a specific wavelength of electromagnetic radiation.

CA 02221~6~ 1997-12-0~

In one embodiment, the present invention provides a composition comprising a colorant which, in the presence of a radiation transorber, is mutable when exposed to a specific wavelength of radiation, while at the same time, provides light stability to the colorant when the composition is exposed to sunlight or artificial light. The radiation transorber may be any material which is adapted to absorb radiation and interact with the colorant to effect the mutation of the colorant. Generally, the radiation transorber cont~ins a photoreactor and a wavelength-specific sensitizer. The wavelength-specific sensitizer generally absorbs radiation having a specific wavelength, and therefore a specific amount of energy, and transfers the energy to the photoreactor. It is desirable that the mutation of the colorant be irreversible.
The present invention also relates to colorant compositions having improved stability, wherein the colorant is associated with a modified photoreactor. It has been determined that conventional photoreactors, which normally contain a carbonyl group with a functional group on the carbon alpha to the carbonyl group, acquire the ability to stabilize colorants when the functional group on the alpha carbon is removed via dehydration.
Accordingly, the present invention also includes a novel method of dehydrating photoreactors that have a hydroxyl group in the alpha position to a carbonyl group. This reaction is neces.s~ry to impart the colorant stabilizing capability to the photoreactor. The novel method of dehydrating photoreactors that have a hydroxyl group in the alpha position to a carbonyl group can be used with a wide variety of photoreactors to provide the colorant stabilizing capability to the photoreactor. The resulting modified photoreactor can optionally be linked to wavelength-selective sensitizer to impart the capability of decolorizing a colorant when exposed to a predetermined narrow wavelength of electromagnetic radiation. Accordingly, the present invention provides a photoreactor capable of stabilizing a colorant that it is admixed with.

CA 02221~6~ 1997-12-0~
SUBSTITUTE SHEET ' . '' In certain embodiments of the present invention, the mixture of colorant and radiation transorber is mutable upon S exposure to radiation. In this embodiment, the photoreactor may or may not be modi~led as described above to impart stability when admixed to a colorant. In one embodiment, an ultraviolet ~ radiation transorber is adapted to absorb ultraviolet radiation and interact with the colorant to effect the irreversible mutation of the colorant. It is desirable that the ultraviolet radiation transorber absorb ultraviolet radiation at a wavelength of from about 4 to about 300 nanon~eters. It is even more desirable that the ultraviolet radiation transorber absorb ultraviolet radiation at a wavelength of 100 to 300 nanometers. The colorant in combination with the ultraviolet radiation transorber remains stable when exposed to sunlight or artificial light. If the photoreactor is modified as described above, the colorant has improved stability when exposed to sunlight or artificial light.
Another stabilizer that is considered part of the present invention is an arylketoalkene having the following general formula:

~I C/ 1 R4--C--C~ R2 wherein Rl is hydrogen, an alkyl, alkenyl, cycloalkyl, heterocycloalkyl, aryl or a heteroaryl group;
R2 is hydrogen, aLkyl, alkenyl, cycloaIkyl, heterocycloalkyl, aryl or a heteroaryl group;
R3 is hydrogen, alkyl, alkenyl, cycloalkyl, heterocycloalkyl, aryl or a heteroaryl group; and R4 is an aryl, heteroaryl, or substituted aryl group.
Preferably, the alkene group is in the trans configuration.

A~ENDED SHEET

SUBSTITUTE SHEET ' .. . . .

5a Desirably, the arylketoalkene stabilizing compound has the following formula:

AM~NDED SHEET

CA 02221~6~ 1997-12-0 wo 97/01605 PCT/U~ 5/~

~CH=CII R~

which efficiently absorbs radiation having a wavelength at about 308 nanometers, or o ~CH=C~C--CH3 which efficiently absorbs radiation having a wavelength at about 2~0 nanometers. Desirably, arylketoalkene stabilizing compound of the present invention is in the trans configuration with respect to the double bond. However, the sensitizer may also be in the cis configuration across the double bond.
Accordingly, this embodiment of the present invention provides a stabilizing molecule, the above arylketoalkene, which when associated with a colorant, stabilizes the colorant.
Therefore, the above arylketoalkene can be used as an additive to any colorant composition. For example, as the arylketoalkene compound is poorly soluble in water, i~ can be directly added to solvent or oil based (not water based) colorant compositions.
Additionally, the arylketoalkene compound can be added to other colorant compositions that contain additives enabling the solubilization of the compound therein. Further, the arylketoalkene stabilizing compounds can be solubilized in an aqueous solution by attaching the compound to a large water soluble molecule, such as a cyclodextrin.
In another embodiment of the present invention, the colored composition of the present invention may also contain a molecular includant having a chemical structure which defines at least one cavity. The molecular includants include, but are not limited to, clathrates, zeolites, and cyclodextrins. Each of the colorant and ultraviolet radiation transorber or modified photoreactor or arylketoalkene stabilizing compound can be associated with one or more molecular includant. The includant CA 02221~6~ 1997-12-0~
SUBSTITUTE SHEET , .' . ,~, , . . - ~- .- :

can have multiple radiation transorbers associated therewith. In other embodiments, the includant can have many modified photoreactors or arylketoalkene stabilizing compounds associated therewith.
In some embodiments, the colorant is at least partially ~ included within a cavity of the molecular includant and the ultraviolet radiation transorber or modified photoreactor or arylketoalkene stabilizer is associated with the molecular includant outside of the cavity. In some embodiments, the ultraviolet radiation transorber or modified photoreactor or arylketoalkene stabilizer is covalently coupled to the outside of the molecular includant.
The present invention also relates to a method of mutating the colorant associated with the composition of the present invention. The method comprises irradiating a composition containing a mutable colorant and an ultraviolet radiation transorber with ultraviolet radiation at a dosage level sufficient to mutate the colorant. As stated above, in some embodiments the composition further includes a molecular includant. In another embodiment, the composition is applied to a substrate before being irradiated with ultraviolet radiation. ~t is desirable that the mutated colorant is stable.
The present invention is also related to a substrate having an image thereon that is formed by the composition of the present invention.~ The colorant, in the presence of the radiation transorber or modified photoreactor or arylketoalkene compound, is more stable to sunlight or artificial light. When a molecular includant is included in the composition, the colorant is stabilized by a lower ratio of radiation transorbers to colorant.
The present invention also includes a dry im~ging process wherein the im~ging process utilizes, for example, the following three mutable colorants: cyan, magenta, and yellow. These .. ..
AM~NDED SHEET

SUBSTITUTE SHEET

7a mutable colorants can be layered on the substrate or can be mixed together and applied as a single layer. Using, for example, laser AMEhlDED S~IEET

CA 02221~6~ 1997-12-0~
SUBSTITUTE SHEET
.. ..

technology witll three lasers at different wavelengths, an image can be created by selectively "erasing" colorants. A further 5 advantage of the present invention is that the rem~ining colorants are stable when exposed to ordinary light.
The present invention also includes a method of storing data utilizing the mutable colorant on a substrate, such as a disc. The colorant is selectively mutated using a laser at the appropriate wavelength to provide the binary information required for storing the information. The present invention is particularly useful for this purpose because the unmutated colorant is stabilized to ordinary light by the radiation transorber and can be further stabilized by the optionally included molecular includant.
The present invention also includes data processing forms for use with photo-sensing apparatus that detect the presence of indicia at indicia-receiving locations of the form. The data processing forms are composed of a sheet of carrier material and a plurality of indicia-receiving locations on the surface of the sheet. The indicia-receiving locations are defined by a colored composition including a mutable colorant and a radiation transorber.
These and other features and jadvantages of the present invention will become apparent after a review of the following detailed description of the disclosed embodiments and the appended claims.

Brief Description of the Figures Figure 1 illustrates an ultraviolet radiation transorber/
mutable colorant/ molecular includant complex wherein the mutable colorant is malachite green, the ultraviolet radiation transorber is IRGACURE(~) 184 (l-hydroxycyclohexyl phenyl ketone), and the molecular includant is B-cyclodextrin.
Figure 2 illustrates an ultraviolet radiation transorber/
muta~e colorant/ molecular includant complex wherein the A~vl~.~DED SHEEF

CA 02221~6~ 1997-12-0~
.
SUBSTITUTE SHEET , mutable colorant is Victoria Pure ~3lue BO (Basic Blue 7), the ultraviolet radiation transorber is IRGACUl~E(~) 184 ( l-hydroxycyclohexyl phenyl ketone), and the molecular includant is ~3-cyclodextrin.
Figure 3 is a plot of the average number of ultraviolet radiation transorber molecules which are covalently coupled to each molecule of a molecular includant in several colored compositions, which number also is referred to by the term, "degree of substitution," versus the decolorization time upon exposure to 222-nanometer excimer lamp ultraviolet radiation.
Figure 4 is an illustration of several 222 nanometer excimer lamps arranged in four parallel columns wherein the twelve numbers represent the locations where twelve intensity measurements were obtained approximately 5.5 centimeters from the excimer lamps.
Figure 5 is an illustration of several 222 nanometer excimer lamps arranged in four parallel columns wherein the nine numbers represent the locations where nine intensity measurements were obtained approximately 5.5 centimeters from the excimer lamps.
Figure 6 is anl illustration of several 222 nanometer excimer lamps arranged in four parallel columns wherein the location of the number " 1" denotes the location where ten intensity measurements were obtained from increasing distances from the lamps at that location. (The measurements and their distances from the lamp are sllmm~ri7ed in Table 12.) Detailed Description of the Invention The present invention relates in general to a light-stable colorant system that is optionally mutable by exposure to narrow band-width radiation. The present invention more particularly relates to a composition comprising a colorant which, in the 3~ presence of a radiation transorber, is stable under ordinary light AMENDED SHEEr SUBSTITUTESH}31~T ~ .'' .' . ~ ;;

9a ~ut is mutable when exposed to specific~ narrow band-width radiation. The radiatiQn transorber is capable of absor~ing AMEN~E~ SHEET

CA 02221~6~ 1997-12-0~

WO 97/0160S PCTIU.,,. ~ IC~9 radiation and interacting with the colorant to effect a mutation of the colorant. The radiation transorber may be any material which is adapted to absorb radiation and interact with the colorant to effect the mutation of the colorant. Generally, the radiation S transorber contains a photoreactor and a wavelength-specific sensitizer. The wavelength-specific sensitizer generally absorbs radiation having a specific wavelength, and therefore a specific amount of energy, and transfers the energy to the photoreactor It is desirable that the mutation of the colorant be irreversible.
The present invention also relates to colorant compositions having improved stability, wherein the colorant is associated with a modified photoreactor. It has been determined that conventional photoreactors which normally contain a carbonyl group with a functional group on the carbon alpha to the carbonyl group acquire the ability to stabilize colorants when the functional group on the alpha carbon is removed. Accordingly, the present invention also includes a novel method of dehydrating photoreactors that have a hydroxyl group in the alpha position to a carbonyl group. This reaction is necessary to hllpal L the colorant stabilizing capability to the photoreactor. The novel method of dehydrating photoreactors that have a hydroxyl group in the alpha position to a carbonyl group can be used with a wide variety of photoreactors to provide the colorant stabilizing capability to the photoreactor. The resulting modified photoreactor can optionally be linked to a wavelength-selective sensitizer to impart the capability of decolorizing a colorant when exposed to a predetermined narrow wavelength of electromagnetic radiation. Accordingly, the present invention provides a photoreactor capable of stabilizing a colorant with which it is admixed.
In certain embodiments of the present invention, the colorant and radiation transorber is mutable upon exposure to radiation. In this embodiment, the photoreactor may or may not be modified as described above to impart stability when admixed to a colorant. In one embodiment, an ultraviolet radiation CA 02221~6~ 1997-12-0~

WO 97/01605 PcT/u~ 1~~p9 transorber is adapted to absorb ultraviolet radiation and interact with the colorant to effect the irreversible mutation of the colorant. It is desirable that the ultraviolet radiation transorber absorb ultraviolet radiation at a wavelength of from about 4 to about 300 nanometers. If the photoreactor in the radiation transorber is modified as described above, the colorant has improved stability when exposed to sunlight or artificial light.
The present invention also relates to a method of mllt~tin~
the colorant in the composition of the present invention. The method comprises irr~ tin~; a composition cont~ining a mutable colorant and a radiation transorber with radiation at a dosage level sufficient to ml~t~te the colorant.
The present invention further relates to a method of stabilizing a colorant comprising associating the modified photoreactor described above with the colorant. Optionally, the photoreactor may be associated with a wavelength-selective sensitizer, or the photoreactor may be associated with a molecular includant, or both.
Thus, the stabilizing composition produced by the process of dehydrating a tertiary alcohol that is alpha to a carbonyl group on a photoreactor is shown in the following general formula:

~I ~C/ 1 R4--C--C~ R2 wherein R, is hydrogen, an alkyl, alkenyl, cycloalkyl, 25heterocycloalkyl, aryl or a heteroaryl group;
R2 is hydrogen, alkyl, alkenyl, cycloalkyl, heterocycloalkyl, aryl or a heteroaryl group;
R3 is hydrogen, alkyl, alkenyl, cycloalkyl, heterocycloalkyl, aryl or a heteroaryl group; and 30R4 is an aryl, heteroaryl, or substituted aryl group.
Preferably, the alkene group is in the trans con~lguration.

S~JBSTITUTE SHEET ,~

Desirably, the arylketoalkene st~bilizin~ compound is represented by the ~lowing form~

~CH=C R~

or ~GH=CH--C--CH3 According~y, this embodiment of the present invention provides a stabili~ing molecule, the above arylketoalkene, which when assvciated with a colorant, stabilizes the coloran~.
Therefo~e, the above arylketoaLkene can be used as ~n additive to any colorant composition. For example, as the arylketoalkene compound is not water soluble, it c~n be ~irectly added to solvent or oil ~ased ~(no~ water ~ased) colorant compositions.
Addition~ly, th~ aryllcetoaLkene compound c~n be added to other colorant compositions that contain additives enabling the s~lubili~ation af the compound therein. Further, the arylketoalkene stabili~ing compounds can be solubili~ed in an aqueous solution by atta~hing the compound to a large water solu~le molecule, such as a cyclodextrin.
After de~mitions of varic~us terms used herein, the mutable colorant composition o~ the pr~sent invention and methods for making and using tha~ composition are described in detail, ~llowed by a detailed description o~ the impr~ved light stable composition of the present invention and methods ~or n~kin~ the improved light stable compositions.

Ahl~NDE~ S~I~ET

CA 02221~6~ 1997-12-0~

Definitions The term "composition" and such variations as "colored composition" are used herein to mean a colorant, and a radiation transorber or a modified photoreactor or an aryL~etoalkene S stabilizer. Where the colored composition includes the modified photoreactor, it may further comprise a wavelength-selective sen~iti7er. Where the colored composition includes the aryLketoaL~ene stabilizer, it may further comprise a photoreactor.
When reference is being made to a colored composition which is adapted for a specific application, the term "composition-based" is used as a modifier to indicate that the material includes a colorant, an ultraviolet radiation transorber or a modified photoreactor or an arylketoalkene stabilizer, and, optionally, a molecular includant.
As used herein, the term "colorant" is meant to include, without limit~tion, any material which typically will be an organic material, such as an organic colorant or pigment. Desirably, the colorant will be subst~nti~lly transparent to, that is, will not significantly interact with, the ultraviolet radiation to which it is exposed. The term is meant to include a single material or a mixture of two or more materials.
As used herein, the term "irreversible" means that the colorant will not revert to its original color when it no longer is exposed to ultraviolet radiation.
The term "radiation transorber" is used herein to mean any material which is adapted to absorb radiation at a specific wavelength and interact with the colorant to affect the mutation of the colorant and, at the same time, protect the colorant from fading in sunlight or artificial light. The term "ultraviolet radiation transorber" is used herein to mean any material which is adapted to absorb ultraviolet radiation and interact with the colorant to effect the mutation of the colorant. In some embodiments, the ultraviolet radiation transorber may be an organic compound. Where the radiation transorber is compnsed CA 0222l~6~ l997-l2-0 WO 97/01605 PcT/u' _5/~1C~

of a wavelength-selective sensitizer and a photoreactor, the ~hotoreactor mav oDtionally be modified as described below.
., .
The term "compound" is intended to include a single material or a mixture of two or more materials. If two or more S materials are employed, it is not necessary that all of them absorb radiation of the same wavelength. As discussed more fully below, a radiation transorber is comprised of a photoreactor and a wavelength selective sensitizer. The radiation transorber has the additional property of m~king the colorant with which the radiation transorber is associated light stable to s-lnli~ht or alci~lcial light.
The term "light-stable" is used herein to mean that the colorant, when associated with the radiation transorber or modified photoreactor or arylketoalkene stabilizer molecule, is more stable to light, including, but not limited to, sllnli~ht or artificial light, than when the colorant is not associated with these compounds.
The term "molecular includant," as used herein, is intended to mean any substance having a chemical structure which (lefines at least one cavity. That is, the molecul~r includant is a cavity-cont~ining structure. As used herein, the term "cavity" is meant to include any opening or space of a size sufficient to accept at least a portion of one or both of the colorant and the ultraviolet radiation transorber.
The term "functionalized molecular includant" is used herein to mean a molecular includant to which one or more molecules of an ultraviolet radiation transorber or modified photoreactor or arylketoalkene stabilizer are covalently coupled to each molecule of the molecular includant. The term "degree of substitution" is used herein to refer to the number of these molecules or leaving groups (defined below) which are covalently coupled to each molecule of the molecular includant.
The term "derivatized molecular includant" is used herein to mean a molecular includant having more than two leaving groups covalently coupled to each molecule of molecular CA 0222l~6~ l997-l2-0~

WO 97/0160S PcT/u:~ 5.'~16W

includant. The term "leaving group" is used herein to mean any leaving group capable of participating in a bimolecular nucleophilic substitution reaction.
The term "artificial light" is used herein to mean light S having a relatively broad bandwidth that is produced from conventional light sources, including, but not limi~etl to, conventional incandescent light bulbs and fluorescent light bulbs.
The term "ultraviolet radiation" is used herein to mean electromagnetic radiation having wavelengths in the range of from about 4 to about 400 nanometers. The especially desirable ullraviolet radiation range for the present invention is between approxim~tely 100 to 375 nanometers. Thus, the term includes the regions commonly referred to as ultraviolet and vacuum ultraviolet. The wavelength ranges typically ~c.~igned to these two regions are from about 180 to about 400 nanometers and from about 100 to about 180 nanometers, respectively.
The terrn "thereon" is used herein to mean thereon or therein. For example, the present invention includes a substrate having a colored composition thereon. According to the 0 definition of "thereon" the colored composition may be present on the substrate or it may be in the substrate.
The term "mutable," with reference to the colorant, is used to mean that the absorption maximum of the colorant in the visible region of the electromagnetic spectrum is capable of being mutated or changed by exposure to radiation, preferably ultraviolet radiation, when in the presence of the radiation transorber. In general, it is only necessary that such absorption m~ximum be mutated to an absorption m~ximum which is different from that of the colorant prior to exposure to the ultraviolet radiation, and that the mutation be irreversible. Thus, the new absorption maximum can be within or outside of the visible region of the electromagnetic spectrum. In other words, the colorant can mutate to a different color or be rendered colorless. The latter is also desirable when the colorant is used in data processing forms for use with photo-sensing apparatus that CA 0222l~6~ l997-l2-0~

WO 97/01605 PcT/u:~ 5'~ S~i~9 detect the presence of indicia at indicia-receiving locations of the form.

Functionalized Molecular Includant S In several embo-limen~, the radiation transorber molecule, the wavelength-selective sen~iti7çr, the photoreactor, or the aryL~etoalkene stabilizer may be associated with a rnolecular includant. It is to be noted that in all the forn ~ c, the number of such molecules can be between approximately 1 and approximately 21 molecules per molecular includant. Of course, in certain situations, there can be more than 21 molecules per molecular includant molecule. Desirably, there are more than three of such molecules per molecular includant.
The degree of substitution of the functionalized molecular includant may be in a range of from 1 to approxim~tely 21. As another example, the degree of substitution may be in a range of from 3 to about 10. As a further example, the degree of substitution may be in a range of from about 4 to about 9.
The colorant is associated with the functionalized molecular includant. The term "associated" in its broadest sense means that the colorant is at least in close proximity to the functionalized molecular includant. For example, the colorant may be m~int~ined in close proximity to the functionalized molecular includant by hydrogen bonding, van der Waals forces, or the like.
Alternatively, the colorant may be covalently bonded to the functionalized molecular includant, although this normally is neither desired nor necessary. As a further example, the colorant may be at least partially included within the cavity of the functionalized molecular includant.
The examples below disclose methods of preparing and associating these colorants and ultraviolet radiation transorbers to ~-cyclodextrins. For illustrative purposes only, Examples 1, 2, 6, and 7 disclose one or more methods of preparing and associating colorants and ultraviolet radiation transorbers to cyclodextrins.

CA 02221~6~ 1997-12-0~

WO 97/01605 PCT/u:~r~s~ 16~9 In those embodiments of the present inveniton in which the ult~aviolet radiation transorber is covalently coupled to the molecular includant, the efficiency of energy transfer from the ultraviolet radiation transorber to the colorant is, at least in part, S a function of the number of ultraviolet radiation transorber molecules which are attached to the molecular includant. It now is known that the synthetic methods described above result in covalently coupling an average of two transorber molecules to each molecule of the molecular includant. Because the time required to mutate the colorant should, at least in part, be a function of the number of ultraviolet radiation transorber molecules coupled to each molecule of molecular includant, there is a need for an improved colored composition in which an average of more than two ultraviolet radiation transorber molecules are covalently coupled to each molecule of the molecular includant.
Accordingly, the present invention also relates to a composition which includes a colorant and a functionalized molecular includant. For illustrative purposes only, Examples 12 through 19, and 21 through 22 disclose other methods of preparing and associating colorants and ultraviolet radiation transorbers to cyclodextrins, wherein more than two molecules of the ultraviolet radiation transorber are covalently coupled to each molecule of the molecular includant. Further, Examples 29 and 31 disclose methods of preparing and associating arylketoalkene stabilizers with cyclodextrin, wherein the cyclodextrin has an average of approximately 3 or 4 stabilizer molecules attached thereto.
The present invention also provides a method of m~king a ~ 30 functionalized molecular includant. The method of m~kinp; a functionalized molecular includant involves the steps of providing - a derivatized ultraviolet radiation transorber having a nucleophilic group, providing a derivatized molecular includant having more than two leaving groups per molecule, and reacting the derivatized ultraviolet radiation transorber with the CA 02221~6~ 1997-12-0~

WO 97/0160~; PCT/llS96/04689 derivatized molecular includant under conditions sufficient to result in the covalent coupling of an average of more than two ultraviolet radiation transorber molecules to each molecular includant molecule. 13y way of example, the derivatized S ultraviolet radiation transorber may be 2-L~-(2-methyl-2-mercaptomethylpropionyl)phenoxy]ethyl 1,3-dioxo-2-isoindoline-acetate. As another example, the derivatized ultraviolet radiation transorber may be 2-mercaptomethyl-2-methyl-4'-t2-[p-(3-oxobutyl)phenoxy]ethoxy~propiophenone.
In general, the derivatized ultraviolet radiation transorber and the derivatized molecular includant are selected to cause the covalent coupling of the ultraviolet radiation transorber to the molecular includant by means of a bimolecular nucleophilic substitution reaction. Consequently, the choice of the nucleophilic group and the leaving groups and the preparation of the derivatized ultraviolet radiation transorber and derivatized molecular includant, respectively, may be readily accomplished by those having ordinary skill in the art without the need for undue experimentation.
The nucleophilic group of th~ derivatized ultraviolet radiation transorber may be any nucleophilic group capable of particip~ting in a bimolecular nucleophilic substitution reaction, provided, of course, that the reaction results in the covalent coupling of more than two molecules of the ultraviolet radiation transorber to the molecular includant. The nucleophilic group generally will be a Lewis base, i.e., any group having an unshared pair of electrons. The group may be neutral or negatively charged. Examples of nucleophilic groups include, by way of illustration only, aliphatic hydroxy, aromatic hydroxy, aL~oxides, carboxy, carboxylate, amino, and mercapto.
Similarly, the leaving group of the derivatized molecular includant may be any leaving group capable of participating in a bimolecular nucleophilic substitution reaction, again provided that the reaction results in the covalent coupling of more than two molecules of the ultraviolet radiation transorber to the molecular CA 0222l~6~ l997-l2-0~

WO 97/01605 PCTtUS96/04689 includant. Examples of leaving groups include, also by way of illustra~i~n orl,~, r-t~ enesulfonates (tosylates), p-bromobenzenesulfonates (brosylates), p-nitrobenzenesulfonates (nosylates), methanesulfonates (mesylates), oxonium ions, aL~yl S perchlorates, ammonioaL~ane sulfonate esters (betylates), aL~yl fluorosulfonates, trifluoromethanesulfonates (trifl~tes), nonafluorobutanesulfonates (nOn~ tes)~ and 2,2,2-trifluoroethanesulfonates (tresylates).
The reaction of the derivatized ultraviolet radiation transorber with the derivatized molecular includant is carried out in solution. The choice of solvent depends upon the solubilities of the two derivatized species. As a practical matter, a particularly useful solvent is N,N-dimethylformamide (DMF).
The reaction conditions, such as temperature, reaction time, and the like generally are matters of choice based upon the natures of the nucleophilic and leaving groups. Elevated temperatures usually are not required. For example, the reaction temperature may be in a range of from about 0~C to around ambient temperature, i.e., to 20~-25~C.
The preparation of the functionalized molecular includant as described above generally is carried out in the absence of the colorant. However, the colorant may be associated with the derivatized molecular includant before reacting the derivatized ultraviolet radiation transorber with the derivatized molecular includant, particularly if a degree of substitution greater than about three is desired. When the degree of substitution is about three, it is believed that the association of the colorant with the functionalized molecular includant still may permit the colorant to be at least partially included in a cavity of the function~li7e-1 molecular includant. At higher degrees of substitution, such as about six, steric hindrance may partially or completely prevent the colorant from being at least partially included in a cavity of the functionalized molecular includant. Consequently, the colorant may be associated with the derivatized molecular includant which normally will exhibit little, if any, steric CA 0222l~6~ l997-l2-0~

WO 97/01605 PCTtUS96/04689 hindrance. In this instance, the colorant will be at least partially included in a cavity of the derivatized molecular includant. The above-described bimolecular nucleophilic substitution reaction then may be carried out to give a colored composition of the present invention in which the colorant is at least partially included in a cavity of the functionalized molecular includant.

Mutable Compositions As stated above, the present invention provides compositions comprising a colorant which, in the presence of a radiation transorber, is mutable when exposed to a specific wavelength of radiation, while at the same time, provides light stability to the colorant with respect to slmli~ht and artificial light. Desirably, the mllt~te~1 colorant will be stable, i.e., not appreciably adversely affected by radiation normally encountered in the environment, such as natural or artificial light and heat.
Thus, desirably, a colorant rendered colorless will remain colorless inde~mitely.
The dye, ~or example, may be an organic dye. Organic dye classes include, by way of illustration only, triarylmethyl dyes, such as Malachite Green Carbinol base {4-(dimethylamino)-a-[4-(dimethylamino)phenyl]-a-phenylbenzene-methanol }, M~ hit~
Green Carbinol hydrochloride ~ N-4-[[4-(dimethylamino)phenyl]phenylmethylene]-2,5-cyclohexyldien- 1 -ylidene]-N-methyl-meth~n~minium chloride or bis~7-(dimethylamino)phenyl]phenylmethylium chloride }, and Malachite Green oxalate ~ N-4-[[4-(dimethylamino)phenyl]phenylmethylene]-2,5-cyclohexyldien- 1-ylidene]-N-methylmeth~n~minium chloride or bisCp-(dimethyl-amino)phenyl]phenylmethylium oxalate}; monoazo dyes, such as Cyanine Black, Chrysoidine [Basic Orange 2; 4-(phenylazo)-1,3-benzene~ mine monohydrochloride~, Victoria Pure Blue BO, Victoria Pure Blue B, basic fuschin and ~-Naphthol Orange;
t~ 7ine dyes, such as Methylene Green, zinc chloride double salt [3,7-bis(dimethylamino)-6-nitrophenothi~7in-S-ium chloride, zinc CA 02221~6~ 1997-12-0~

chloride double salt]; oxazine dyes, such as Lumichrome (7,8-dimethylalloxazine); naphth~limide dye~, such as Lucifer Yellow CH { 6-arnino-2-[(hydrazinocarbonyl)amino]-2,3-dihydro- 1,3-dioxo-lH-benz[de]isoquinoline-5,8-disulfonic acid dilithium salt};
azine dyes, such as Janus Green B {3-(diethylamino)-7-[[4-(dimethylamino)phenyl]azo]-5-phenylphen~7.inium chloride };
cyanine dyes, such as Indocyanine Green {Cardio-Green or Fox Green; 2-[7-[1,3-dihydro-1,1-dimethyl-3-(4-sulfobutyl)-2H-benz[e]indol-2-ylidene]- 1 ,3,5-heptatrienyl]- 1,1-dimethyl-3-(4-sulfobutyl)-lH-benz[e]indolium hydroxide inner salt sodium salt};
indigo dyes, such as Indigo {Indigo Blue or Vat Blue 1; 2-(1,3-dihydro-3-oxo-2H-indol-2-ylidene)- 1 ,2-dihydro-3H-indol-3-one };
collm~rin dyes, such as 7-hydroxy-4-methylcollm~rin (4-methylumbelliferone); benzimidazole dyes, such as Hoechst 33258 [bisben7.imide or 2-(4-hydroxyphenyl)-5-(4-methyl- 1-pipera-zinyl)-2,5-bi- 1 H-benzimidazole trihydrochloride pentahydrate];
paraquinoidal dyes, such as Hematoxylin { Natural Black 1; 7,1 lb-dihydrobenz[b]indeno[ 1 ,2-d]pyran-3,4,6a,9, 10(6H)-pentol };
fluorescein dyes, such as Fluorescein~mine (5-aminofluorescein);
diazonium salt dyes, such as Diazo Red RC (Azoic Diazo No. 10 or Fast Red RC salt; 2-methoxy-5-chlorobenzenediazonium chloride, zinc chloride double salt); azoic diazo dyes, such as Fast Blue BB salt (Azoic Diazo No. 20; 4-benzoylamino-2,5-diethoxybenzene diazonium chloride, zinc chloride double salt);
phenylene~ mine dyes, such as Disperse Yellow 9 [N-(2,4-dinitrophenyl)-1,4-phenylene~ mine or Solvent Orange 53];
diazo dyes, such as Disperse Orange 13 [Solvent Orange 52; 1-phenylazo-4-(4-hydroxyphenylazo)naphthalene]; anthraquinone dyes, such as Disperse Blue 3 [Celliton Fast Blue FFR; 1-methylamino-4-(2-hydroxyethylamino)-9, 10-anthraquinone], Disperse Blue 14 [Celliton Fast Blue B; 1,4-bis(methylani~no)-9,10-anthraquinone], and ~1i7.~rin Blue Black B (Mordant Black 13); trisazo dyes, such as Direct Blue 71 {Benzo Light Blue FFL
or Sirius Light Blue BRR; 3-[(4-[(4-[(6-amino-1-hydroxy-3-sulfo-2-naphthalenyl)azo]-6-sulfo- 1 -naphthalenyl)azo]- l-naphtha-CA 02221~6~ 1997-12-0 WO 97/01605 PCT/U !3_.';1~1 J~~

lenyl)azo]-1,5-naphthalenedisulfonic acid tetrasodium salt3;
xar~ene dyes, such as '~,7-dt~hlorofluorescein; proflavine dyes, such as 3,6-~liAminoacridine hemisulfate (Proflavine);
sulfonaphthalein dyes, such as Cresol Red (o-cresolsulfonaphthalein); phthalocyanine dyes, such as Copper Phthalocyanine {Pigment Blue 15; (SP-4-1)-[29H,31H-phthalocyanato(2-)-NZ9,N30,N3l,N32~copper}; carotenoid dyes, such as trans-13-carotene (Food Orange 5); c~rminic acid dyes, such as t~rmine, the aluminum or calcium-alllminllm lake of carminic acid (7-a-D-glucopyranosyl-9, 10-dihydro-3,5,6,8-tetrahydroxy- 1-methyl-9,10-dioxo-2-anthracenecarbonylic acid); azure dyes, such as Azure A [3-amino-7-(dimethylamino)phenot~ 7.in-5-ium chloride or 7-(dimethylamino)-3-imino-3H-phenothi~7ine hydrochloride]; and acridine dyes, such as Acridine Orange [13asic Orange 14; 3,8-bis(dimethylamino)acridine hydrochloride, zinc chloride double salt] and Acriflavine (Acriflavine neutral; 3,6-~ mino-10-methylacridinium chloride mixture with 3,6-acridinef liAmine).
Tlle present invention includes unique compounds, namely, radiation transorbers, that are capabl~ of absorbing narrow ultraviolet wavelength radiation, while at the same time, imparting light-stability to a colorant with which the compounds are associated. The compounds are synthesized by combining a wavelength-selective sensitizer and a photoreactor. The 2~ photoreactors oftentimes do not efficiently absorb high energy radiation. When combined with the wavelength-selective sensitizer, the resulting compound is a wavelength specific compound that efficiently absorbs a very narrow spectrum of radiation. The wavelength-selective sensitizer may be covalently coupled to the photoreactor.
By way of example, the wavelength-selective sen~iti7~r may be selected from the group consisting of phthaloylglycine and 4-(4-oxyphenyl)-2-butanone. As another example, the photoreactor may be selected from the group consisting of 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methylpropan- 1 -one and CA 0222l~6~ l997-l2-0~

WO 97/01605 PcT/u~ ~/ 1G%9 cyclohexyl-phenyl ketone ester. Other photoreactors are listed by way of example, in the detailed description below regarding the impoved stabilized composition of the present invention. As a further example, the ultraviolet radiation transorber may be 2-~-2-methyllactoyl)phenoxy]ethyl 1,3-dioxo-2-isoin-dolineacetate.
As still another example, the ultraviolet radiation transorber may be 2-hydroxy-2-methyl-4'-2-tp-(3-oxobutyl)phenoxy]-propiophenone.
Although the colorant and the ultraviolet radiation transorber have been described as separate compounds, they can be part of the same molecule. For example, they can be covalently coupled to each other, either directly, or indirectly through a relatively small molecule, or spacer. Alternatively, the colorant and ultraviolet radiation transorber can be covalently coupled to a large molecule, such as an oligomer or a polymer.
Further, the colorant and ultraviolet radiation transorber may be associated with a large molecule by van der Waals forces, and hydrogen bonding, among other me~n.c Other variations will be readily apparent to those having ordinary skill in the art.
For example, in an embodiment of the composition of the present invention, the composition further comprises a molecular includant. Thus, the cavity in the molecular includant can be a tunnel through the molecular includant or a cave-like space or a dented-in space in the molecular includant. The cavity can be isolated or independent, or connected to one or more other cavities.
The molecular includant can be inorganic or organic in nature. In certain embodiments, the chemical structure of the molecular includant is adapted to form a molecular inclusion complex. Examples of molecular includants are, by way of illustration only, clathrates or intercalates, zeolites, and cyclodextrins. Examples of cyclodextrins include, but are not limited to, a-cyclodextrin, ,B-cyclodextrin, y-cyclodextrin, hydroxypropyl ~-cyclodextrin, hydroxyethyl ,B-cyclodextrin, sulfated ~-cyclodextrin, hydroxyethyl a cyclodextrin, CA 02221~6~ 1997-12-0~

WO 97/01605 PCT/u~5~r~1fo9 carboxymethyle a cyclodextrin, carboxymethyl ~3 cyclodextrin, carboxymethyl ~ cyclodextrin. octyl succinated a cyclodextrin, octyl succinated ,B cyclodextrin, octyl succinated ~ cyclodextrin and sulfated ~ and ~-cyclodextrin (American Maize-Products Company, Hammond, Indiana).
The desired molecular includant is a-cyclodextrin. More particularly, in some embodiments, the molecular includant is an a-cyclodextrin. In other embodiments, the molecular includant is a 13--cyclodextrin. Although not wanting to be bound by the following theory, it is believed that the closer the transorber molecule is to the mutable colorant on the molecular includant, the more efficient the interaction with the colorant to effect mutation of the colorant. Thus, the molecular includant with functional groups that can react with and bind the transorber molecule and that are close to the binding site of the mutable colorant are the more desirable molecular includants.
In some embodiments, the colorant and the ultraviolet radiation transorber are associated with the molecular includant.
The term "associated", in its broadest sense, means that ~e colorant and the ultraviolet radiation transorber are at least in close proximity to the molecular includant. For exarnple, the colorant and/or the ultraviolet radiation transorber can be m~int~ined in close proximity to the molecular includant by hydrogen bonding, van der Waals forces, or the like.
Alternatively, either or both of the colorant and the ultraviolet radiation transorber can be covalently bonded to the molecular includant. In certain embodiments, the colorant will be associated with the molecular includant by means of hydrogen bonding and/or van der Waals forces or the like, while the ultraviolet radiation transorber is covalently bonded to the molecular includant. In other embodiments, the colorant is at least partially included within the cavity of the molecular includant, and the ultraviolet radiation transorber is located outside of the cavity of the molecular includant.

CA 02221~6~ 1997-12-0~
SUBSTITUTE SHEET ,;
,. .

In one embodiment wherein the colorant and the ultraviolet S radiation transorber are associated with the molecular includant, the colorant is crystal violet, the ultraviolet radiation transorber is a dehydrated phthaloylglycine-2959, and the molecular includant is ,13-cyclodextrin. In yet another embodiment wherein the colorant and the ultraviolet radiation transorber are associated with the molecular includant, the colorant is crystal violet, the ultraviolet radiation transorber is 4(4-hydroxyphenyl) butan-2-one-2959 (chloro substituted), and the molecular includant is ,13--cyclodextrin .
In another embodiment wherein the colorant and the ultraviolet radiation transorber are associated with the molecular includant, the colorant is malachite green, the ultraviolet radiation transorber is IRGACURE(~) 184, and the molecular includant is ,B--cyclodextrin as shown in Figure 1. In still another embodiment wherein the colorant and the ultraviolet radiation transorber are associated with the molecular includant, the colorant is Victoria Pure Blue BO, the ultraviolet ;adiation transorber is IRGACURE(~) 184, and the molecular includant is ,~--cyclodextrin as shown in Figure 2.
The present invention also relates to a method of mllt~ting the colorant in the composition of the present invention.
Briefly described, the method comprises irr~ ting a composition containing a mutable colorant and a radiation transorber with radiation at a dosage level sufficient to mutate the colorant. As stated above, in one embodiment the composition further includes a molecular includant. In another embodiment, the composition is applied to a substrate before being irradiated with ultraviolet radiation. The composition of the present invention may be irradiated with radiation having a wavelength of between about 4 to about 1,000 nanometers. The radiation to which the composition of the present invention is exposed generally will AAhE~NDED SHEET

SUBSTITUTE SHEET

25a have a wavelength of from about 4 to about 1,000 nanometers.
Thus, the radiation may be ultraviolet radiation, including near ultraviolet and far or vacuum ultraviolet radiation; visible ,DED SH~ET

-CA 0222l~6~ l997-l2-0~

WO 97/01605 PCT/u~ 1~9 2~

radiation; and near infrared radiation. Desirably, the composition is irradiated with radiation having ~ wavelength of from abu~t 4 to about 700 nanometers. More desirably, the composition of the present invention is irradiated with ultraviolet radiation having a wavelength of from about 4 to about 400 nanometers. It is more desirable that the radiation has a wavelength of between about 100 to 375 nanometers.
Especially desirable radiation is incoherent, pulsed ultraviolet radiation produced by a dielectric barrier discharge lamp. Even more preferably, the dielectric barrier discharge lamp produces radiation having a narrow bandwidth, i.e., the half width is of the order of approximately S to 100 nanometers.
Desirably, the radiation will have a half width of the order of approximately 5 to S0 nanometers, and more desirably will have a lS half width of the order of S to 25 nanometers. Most desirably, the half width will be of the order of approximately 5 to 15 nanometers.
The amount or dosage level of ultraviolet radiation that the colorant of the present invention is exposed to will generally be that amount which is necessary to n-~.it~te the colorant. The amount of ultraviolet radiation necessary to mutate the colorant can be determined by one of ordinary skill in the art using routine experimentation. Power density is the measure of the amount of radiated electromagnetic power traversing a unit area and is usually expressed in watts per centimeter squared (W/cm2). The power density level range is between approximately S mW/cm2 and lS mW/cm2, more particularly 8 to 10 mW/cm2. The dosage level, in turn, typically is a function of the time of exposure and the intensity or flux of the radiation source which irradiates the colored composition. The latter is affected by the distance of the composition from the source and, depending upon the wavelength range of the ultraviolet radiation, can be affected by the atmosphere between the radiation source and the composition.
Accordingly, in some in~t~nces it may be a~Lo~liate to expose CA 02221~6~ 1997-12-0~

the composition to the radiation in a controlled atmosphere or in a vacuum~ although in general n~ith~r apnr~l~ is desired.
With regard to the mutation properties of the present invention, photochemical processes involve the absorption of light quanta, or photons, by a molecule, e.g., the ultraviolet radiation transorber, to produce a highly reactive electronically excited state. However, the photon energy, which is proportional to the wavelength of the radiation, cannot be absorbed by the molecule unless it matches the energy difference between the unexcited, or original, state and an excited state. Consequently, while the wavelength range of the ultraviolet radiation to which the colored composition is exposed is not directly of concern, at least a portion of the radiation must have wavelengths which will provide the necessary energy to raise the ultraviolet radiation transorber to an energy level which is capable of interacting with the colorant.
It follows, then, that the absorption ma~illlulll of the ultraviolet radiation transorber ideally will be matched with the wavelength range of the ultraviolet radiation to increase the efficiency of the mutation of the colorant. Such efficiency also will be increased if the wavelength range of the ultraviolet radiation is relatively narrow, with the maximum of the ultraviolet radiation transorber coming within such range. For these reasons, especially suitable ultraviolet radiation has a wavelength of from about 100 to about 375 nanometers.
Ultraviolet radiation within this range desirably may be incoherent, pulsed ultraviolet radiation from a dielectric barrier discharge excimer lamp.
The terrn "incoherent, pulsed ultraviolet radiation" has reference to the radiation produced by a dielectric barrier discharge excimer lamp (referred to hereinafter as "excimer lamp"). Such a lamp is described, for example, by U.
Kogelschatz, "Silent discharges for the generation of ultraviolet and vacuum ultraviolet excimer radiation," Pure & Appl. Chem., 62, No. 9, pp. 1667-1674 (1990); and E. Eliasson and U.

CA 0222l~6~ l997-l2-0 WO 97/01605 PCT/U5~ 16Y~

Kogelschatz, "UV Excimer Radiation from Dielectric-Barrier ~i~ch~ges," Appl. Phys. B, A6, pp. 299-303 (1988). Excimer lamps were developed origin~lly by ABB Infocom Ltd.
Lenzburg, Switzerland. The excimer lamp technology since has been acquired by Haraus Noblelight AG, Hanau, Germany.
The excimer lamp ernits radiation having a very narrow bandwidth, i.e., radiation in which the half width is of the order of 5-15 nanometers. This emitted radiation is incoherent and pulsed, the frequency of the pulses being dependent upon the frequency of the altern~ting current power supply which typically is in the range of from about 20 to about 300 kHz. An excimer larnp typically is identified or referred to by the wavelength at which the maximum intensity of the radiation occurs, which convention is followed throughout this specification. Thus, in comp~ri~on with most other commercially useful sources of ultraviolet radiation which typically emit over the entire ultraviolet spectrum and even into the visible region, excimer lamp radiation is subst~nti~lly monochromatic.
Excimers are unstable molecular complexes which occur only under extreme conditions, such as those temporarily existing in special types of gas discharge. Typical examples are the molecular bonds between two rare gaseous atoms or between a rare gas atom and a halogen atom. Excimer complexes dissociate within less than a microsecond and, while they are dissociating, release their binding energy in the form of ultraviolet radiation.
Known excimers, in general, emit in the range of from about 125 to about 360 nanometers, depending upon the excimer gas mixture.
For example, in one embodiment, the colorant of the present invention is mutated by exposure to 222 nanometer excimer lamps. More particularly, the colorant crystal violet is mutated by exposure to 222 nanometer lamps. Even more particularly, the colorant crystal violet is mllt~ted by exposure to 222 nanometer excimer lamps located approximately 5 to 6 centimeters from the colorant, wherein the lamps are arranged in CA 0222l~6~ l997-l2-0 WO 97/01605 PcT/u:~5~li1 four parallel columns approximately 30 centimeters long. It is to be ur~erstood that the arrangement of the lamps is not crltiral to this aspect of the invention. Accordingly, one or more lamps may be arranged in any configuration and at any distance which results S in the colorant mllt~tin~ upon exposure to the lamp's ultraviolet radiation. One of ordinary skill in the art would be able to determine by routine experimentation which configurations and which distances are aL,~ro~liate. Also, it is to be understood that different excimer lamps are to be used with different ultraviolet radiation transorbers. The excimer lamp used to mtlt~te a colorant associated with an ultraviolet radiation transorber should produce ultraviolet radiation of a wavelength that is absorbed by the ultraviolet radiation transorber.
In some embodiments, the molar ratio of ultraviolet radiation transorber to colorant generally will be equal to or greater than about 0.5. As a general rule, the more efficient the ultraviolet radiation transorber is in absorbing the ultraviolet radiation and interacting with, i.e., transferring absorbed energy to, the colorant to effect irreversible mutation of the colorant? the lower such ratio can be. Current theories of molecular photo chemistry suggest that the lower limit to such ratio is 0.5, based on the generation of two free radicals per photon. As a practical matter, however, ratios higher than 1 are likely to be required, perhaps as high as about 10. However, the present invention is not bound by any specific molar ratio range. The important feature is that the transorber is present in an amount sufficient to effect mutation of the colorant.
While the mech~ni~m of the interaction of the ultraviolet radiation transorber with the colorant is not totally understood, it is believed that it may interact with the colorant in a variety of ways. For example, the ultraviolet radiation transorber, upon absorbing ultraviolet radiation, may be converted to one or more free radicals which interact with the colorant. Such free radical-generating compounds typically are hindered ketones, some examples of which include, but are not limited to: benzildimethyl CA 02221~6~ 1997-12-0~
SUBSTITUTE SHEET

ketal (available commercially as IRGACURE(~) 651, Ciba-Geigy Corporation, Hawthorne, New York); l-hydroxycyclohexyl phenyl ketone (IRGACURE(~) 500); 2-methyl-1-[4-(methylthio)phenyl3-2-morpholino-propan-1-one] (Il~GACURE
907); 2-benzyl-2-dimethylamino- 1-(4-morpholinophenyl)butan- 1-one (IRGACURE(~) 369); and l-hydroxycyclohexyl phenyl ketone (IRGACURE(~) 184).
Alternatively, the ultraviolet radiation may initiate an electron transfer or reduction-oxidation reaction between the ultraviolet radiation transorber and the colorant. In this case, the ultraviolet radiation transorber may be, but is not limited to, Michler's ketone (p-dimethylaminophenyl ketone) or benzyl trimethyl st~nn~te. Or, a cationic mechanism may be involved, in which case the ultraviolet radiation transorber can be, for example, bis[4-(diphenylsulphonio)phenyl)] sulfide bis-(hexafluorophosphate) (DEGACURE(~) KI85, Ciba-Geigy Corporation, Hawthorne, New York); CYRACURE~) UVI-6990 (Ciba-Geigy Corporation), which is a mixture of bis[4-(diphenylsulphonio)phenyl] sulfide bis(hexafluorophosphate) with related monosulphonium hexafluorophosphate salts; and nS-2,4-(cyclopentadienyl) [ 11,2,3 ,4,5 ,6-n-(methylethyl)benzene]-iron(II) hexafluorophosphate (IRGACURE(~3) 261).
Stabilizing Compositions With regard to the light stabilizing activity of the present invention, it has been determined that in some embodiments it is necessary to modify a conventional photoreactor to produce the improved light stable composition of the present invention. The simplest form of the improved light stable composition of the present invention includes a colorant admixed with a photoreactor modified as described below. The modiffed photoreactor may or may not be combined with a wavelength-selective sensitizer.
Many conventional photoreactor molecules have a functional A,A,i~END~D SH~ET

SUBSTITUTE SHEET ~ . . . .

30a group that is alpha to a carbonyl group. The functional grouE;

AM~DED SHEET

CA 02221~6~ 1997-12-0~
SUBSTITUTE SHEET . ~ , ,, includes, but is not limited to, hydroxyl groups, ether groups, ketone groups, and phenyl groups.
For example, a preferred radiation transorber that can be used in the present invention is designated phthaloylglycine-2959 and is represented by the following formula:

o ~ 11~ ~ CH3 The photoreactor portion of the ultraviolet radiation transorber has a hydroxyl group (shaded portion) alpha to the carbonyl carbon. The above molecule does not light-stabilize a colorant. However, the hydroxyl group can be removed by dehydration (see Example 4 and 5) yielding the following compound:
o 11~ ~ ~CH2 This dehydrated phthaloylglycine-2959 is capable of light-stabilizing a colorant. Thus, it is believed that removal of the functional group alpha to the carbonyl carbon on any photoreactor molecule will impart the light-stabilizing capability to the molecule. While the dehydrated ultraviolet radiation transorber can impart light-stability to a colorant simply by mixing the molecule with the colorant, it has been found that the molecule is much more efficient at stabilizing colorants when it is attached to an includant, such as cyclodextrin, ~s described herein.

A!'-''ENDED SHEET

SUBSTITUTE SHEET ' ', . , 3la It is to be understood that stabilization of a colorant can be accomplished according to the present invention by utilizing only A~ NDED SHEET

CA 02221~6~ 1997-12-0~
SUBSTITUTE SHEET - ~ '. .

the modified photoreactor. In other words, a modified photoreactor without a wavelength selective sensitizer may be used to stabilize a colorant. An example of a photoreactor that is modified according to the present invention is DAROCUR(~) 2959. The unmodified DAROCUR(~) 2959 an-l the dehydrated DAROCUR(~) 2959 are shown below.

HO(CH2)2 ~~C C\ OH

Unmodified DAROCUR (3) 2959 HO(CH2)2 ~~

Dehydrated DAROCUR(~) 2959 Other photoreactors can be modified. according to the present invention to provide stabilizers for dyes. These photoreactors include, but are not limited to: l-Hydroxy-cyclohexyl-phenyl ketone l("HCPK") (IRGACURE(~) 184, Ciba-Geigy); a,a-dimethoxy-a-hydroxy acetophenone (DAROCUR~) 1173, Merck); 1-(4-Isopropylphenyl)-2-hydroxy-2-methyl-propan-1-one (DAROCUR(g) 1116, Merck); 1-[4-(2-Hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-propan- 1 -one (DAROCUR(~) 2959, Merck); Poly[2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl] propan- l-one] (ESACURE(~) KIP, Fratelli Lamberti); Benzoin (2-Hydroxy-1,2-diphenylethanone) (ESACURE(~) BO, Fratelli Lamberti); Benzoin ethyl ether (2-Ethoxy- 1 ,2-diphenylethanone) (DAITOCURE(~) EE, Siber Hegner); Benzoin isopropyl ether (2-Isopropoxy- 1,2-diphenylethanone) (VICURE(~9 30, Stauffer); Benzoin n-butyl ether (2-Butoxy- 1 ,2-diphenylethanon~) (ESACURE(~ EB 1, ENDED SH~ET

SUBSTITUTE SHEET

32a Fratelli Lamberti); mixture of benzoin butyl ethers (TRIGONAL(~) 14, Akzo); Benzoin iso-butyl ether (2-Isobutoxy-1,2-diphenylethanone) (VICURE~3)10, Stauffer); blend AMENDED SHEET

CA 02221~6~ 1997-12-0~
SUBSTITUTE SHEET ; ~ , ~, . ".

of benzoin n-butyl ether and benzoin isobutyl ether (ESACU~
EB3, ESACURE(~) EB4, Fratelli Lamberti); Benzildimethyl ketal (2,2-Dimethoxy-1,2-diphenylethanone) ("BDK") (IRGACU~E(~) 651, Ciba-Geigy); 2,2-Diethoxy-1,2-diphenylethanone (UVATONE(~) 8302, Upjohn); o~,oc-Diethoxyacetophenone (2,2-Diethoxy-1-phenyl-ethanone) ("DEAP", Upjohn), (DEAP, Rahn);
and a,a -Di-(n-butoxy)-acetophenone (2,2-Dibutoxyl- 1 -phenyl-ethanone) (UVATONE~ 8301, Upjohn).
It is known to those of ordinary skill in the art that the dehydration by conventional means of the tertiary alcohols~that are alpha to the carbonyl groups is difficult. One conventional reaction that can be used to dehydrate the phthaloylglycine-2959 is by reacting the phthaloylglycine-2959 in anhydrous benzene in the presence of p-toluenesulfonic acid. After refluxing the mixture, the final product is isolated. However, the yield of the desired dehydrated alcohol is only about 15 to 20% by this method.
To increase the yield of the desired dehydrated phthaloylglycine-2959, a new reaction was invented. The reaction is sllmm~ri~ed as follows:
i R~O I H ZnCI2 ~ ~--C//

C H3 Xylene C_H3 .
It is to be understood that the groups on the carbon alpha to the carbonyl group can be groups other than methyl groups such as aryl or heterocyclic groups. The only limitation on these groups are steric limit~tions. Desirably, the metal salt used in the Nohr-MacDonald elimin~tion reaction is ZnCl2. It is to be understood that other transition metal salts can be used in performing the Nohr-MacDonald elimin~qtion reaction but ZnCl2 is the preferred metal salt. The amount of metal salt used in the Nohr-MacDonald elimination reaction is preferably AMENDED ShL~-~

SUBSTITUTE SHEET . . ,~
.. . . ..
,~ .. .. .. .. .. .

33a approximately equimolar to the tertiary alcohol compound, such AMENDED SHEET

WO 97/01605 PcT/u~ ~'~

as the photoreactor. The concentration of tertiary alcohol in the reactiG~ solution is betwee~ Aill~t~y 4% and 50% w/v.
Thus, ~e stabilizing composition produced by the process of dehydrating a tertiary alcohol that is alpha to a carbonyl group on a photoreactor is shown in the following general form~
Rl R4--C--C~ R2 wherein Rl is hydrogen, an alkyl, alkenyl, cycloalkyl, heterocycloalkyl, aryl or a heteroaryl group;
R2 is hydrogen, alkyl, alkenyl, cycloalkyl, heterocycloalkyl, aryl or a heteroaryl group;
R3 is hydrogen, alkyl, alkenyl, cycloalkyl, heterocycloalkyl, aryl or a heteroaryl group; and R4 is an aryl, heteroaryl, or substituted aryl group.
Another requirement of the reaction is that it be run in a non-aqueous, non-polar solvent. The ~lefell~d solvents for r lnnin~ the Nohr-MacDonald elimina ion reaction are aromatic hydrocarbons including, but not limi~ to, xylene, bçn7en~, toluene, cumene, mesitylene, p-cymene, butylbenzene, styrene, and divinylben7en~- It is to be understood that other substituted aromatic hydrocarbons can be used as solvents in the present invention. p-Xylene is the preferred aromatic hydrocarbon solvent, but other isomers of xylene can be used in performing the Nohr-MacDonald elimin~tion reaction.
An important re41Lirelllent in performing the Nohr-MacDonald elimin~tion reaction is that the reaction be run at a relatively high temperature. The reaction is desirably performed at a temperature of between appro~cim~t~ly 80~C and 150~C. A
suitable temperature for dehydrating phthaloylglycine-2959 is approxim~t.oly 124~C. The time the reaction runs is not critical.
The reaction should be run between approxim~t~ly 30 minutes to 4 hours. However, depending upon the reactants and the solvent used, the timing may vary to achieve the desired yield of product.

CA 02221~6~ 1997-12-0~ .
SUBSTITUTE SHEET ' , . ~

It is to be understood that the dehydrated phthaloylglycine-2959 can be attached to the molecular includant in a variety of ways. In one embodiment, the dehydrated phthaloylglycine-2959 is covalently attached to the cyclodextrin as shown in the following structure:
Beta-CD

o C_~
[[~--CH2C--o(CH2)20~ C--CH2--S--CH2CH2r In another embodiment, as shown below, only the modi~led DAROCUR(~) 2959 without the phthaloyl glycine attached is reacted with the cyclodextrin to yield the following compound.
This compound is capable of stabilizing a dye that is associated with the molecular includant. It is to be understood that photoreactors other than DAROCUR(~ 2959 can be used in the present invention.

HO~C--ICl--CH2--S--CH2CH2 3 In yet another embodiment, the dehydrated phthaloylglycine-2959 can be attached to the molecular includant AMENOED Sll~ET

SUBSTITUTE SHEET '. . ' . S~, . , 35a via the opposite end of the molecule. One example of this embodiment is shown in the following formula:

AME~JDED SHEET

CA 02221~6~ 1997-12-0~
SUBSTITUTE SHEET ~ . . . , ~".-;

~N~H,C O~C~,~,O~ CH3 Another stabilizer that is considered part of the present invention is an arylketoalkene having the following general formula:

R1--C--CH=CH--R2 wherein if R, is an aryl group, then R2 is a hydrogen;
heterocyclic; alkyl; aryl, or a phenyl group, the phenyl group optionally being substituted with an alkyl, halo, amino, or a thiol group; and if R2 is an aryl group, then Rl is hydrogen;
heterocyclic; alkyl; aryl, or a phenyl group, the phenyl group optionally being substituted with an alkyl, halo, amino, or a thiol group. Preferably, ~he alkene group is in the trans configuration although it can be in the cis configuration.
Desirably, the arylketoalkene stabilizing compound has the following formula:
o (~CH=CltC~>-or ~CH¢H--C--CH3 AMENDED SHEET

SUBSTITUTE SHEET

36a The arylketoalkene may also function as a wavelength-specific sensitizer in the present invention, and it may be associated with any of the previ~usly discussed photoreactors.

AMENDED S~tEFT

CA 0222l565 l997-l2-05 5 PCT/u:~sh~1c~9 One method of associating a photoreactor with the arylketoalkene comE>o~A of the present in~en~o~ is descIibed in F~mple 32.
The arylketoalkene compound may optionally be covalently bonded to the reactive species-generating photoiniti~tor. It is to S be understood that the arylketo~lk~ne compound of the present invention is not to be used with photoreactors in a composition where stability in natural sunlight is desired. More particularly, as the arylketoaLlcene compounds absorb radiation in the range of about 270 to 310 depen-ling on the identity of Rl and R2, then these compounds are capable of absorbing the aupl~liate radiation from sunlight. Accordingly, these compounds when admixed with a photoreactor can effect a mutation of the colorant upon exposure to slmlight Where such a change in color is not desired, then a photoreactor is not to be admixed with the arylk~to~lk~n.o compound of the present invention, and the arylk~-to~lkPne compound is to be used with a colorant without a photoreactor.
In the embodiment where the arylkPto~lk~ne compound is covalently attached to another molecule, whichever Rl or R2 that is an aryl group will have a group incl~lfling, but not limited to, a carboxylic acid group, an aldehyde group, an amino group, a haloalkyl group, a hydroxyl group, or a thioaLkyl group ~tt~rh~
thereto to allow the arylketoalkene to be covalently bonded to the other molecule. Accordingly, the arylkPto~lkPnP stabilizing compound is represented by the following formula:
HOOC~CH=C R~
or HOOC~H=C~C--CH3 or CA 02221~6~ 1997-12-0~
SUBSTITUTE SHEET

, <~CH=CI I C~OOH

Although it is preferred that the group attached to the aryl group is para to the remainder of the stabilizer molecule, the group may also be ortho or meta to the remainder of the molecule.
It is to be understood that~ the arylketoalkene stabilizing compound can be an extended conjugated bond system arylketoaL~ene compound. In this embodiment, Rl, or R2, or both Rl and R2, in the above general formula are phenyl groups substituted with one or more groups that extend the area of conjugation of the delocalized, pi electrons. More particularly, Rl, or R2, or both Rl and R2, are phenyl groups substituted with one or more carbonyl, ethylene, phenyl, ester, aryl, substituted aryl, or vinylic groups, wherein the groups are sequentially arranged such that only one of the groups is directly attached to the phenyl group, and the other groups are bonded to that attached group thereby extending the conjugation of the compound by forming a chain of unsaturated groups. It is to be understood that the extended conjugated compound of the present invention includes any combination of the above groups, and any number of the above groups.
A desirable extended conjugated arylketoaL~ene stabilizing compound of the present invention has the following forrnula:

HOOC ~3CH =CH--C~ '~I ~3CH=CH--C~

AM~NDED S~tEET

CA 02221~6~ 1997-12-0~
SUBSTITUTE SHEET ' . , . .-~
. :~ .. . .. - :=

Another desirable arylketoalkene stabilizing compound has the following formula:

HOOC ~3CH=CH--C~O--C~CH=CH--C--CH3 The extended stabilizing compounds of the present invention may be produced by any method known to one of ordinary skill in the art. For example, one method is described in Examples 38 and 39 which utilizes an intermediate molecule having the following formula:

HOOC~Ct ~ CH--C~30H
It is to be understood that the hydroxy group on the phenyl group of the above intermediate may be substituted with any other group that will provide a linkage between the molecules shown in Examples 38 and 39 such that the product will have an exlended conjugated bond system. The resultant link~e between the molecules produced in Examples 38 and 39 is an ester linkage (-O-(C=O)-). However, the linkage may include, but is not limited to, a ketone linkage (-(C~O)-), an ether linkage (-O-), a sulfide linkage (-S-), an amino linkage (-NH-), or an amide linkage. A
desirable linkage is an ester linkage.
A desirable arylketoalkene stabilizing compound with a ketone linkage has the following formula:

HOOC~3CH=CH--C~3--C~CH=CH--C--CH3 AMEN~D SH~ET

CA 02221~6~ 1997-12-0~
SUBSTITUTE SHEET ' ' "

Yet another desirable arylketoalkene stabilizing compound with a ketone linkage has the following formula:

HOOC~CH=CH--8~C~CH=CH--C~

The extended conjugated arylketoalkene stabilizing compound of the present invention is not limited to only two of the compounds shown in Examples' 38 and 39 linked together. It is to be understood that the extended conjugated compound may include a multiplicity of the compounds'shown in Examples 38 and 39 linked together.
The extended conjugated arylketoalkene stabilizing compound of the present invention is extremely stable. Although not wanting to be limited by the following, it is believed that the above extended conjugated compounds are low triplet state energy species, and are yellow in color. As the chain of conjugation is extended, it is believed that the color shifts to red or orange.
Accordingly, this embodiment of the present invention provides a stabiliz-ing arylketoalkene which, when associated with a colorant, stabilizes the colorant. Therefore, the above arylketoalkene can be used as an additive to any colorant composition. For example, as the arylketoalkene compound is not water soluble, it can be directly added to solvent or oil colorant compositions. Additionally, the arylketoaLkene compound can be added to other colorant compositions that contain additives enabling the solubilization of the compound therein.
Further, the arylketoaLkene stabilizing compounds can be solubilized in aqueous solution by a variety of means. One means of solubili7.in~ the arylketoalkene stabili7in~ compound of the present invention is to attach the compound to a large water soluble molecule, such as a cyclodextrin, as described in Examples 28 through 31, and Examples 40 and 41. Desi'rably, between AMENDED SHEET

SUBSTITUTE SHEET - . .. ,~
. .

40a about 1 and 12 arylketoalkene molecules can be attached to a cyclodextrin molecule. More desirably, between about 4 to about AMENDED SHEET

CA 0222l~6~ l997-l2-0~

~ 9 arylkPto~lkPne molecules are ~tt~hPd to a cyclodextrin molecule. Accordingly, the arylketoalkene compound ~tt~hPd to cyclodextrin can be added to any aqueous colorant system to st~bili7~ the colorant therein. It is to be understood that the S stabilizing arylketo~lkPrlP-s do not have to be ~tt~rhe~l to the molecl-lAr inclu~l~nts to exhibit their stabilizing activity.
Therefore, this embo-lim-Pnt provides a method for stabilizing colorant compositions by admixing the alyk~loalkene compound with the colorant composition in an amount effective to stabilize the composition. The arylketoalkenes desirably should be present in the colorant medium or solution at a conce~ L.on of approximately 0.1 to 50% by weight, desirably between approximately 20% and 30% by weight. If no cyclodextrin is used, the desirable range is approximately 1 part dye to approximately 20 parts arylketoalkene.
Although the arylketoaL~ene compound need only be associated with the colorant, in some embo-lim~nt~ of the present invention, the arylketo~lkPnP- compound may be covalently bonded to the colorant.
Although not wanting to be limited by the following, it is theorized that the arylketoalkene compound of the present invention stabilizes colorants through functioning as a singlet oxygen scavenger. In the alternative, it is theorized that the arylketoalkene compound functions as a stabilizer of a colorant via the resonance of the unshared electron pairs in the p orbitals, e.g., it functions as an energy sink.
As a practical matter, the colorant, ultraviolet radiation transorber, modified photoreactor, arylketoalkene stabilizer, and molecular includant are likely to be solids depending upon the - 30 constituents used to prepare the molecules. However, any or allof such m~ten~l~ can be a liquid. The colored composition can be a liquid either bec~ e one or more of its components is a liquid, or, when the mol~c~ r includant is organic in nature, a solvent is employed. Suitable solvents include, but are not limited to, amides, such as N,N-dimethylformamide; sulfoxides, such as CA 0222l565 l997-l2-05 WO 97/01605 PCT/u~7~ .SII~ 16~!~

tlim~thylsulfoxide; ketones, such as acetone, methyl ethyl ketone, and me~yl butyl ketone; aliphatic and aro~r,atic hydrocarbons, such as hPx~n~, octane, ben7Pn~, toluene, and the xylenes; esters, such as ethyl ~f~et~ttq; water; and the like. When the molecular includant is a cyclo~e~trin, particularly suitable solvents are the ~mifl~s and sulfoxides.
In an embo~lim~-nt where the composition of the present invention is a solid, the effectiveness of the above compounds on the colorant is ill~Loved when the colorant and the selected compounds are in intim~t~ contact. To this end, the thorough blen-lin~ of the components, along with other components which may be present, is desirable. Such blen-ling generally is accomplished by any of the means known to those having ordinary skill in the art. When the colored composition includes a polymer, blen-ling is f~ilit~t~-l if the colorant and the ultraviolet radiation transorber are at least partly soluble in softened or molten polymer. In such case, the composition is readily pl~ared in, for example, a two-roll mill. ~ltern~tively, the composition of the present invention can be a liquid because one or more of its components is a liquid.
For some applications, the composition of the present invention typically will be lltili7~-1 in particulate form. In other applications, the particles of the composition should be very small. Methods of folming such particles are well known to those having or&nary skill in the art.
The colored composition of the present invention can be ili7e-l on or in any substrate. If one desires to ~ te the colored composition that is present in a substrate, however, the substrate should be subst~nti~lly transparent to the ultraviolet radiation which is employed to mllt~te the colorant. That is, the ultraviolet radiation will not significantly interact with or be absorbed by the substrate. As a practical matter, the composition typically will be placed on a substrate, with the most common substrate being paper. Other substrates, including, but not limite(l CA 02221~6~ 1997-12-0~

WO 97/0160S PCT/US~5.~ 16~9 to, woven and nonwoven webs or fabrics, films, and the like, can be used, however.
The colored composition optionally may also contain a carrier, the nature of which is well known to those having ordinary skill in the art. For many applications, the carrier will be a polymer, typically a thermosetting or th~-.rmoplastic polymer, with the latter being the more common.
Further examples of th~.rmoplastic polymers include, but are not limit~l to: end-capped poly~et~lc, such as poly(oxymethylene) or polyformaldehyde, poly(trichloro~cet~l~le.hyde), poly(n-v~l~r~l~ehyde), poly(~cet~klehyde), poly(propionaldehyde), and the like; acrylic polymers, such as polyacrylamide, poly(acrylic acid), poly(m~th~r,rylic acid), poly(ethyl acrylate), poly(methyl lS methacrylate), and the like; fluorocarbon polymers, such as poly(tell~Lluoroethylene), perfluorin~te~l ethylenepropylene copolymers, ethylenetetrafluoroethylene copolymers, poly-(chlorotrifluoroethylene), ethylene-chlorotrifluoroethylene copolymers, poly(vinylidene fluoride), poly(vinyl fluoride), and the like; epoxy resins, such as the con~len.c~tion products of epichlorohydrin and bisphenol A; polyamides, such as poly(6-aminocaproic acid) or poly(~-caprol~c.t~m), poly(hP-Y~methylene adipamide), poly(h~x~m~.thylene sebac~mide), poly(l 1-aminolm-1ec~noic acid), and the like; polyaramides, such as poly(imino-1,3-phenyl~nP.iminoisophthaloyl) or poly(m-phenylene isophth~l~mide), and the like; parylenes, such as poly-p-xylylene, poly(chloro-p-xylene), and the like; polyaryl ethers, such as poly(oxy-2,6--1im~thyl- 1 ,4-phenylene) or poly(p-phenylene oxide), and the like; polyaryl sulfones, such as ~ 30 poly(oxy-1,4-phenylenesulfonyl-1,4-phenyleneoxy-1,4-phenylene-isopropylidene- 1 ,4-phenylene), poly(sulfonyl- 1 ,4-phenyleneoxy-1,4-phenylenesulfonyl-4,4-biphenylene), and the like;
polycarbonates, such as poly(bisphenol A) or poly(carbonyldioxy-1 ,4-phenyleneisopropylidene- 1 ,4-phenylene), and the like;
polyesters, such as poly(ethylene terephth~l~te), CA 02221~6~ 1997-12-0~

WO 97/01605 ~ PCT/u~ _5/l 1~29 poly(tetramethylene terephth~l~te), poly(cyclohexylene-1,4-llimP.thylene terephth~l~te) or poly(oxymethylene- 1,4-cyclohexylen.om~thyleneoxyterephthaloyl), and the like; polyaryl sulfides, such as poly~z7-phenylene sulfide) or poly(thio- 1,4-phenylene), and the like; polyimides, such as poly-(pyromellitimido-1,4-phenylene), and the like; polyolefins, such as polyethylene, polypropylene, poly(1-butene), poly(2-butene), poly(1-~..1~~io), poly(2-p~.nten~), poly(3-methyl-1-penten~), poly(4-methyl- l-pe.nt~.nP.), 1 ,2-poly- 1 ,3-bllt~ ne, 1 ,4-poly- 1,3-bllt~rlien~., polyisoprene, polychlolople~e, polyacrylonitrile, poly(vinyl ~cet~t~.), poly(vinylidene chloride), polystyrene, and the like; and copolymers of the foregoing, such as acrylonitrile-bllt~ .n~styrene (ABS) copolymers, styrene-n-l,ulyhllethacrylate copolymers, ethylene-vinyl ~cet~te copolymers, and the like.
Some of the more commonly used thermoplastic polymers include styrene-n-butyl methacrylate copolymers, polystyrene, styrene-n-butyl acrylate copolymers, styrene-butadiene copolymers, polycarbonates, poly(methyl methacrylate), poly(vinylidene fluoride), polyamides (nylon-12), polyethylene, polypropylene, ethylene-vinyl ~et~te copolymers, and epoxy resins.
Examples of thermosetting polymers include, but are not limit~fl to, alkyd resins, such as phthalic anhydride-glycerol resins, maleic acid-glycerol resins, adipic acid-glycerol resins, and phthalic anhydride-pentaerythritol resins; allylic resins, in which such monomers as diallyl phth~l~te, diallyl isophth~l~te diallyl m~ t~, and diallyl chlorendate serve as nonvolatile cross-linkin~ agents in polyester compounds; amino resins, such as z~nilin~--form~ldehyde resins, ethylene urea-formaldehyde resins, dicy~ntli~mide-formaldehyde resins, mel~min~-formaldehyde resins, sulfona-m--ide-form~ phyde resins, and urea-formaldehyde resins; epoxy resins, such as cross-linked epichlorohydrin-bisphenol A resins; phenolic resins, such as phenol-formaldehyde resins, including Novolacs and resols; and therrnoset~ng polyesters, silicones, and urethanes.

-In addition to the colorant, and ultraviolet radiation transs~rb~r or function~li7e~1 molec~}ar inc~ *nt modified photoreactor, arylketo~lkP-ne stabilizer, and optional carrier, the colored composition of the present invention also can contain S additional components, depen-lin~ upon the application for which it is intentlP-l Fx~mrles of such additional components include, but are not limit~P~ to, charge carriers, st~hili7Prs ~g~inct thermal oxidation, viscoel~ctic properties modifiers, cross-linking agents, plasticizers, charge control additives such as a qn~tern~ry ammonium salt; flow control additives such as hydrophobic silica, zinc ~ d~e, calcium stearate, lithium ste~dle, polyvinyls~ ~, and polyethylene powders; and fillers such as calcium carbonate, clay and talc, ~mon~ other additives used by those having ordinary skill in the art. Charge carriers are well known to those having ordinary skill in the art and typically are polymer-coated metal particles. The i-lP-nti*Ps and amounts of such additional components in the colored composition are well known to one of ordinary skill in the art.
The present illv~ll~ion is further llesr-ribed by the examples which follow. Such examples, however, are not to be construed as limiting in any way either the spirit or scope of the present invention. In the examples, all parts are parts by weight unless stated otherwise.

FY:~ml le This example describes the preparation of a ~-cyclodextrin molecular includant having (1) an ultraviolet radiation transorber covalently bonded to the cyclodextrin outside of the cavity of ~e cyclo-3Pxtrin, and (2) a colorant associated with the cyclodextrin by means of hydrogen bonds and/or van der Waals forces.

A. Friedel-Crafts Acylation of Transorber A 250-ml, three-necked, round-bottomed reaction flask was fitted with a con-lPn~er and a pressure-eqll~li7in~ addition funnel equipped with a nitrogen inlet tube. A magnetic stirring bar was CA 02221~6~ 1997-12-0~
SUBSTITUTE SHEET .

placed in the flask. While being flushed with nitrogen, the flask was charged with 10 g (0.05 mole) of l-hydroxycyclohexyl phenyl ketone (IRGACURE(~) 184, Ciba-Geigy Corporation, Hawthorne, New York), 100 ml of anliydrous tetrahydofuran (Aldrich Chemical Company, Inc., Milwaukee, Wisconsin), and 5 g (0.05 mole) of succinic anhydride (Aldrich Chemical Co., Milwaukee, WI). To the continuously stirred contents of the flask then was added 6.7 g of anhydrous aluminum chloride (Aldrich Chemical Co., Milwaukee, Wisconsin). The resulting reaction mixture was m~int~ined at about 0~C in an ice bath for about one hour, after which the mixture was allowed to warrn to ambient temperature for two hours. The reaction mixture then was poured into a mixture of 500 ml of ice water and 100 ml of diethyl ether. The ether layer was removed after the addition of a small amount of sodium chloride to the aqueous phase to aid phase separation. The ether layer was dried over anhydrous magnesium sulfate. The ether was removed under reduced pressure, leaving 12.7 g (87 percent) of a white crystalline powder. The material was shown to be 1 -hydrox~ cyclohexyl 4-(2-carboxyethyl)carbonylphenyl ketone by nuclear magnetic resonance analysis.

B. Preparation of Acylated Transorber Acid Chloride A 250-ml round-bottomed flask fitted with a condenser was charged with 12.0 g of 1-hydroxycyclohexyl 4-(2-carboxyethyl)carbonylphenyl ketone (0.04 mole), 5.95 g (0.05 mole) of thionyl chloride (Aldrich Chemical Co., Milwaukee, Wisconsin), and 50 ml of diethyl ether. The resulting reaction mixture was stirred at 30~C for 30 minutes, after which time the solvent was removed under reduced pressure. The residue, a white solid, was maintained at 0.01 Torr for 30 minutes to remove residual solvent and excess thionyl chloride, leaving 12.1 A~ENDED SHE~r SUBSTITUTE SHEET , ~
.. . .. ..

46a g (94 percent) of l-hydroxycyclohexyl 4-(2-chloroforrnylethyl)carbonyl~nenyl ketone.

AMENDED SHEET

WO 97/01605 PCT/u' ,~ ~9 C. Covalent Bonding of Acylated Transorber to Cyclodextrin A 250-ml, three-necked, round-bottomed reaction flask cont~ining a m~gnetic stirring bar and fitted with a thermometer, con~lPn.c~Pr, and pressure-eq~ in~ addition funnel equipped with a nitrogen inlet tube was charged with 10 g (9.8 mmole) of ~-cyclo~e~trin (American Maize-Products ColllyaLly~ ~mmonfl, Indiana), 31.6 g (98 mmoles) of l-hydroxycyclohexyl 4-(2-chloroformylethyl)carbonylphenyl ketone, and 100 ml of N,N-di..~ll.ylformamide while being co~ uously fl~lshe~ with nitrogen. The reaction ll~i~ e was heated to 50~C and 0.5 ml of triethyl~mine added. The reaction ll~i~lulc was m~int~ine~l at 50~C for an hour and allowed to cool to ambient temp~dlule. In this yrepardlion~ no ~le~ t was made to isolate the product, a ~-cyclodextrin to which an ultraviolet radiation transorber had been covalently coupled (lef~ Gd to hereinafter for CO~ n~e as ~-cyclodextrin-transorber).
The foregoing procedure was repeated to isolate the product of the reaction. At the conclusion of the procedure as described, the reaction mixture was conce~ ated in a rotary evaporator to roughly 10 percent of the original volume. The residue was poured into ice water to which sodium chloride then was added to force the product out of solution. The resulting precipitate was isolated by filtration and washed with diethyl ether. The solid was dried under reduced pressure to give 24.8 g of a white powder. In a third ~iG~aldlion, the residue rem~inin~
in the rotary evaporator was placed on top of an approxim~tP-ly 7.5-cm column cont~ining about 15 g of silica gel. The residue was eluted with N,N-dimethylformamide, with the eluant being monitored by means of Wh~tm~n(~) Flexible-Backed TLC Plates (Catalog No. 05-713-161, Fisher Scientific, Pittsburgh, Pennsylvania). The eluted product was isolated by evaporating the solvent. The structure of the product was verified by nuclear m~gnPtic resonance analysis.

WO 97/01605 PCT/U' ~ fq9 D. Association of Colorant with Cyclodextrin-Transorber-Preparation of Colored Composition To a solution of 10 g (estim~tP~1 to be about 3.6 mmole) of 13--cyclodextrin-transorber in 150 ml of N,N--lim~thylfonn~mi~l~
S in a 250-ml round-bottomed flask was added at ambient tç.~ dlule 1.2 g (3.6 mmole) of ~Al~rhite Green oxalate (Aldrich ~'h~mic~l Company, Inc., Milwaukee, Wisconsin), referred to hereinafter as Colorant A for convenitonGe The reaction mi~ e was stirred with a m~gn~tic stirring bar for one hour at ~mhient tempe~ e. Most of the solvent ~en was removed in a rotary evaporator and the residue was eluted from a silica gel column as already described. The ,13--cyclodextrin-transorber Colorant A inclusion complex moved down the column first, cleanly separating from both free Colorant A and ,B--cyclodextrin-transorber. The eluant cont~ining the complex was coll~cte-l and the solvent removed in a rotary evaporator. The residue was subjected to a re~ çe-l pressure of 0.01 Torr to remove residual solvent to yield a blue-green powder.
E. Mutation of Colored Composition The ~-cyclodextrin-transorber Colorant A inclusion complex was exposed to ultraviolet radiation from two different lamps, Lamps A and B. Lamp A was a 222-nanometer excimer lamp ~semhly org~ni7~-1 in banks of four cylindrical lamps having a length of about 30 cm. The lamps were cooled by circ~ tin~ water through a centrally located or inner tube of the lamp and, as a consequence, they operated at a relatively low temperature, i.e., about 50~C. I~e power density at the lamp's outer surface typically is in the range of from about 4 to about 20 joules per square meter (J/m2). However, such range in reality merely reflects the capabilities of current excimer lamp power supplies; in the future, higher power densities may be practical.
The distance from the lamp to the sample being irradiated was 4.5 cm. Lamp B was a S00-watt Hanovia m~ m pressure mercury lamp (Hanovia Lamp Co., Newark, New Jersey). The fli~t~nre from Lamp B to the sample being irradiated was about 15 cm.

CA 02221~6~ 1997-12-0~

WO 97101605 PCT/U~,5/1, 1~~9 4!~

- A few drops of an N,N-dimethylform~mide solution of the ,B-cyclo~extrin-transorber Colorant A inclusion complex were ~ placed on a TLC plate and in a small polyethylene weighing pan.
Both samples were exposed to Lamp A and were decolorized S (.. ~ 1 to a colorless state) in 15-20 seconds. ~imil~r results were obtained with Lamp B in 30 seconds.
A first control sample con~ tin~ of a solution of Colorant A and 13--cyclodextrin in N,N-dimethylro~ ...;de was not decolorized by Lamp A. A second control sample con.~i~tin~ of Colorant A and l-hydroxycyclohexyl phenyl ketone in N,N-im~thylformamide was decolorized by Lamp A within 60 seconds. On st~ntlin~, however, the color began to reappear within an hour.
To evaluate the effect of solvent on decolorization, 50 mg of the ~--cyclodextrin-transorber Colorant A inclusion complex was dissolved in 1 rnl of solvent. The resulting solution or mixture was placed on a glass microscope slide and exposed to Lamp A for 1 mimlte. The rate of decolorization, i.e., the time to render the sample colorless, was directly proportional to the solubility of the complex in the solvent, as sllmm~ri7e~1 below.
Table 1 Solvent Solubility Decolorization Time N,N-Dimethylform~mide Poor 1 ~ e Dimethylsulfoxide Soluble <10 seconds Acetone Soluble <10 seconds He~cane Insoluble --Ethyl Acetate Poor 1 minute Finally, 10 mg of the ,B--cyclodextrin-transorber Colorant ~ A inclusion complex were placed on a glass microscope slide and crushed with a pestle. The resulting powder was exposed to Lamp A for 10 seconds. The powder turned colorless. Similar results were obtained with Lamp B, but at a slower rate.

CA 0222l565 l997-l2-05 F,Y~mrle 2 Because of the possibility in the prepara~ion of the colored composition ~i~sçribed in the following examples for the acylated transorber acid chloride to at least partially occupy the cavity of the cyclodextrin, to the partial or complete e~cl~lQion of colorant, a modified plepaldLive procedure was carried out. Thus, this example ~esrribes the ~r~aralion of a ,~cyclodextrin molecular includant having (1) a colorant at least partially included within the cavity of the cyclodextrin and associated therewith by means of hydrogen bonds and/or van der Waals forces, and (2) an ultraviolet radiation transorber covalently bonded to the cyclo-l~.xtrin subst~nti~lly outside of the cavity of the cyclodextrin.
A. Association of Colorant with a Cyclodextrin To a solution of 10.0 g (9.8 rnmole) of ~--cyclodextrin in 150 ml of N,N--lim~thylform~mide was added 3.24 g (9.6 mmoles) of Colorant A. The resulting solution was stirred at ~mhjent temp~ ule for one hour. The reaction solution was concentrated under reduced pressure in a rotary evaporator to a volume about one-tenth of the original volume. The residue was passed over a silica gel column as described in Part C of Example 1. The solvent in the eluant was removed under reduced pressure in a rotary evaporator to give 12.4 g of a blue-green powder, ~-cyclodextrin Colorant A inclusion complex.
B. Covalent Bonding of Acylated Transorber to Cyclodextrin Colorant Inclusion Complex - Preparation of Colored Composition A 250-ml, three-necked, round-bottomed reaction flask cont~inin~ a m~gn~tic stirring bar and fitted with a thermometer, con~le-n~er, and pressure-eqll~li7ing addition funnel equipped with a nitrogen inlet tube was charged with 10 g (9.6 mmole) of 13-cyclodextrin Colorant A inclusion complex, 31.6 g (98 mmoles) of l-hydroxycyclohexyl 4-(2-chloroforrnylethyl)carbonylphenyl CA 02221~6~ 1997-12-0~
SUBSTITUTE SHEET ' , , . . . ~~
. :. . , ' - :

ketone prepared as described in Part B of Example 1, and 150 rnl of N,N-dimethylform~mide while being continuously flushed with nitrogen. The reaction mixture was heated to 50~C and 0.5 ml of triethylamine added. The reaction mixture was maintained at 50~C for an hour and allowed to cool to ambient temperature.
The reaction mixture then was worked up as described in Part A, above, to give 14.2 g of ,B--cyclodextrin-transorber Colorant A
inclusion complex, a blue-green powder.

C. Mutation of Colored Composition The procedures described in Part E of Example 1 were repeated with the ,13-cyclodextrin-transorber Colorant A inclusion complex prepared in Part B, above, with essentially the same results.

Example 3 This example describes a method of preparing an ultraviolet radiation transorber, 2-[p - ( 2 -methyllactoyl)phenoxy] ethyl 1,3 -dioxo-2-isoindolineacetate, designated phthaloylglycine-2959.
i The following was admixed in a 250 ml, three-necked, round bottomed flask fitted with a Dean & Stark adapter with condenser and two glass stoppers: 20.5g (0.1 mole) of the wavelength selective sensitizer, phthaloylglycine (Aldrich Chemical Co., Milwaukee, Wisconsin); 24.6 g (0.lmole) of the photoreactor, DAROCUR@~) 2959 (Ciba-Geigy, Hawthorne, New York); 100 ml of benzene (Aldrich Chemical Co., Milwaukee, Wisconsin); and 0.4 g p-toluenesulfonic acid (Aldrich Chemical Co., Milwaukee, Wisconsin). The mixture was heated at reflux for 3 hours after which time 1.8 ml of water was collected. The solvent was removed under reduced pressure to give 43.1 g of white powder. The powder was recrystallized from 30% ethyl acetate in hexane (Fisher) to yield 40.2 g (93%) of a white AME~DED S~IEE~

SUBSTITUTE SHEET i .~ ., .. .n 51a crystalline powder having a melting point of 153-4~C. The reaction is s-lmm~ri7:ed as follows:

~ ENDED S~tEET

CA 02221~6~ 1997-12-0~ -SUBSTITUTE SHEET
~-- ~-- --¢~N--CH2CO2H + HO--(CH2)2--~~ /CH3 p-toluene . CH3 O ~ sulfonic acid Benzene ~ 11~ ~~ ~ H3 5The resulting product, designated phthaloylglycine-2959, had the following physical parameters:

IR [NUJOL MULL] vm~ 3440, 1760, 1740, 1680, 1600 cm-1 10lH NMR [CD~13] ~ppm 1.64[s], 4.25[m], 4.49[m], 6.92[m], 7.25[m], 7.86[m], 7.98[m], 8.06[m] ppm.
~, E~ample 4 15This example describes a method of dehydrating the phthaloylglycine-2959 produced in Example 3.
The following was admixed in a 250 ml round bottomed flask fitted with a Dean & Stark adapter with condenser: 21.6 g (0.05 mole) phthaloylglycine-2959; 100 ml of anhydrous benzene 20(Aldrich Chemical Co., Milwaukee, Wisconsin); and 0.1 g p-toluenesulfonic acid (Aldrich Chemical Co., Milwaukee, Wisconsin). The mixture was refluxed for 3 hours. After 0.7 ml of water had been collected in the trap, the solution was then removed under vacuum to yield 20.1 g (97%) of a white solid.
25However, analysis of the white solid showed that this reaction AM~NDED SH~T

SUBSTITUTE SHE =ET . , ;

52a yielded only 15 to 20% of the desired deydration product. The reaction is sllmm~n7ed as follows:

CA 02221~6~ 1997-12-0~
- SUBSTITUTE SHEET

O

~ ~H2(~ H2)2~ ~ ~--OH

p- to luene sul:Eonic acid Benz ene O

~H2C~(CH2)20~ CH3 The resulting reaction product had the following physical parameters:

IR (NUJ~L) vm~", 1617cm 1 (C=C-C=O).

Example 5 This exarnple describes the Nohr-MacDonald elimin~tion reaction used to dehydrate the phthaloylglycine-2959 produced in Example 3.
Into a 500 ml round bottomed flask were placed a stirring m~gnet, 20.0 g (0.048 mole) of the phthaloylglycine-2959, and 6.6 g (0.048 mole) of anhydrous zinc chloride (Aldrich Chemical Co., Milwaukee, Wisconsin). 250 ml of anhydrous p-xylene (Aldrich Chemical Co., Milwaukee, Wisconsin) was added and the mixture refluxed under argon atmosphere for two hours. The reaction mixture was then cooled, resulting in a white precipitate which was collected. The white powder was then recrystallized from 20% ethyl acetate in hexane to yield 18.1 g (95%) of a white powder. The reaction is sllmm~ri7.ed as follows:

AMEN~ED SHEET

SUBSTITUTE SHEET ; ' ~N~H2C--O(CH2)2O~\COHHH

~ -H20 ZnCI2 p-Xylene o 1 26~C

¢~N ~H2C--O(CH2)20~CH2 The resulting reaction product had the following physical parameters:

Melting Point: 138~C to 140~C.
Mass spectrum: m/e: 393 M +, 352, 326, 232, 160.

IR (KB) vmax 1758, 1708, 1677, 1600 cm-l lH NMR [DMSO] ~ppm 1.8(s), 2.6(s), 2.8 ~d), 3.8 (d), 4.6 (m), 4.8 (m), 7.3(m), 7.4 (m), 8.3 (m), and 8.6 (d) 13C NMR [DMSO] ~ppm 65.9 (CH2=).

Example 6 This example describes a method of producing a ,B--cyclodextrin having dehydrated phthaloylglycine-2959 groups from Example 4 or 5 covalently bonded thereto.

AMENDED SHEET

SUE~STITUTE SHEET " . ' . '. .

54a The ~llowing was admixed in a 100 n~.l round-bottomed llask: 5.0 g (4 mms:)le) ,B-cyclodextrin ~American Maize Product S Company, Hammond, ~n~ n~) (design~te~ C~ in the following re~ction); 8.3 g ~0 mmole) dehydra~ed phthaloylglycine-2959; 50 I~MENDED SH~ET

W0 97/01605 - PCT/~ 5/~1G~9 ml of anhydrous DMF; 20 ml of benzene; and 0.01 g p-tolulenesulfonyl chloride (Aldrich Chemical Co., Milwaukee, Wisconsin). The mixture was rhillPd in a salt/ice bat,h and stirred for 24 hours. The react,ion mixture was poured into 150 ml of weak sodium bicarbonate solution and extracted t,hree times with 50 ml ethyl ether. The aqueous layer was then filtered to yield a white solid comprising the 13-cyclodextrin with pht,haloylglycine-2959 group ~ he-l A yield of 9.4 g was obtained. Reverse phase TLC plate using a 50:50 DMF:acetonitrile mixtllre showed a new product peak co~ aLed to the starting materials.
~-cyclodextrin --CH2C Y~(CH2)20{~ ~ + _~t H0--CH2'CH2~
,B cyclodextrin R ~H2 o--CH2CH~
~H2C~(cH2)20~ -aHOEH3 The ,B-cyclodextrin molecule has several primary alcohols and secondary alcohols with which the phthaloylglycine-2959 can react. The above representative reaction only shows a single phthaloylglycine-2959 molecule for illustrative purposes.

Example 7 This example describes a method of assoc~ ng a colorant and an ultraviolet radiation transorber with a molecular includant.
More particularly, this example describes a method of associating the colorant crystal violet with the moleclll~r includant ,B--cyclodextrin covalently bonded to the ultraviolet radiation transorber dehydrated phthaloylglycine-2959 of Example 6.

SUBSTITU'rE SHEET

The following was placed in a 100 ml beaker: 4.0 g ~--cyclodextrin having a dehydrated phthaloylglycine-2959 group;
and 50 ml of water. The water was h~ated to 70~C at which point thé solution became clear. Next, 0.9 g (2.4 mmole) crystal violet (Aldrich Chemical Company, Milwaukee, Wiscnnsin) was added to the solution, and the solution was stirred for 20 minutes. Next, the solution was then ~iltere~. The ~iltrand was washed with the lQ filtrate and then dried in a vacuum oven a~ 84~C. A violet-blue powder was obtained having 4.1 g (92%) yield. The resulting reaction product had the following physical p~rameters-U.~f. Spectrum DMF vmax 610 nm ~cf cv vmax 604 nm).
1~
E~ample X
This example describes a method of producing the ultraviolet radiation transorber 4(4-hydroxyphenyl) butan-2-one-~95g ~chloro substituted).
2~ The following was admixed in a 250 ml round-bottomed fl~sk fitted with a condenser and m~p~netic s~ir bar: 17.6 g (0.1 mole~ of the waveleng~h selective sensitizer, 4(4-hydroxyphenyl3 butan-2-one ~Aldrich Chemical Company, Milwauk~e, Wisconsin3; ~6.4 g (0.1 mole) of the photoreactor, chloro su~stituted 1~3AROCUR~ 2g59 (Ciba-l~eigy Corporation, Hawthorn~, New Yorlc); 1.~ ml of pyridine ~AIdrich Chemical Company, Milwaukee, Wisconsin), and 100 ml of anhydrous tetrahydro~uran ~Aldrich Chemical Company, Milwaukee, Wisconsin). The mixture was refluxed for 3 hours and the solvent parti~l~y removed under reducs~d pressure (6(~% taken off~. The reacti~n mixture wa~ then poured into ice water and extracted wi~h two 50 ml aliquo~s o~ diethyl ~ther. After drying over anhydrous m~n~sium sulfate and removal o~ solvent, 39.1 g of whitc solvent rern~ined Recrysf~lli7~t;0n of the powder from 3S 30~ ethyl acetate in hexane gave 36.7 g (9~%) of a white j~hE~ ED SHEET

SUBSTITUT~ SHEET -56a crystalline powder, having a melting ~oint of 142-3~C. The reaction is sllmm~ ed in the following reaction:

.

i~'AEN~3ED SHEET

CA 02221~6~ 1997-12-0~
SUBSTITUTE SHEET ~ .' '., ~ ,~7~ '''', CH3--C--CH2CH2~0H + Cl(CH2)2--~~ CH3 CH3--C--CH2CH2~~--(CH2)2--~~C--C--OH

The resulting reaction product had the following physical parameters:

IR [NUJOL MULL ] vma" 3460, 1760, 1700, 1620, 1600 cm-l lH [CDC13] ~ppm 1.62[s], 4.2[m], 4.5[m], 6.9[m] ppm.

The ultraviolet radiation transorber produced in this example, 4(4-hydroxyphenyl) butan-2-one-2959 (chloro substituted), may be associated with ~--cyclodextrin and a colorant such as crystal violet, using the methods described above wherein 4(4-hydroxyphenyl) butan-2-one-2959 (chloro substituted)iwould be substituted for the dehydrated phthaloylglycine-2959.

Example 9 Stabilizing activity of the radiation transorber This example demonstrates the ability of the present invention to stabilize colorants against light. Victoria Pure Blue BO is admixed in acetonitrile with phthaloylglycine-2959, represented by the following formula:

AMENDED SIIEFT

CA 02221~6~ 1997-12-0~
SUBSTITUTE SHEET

~N--C H2C--O(CH2)20~C ~CCoHH. H

O

and dehydrated phthaloylglycine-2959, represented by the following formula:

o ~N--CH2C--O(CH2)2~~J~ ~C H~z ~

.Solutions were prepared according to Table 2. The dye solutions were carefully, uniformly spread on steel plates to a thickness of approximately 0.1 mm. The plates were then immediately exposed to a medium pressure 1200 watt high intensity quartz arc mercury discharge lamp (Conrad-Hanovia, Inc., Newark, New Jersey) at a distance of 30 cm from the light.
The mercury discharge light is a source of high intensity, broad spectrum light that is used in accelerated fading analysis. Table 2 shows the results of the fade time with the various solutions. Fade time is defined as the time until the dye became colorless to the naked eye.

AMENDED SHEET

CA 02221~6~ 1997-12-0~
SUBSTITUTE SHEET .. .. .. .

Table 2 Phthaloylglycine-2959 Victoria pure Fade Blue BO T'me 3 parts by wei, ,h. : part by we gnt 2 m n : 0 parts by we ght ' part by we gnt I 1/2 min 20 parts by we gnt : part by we gnt 30 sec Dehydrated Victoria pure Fade Phthaloylglycine-2959 Blue BO T me 3 parts by wei,~h, part by we gnt ' m n 0 parts by we g1t : part by we g 1t ~ m n ~0 parts by we gnt part by we gnt >10 min s As can be seen in Table 2, when phthaloylglycine-2959 was adrnixed with Victoria Pure Blue BO, the dye faded when exposed to the mercury discharge light. However, when dehydrated phthaloylglycine-2959 was admixed with the Victoria Pure Blue BO at a ratio of 10 parts dehydrated phthaloylglycine-2959 to one part Victoria Pure Blue BO, there was increased stabilization of the dye to light. When the ratio was 20 parts dehydrated phthaloylglycine-2959 to one part Victoria Pure BluejBO, the dye was subst~nti~lly stabilized to the mercury discharge light in the 15 '- time limits of the exposure.

Example 10 To determine whether the hydroxy and the dehydroxy 2959 have the capability to stabilize colorants the following experiment was conducted. The following two compounds were tested as described below.

AM~NDED SHFET

SUBS~ITIJTE SHEET ~ 7' HO (CH2)2 ~--C~ OH

HO (CH2)2 ~ O ~

' Dehydroxy 2959 20 parts by weight of the hydroxy and the dehydroxy 2959 were admixed separately to one part by weight of Victoria Pure Blue BO in acetonitrile. The dye solutions were carefully uniformly spread on steel plates to a thickness of approximately 0.1 mm.
The plates were then immediately exposed to a mercury discharge light at a distance of 30 cm from the light. The mercury discharge light is a source of high intensity, broad spectrum light that is used in accelerated fading analysis. Table 3 shows the results of the fade time with the various solutions. Fade time is defined as the time until the dye became colorless to the nalked eye.
Table 3 Compound Victoria l~ure Fade Time Blue 20 parts "~59 (~Iydroxy) ~ part < ~. m n 20 parts :'~959 (~ehydroxy)part <: ~n None part < " m n A','~NDED SHEET

SUBSTITUTE SHEET . . . . . . .
J

60a Example 11 Stabilizing activity of the radiation transorber and a molecular includant This example demonstrates the capability of dehydrated phthaloylglycine-2959 bound to ,3--cyclodextrin..to stabilize dyes ~ against light. The Victoria Pure Blue BO associated with the AMENDED SHEET

CA 0222l565 1997-l2-05 ~1 radiation transorber, as di~c~lsse-l in the examples above, was tested to determine its capability to stabilize the associated dye against light emitted from a mercury discharge light. In addition, the Victoria Pure Blue B0 alone and Victoria Pure Blue B0 S admixed with ,13-cyclodextrin were tested as controls. The compositions tested were as follows:

1. Victoria Pure Blue B0 only at a concentration of lOmg/ml in acetonitrile.
2. Victoria Pure Blue B0 included in 13-cyclodextrin at a concentration of 20 mg/ml in acetonitrile.

3. The Victoria Pure Blue B0 included in 13--cyclodextrin to which the radiation transorber (dehydrated phthaloylglycine-2959) is covalently attached at a concentration of 20 mg/rnl in acetonitrile.

The protocol for testing the stabilizing qualities of the three compositions is as follows: the dye solutions were carefully, uniformly spread on steel plates to a thickness of approximately 0.1 rnm. The plates were then imm~ tely exposed to a medium pressure 1200 watt high int~n~ity quartz arc mercury discharge lamp (Conrad-Hanovia, Inc., Newark, New Jersey) at a distance of 30 cm from the lamp.

Table 4 Comp~.sition Fade Time 5 sec ~' 5 sec >10 minutesa a There is a phase change after 10 minutes due to ext~eme heat As shown in Table 4, only composition number 3, the Victoria Pure Blue B0 included in cyclodextrin with the radiation CA 02221~6~ 1997-12-0~
SUBS~ITUTE SHEET ~, .. .. ~, transorber covalently attached to the ,13--cyclodextrin was capable of stabilizing the dye under the mercury discharge light.
Example 12 Preparation of epoxide intermediate of dehydrated ~ phthaloylglycine-2959 The epoxide intermediate of dehydrated phthaloylglycine 2959 was prepared according to the following reaction:

[~ ~ ~3 lo--C~CH2 H202/NaOH

--CH2C--o(CH2)20~3 lo~\C C,H2 O I .
In a 250 ml, three-necked, round bottomed flask fitted with an addition funnel, thermometer and m~netic stirrer was placed 30.0 g (0.076 mol) of the dehydrated phthaloylglycine-2959, 70 ml methanol and 20.1 ml hydrogen peroxide (30% solution). The reaction mixture was stirred and cooled in a water/ice bath to m~int~in a temperature in the range 15~-20~ C. 5.8 ml of a 6 N
NaOH solution was placed in the addition funnel and the solution was slowly added to maintain the reaction mixture temperature of . 15~-20~ C. This step took about 4 minutes. The mixture was then stirred for 3 hours at about 20~-25~ C. The reaction mixture was then poured into 90 ml of water and extracted with two 70 ml ~ portions of ethyl ether. The organic layers were combined and AM~NDED S~l~E~

SUBSTITUTE SHEET , ~ , 62a washed with 100 ml of water, dried with anhydrous MgSO4, filtered, and the ether removed on a rotary evaporator to yield a .

Al\lEN~ED S~FET

CA 02221~6~ 1997-12-0~
SUBSTITUTE SHEET

white solid (yield 20.3 g, 65%). The IR showed the stretching of the C-O-C group and the material was used without further purification.

Example 13 ~ Attachment of epoxide intermediate to thiol cyclodextrin The attachment of the epoxide intermediate of dehydrated phthaloylglycine 2959 was done according to the following reaction:

~N--CH2C--o(CH2)2O~c CH
~ (HS--CH2CH
DIvlF
ooc Beta-CD
o oCH3 ~ 1~l o~~ I H--CH2--(S--CH2CH2~

In a 250 ml 3-necked round bottomed flask fitted with a stopper and two glass stoppers, all being wired with copper wire and attached to the flask with rubber bands, was placed 30.0 g (0.016 mol) thiol cyclodextrin and 100 ml of anhydrous dimethylformarnide (DMF) (Aldrich Chemical Co., Milwaukee, Wisconsin). The reaction mixture was cooled in a ice bath and 0.5 ml diisopropyl ethyl amine was added. Hydrogen sulfide was bubbled into the flask and a positive pressure maintained for 3 hours. During the last hour, the reaction mixture was allowed to warm to room temperature.
The reaction mixture was flushed with argon for 15 minutes and then poured into 70 ml of water to which was then added 100 ml acetone. A white precipitate occurred and was AM~ND~D SHrET

SUBSTITUTE SHEET .. .. ..

63a filtered to yield 20.2 g (84.1%) of a white powder which was used without further purification.

AMENDED Sl IEET

CA 02221~6~ 1997-12-0~

SUBSTITUTE SHEET
.

In a 250 ml round bottomed flask fitted with a magnetic stirrer and placed in an ice bath was placed 12.7 g (0.031 mol) epoxide interrnediate of dehydrated phthaloylglycine 2959, 80 ml of anhydrous DMF (Aldrich Chemical Co., Milwaukee, Wisconsin) and 15.0 g (0.010 mol) thiol CD. After the reaction ~ mixture was cooled, 0.5 ml of diisopropyl ethyl arnine was added and the reaction mixture stirred for l hour at 0~C to 5~C followed by 2 hours at room temperature. The reaction mixture was then poured into 200 ml of ice water and a white precipitate formed immediately. This was filtered and washed with acetone. The damp white powder was dried in a convection oven at 80~C for 3 hours to yield a white powder. The yield was 24.5 g (88%).
Example 14 Insertion of Victoria Pure Blue in the cyclodextrin cavity In a 250 ml Erlenmeyer flask was placed a magnetic stirrer, 40.0 g (0.014 mol) of the compound produced in Example 13 and 100 ml water. The flask was heated on a hot plate to 80~C. When the white cloudy mixture became clear, 7.43 g (0.016 mol) of Victoria Pure Blue BO powder was then added to the hot solution and stirred for 10 minutes tlien allowed to cool to 50~C. The contents were then filtered and washed with 20 ml of cold water.
The precipitate was then dried in a convention oven at 80~C
for 2 hours~to yield a blue powder 27.9 g (58.1%).

Example 15 The preparation of a tosylated cyclodextrin with the dehydroxy phthaloylglycine 2959 attached thereto is performed by the following reactions:

AMENDED SHEET

CA 02221~6~ 1997-12-0~
SUBSTITUTE SHEET ~ .
, . . .

~N~H2C--O(CH2)20~ ~CH2 DMF

~N ~H2C--o(CH2)20~3--C--C ~H
O
s To a 500 ml 3-necked round bottomed flask fitted with a bubble tube, condenser and addition funnel, was placed 10 g (0.025 mole) of the dehydrated phthaloylglycine 2959 in 150 ml of anhydrous N,N-diethylformamide (Aldrich Chemical Co., Milwaukee, Wisconsin) cooled to 0~C in an ice bath and stirred with a magnetic stirrer. The synthesis was repeated except that the flask was allowed to warm I p to 60~C using a warm water bath and the H2S pumped into the reaction flask till the stoppers started to move (trying to release the pressure). The flask was-then stirred under these conditions for 4 hours. The saturated solution was kept at a positive pressure of H2S. The stoppers were held down by wiring and rubber bands. The reaction mixture was then allowed to warm-up overnight. The solution was then flushed with argon for 30 minutes and the reaction mixture poured onto 50 g of crushed ice and extracted three times (3 x 80 ml) with diethyl ether (Aldrich Chemical Co., Milwaukee, Wisconsin).
The organic layers were condensed and washed with water and dried with MgSO4. Removal of the solvent on a rotary evaporator gave 5.2 g of a crude product. The product was AMENDED SI~ET

-SUBSTITUTE SHEET ... ... ...
.: . . ',-' "~

65a puri~;ed on a silica column using 20% ethyl acetate in hexane as eluant. 4.5 g of a white solid was obtained.

AMENDED SHEET

CA 02221~6~ 1997-12-0~

SUBSTITUTE SHEET
~ .. . .. -. . ,... ;
. ~ .. .. . -- ~-- ~ -- .

A tosylated cyclodextrin was prepared according to the following reaction:
s ~7 CH3~ ~1 Pyridine O~C

C ~ CH2--[OTs]x ~7 .
To a 100 ml round bottomed flask was placed 6.0 g 13-cyclodextrin (American Maize Product Company), 10.0 g (0.05 mole) p - toluenesulfonyl chloride (Aldrich Chemical Co ., Milwaukee, Wisconsin), 50 ml of pH 10 buffer solution (Fisher).
The resultant mixture was stirred at room temperature for 8 hours after which it was poured on ice (approximately 100 g) and extracted with diethyl ether. The aqueous layer was then poured into 50 ml of acetone ~Fisher) and the resultant, cloudy mixture filtered. The resultar~t white powder was then run through a sephadex column (Aldrich Chemical Co., Milwaukee, Wisconsin) using n-butanol, ethanol, and water (5:4:3 by volume) as eluant to yield a white powder. The yield was 10.9%.
The degree of substitution of the white powder (tosyl-cyclodextrin) was determined by 13C NMR spectroscopy (DMF-d6) by comparing the ratio of hydroxysubstituted carbons versus tosylated carbons, both at the 6 position. When the 6-position carbon bears a hydroxy group, the NMR peaks for each of the six carbon atoms are given in Table 5.

AMEN~ED SHEET

CA 02221~6~ 1997-12-0~
SUBSTITUTE SHEET
, ~ ~-- . . .

Table 5 Carbon Atom NMR Peak (ppm) 101.8 2 72.9 3 72.3 4 81.4 71.9 6 59.8 s The presence of the tosyl group shifts the NMR peaks of the 5-position and 6-position carbon atoms to 68.8 and 69.5 ppm, respectively.
The degree of substitution was calculated by integrating the 10NMR peak for the 6-position tosylated carbon, integrating the NMR peak for the 6-position hydroxy-substituted carbon, and dividing the former by the latter. The integrations yielded 23.6 and 4.1, respectively, and a degree of substitution of 5.9. Thus, the average degree of substitution in this example is about 6.
15The tosylated cyclodlextrin with the dehydroxy phthaloylglycine 2959 attached', was prepared according to the following reaction: ~

11~ ~3CIl--C<H + (TsO CH2)~

[~--CH2C--O(CH2)2o~--C~--H

AMENDED SHEET

SUBSTITUTE SHEET ~ , , - .-- . , 67a To a 250 ml round bottomed flask was added 10.0 g (4-8 mole) of tosylated substituted cyclodextrin, 20.7 g (48 mmol) of 5thiol (mercapto dehydrated phthaloylglycine 2959) in 100 ml of AMENDED SHEET

CA 0222l~6~ l997-l2-0~

WO 97/01605 PCTIUS5.S,(,1C'?9 ~8 DMF. The reaction mixture was cooled to 0~ C in an ice bath and stirred using a m~nPtic stirrer. To the solution was slowly dropped in 10 ml of ethyl diisopropylamine (Aldrich ~h~mic~l Co., Milwaukee, Wisconsin) in 20 ml of DMF. The reaction was S kept at 0~ C for 8 hours with stirring. The reaction ~ ure was e~ cte-l with diethyl ether. The aqueous layer was then treated with 500 ml of acetone and the precipitate filtered and washed with acetone. The product was then run on a sephadex column using n-butanol, ethanol, and water (5:4:3 by volume) to yield a white powder. The yield was 16.7 g.
The degree of substitution of the function~li7e~1 molecular includant was determined as described above. In this case, the presence of the derivatized ultraviolet radiation transorber shifts the NMR peak of the 6-position carbon atom to 63.1. The degree of substitution was calculated by integrating the NMR peak for the 6-position substituted carbon, integrating the NMR peak for the 6-position hydroxy-substituted carbon, and dividing the former by the latter. The integrations yielded 67.4 and 11.7, respectively, and a degree of substitution of 5.7. Thus, the average degree of substitution in this example is about 6. The reaction above shows the degree of substitution to be "n". Although n represents the value of substitution on a single cyclodextrin, and therefore, can be from 0 to 24, it is to be understood that the average degree of substitution is about 6.
Example 16 The procedure of Example 1~ was repeated, except that the amounts of 13-cyclodextrin and p-toluenesulfonic acid (Aldrich) were 6.0 g and 5.0 g, respectively. In this case, the degree of substitution of the cyclodextrin was found to be about 3.

CA 0222l~6~ l997-l2-0~

WO 97/01605 PCT/US~15/~ ~9 ~!

li,x~mple 17 The procedure o~ E~nple 15 was repeated, except that the ~ derivatized molecular includant of Example 16 was employed in place of that from Fx~mrle 15. The average degree of S substitution of the function~li7~1 molecular includant was found to be about 3.

FY~mrle 18 This example describes the preparation of a colored 1~ composition which includes a mutable colorant and the function~li7~-~ molecular includant from Fx~mple 15.
In a 250-ml Erlenmeyer flask cont~ining a m~gn~tic stirring bar was placed 20.0 g (5.4 mmoles) of the function~li7~1 molecular includant obtained in Example 15 and 100 g of water.
The water was heated to 80~C, at which temperature a clear solution was obtained. To the solution was added slowly, with stirring, 3.1 g (6.0 mmoles) of Victoria Pure Blue BO (Aldrich).
A precipitate formed which was removed from the hot solution by filtration. The precipitate was washed with 50 ml of water and 2~ dried to give 19.1 g (84 percent) of a blue powder, a colored composition consisting of a mutable colorant, Victoria Pure Blue B0, and a m~lecular includant having covalently coupled to it an average of about six ultraviolet radiation transorber molecules per molecular includant molecule.
Example 19 The procedure of Example 18 was repeated, except that the functiona!ized molecular includant from Example 17 was employed in place of that from Example 15.
3~
Example 20 - This example describes mutation or decolorization rates for the compositions of Examples 7 (wherein the ,B-cyclodextrin has dehydrated phthaloyl glycine-2959 from Example 4 covalently bonded thereto), 18 and 19.

WO 97/01605 PcT/u:~5~ 9 In each case, approximately 10 mg of the composition was placed on a steel plate (Q-Panel Company, Cleveland, Ohio).
Three drops (about 0.3 ml) of acetonitrile (Burdick & Jackson, Muskegon, Michigan) was placed on top of the composition and the two m~tPri~ were quickly mixed with a sp~ and spread out on the plate as a thin film. Within 5-10 seconds of the addition of the acetonitrile, each plate was exposed to the radiation from a 222-nanometer excimer lamp assembly. The ~semhly consisted of a bank of four cylindrical lamps having a length of about 30 cm. The lamps were cooled by circlll~ting water through a centrally located or inner tube of the lamp and, as a consequence, they operated at a relatively low tempeLatule, i.e., about 50~C. The power density at the lamp's outer surface typically was in the range of from about 4 to about 20 joules per square meter (J/m2). However, such range in reality merely reflects the capabilities of current excimer lamp power supplies;
in the future, higher power ~lPn~itiçs may be practical. The distance from the lamp to the sample being irr~ t~-1 was 4.5 cm.
The time for each film to become colorless to the eye was measured. The results are sllmm~ri7~a in Table 6.

Table 6 Decolorization Times for Various Compositions CompositionDecolorization Times (Seconds) Example 18 Example 19 3-4 Example 7 7-8 While the data in Table 6 demonstrate the clear superiority of the colored compositions of the present invention, such data were plotted as degree of substitution versus decolorization time.
The plot is shown in Figure 3. Figure 3 not only demonstrates the significant improvement of the colored compositions of the CA 02221~6~ 1997-12-0~

WO 97/01605 PCT/u~ 16~') present invention when co~ ared with compositions having a degree of substitution less than three, but also indicates that a degree of substitution of about 6 is about o~ That is, the figure indicates that little if any improvement in decolonization S time would be achieved with degrees of substitution greater than about 6.

Example 21 This example describes the preparation of a complex consisting of a mutable colorant and the derivatized molecular includant of Example 15.
The procedure of Example 18 was repeated, except that the functionAli7~A molec~ r includant of Example lS was replaced with 10 g (4.8 mmoles) of the derivatized molecular includant of lS Example lS and the amount of Victoria Pure Blue BO was re~lllce~l to 2.5 g (4.8 mmoles). The yield of washed solid was 10.8 g (86 percent) of a mutable colorant associated with the 13-cyclodextrin having an average of six tosyl groups per molecule of molecular includant.

~Y:~mrle 22 This example describes the preparation of a colored composition which includes a mutable colorant and a function~li7~1 moleclll~r inclu(l~nt The procedure of ~repA. in~; a functionAli7~1 molecular includant of Example 15 was repeated, except that the tosylated ~-cyclodextrin was replaced with 10 g (3.8 mmoles) of the complex obtained in Example 21 and the amount of the derivatized ultraviolet radiation transorber prepared in F.x~mple 15 was 11.6 g (27 mmoles). The amount of colored composition obtained was 11.2 g (56 percent). The average degree of substitution was determin~d as described above, and was found to be 5.9, or about 6.

CA 02221~6~ 1997-12-0~
SUBSTITUTE SHEET
.. . ~ ...
, Example 23 The following two compounds were tested for their ability to stabilize Victoria Pure Blue BO:
o r~ O CH2--S CH~¦ 3 ~
L~N--CH2C--O(CH2)2O~3C--C--H 1~
J

Dehydroxy Compound r,~ 11 CH2--S--CH~3 ~ ~/
LI~N CH2C--O(CH2)2O~C--C--OH ~

Hydroxy Compound This example further demonstrates the ability of the present invention to stabilize colorants against light. The two compounds containing Victoria Pur~ Blue BO as an includant in the cyclodextrin cavity were tested for light fastness under a medium pressure mercury discharge lamp. 100 mg of each compoùnd was dissolved in 20 ml of acetonitrile and was uniformly spread on 15 ~ steel plates to a thickness of approximately 0.1 mm. The plates were then immediately exposed to a medium pressure 1200 watt high intensity quartz arc mercury discharge lamp (Conrad-Hanovia, Inc., Newark, New Jersey) at a distance of 30 cm from the lamp. The light fastness results of these compounds are s~lmm~rized in Table 7.

AMENDED StltET

CA 02221~6~ 1997-12-0~
SUBSTITUTE SHEET 1 ~ ~..... ,.. ",~

Table 7 Cyclodextrin Compound Fade Time Dehydroxy Compound ilO mina Hydroxy Compound <20 sec a There is a phase change after 10 minutes due to extreme heat Example 24 This example describes the preparation of films consisting of colorant, ultraviolet radiation transorber, and thermoplastic polymer. The colorant and ultraviolet radiation transorber were ground separately in a mortar. The desired amounts of the ground components were weighed and placed in an aluminum pan, along with a weighed amount of a thermoplastic polymer.
The pan was placed on a hot plate set at 150~C and the mixture in the pan was stirred until molten. A few drops of the molten mixture were poured onto a steel plate and spread into a thin film by means of a glass microscope slide. Each steel plate was 3 x 5 inches (7.6 cm x 12.7 cm) and was obtained from Q-Panel Company, Cleveland, Ohio. The film on the steel plate was estim~te~ to have a thickness of the order of 10-20 micrometers.
In every instance, the colorant was Malachite Green oxalate (Aldrich Chemical Company, Inc., Milwaukee, Wisconsin), referred to hereinafter as Colorant A for convenience. The ultraviolet radiation transorber ("UVRT") consisted of one or more of IRGACURE(g) 500 ("UVRT A"), IRGACURE(~) 651 ("WRT B"), and IRGACURE~g) 907 ("UVRT C"), each of which was described earlier and is available from Ciba-Geigy Corporation, Hawthorne, New York. The polymer was one of the following: an epichlorohydrin-bisphenol A epoxy resin ("Polymer A"), EPON(~) 1004F (Shell Oil Company, Houston, Texas); a poly(ethylene glycol) having a weight-average molecular weight of about 8,000 ("Polymer B"), CARBOWAX~
8000 (Aldrich Chemical Company); and a poly(ethylene glycol) AMENDED SH~ET

SUBSTITUTE ~HEET . , ~

, ~

73~
having a weight-average molecular weight of a~out 4,600 ("Polymer C"), CARBOWAX~) 4600 (Aldrich Chemical S Company~. A control film ~a~ prepared AMEN~D S~EET

CA 0222l565 l997-l2-05 WO 97/01605 PCT/US5~ 9 which consisted only of colorant and polymer. The compositions of the films are sllmm~ri7ed in Table 8.

Table 8 S Compositions of Films Cont~inin~
Colorant and Ultraviolet Radiation Transorber ("UVRT") Colo ant UVRT Polymer Film Type Parts Type Parts Type Parts While still on the steel plate, each film was exposed to ultraviolet radiation. In each case, the steel plate having ~e film sample on its surface was placed on a moving conveyor belt having a variable speed control. Three different ultraviolet radiation sources, or lamps, were used. Lamp A was a 222-nanometer excimer lamp and Lamp B was a 308-nanometer excimer lamp, as already described. Lamp C was a fusion lamp system having a "D" bulb (Fusion Systems Corporation, Rockville, Maryland). I~e excimer lamps were organized in banks of four cylindrical lamps having a length of about 30 cm, with the lamps being oriented normal to the direction of motion of the belt. The lamps were cooled by circulating water through a centrally located or inner tube of the lamp and, as a consequence, they operated at a relatively low temperature, i.e., about 50~C. The power density at the lamp's outer surface typically is in the range of from about 4 to about 20 joules per S square meter (J/m2).
However, such range in reality merely reflects the capabilities of current excimer lamp power supplies; in the future, higher power ~lencities may be practical. With Lamps A and B, the distance from the lamp to the film sample was 4.5 cm and the belt was set to move at 20 ft/min (0.1 m/sec). With Lamp C, the belt speed was 14 ft/min (0.07 m/sec) and the lam~-to-sample ~list~nce was 10 cm. The results of exposing the film samples to ultraviolet radiation are sllmm~ri7e~1 in Table 9. Except for Film F, the table records the number of passes under a lamp which were required in order to render the film colorless. For Film F, the table records the number of passes tried, with the film in each case rem~inin,Q~ colored (no change).
Table 9 Results of Exposing Films Co.. l;li.. i.. g Colorant and Ultraviolet Radiation Transorber (UVRT) to Ultraviolet Radiation Excimer Lamp Film Lamp A Lamp B Fusion Lamp E

WO 97/01605 PCT/u~ 8!~

Example 2S
This Fx~mrle demonstrates that the 222 nanometer excimer lamps illustrated in Figure 4 produce uniform int~ncity re~-lin.~
on a surface of a substrate 5.5 centim~-t~rs from the lamps, at the numbered locations, in an amount sufficient to ~ e the colorant in the compositions of the present h~vel~lion which are present on the surface of the substrate. The lamp 10 comprises a l~mp housing 15 with four excimer lamp bulbs 20 positioned in parallel, the excimer lamp bulbs 20 are approxim~tely 30 cm in length. The lamps are cooled by circ~ ting water through a centrally located or inner tube (not shown) and, as a conse~quence, the lamps are operated at a relatively low tempel~lure, i.e., about SO C. The power density at the lamp's outer surface typically is in the range of from about 4 to about 20 joules per square meter (J/m2).
Table 10 ~llmm~ri7es the int~n.~ity re~ling~ which were obtained by a meter located on the surface of the substrate. The re~in~ numbered 1, 4, 7, and 10 were located approxim~tely 7.0 cel-ltim~ters from the left end of the column as shown in Figure 4. The re~ling.~ numbered 3, 6, 9, and 12 were located approxirnately 5.5 centim~ters from the right end of the column as shown in Figure 4. The re~ling~ numbered 2, 5, 8, and 11 were centrally located appro~imately 17.5 centimeters from each end of the column as shown in Figure 4.

CA 02221~6~ 1997-12-0~

WO 97/0160S PCT/U555.'.,1~i~9 Back~round (,uW) R~tlin~ (mW/cm ) 24.57 9.63 19.56 9.35 22.67 9.39 19.62 9.33 17.90 9.30 19.60 9.30 21.41 9.32 17.91 9.30 23.49 9.30 19.15 9.36 17.12 9.35 21.44 9.37 Example 26 This Example demonstrates that the 222 nanometer excimer lamps illustrated in Figure S produce uniform inten~ity re~-lin~
on a surface of a substrate 5.5 centim.o-ters from the lamps, at the numbered locations, in an amount sufficient to mllt~te the colorant in the compositions of the present invention which are present on the surface of the substrate. The excimer lamp 10 comprises a lamp housing 15 with four excimer lamp bulbs 20 positioned in parallel, the excimer lamp bulbs 20 are approxim~tely 30 cm in length. The lamps are cooled by circlll~ting water through a centrally located or inner tube (not shown) and, as a consequence, the lamps are operated at a relatively low temperature, i.e., about 50~C. The power density at the lamp's outer surface typically is in the range of from about 4 to about 20 joules per square meter (Jlm2).
Table 11 snmm~i7eS the intensity re~flin~ which were obtained by a meter located on the surface of the substrate. The readings numbered 1, 4, and 7 were located approximately 7.0 WO 97/01605 PcT/u~ ?9 cen*m.qters from the left end of the columns as shown in Figure 5. The re~iings numbered 3, 6, and 9 were located approxim~tely 5.5 centim~t~-rs from the right end of the columns as shown in Figure 5. The re~tling.~ numbered 2, 5, 8 were centrally located approxim~ly 17.5 centim~-ters from each end of the columns as shown in Figure 5.

Table 11 Background (,uW) Re~lin~ ~mW/cm2) 23.46 9.32 16.12 9.31 17.39 9.32 20.19 9.31 16.45 9.29 20.42 9.31 18.33 9.32 15.50 9.30 20.90 9.34 Example 27 This Example demonstrates the intçn~city produced by the 222 nanometer excimer lamps illustrated in Figure 6, on a surface of a substrate, as a function of the distance of the surface from the lamps, the intçn~ity being sufficient to mllt~te the colorant in the compositions of the present invention which are present on the surface of the substrate. The excimer lamp 10 comprises a lamp housing 15 with four excimer lamp bulbs 20 positioned in parallel, the excimer lamp bulbs 20 are approxim~t.oly 30 cm in length. The lamps are cooled by circlll~ting water through a centrally located or inner tube (not shown) and, as a consequence, the lamps are operated at a relatively low tempel~lu.e, i.e., about 50~C. The power density at the lamp's outer surface typically is SUBSTI~UTE SH~l~T ~ .. .. ..
., .. , ..... .. .. ~

in the range of ~rom ~QUt 4 to about 20 joules per square me~er . (J/m2).
STable 12 s-lmm~r;~es the inten~ity re~clin~s which were obt~ined by a meter located on the sur~ace of the su~strate at position 1 ~s shown in Figure 6. Position 1 was.centrally located ~ approximately 17 centimeters from each end of the c~lumn as shown in Figure 6.
Table ~2 Distance ~cm) Background ~W) R.P,~f1tn~
(mWJcm2) .5 1~.~5 9.30 6.0 15.7~ 9.3 18.60 9 3 20.90 9.3~
~0 21.67 g.48 ~.86 g.ti9 22.50 1 1 . 14 ~6.2~ ~. 10 24.71 17.S8 26.95 5.2 ~,x~mple 28 lSThis example describes a method of m:~kin~ the following waYelength-selective sensiti~er:
o HOOC ~CH=CH--~ ~

The wavelength-selective sensitizer is synthesi~ed as sl-rnmz.ri~ed T:~,low:
hMENOEI~ S~IE~T

CA 02221~6~ 1997-12-05 SUBSTITUTE SHEET ,; ~ 1.. . 1. .;
. . .
.,, ~, . .. .. .. ..

o HOOC~CHO + H3C~ ~> NaOH/EtOH/H20 HOOC~H~Hff~>

To a 250 ml round bottom flask fitted with a magnetic stir bar, and a condensor, was added 10.8 g (0.27 mole) sodium hydroxide (Aldrich), 98 g water and 50 g ethanol. The solution was stirred while being cooled to room temperature in an ice bath. To the stirred solution was added 25.8 g (0.21 mole) acetophenone (Aldrich) and then 32.2 g (0.21 mole) 4-carboxybenzaldehyde (Aldrich). The reaction mixture was stirred at room temperature for approximately 8 hours. The reaction mixture temperature was checked in order to prevent it from exceeding 30~C. Next, dilute HCL was added jto bring the mixture to neutral pH. The white/yellow precipitate'was filtered using a Buchner funnel to yield 40.0 g (75%) after drying on a rotary pump for four hours. The product was used below without further purification.
The resulting reaction product had the following physical parameters:
Mass. Spec. m~'e (m+) 252, 207, 179, 157, 105, 77, 51.

Example 29 This example describes a method of covalently bonding the compound produced in Example 28 to cyclodextrin as is sllmm~ri7ed below:
AMENDED SHEET

SUBSTITUTE SHEET . .. .. ~, HO II~CH=C~R~ Cl/ C
o c ~ DMF

CIOC~--CH=CH--C~>

O C _ ~O(CH2)20H
CIOC~CH=CH--C~ +

DMF

~O(CH2)20C ~C--C=C

To a 250 ml round bottom flask fitted with a magnetic stir bar, condensor, and while being flushed with argon, was placed 5.0 g (0.019 mole) of the composition prepared in Example 29, and 50 ml of anhydrous DMF (Aldrich). To this solution was slowly dropped in 2.5 g (0.019 mole) oxalyl chloride (Aldrich) over thirty minutes with vigorous stirring while the reaction flask was cooled in an ice-bath. After one hour, the reaction was allowed to warm to room temperature, and then was stirred for one hour. The reaction mixture was used "as is" in the following step. To the above reaction mixture 5.3 g (0.004 mole) of hydroxyethyl substituted alpha-cyclodextrin (American Maize AMENDED SHcET

SUBSTITUTE SHEET ~ , . , 81a Company), dehydrated by Dean and Stark over benzene for two hours to remove any water, was added and the reaction mixture S stirred at room temperature with 3 drops of triethylamine added.

AMENDED S~tE~

CA 02221~6~ 1997-12-0~
SUBSTITUTE SHEET
.... .. .. .. .

After four hours the reaction mixture was poured into 500 rnl of acetone and the white precipitate filtered using a Buchner Funnel.
The white powder was dried on a rotary pump (0.1 mm Hg) for four hours to yield 8.2 g product.
The resulting reaction product had the following physical parameters:
NMR (DMSO-d6) ~ 2.80[M, CD], 3.6-4.0 [M, CD], 7.9 [C, aromatus] ,8.2 [M, aromatus of C], 8.3 [M, aromatus of C] ppm.

Example 30 This example describes a method of making the following wavelength-selective sensitizer, namely 4-[4'-carboxy phenyl]-3-1 5 buten-2-one:

HOOC~CH =C H~ ~ H3 The wavelength-selective sensitizer is synthesized ~s sllmm~ri7e-1 below:

HOOC ~CHO + H3C--C {~ H3 NaoHlEtoH/H2o HOOC~CH=CH--C{~H3 The method of Example 28 was followed except thzt acetone (Fisher, Optima Grade) was added first, and then the çarboxybenzaldehyde was added. More particularly, 32.2 g (0.21 mole) of carboxybenzaldehyde was reacted with 12.2 g (0.~l AMENDED SHEEr SUBSTITUTE SHEET a 82a mole) of acetone in the sodium hydroxide/ethanol/water mixture described in Example 28. Dilute HCl was added to bring the AMENDED SHEET

SUBSTITUTE SHEET

reaction mixture to neutral pH, yielding 37.1 g (91%) of a pale yellow powder which was used without further purification in the S following examples.
The resulting reaction product, namely 4- [4 ' -carboxy phenyl]-3-buten-2-one, had the following physical parameters:
Mass. Spec. 190 (m+), 175, 120.

Exannple 31 This example describes a method of covalently bonding the 4-[4'-carboxy phenyl]-3-buten-2-one produced in Example 30 to cyclodextrin as is sllmm~ri7ed below:

HOOC~CH=C~C~H3 + C--C

O C
~ DMF

Cld:)C~H=Cl~C--CH3 Ol C ~ ~ O(CH2)20H
CIOC~CH=CI I C--CH3 +

~, DMF

~c ' 7~0(CH2)20C~H =CH -C--CH3 AMENDED Sll~ET

SUBSTITUTE SHEET ~ t;

83a The method of Example 29 was followed except that 5.0 g of the 4-[4'-carboxy phenyl]-3-buten-2-one was used. More AMENDED SH~ET

CA 02221~6~ 1997-12-0~
:
SUBSTITUTE SHEET

particularly, 5.0 g (0.026 mole) of the 4-[4'-carboxy phenyl]-3-buten-2-one produced in Example 30 was reacted with 3.3 g (0.026 mole) of oxalyl chloride in anyhydrous DMF at about 0~C.
Next, approximately 7.1 g (0.005 mole) hydroxyethy~ substituted cyclodextrin was added to the mixture (5: 1 ratio) under the conditions described in Example 30 and was further processed as described therein, to produce 10.8 g of white powder. The NMR
of the product showed both the aromatic protons of the 4-[4'-carboxy phenyl]-3-buten-2-one produced in Example 30 and the glucose protons of the cyclodextrin.

Example 32 This example describes a method of covalently bonding the compound produced in Example 28 to a photoreactor, namely DAROCUR@~) 2959, as is sllmn~ri7.ed below:

<~--CH=CH~ OH + Ho~cH2)2 - o~--C~--OH

Benzene Tosyl acid --C H=C H ~--O(CH2)2--O ~ C H3 To a 500 ml round bottom flask fitted with a magnetic stir bar, and condensor, was placed 20 g (0.08 mole) of the composition prepared in Example 28, 17.8 g (0.08 mole) DAROCUR(~) 2959 (Ciba-Geigy, N.Y.), 0.5 g p-toluenesulfonic acid (Aldrich), and 300 ml anhydrous benzene (Aldrich). The Dean and Stark adapter was put on the flask and the reaction mixture heated at reflux for 8 hours after which point 1.5 ml of water had been collected (theo. 1.43 ml). The reaction mixture AMENDED SHEET

SUBSTITUTE SHEET

84a ~ .
was then cooled and the solvent removed on a rotary evaporator to yield Al~.,lENDED SHEFT

CA 02221~6~ 1997-12-0~
SUBSTITUTE SHEET . . , ,, 35.4 g. The crude product was recrystalized from 30% ethyl acetate in hexane to yield 34.2 g (94%) of a white powder.
The resulting reaction product had the following physical parameters:
Mass. Spectrum: 458 (m+), 440, 399, 322, 284.

Example 33 To determine whether the 4-[4'-carboxy phenyl]-3-buten-2-one produced in Example 30 has the capability to stabilize colorants, the following experiment was co~ducted. Test films were made up containing 90% CARBOWAX(~) 4600 and 10% of a 1 part Victoria Pure Blue BO (Aldrich) to 19 parts 4-[4'-carboxy phenyl]-3-buten-2-one. The mixture was melted on a hot plate, stirred, then drawn down on metal plates (at approximately 60~C), using a #3 drawdown bar. A similar sample was made with only 1% Victoria Pure Blue BO in 99% CARBOWAX(~).
The plates were exposedL to a 1200 Watt Mercury medium pressure lamp for one hour, the lamp being about 2 feet from the plates. After one hour, the ~7ictoria Pure Blue BO plate was essentially colorless, while the plate having the mixture of Victoria PurellBlue BO and 4-[4'-carboxy phenyl]-3-buten-2-one thereon had not changed.
Example 34 A further experiment to determine the colorant stabilizing capability of the 4-[4'-carboxy phenyl]-3-buten-2-one produced in Fx~mple 30 is as follows. The experiment used in Example 33 was repeated except that no CARBOWAX(~) was used. Instead, the materials were dissolved in acetonitrile and a film formed, allowed to dry, and then exposed to the 1200 Watt lamp. Again, after one hour, the dye (Victoria Pure Blue BO) was essentially colorless while the mixture cont~ining the 4-[4'-carboxy phenyl]-3-buten-2-one was unchanged in color.

AI~ENDED SllEET

CA 02221~6~ 1997-12-0~

WO 97/01605 PCT/US!15f~ 16~9 F,x~mrle 35 A further experim~nt to determine the colorant stabilizing capability of the compounds produced in Examples 28, 29, 30 (4-[4'-carboxy phenyl]-3-buten-2-one), and 31 (4-~4'-carboxy phenyl]-3-buten-2-one/cyclodextrin) was as follows. The experiment used in Example 34 was repeated for all four compounds, separately. More particularly, five metal plates were prepared using the acetonitrile slurry method of Example 34, with the compositions as follows:
(1) Victoria Pure Blue BO only;
(2) Victoria Pure Blue BO + the compound produced in Example 28;
(3) Victoria Pure Blue BO + the compound produced in Example 30;
(4) Victoria Pure Blue BO + the compound produced in Example 29;
(5) Victoria Pure Blue BO + the compound produced in Fx~mple 31.
In compositions (2) through (5), the compositions contained one part Victoria Pure Blue BO per 20 parts of the compounds produced in the above examples. More particularly, 0.1 g of Victoria Pure Blue BO was mixed with approximately 2.0 g of one of the compounds produced in the above examples, in 10 ml of acetonitrile. The mixtures were drawn down using a #8 bar and allowed to air dry in a ventilation hood. All of the plates were simlllt~n~ously exposed to the 1200 Watt mercury lamp for one hour. Each plate was half covered with aluminum foil during exposure to the lamp to m~int~in a lefelence point with respect to fading of the colorant. After one hour under ~e lamp, mixture (1 ) had gone colorless, while mixtures (2) through (5) all remained unchanged.

CA 02221~6~ 1997-12-0~

SUBSTITUTE SHEET . ' 17 ~

Example 36 Another experiment to determine the colorant stabilizing capability of the compound produced in Example 29 was as follows. Briefly described, the compound of Example 29 was used with color inks removed from the colo~ cartridges of a CANON(~ BJC-600e bubble jet color printer. The ink was re-installed into the cartridges, which were installed into the ink jet printer, and color test pages were generated. The fortieth color test page was used in the present study.
More particularly, the four cartridges were of BJI-201, and the four inks (cyan, magenta, black, and yellow) were prepared as follows:
(1) Cyan About 3 . 8 ml of the colored ink in the cartridge was removed, having a viscosity of 12 seconds for 3 ml measured in a 10 ml pipette. About 0.4 g of the compound produced in Example 29 was added to the 3.8 ml and mixed for 15 minutes.
The ink solution prepared was hazy, and had a viscosity of 19 seconds for 3 ml.
(2) Magenta About 4. 8 ml o,f the colored ink in the cartridge was removed, having a viscosity of 12 seconds for 3 ml. About 0.43 g of the compound of Example 29 was added to the 4.8 ml and mixed for fifteen minutes, producing a ink solution having a viscosity of 18 seconds for 3 ml.
(3) Black About 7.2 ml of the ink in the cartridge was removed, having a viscosity of 8 seconds for 3 ml. About 0.72 g of the compound of Example 29 was added to the 7.2 ml and mixed for fifteen minutes, producing a hazy ink solution having a viscosity of 15 seconds for 3 ml.
(4) Yellow A~'tENDED Sl IEFT

SUBSTITUTE SHEET ~ " , . . ;

87a About 4.0 ml of the colored ink in the cartridge was removed, having a viscosity of 4 seconds for 3 ml. About 0.41 g Sof the compound of Example 29 was added to the 4.0 ml and A~J;EN~ED SH~ET

CA 0222l~6~ l997-l2-0 WO 97/0160S PCT/USg~ ,1~~!~

mixed for fifteen minutes, producing a hazy ink solution having a viscosity of 7 seconds for 3 ml.
The cartridges were then refilled with the corresponding ink solutions (1) through (4) above. Forty pages were run off, and the fortieth page was exposed to a 1200 Watt medium pressure mercury lamp with a control sheet for nine hours. The control sheet is the fortieth color test page run off using the ink compositions that were in the original ink cartridges.
The results of this experimPnt were as follows. After three hours under the 1200 Watt lamp, the control was 40 to 50%
bleached, while the inks cont~ining the compound produced in Example 29 were unchanged. After nine hours, the control was 50 to 60% blç~rh~-~ while the inks cont~ining the compound of Example 29 were only about lO to 20 % bleached. Accordingly, the compound produced in Example 29 is capable of stabilizing the dyes found in st~nfl~rd ink jet inks.

Example 37 Another experiment to determine the colorant stabilizing capability of the compound produced in Example 29is as follows.
The stability of the ink solutions produced in Example 36 were studied as described below.
The forty-eighth sheet (test sheet) was generated using the ink solutions (l) through (4) of Example 36 each cont~inin~ about 10% of the compound of Example 29, and was then exposed to a 1200 Watt lamp along with a control sheet (generated from the commercially available ink from the cartridges before the compound of Example 29 was added). The sheets were monitored each hour of exposure and "fade" was determined by the eye against an unexposed sheet. The results of exposing the sheets to the 1200 Watt lamp are snmm~rized in Table 13, where NC= no change.

SUBSTITUTE SHEET '~

Table 13 Irradiation Time (Hour) Control Sheet TestSheet 5- 10% NC
2 10-15% NC
3 20% NC
4 30% NC
50% NC
S
Accordingly, the compound prepared in Example 29 works well as a dye stabilizer to visible and ultraviolet radiation.

This example describes a method of preparing the following wavelength-selective sensitizer:

HOOC~3CH=CH--C~3 101 ~3CH--CH--C~3 The wave~ength-selective sensitizer is synthesized as sllmm~ ed below:

HOOC~CHO + H3C--C~30H

NaOH
EtOH/H20 HOOC~,3CH=CH--C ~OH

AMENDED SflEET

CA 02221~6~ 1997-12-0~
SUBSTITUTE SHEET ' , ~, To a 250 ml round bottom flask fitted with a magnetic stir bar, is placed 14.6 g (0.097 mole) 4-carboxybenzaldehyde (Aldrich), 13.2 g (0.097 mole) 4'-hydroxyacetophenone (Aldrich), 50 ml of ethanol, 100 rnl of water containing 10.8 g sodium hydroxide (Fisher). The solution is stirred at room temperature for four hours after ~hich the reaction mixture is neutralized with hydrochloric acid (2N). The resultant precipitate is filtered on a Buchner funnel and washed with water. The light yellow powder is dried under vacuum for 8 hours to yield 22.1 g, (85%) of product.
The reaction product has the following physical parameters:
Mass. Spectrum m/e: 268 (m+), 245, 218, 193, 179, 151, 125, 73.

B- HOOC~CH--CH--C~OH

HOOC~CH =CH--C~

,¦ Benzene HOOC ~CH =CH--C~30--C~CH=CH--C~
A 250 ml round bottom flask is fitted with a Dean and Stark adaptor and condensor. 10.0 g (0.037 mole) of the product produced above in reaction A, 9.36 g (0.037 mole) of the wavelength-selective sensitizer produced in Example 28, 100 ml of dry benzene (Aldrich) and 0.3 g of p-toluene sulfonic acid (Aldrich) are placed into the flask and the reaction mixture heated at reflux for eight hours. The solvent is then removed under A~lENDED Sll~ET

SUBSTITUTE SHEET '' . .' .
, . .. .

90a reduced pressure to yield a pale yellow solid. The solid is pumped under vacuum to yield 17.2 g (95%) of product.
The reaction product has the following physical parameters:

A.~iEN~ED SH~ET

CA 02221~6~ 1997-12-0~
SUBSTITUTE SHEET ~ 7 Mass. Spectrum m/e: 501, 484, 234, 193, 179, 125.

S EXA~lPLE 39 This example describes a method of preparing the following wavelength-selective sensitizer:

HOOC~3CH =CH--C~30--C~3CH=CH--C--CH3 The wavelength-selective sensitizer is synthesized as sllmm~rized below:

HOOC ~3CH--CH--C~3OH

HOOC~CH =CH--C--CH3 HOOC~3CH=CH--C~3 101~3CH--CH--C--CH3 Into a 250 ml round bottom flask fitted with a Dean and Stark adaptor is placed 10.0 g (0.037 mole) of the product produced in Example 38 (reaction A), 7.1 g (0.037 mole) of the wavelength-selective sensitizer produced in Example 30, 100 ml of dry benzene (Aldrich) and 0.3 g of p-toluene sulfonic acid (Aldrich). The reaction mixture is heated at reflux for eight hours. The solvent is then removed under reduced pressure to yield a light yellow solid. The solid is pumped under vacuum to yield 15.2 g (93%) of product.
The reaction product has the following physical parameters:

AMENDED SH~ET

. .
SUBSTITUTE SHEET . . . .
. : , , '; . ~ .
~ ~ ~ O ~ ~ ~

91a Mass. Spectrum n/e: 439 (m+), 424, 266, 174.

AMENDED S~EET

- ' -CA 02221~6~ 1997-12-0~
SUBSTITUTE SHEET ;

This example describes a method of covalently bonding the compound produced in Example 3 8 to cycl~dextrin as is sllmm~rized below: ' ~,(OCH2CH20H)x Cl--C~3CH =CH--C~O--C~3CH=CH--C~3 ~ 0CH2CH20--C ~ C~ C ~--o--C ~3 " ~3 ) X

First, the compound produced in Example 38 is treated 1~) with oxalyl chloride to produce the acid chloride of the compound produced in Example 38. (See Example 29) Next, into a 250 ml round bottom flask fitted with a magnetic stir bar is placed 20.0 g (0.015 mole) of hydroxyethyl-substituted alpha-cyclodextrin (American Maize Company, Hammond, Indiana), 22.2 g (0.030 mole) of the acid chloride form of the wavelength-selective sensitizer produced in Example 3 8, 100 ml of dry dimethylsulfoxide (Aldrich), and 3 drops of triethyl~mine. The reaction mixture is stirred for eight hours and then poured into 300 ml of acetone. The resultant white precipitate is filtered, and pumped under vacuum to yield 20.6 g of product.

AMENDED SHEET

CA 02221~6~ 1997-12-0~
SUBSTITUTE SHEET

This example describes a method of covalently bonding the compound produced in Example 39 to cyclodextrin as is sllmm~ri7ed below:

~(OCH2CH20H)x ~ ~ CH = CH--C ~3 0--C ~3 ~

~(OCH2CH20 ~ C ~ C H = C H--C ~3 ~ ~3C H - C H - C - CH3 First, the compound produced in Example 39 is treated with oxalyl chloride to form Lhe acid chloride derivative of the compound produced in Example 39. (See Example 29) Into a 250 ml round bottom flask fitted with a magnetic stir bar is placed 20.0 g ~(0.015 mole) of hydroxyethyl-substituted alpha-cyclodextrin (American Maize Company, Hammond, Indiana), 21.0 g (0.03 mole) of the acid chloride form of the wavelength-selective sensitizer produced in Example 39, 100 ml of dry dimethylsulfoxide (Aldrich), and 3 drops of triethylamine. The reaction mixture is stirred for eight hours and then poured into 300 ml of acetone. The resultant white precipitate is filtered, and pumped under vacuum to yield 22.1 g of product.

AMENDED SH~ET

CA 02221~6~ 1997-12-0~

SU~STITUTE SHEET ~' ''. .'' .''~ ' . 94 The following three compounds were tested for their ability to stabilize various colorants:

HOOC~H--CH--and HOOC ~3CH =CH--C~30--C~3 CH=CH--C~3 and HOOC ~3CH =CH--C~30--C~3CH--CH--C--CH3 More particularly, this example determines the colorant stabilizing capability of the compounds produced in Examples 29, 40 and 41. Briefly described, the compounds produced in Examples 29, 40 and 41 are used with color inks removed from the ink cartridges (5020036-Black and 5020036-Color) removed from an Epson Stylus Color Printer (Model EscP2) and from the ink removed from the ink cartridges (HP51640Y-yellow, HP51640C-cyan, HP51640M-magenta, and HP51640A-black) removed from ~n Hewlett-Packard Desk Jet Color Printer (Model 1200C). More particularly, the above ink cartridges are drilled and 5 ml of the ink therein is removed by syringe. Next, an amount of the compound from Examples 29, 40 or 41 is added to the inks from the above cartridges. More particularly, the compounds are measured in moles so that the number of molecules of each compound would be the same. The admixture is mixed for ten minutes, and then placed back into the ink cartridge from which it came, and the hole covered by tape.
Table 14 below provides the weights and moles for each of the compounds.

AMENDED SltEET

CA 0222l~6~ l997-l2-0~

WO 97/01605 PCT/US~5/~, 16Q~e ~5 Compound Produced in: Weight of compound in Sm (5~) of ink Example 29 0.25g 0.50g 0.6g (5%) (10%) (12%) Example 40 0.33g 0.66g 0.81g (6.6%) (13.2%) (16%) Example 41 0.31g 0.62g 0.76g (6.2%) (12.4%) (15%) Moles 1.2xlO- 2.4xlO- 2.9xlO-4mole 4mole 4mole The cartridges cont~inin~ the admixture are then placed S back into their respective printers, and 150 color test sheets aregenerated by the printer. Sheets number 50 and number 100 are then fade tested by exposure to a medium pressure 1200 Watt Mercury Lamp. The sheets are affixed to a poster board with scotch tape, and then are placed approximately 18 inches directly under the lamp. The sheets are exposed for approximately eight hours and then visually compared with unexposed sheets to determine the percentage of fading. Table 15 provides the percent fade of ~e sheets produced by the Hewlett-Packard Desk Jet 1200C Color Printer, and Table 16 provides the percent face of the sheets produced by the Epson Stylus Color Printer (Model EscP2). The percentages following the identification of the compounds produced in Examples 29, 40, or 41 represent the percent of each compound in the ink composition (weight/weight).
Also, "N/C" as used in Tables 15 and 16 represents "no change".

WO 97/01605 PCTIU~,.S.~ ~C~!~

Hewlett-Packard DeskJet 1200C Color Printer Percent Fade Results Compound ConcPntr~tion# of Pages~70 Fade of % Fade of Produced in: Generated Sheet Sheet #100 ~50 Control 200 80-90 80-90 FY~mplt~ 291.2xlO-4mole 195 N/C N/C
(5%) F.Y~mplP 401.2xlO-4mole 194 10-15 10-15 (6.6%) F.Y~mpl-~ 411.2xlO-4mole 194 10-15 10-15 (6.2%) F-~m. '- 292.4xlO~4mole 196 N/C N/C
(10%) FY~mplP 40 2.4xlO~4mole 194 5-10 5-10 (13.2%) FY~mr'~ 41 2.4xlO~4mole 195 5-10 5-10 (12.4%) FY~mrl~ 29 2.9xlO~4mole 198 N/C N/C
(12%) FY~mpl~ 40 2.9xlO~4mole 196 5-10 5-10 (16%) F.Y~mpl~ 41 2.9xlO-4mole l9? 5-10 5-10 (15%) WO 97/0160!i PCT/US95.~ 9 ~7 Epson Stylus Color Printer (Model EscP2) Percent Fade Results s Compound Concen~ation # of Pages % Fade of % Fade of Produced in: Generated Sheet Sheet #50 #100 Control 153 80-90 80-90 Example 291.2xlO-4mole 152 N/C N/C
(5%) Example 401.2xlO-4mole 153 10-15 10-15 (6.6%) F.x~mrl~ 411.2xlO-4mole 154 10-15 10-15 (6.2%) Example 292.4xlO~4mole 150 N/C N/C
(10%) F.x~mrle 402.4xlO~4mole 152 5-10 5-10 (13%) F.x~mrlP 412.4xl()-4mole 151 5-10 5-10 (12%) Example Z!92.9xlO~4mole 152 N/C N/C
(12%) F.x~mrle 402.9xlO~4mole 150 5-10 5-10 (16%) Example 412.9xlO~4mole 151 5-10 5-10 (15%) Having thus described the invention, numerous changes and modifications hereof will be readily apparent to those having ordinary skill in the art, without departing from the spirit or scope of the invention.

Claims

We Claim:

1. A colorant stabilizing composition comprising a colorant associated with a compound having the formula:

wherein when R1 is an aryl group, R2 is a hydrogen; alkyl;
aryl; heterocyclic; or phenyl group, the phenyl group being substituted with an alkyl, halo, amino, or thiol group;
wherein when R2 is an aryl group, R1 is a hydrogen; alkyl, aryl; heterocyclic; or phenyl group, the phenyl group being substituted with an alkyl, halo, amino, or thiol group; and, wherein at least one of R1 and R2 is an aryl group substituted with one or more carbonyl, ethylene, phenyl, ester, aryl, substituted aryl, or vinylic groups, wherein the groups are sequentially arranged forming a chain of unsaturated groups.

2. The composition of Claim 1, wherein the compound is associated with a molecular includant.

5. The composition of Claim 1, wherein the compound has the following formula:

.

6. The composition of Claim 1, wherein the compound has the following formula:

.

7. The composition of Claim 1, wherein the compound has the following formula:

.

8. The composition of Claim 1, wherein the compound has the following formula:

.

9. A method of light-stabilizing a colorant comprising admixing the colorant with a compound having the formula:

wherein when R1 is an aryl group, R2 is a hydrogen; alkyl;
aryl; heterocyclic; or phenyl group, the phenyl group being substituted with an alkyl, halo, amino, or thiol group;
wherein when R2 is an aryl group, R1 is a hydrogen; alkyl;
aryl; heterocyclic; or phenyl group, the phenyl group being substituted with an alkyl, halo, amino, or thiol group; and, wherein at least one of R1 and R2 is an aryl group substituted with one or more carbonyl, ethylene, phenyl, ester, aryl, substituted aryl, or vinylic groups, wherein the groups are sequentially arranged forming a chain of unsaturated groups.

10. The method of Claim 9, wherein the compound is associated with a molecular includant.

11. The method of Claim 9, wherein the compound has the following formula:

12. The method of Claim 9, wherein the compound has the following formula:

13. The method of Claim 9, wherein the compound has the following formula:

14. The method of Claim 9, wherein the compound has the following formula:

15. A colorant stabilizing composition comprising a mixture of a colorant and an arylketoalkene stabilizer selected from the group consisting of , , , , and .

16. The composition of Claim 15, further comprising a molecular includant.

17. The composition of Claim 16, wherein the molecular includant is selected from the group consisting of clathrates, zeolites and cyclodextrins.

18. The composition of Claim 17, wherein the cyclodextrin is selected from the group consisting of .alpha.-cyclodextrin, .beta.-cyclodextrin, .gamma.-cyclodextrin, hydroxypropyl .beta.-cyclodextrin, hydroethyl .beta.-cyclodextrin, sulfated .beta.-cyclodextrin, hydroxyethyl .alpha.-cyclodextrin, carboxymethyl .alpha.-cyclodextrin, carboxymethyl .beta.-cyclodextrin, carboxymethyl .gamma.-cyclodextrin, octyl succinated .alpha.-cyclodextrin, octyl succinated .beta.-cyclodextrin, octyl succinated .gamma.-cyclodextrin, and sulfated .gamma.-cyclodextrin.

19. The composition of Claim 18, wherein the molecular includant is .beta.-cyclodextrin.

20. The composition of Claim 16, wherein the colorant is at least partially included within a cavity of the molecular includant.

21. The composition of Claim 16, wherein the molecular includant is covalently bonded to the stabilizer.

22. A method of stabilizing a colorant comprising mixing with the colorant an arylketoalkene stabilizer selected from the group consisting of , , , , , and .

23. The method of Claim 22, wherein said composition further comprises a molecular includant.

24. The method of Claim 23, wherein the molecular includant is selected from the group consisting of clathrates, zeolites and cyclodextrins.

25. The method of Claim 24, wherein the cyclodextrin is selected from the group consisting of .alpha.-cyclodextrin, .beta.-cyclodextrin, .gamma.-cyclodextrin, hydroxypropyl .beta.-cyclodextrin, hydroethyl .beta.-cyclodextrin, sulfated .beta.-cyclodextrin, hydroxyethyl .alpha.-cyclodextrin, carboxymethyl .alpha.-cyclodextrin, carboxymethyl .beta.-cyclodextrin, carboxymethyl .gamma.-cyclodextrin, octyl succinated .alpha.-cyclodextrin, octyl succinated .beta.-cyclodextrin, octyl succinated .gamma.-cyclodextrin, and sulfated .gamma.-cyclodextrin.

26. The method of Claim 25, wherein the molecular includant is .beta.-cyclodextrin.

27. The method of Claim 23, wherein the colorant is at least partially included within a cavity of the molecular includant.

28. The method of Claim 23, wherein the molecular includant is covalently bonded to the stabilizer.
CA002221565A 1995-06-28 1996-04-05 Novel colorants and colorant modifiers Abandoned CA2221565A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US57095P 1995-06-28 1995-06-28
US60/000,570 1995-06-28

Publications (1)

Publication Number Publication Date
CA2221565A1 true CA2221565A1 (en) 1997-01-16

Family

ID=21692077

Family Applications (1)

Application Number Title Priority Date Filing Date
CA002221565A Abandoned CA2221565A1 (en) 1995-06-28 1996-04-05 Novel colorants and colorant modifiers

Country Status (12)

Country Link
US (2) US6033465A (en)
EP (1) EP0846146B1 (en)
JP (1) JP2000506550A (en)
AR (1) AR002608A1 (en)
AT (1) ATE206150T1 (en)
AU (1) AU5535296A (en)
BR (1) BR9609295A (en)
CA (1) CA2221565A1 (en)
ES (1) ES2161357T3 (en)
MX (1) MX9710016A (en)
WO (1) WO1997001605A1 (en)
ZA (1) ZA965031B (en)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050131269A1 (en) * 1995-06-07 2005-06-16 Talmadge Karen D. System and method for delivering a therapeutic agent for bone disease
JP2002509162A (en) * 1998-01-20 2002-03-26 キンバリー クラーク ワールドワイド インコーポレイテッド Coating composition containing high refractive index beads
KR20070061475A (en) * 2004-02-05 2007-06-13 모토리카 리미티드 Gait rehabilitation methods and apparatuses
KR100965284B1 (en) * 2007-10-25 2010-06-23 한종수 The composition of decolorable ink and decoloring method
US8142283B2 (en) * 2008-08-20 2012-03-27 Cfph, Llc Game of chance processing apparatus
DE102008049848A1 (en) * 2008-10-01 2010-04-08 Tesa Se Multigrade indicator
EP2569055A2 (en) * 2010-05-12 2013-03-20 Merck Patent GmbH Photo-stabilizing agents

Family Cites Families (725)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA552565A (en) 1958-02-04 Scalera Mario Stabilization of copperized azo dyestuffs
CA458808A (en) 1949-08-09 L. Gardner Frank Cleat assembly for athletic shoes
US582853A (en) * 1897-05-18 Adolf feer
CA517364A (en) 1955-10-11 H. Von Glahn William Stabilized diazonium salts and process of effecting same
CA460268A (en) 1949-10-11 L. Walsh William Stable diazonium salt preparation and process of preparing same
US28225A (en) * 1860-05-08 Improvement in apparatus for defecating cane-juice
US2809189A (en) * 1957-10-08 Method of producing stabilized
CA465496A (en) 1950-05-30 Z. Lecher Hans Stabilization of colouring compositions containing diazonium salts
CA537687A (en) 1957-03-05 J. Leavitt Julian Stable solutions of mixtures of naphthols and stabilized diazo compounds
US3248337A (en) * 1966-04-26 Composite reducing agent for use in the textile industry
CA413257A (en) 1943-06-15 Albert Genest Homer Hat bat shrinking and felting machine
CA779239A (en) 1968-02-27 General Electric Company Information recording
CA465495A (en) 1950-05-30 Z. Lecher Hans Stabilization of colouring compositions containing diazonium salts
CA461082A (en) 1949-11-15 Jozsef Biro Laszlo Writing paste
US2628959A (en) * 1953-02-17 Process for making stabilized
US1325971A (en) * 1919-12-23 Kazue akashi
CA465499A (en) 1950-05-30 American Cyanamid Company Stabilization of printing pastes containing diazonium salts
US2381145A (en) * 1945-08-07 Stable diazo salt preparation
US2171976A (en) * 1939-09-05 Process of manufacturing stabilized
US2185153A (en) * 1939-12-26 Stable ice color producing
US28789A (en) * 1860-06-19 Boiler foe
CA463022A (en) 1950-02-07 General Aniline And Film Corporation Stable diazo salt preparation
US575228A (en) * 1897-01-12 Moritz von gallois
CA463021A (en) 1950-02-07 Streck Clemens Stable diazo salt preparation and process of preparing them
US1876880A (en) * 1932-09-13 Othmab dbapal
CA483214A (en) 1952-05-13 General Aniline And Film Corporation Diazo amino printing colors
US2612495A (en) * 1952-09-30 Process of effecting same
US2237885A (en) * 1941-04-08 Stable diazo compounds
US3123647A (en) * 1964-03-03 Certificate of correction
CA571792A (en) 1959-03-03 Ciba Limited Process for printing textiles and printing preparations therefor
US893636A (en) * 1904-06-14 1908-07-21 Frederick J Maywald Coloring material and process of making same.
BE398850A (en) * 1932-09-30
US1013544A (en) * 1910-08-30 1912-01-02 Equilibrator Company Ink.
US1364406A (en) * 1920-04-24 1921-01-04 Chester Novelty Company Inc Ink-stick
US1436856A (en) * 1922-01-31 1922-11-28 George W Brenizer Printing process ink
NL21515C (en) * 1924-12-28
US1803906A (en) * 1928-02-16 1931-05-05 Kalle & Co Ag Diazo-types stabilized with alpha derivative of thiocarbonic acid and alpha processof preparing them
US1844199A (en) 1928-08-30 1932-02-09 Rca Corp Pyro-recording paper
DE498028C (en) * 1929-05-15 1930-07-14 I G Farbenindustrie Akt Ges Fixable layer for the color fading process
GB355686A (en) 1929-06-08 1931-08-26 Kodak Ltd Improvements in or relating to combined kinematographic and sound record films
CH147668A (en) 1929-06-17 1931-06-15 Chem Ind Basel Process for the production of a solid, stable diazo preparation.
US1884199A (en) * 1929-07-26 1932-10-25 Remington Typewriter Co Typewriting machine
DE503314C (en) * 1929-07-30 1930-07-29 I G Farbenindustrie Akt Ges Layers of fading paint
BE369421A (en) * 1929-09-09
US1962111A (en) * 1930-01-07 1934-06-12 Firm Chemical Works Formerly S Stable tetrazomonoazo compounds and their preparation
US2058489A (en) * 1930-06-16 1936-10-27 Nat Aniline & Chem Co Inc Dye powder compositions
BE381968A (en) * 1930-08-14
BE390157A (en) * 1931-08-04
US2062304A (en) * 1931-11-19 1936-12-01 Gaspar Bela Process for the production of a colored sound film
US2005378A (en) * 1931-12-16 1935-06-18 Waldhof Zellstoff Fab Manufacture of cellulose material
US2005511A (en) * 1931-12-22 1935-06-18 Chemical Works Formerly Sandoz Basic derivatives of porphins and metalloporphins and process for their manufacture
US2049005A (en) * 1932-01-04 1936-07-28 Gaspar Bela Color-photographic bleach out dyestuff layers
US1975409A (en) 1932-05-19 1934-10-02 Gen Aniline Works Inc Solid stable diazoazo salts and process of preparing them
BE397731A (en) * 1932-07-21
US2125015A (en) * 1932-10-26 1938-07-26 Gaspar Bela Multicolor photographic material and a process for using the same
US2106539A (en) 1933-07-13 1938-01-25 Gen Aniline Works Inc Stable diazo salt preparations and process of preparing them
US2054390A (en) * 1934-08-09 1936-09-15 Photographic bleachjng-out layers
DE678456C (en) * 1935-01-05 1939-07-18 Bela Gaspar Dr Process for the production of photographic or cinematographic images with and without sound recordings, in which dye images are combined with a silver image
US2090511A (en) * 1935-04-18 1937-08-17 Calco Chemical Co Inc Colloidized vat dye
BE417861A (en) 1935-05-04
GB458808A (en) * 1935-06-28 1936-12-28 Kenneth Herbert Saunders The manufacture of new stabilised diazo compounds and compositions of matter
US2220178A (en) * 1936-01-09 1940-11-05 Gen Aniline & Film Corp Process of producing a sound track on a light-sensitive color film
GB486006A (en) * 1936-10-27 1938-05-27 Christopher William Crouch Whe Improvements in colour photography
US2159280A (en) * 1936-12-31 1939-05-23 Eastman Kodak Co Sound image on multilayer film
GB492711A (en) 1937-03-22 1938-09-22 Bela Gaspar Process for the production of a combined coloured picture and sound record film
US2181800A (en) * 1937-06-23 1939-11-28 Calco Chemical Co Inc Colloidized azo coloring matter
CH197808A (en) 1937-06-28 1938-05-31 Fritz Busenhart Air humidifier on radiators.
US2230590A (en) * 1938-01-22 1941-02-04 Gen Aniline & Film Corp Color photographic process
BE433290A (en) * 1938-03-16
US2154996A (en) * 1938-06-24 1939-04-18 West Virginia Pulp & Paper Com Manufacture of calcium sulphite filled paper
GB518612A (en) 1938-07-27 1940-03-04 Bela Gaspar Process for the manufacture of combined picture and sound films
BE437152A (en) * 1938-12-03
US2416145A (en) * 1938-12-27 1947-02-18 Eterpen Sa Financiera Writing paste
US2349090A (en) * 1939-05-25 1944-05-16 Ici Ltd Stabilized polydiazo-phthalocyanines
GB539912A (en) 1939-08-07 1941-09-29 Durand & Huguenin Ag Process for the manufacture of new preparations containing the components for the production of ice colours and their application to textile printing
US2243630A (en) * 1939-10-10 1941-05-27 Rohm & Haas Reaction of polysaccharides with aminomethyl pyrroles
NL54339C (en) * 1939-11-20
US2364359A (en) * 1940-11-06 1944-12-05 American Cyanamid Co Printing compositions and methods of printing therewith
GB600451A (en) 1940-11-06 1948-04-09 American Cyanamid Co Direct dye planographic printing compositions
US2356618A (en) * 1941-05-23 1944-08-22 Du Pont Stabilized diazo printing paste
US2361301A (en) * 1941-07-03 1944-10-24 Du Pont Stabilization of azo dyestuffs
US2346090A (en) * 1942-08-19 1944-04-04 Eastman Kodak Co Photographic bleach-out layer
US2402106A (en) * 1942-09-09 1946-06-11 Gen Aniline & Film Corp Stable diazonium salts
US2382904A (en) * 1942-10-10 1945-08-14 Du Pont Stabilization of organic substances
US2386646A (en) * 1943-07-05 1945-10-09 American Cyanamid Co Stabilization of coloring compositions containing diazonium salts
FR996646A (en) 1945-05-11 1951-12-24 Process for obtaining color films by subtractive trichrome synthesis, and its application to sound cinematography
GB618616A (en) 1946-09-25 1949-02-24 George Trapp Douglas Improvements in textile printing processes
GB626727A (en) 1946-11-29 1949-07-20 Geoffrey Bond Harrison Improvements in or relating to the recording of sound tracks in colour film
US2527347A (en) * 1946-12-27 1950-10-24 Gen Aniline & Film Corp Nondusting compositions for stabilizing diazo salts
US2477165A (en) * 1946-12-27 1949-07-26 Gen Aniline & Film Corp Nondusting compositions containing stabilized diazo compounds
US2580461A (en) * 1947-08-27 1952-01-01 Sulphite Products Corp Ultraviolet-radiation impervious wrapping material
US2612494A (en) * 1948-10-22 1952-09-30 Gen Aniline & Film Corp Stabilized diazonium salts and process of effecting same
US2647080A (en) * 1950-06-30 1953-07-28 Du Pont Light-stabilized photopolymerization of acrylic esters
US2601669A (en) * 1950-09-30 1952-06-24 American Cyanamid Co Stabilized barium and strontium lithol toners
US2768171A (en) * 1951-03-28 1956-10-23 Ici Ltd Acid stabilized isothiouronium dyestuffs
US2680685A (en) * 1951-04-10 1954-06-08 Us Agriculture Inhibition of color formation in nu, nu-bis (2-hydroxyethyl) lactamide
DE903529C (en) * 1951-09-01 1954-02-08 Kalle & Co Ag Photosensitive layers
US2773056A (en) * 1952-07-12 1956-12-04 Allied Chem & Dye Corp Stable finely divided alkyl amine dyes
US2834773A (en) * 1952-09-23 1958-05-13 American Cyanamid Co Stabilization of copperized azo dyestuffs
US2732301A (en) * 1952-10-15 1956-01-24 Chxcxch
US2798000A (en) * 1952-12-16 1957-07-02 Int Minerals & Chem Corp Printing ink with anti-skinning agent
US2827358A (en) * 1953-06-15 1958-03-18 American Cyanamid Co Preparation of stable compositions of sulfuric acid half esters of leuco vat dyestuffs
BE529607A (en) * 1953-06-18
BE540426A (en) * 1953-07-13
DE1022801B (en) 1953-11-14 1958-01-16 Siemens Ag Process for the production of branched polymerizing, soluble and stretchable or crosslinked copolymers with low dielectric loss, high dielectric strength and heat resistance
US2728784A (en) * 1954-03-17 1955-12-27 Eastman Kodak Co Stabilization of oxidizable materials and stabilizers therefor
US2955067A (en) * 1954-10-20 1960-10-04 Rohm & Haas Cellulosic paper containing ion exchange resin and process of making the same
US2875045A (en) * 1955-04-28 1959-02-24 American Cyanamid Co Alum containing antioxidant and manufacture of sized paper therewith
DE1119510B (en) * 1956-03-14 1961-12-14 Bayer Ag Process for the production of insoluble, crosslinked high molecular weight polyesters
DE1047013B (en) 1956-05-15 1958-12-18 Agfa Ag Process for photothermographic imaging
DE1039835B (en) 1956-07-21 1958-09-25 Bayer Ag Photographic process for the preparation of dye images
DE1040562B (en) 1956-08-23 1958-10-09 Hoechst Ag Process for the production of solid, durable diazonium compounds
DE1047787B (en) 1956-08-24 1958-12-31 Hoechst Ag Process for the production of solid, durable diazonium compounds
DE1045414B (en) 1956-09-19 1958-12-04 Hoechst Ag Process for the production of solid, durable diazonium compounds
US2992198A (en) * 1956-12-24 1961-07-11 Funahashi Takaji Process of producing liquid color
US2992129A (en) * 1957-03-25 1961-07-11 Ludlow Corp Gummed product printed with conditioner
US2936241A (en) * 1957-05-16 1960-05-10 Sperry Rand Corp Non-printing indicia ink
US2892865A (en) * 1957-09-20 1959-06-30 Erba Carlo Spa Process for the preparation of tertiary esters of benzoylcarbinol
US3076813A (en) * 1957-11-13 1963-02-05 Monsanto Chemicals alpha, beta, gamma, sigma-tetra-arylporphins
US2940853A (en) * 1958-08-21 1960-06-14 Eastman Kodak Co Azide sensitized resin photographic resist
US3071815A (en) * 1958-09-09 1963-01-08 Allied Chem Process for producing free flowing oil soluble fusible organic dyestuffs
DE1154069B (en) 1958-12-27 1963-09-12 Bayer Ag Process for the production of water-insoluble azo dyes on structures made of aromatic polyesters, in particular polyethylene terephthalates, synthetic polyamides and polyurethanes
US3304297A (en) 1959-02-12 1967-02-14 Ciba Ltd Dyestuffs consisting of organic dyestuffs bound to polyhydroxylated organic polymers
DE1132540B (en) 1959-09-15 1962-07-05 Hoechst Ag Process for the production of solutions of coupling components of the ice color series
NL256641A (en) * 1959-10-09
IT649406A (en) * 1960-03-24
US3242215A (en) * 1960-04-04 1966-03-22 Du Pont Bis-(2-chloroacryloyl) aryl compounds
US3075014A (en) * 1960-06-14 1963-01-22 Richardson Merrell Inc Basic substituted alkoxy diphenylalkanols, diphenylalkenes and diphenylalkanes
US3104973A (en) * 1960-08-05 1963-09-24 Horizons Inc Photographic bleaching out of cyanine dyes
NL270002A (en) * 1960-10-08
NL270722A (en) * 1960-10-27
DE1132450B (en) 1960-11-21 1962-06-28 Max Adolf Mueller Dipl Ing Hydrostatic single wheel drive, especially for off-road vehicles
US3154416A (en) * 1961-03-30 1964-10-27 Horizons Inc Photographic process
BE619493A (en) * 1961-06-30
NL282186A (en) 1961-08-22
US3121632A (en) * 1961-08-30 1964-02-18 Horizons Inc Photographic process and composition including leuco triphenylmethane dyes
US3155509A (en) * 1961-09-05 1964-11-03 Horizons Inc Photographic process
US3140948A (en) * 1961-10-18 1964-07-14 Horizons Inc Photography
US3282886A (en) 1962-07-27 1966-11-01 Du Pont Polycarbonamides of improved photostability and dye lightfastness
US3445234A (en) 1962-10-31 1969-05-20 Du Pont Leuco dye/hexaarylbiimidazole imageforming composition
US3305361A (en) 1962-12-28 1967-02-21 Gen Electric Information recording
US3313797A (en) 1963-01-17 1967-04-11 Du Pont Stabilized fiber-reactive dyes
US3300314A (en) 1963-02-01 1967-01-24 Eastman Kodak Co Nonsilver, light-sensitive photographic elements
US3266973A (en) 1963-07-25 1966-08-16 Richard P Crowley Method of preparing adsorbent filter paper containing crystalline zeolite particles, and paper thereof
US3284205A (en) 1963-09-17 1966-11-08 Horizons Inc Benzotriazole and heterocyclic ketimide activators for leuco compounds
NL125868C (en) 1964-01-29
US3363969A (en) 1964-02-12 1968-01-16 Du Pont Dyeing and light stabilizing nylon yarns with sulfonated dyes; sterically hindered phenols, and alkylnaphthalene sulfonates with or without other ultraviolet light absorbers
US3359109A (en) 1964-04-29 1967-12-19 Du Pont Leuco dye-n, n. o-triacylhydroxylamine light-sensitive dye former compositions
US3341492A (en) 1964-05-11 1967-09-12 Celanese Corp Polyamides stabilized with iodine and/or bromine substituted phenols
US3320080A (en) 1964-06-05 1967-05-16 Nat Starch Chem Corp Water resistant paper coating compositions
GB1070863A (en) 1964-06-12 1967-06-07 Gevaert Photo Prod Nv Light-sensitive photographic materials
US3397984A (en) 1965-08-19 1968-08-20 Eastman Kodak Co Silver dye bleach materials improving image density
US3361827A (en) 1965-01-05 1968-01-02 American Plastic & Chemical Co Preparation of benzalacetophenone
US3479185A (en) 1965-06-03 1969-11-18 Du Pont Photopolymerizable compositions and layers containing 2,4,5-triphenylimidazoyl dimers
US3418118A (en) 1965-06-03 1968-12-24 Du Pont Photographic processes and products
CH475214A (en) 1965-06-04 1969-07-15 Ciba Geigy Process for the preparation of sulfonic acid or sulfonate-containing hydroxybenzophenones
US3563931A (en) 1965-08-06 1971-02-16 Shojiro Horiguchi Method of making chromogen-bonded-polymer and products thereof
US3502476A (en) 1965-10-20 1970-03-24 Konishiroku Photo Ind Light-sensitive photographic materials
US3464841A (en) 1965-10-23 1969-09-02 Customark Corp Method of preparing security paper containing an ultraviolet inhibitor
GB1135693A (en) 1966-03-10 1968-12-04 Scholten Chemische Fab Polysaccharide derivatives
US3382700A (en) 1966-03-31 1968-05-14 Inland Steel Co Process for reducing surface checking during hot working of steel
GB1184054A (en) 1966-04-05 1970-03-11 Agfa Gevaert Nv Thermographic Recording Processes and Materials
US3637337A (en) 1966-08-03 1972-01-25 Brian Pilling Improving the dye lightfastness of acrylic substrates with triazine compounds
US3541142A (en) 1966-09-02 1970-11-17 Merck & Co Inc (4-(2-hydroxymethylalkanoyl)phenoxy) acetic acids
US3547646A (en) 1966-12-16 1970-12-15 Keuffel & Esser Co Light-sensitive imaging material containing hydrazones
US3503744A (en) 1967-02-16 1970-03-31 Keuffel & Esser Co Photographic bleaching out of azomethine and azoaniline dyes
US3453258A (en) 1967-02-20 1969-07-01 Corn Products Co Reaction products of cyclodextrin and unsaturated compounds
US3607863A (en) 1967-02-28 1971-09-21 Dyckerhoff Zementwerke Ag Clathrate compounds
US3453259A (en) 1967-03-22 1969-07-01 Corn Products Co Cyclodextrin polyol ethers and their oxidation products
SE312870B (en) 1967-07-17 1969-07-28 Asea Ab
US3565753A (en) 1967-07-17 1971-02-23 Ncr Co Capsule-cellulose fiber units and products made therewith
US3637581A (en) 1967-08-04 1972-01-25 Shojiro Horiguchi Method of making chromogen-bonded-polymer and products thereof
US3642472A (en) 1967-08-30 1972-02-15 Holotron Corp Bleaching of holograms
US3546161A (en) 1968-01-22 1970-12-08 Allied Chem Polyolefins with improved light stability
US3574624A (en) 1968-02-08 1971-04-13 Eastman Kodak Co Photographic elements containing dithiolium salts
US3579533A (en) 1968-03-18 1971-05-18 Antioch College Preparation of porphin,substituted porphin and metal chelates thereof
US3615562A (en) 1968-04-25 1971-10-26 Rca Corp Cyanine dye photographic film
US3549367A (en) 1968-05-24 1970-12-22 Du Pont Photopolymerizable compositions containing triarylimidazolyl dimers and p-aminophenyl ketones
IE33221B1 (en) 1968-07-15 1974-04-17 Fuji Photo Film Co Ltd Pressure-sensitive copying paper
GB1264636A (en) 1968-07-15 1972-02-23
DE1769854C3 (en) 1968-07-26 1982-08-19 Bayer Ag, 5090 Leverkusen Photoinitiators and processes for photopolymerization
US3595658A (en) 1968-10-03 1971-07-27 Little Inc A Non-silver direct positive dye bleachout system using polymethine dyes and colored activators
US3595655A (en) 1968-10-03 1971-07-27 Little Inc A Non-silver direct positive dyes bleachout system using polymethine dyes and colorless activators
US3595657A (en) 1968-10-03 1971-07-27 Little Inc A Non-silver direct positive dye bleachout system using indigoid dyes and colorless activators
US3595659A (en) 1968-10-03 1971-07-27 Little Inc A Non-silver direct positive dye bleachout system using indigoid dyes and colored activators
USRE28225E (en) 1968-10-09 1974-11-05 Photobleachable dye compositions
US3914166A (en) 1968-11-06 1975-10-21 Bayer Ag Butyric acid derivatives as novel photosensitizers
GB1245079A (en) 1968-12-10 1971-09-02 Fuji Photo Film Co Ltd Spiro-indoline derivatives and their use in pressure-sensitive copying paper
US3553710A (en) 1969-03-14 1971-01-05 Edward C Lloyd Erasable trace recorder
US3840338A (en) 1969-04-11 1974-10-08 Oreal Light stabilized hair dye compositions
JPS4912180B1 (en) 1969-04-21 1974-03-22
US3697280A (en) 1969-05-22 1972-10-10 Du Pont Hexaarylbiimidazole-selected aromatic hydrocarbon compositions
US3647467A (en) 1969-05-22 1972-03-07 Du Pont Hexaarylbiimidazole-heterocyclic compound compositions
US3617288A (en) 1969-09-12 1971-11-02 Minnesota Mining & Mfg Propenone sensitizers for the photolysis of organic halogen compounds
US3668188A (en) 1969-11-03 1972-06-06 Monsanto Co Thermally stable polyester fibers having improved dyeability and dye lightfastness
US3660542A (en) 1969-12-11 1972-05-02 Takeda Chemical Industries Ltd Alkylbenzoylcarbinol phosphate esters
CA930103A (en) 1970-03-16 1973-07-17 Dominion Textile Limited Printing and dyeing process for blended fibre fabrics
US3695879A (en) 1970-04-20 1972-10-03 Ibm Hologram life extension
US3669925A (en) 1970-04-28 1972-06-13 Monsanto Co Thermally stable dyeable polyesters having improved dyed lightfastness
US3689565A (en) 1970-05-04 1972-09-05 Horst Hoffmann {60 -methylolbenzoin ethers
US3873500A (en) 1970-06-16 1975-03-25 Agency Ind Science Techn Photosensitive polymers
US3652275A (en) 1970-07-09 1972-03-28 Du Pont HEXAARYLBIIMIDAZOLE BIS (p-DIALKYL-AMINOPHENYL-{60 ,{62 -UNSATURATED) KETONE COMPOSITIONS
GB1325220A (en) 1970-10-07 1973-08-01 Fuji Photo Film Co Ltd Colour-forming composition
NL7113828A (en) 1970-10-15 1972-04-18
US3678044A (en) 1970-10-22 1972-07-18 Chevron Res Substituted flavanones
JPS4926584B1 (en) 1970-11-26 1974-07-10
US3705043A (en) 1970-12-07 1972-12-05 Dick Co Ab Infrared absorptive jet printing ink composition
US3671251A (en) 1970-12-10 1972-06-20 Eastman Kodak Co Sensitized pyrylium photobleachable dye in gelatin
US3707371A (en) 1970-12-14 1972-12-26 Xerox Corp Photosensitive element comprising a polymer matrix including styrene,auramine o,and a proxide and the use thereof in volume recording
JPS509178B1 (en) 1970-12-28 1975-04-10
US3676690A (en) 1971-01-04 1972-07-11 Westinghouse Learning Corp Reflected light document reading head
JPS5121345B1 (en) 1971-01-19 1976-07-01
US3671096A (en) 1971-02-03 1972-06-20 Us Navy Erasable holographic recording
US3887450A (en) 1971-02-04 1975-06-03 Dynachem Corp Photopolymerizable compositions containing polymeric binding agents
US3694241A (en) 1971-04-19 1972-09-26 Grace W R & Co Method for chemically printing
US3879496A (en) 1971-05-12 1975-04-22 Goodrich Co B F Low rubber, high-flow and high impact ABS plastics, improved rubber toughener for producing same, and method of manufacture
US3901779A (en) 1971-05-13 1975-08-26 Dow Chemical Co Vinyl ester resin and process for curing same with ionizing radiation in the presence of amines
US3737628A (en) 1971-06-11 1973-06-05 Automatic Corp Automatically programmed test grading and scoring method and system
BE787339A (en) 1971-09-14 1973-02-09 Agfa Gevaert Nv PHOTOGRAPHIC REGISTRATION AND REPRODUCTION OF INFORMATION
GB1408265A (en) 1971-10-18 1975-10-01 Ici Ltd Photopolymerisable composition
US3926641A (en) 1971-11-18 1975-12-16 Sun Chemical Corp Photopolymerizable compositions comprising polycarboxysubstituted benzophenone reaction products
US4004998A (en) 1971-11-18 1977-01-25 Sun Chemical Corporation Photopolymerizable compounds and compositions comprising the product of the reaction of a hydroxy-containing ester and a monocarboxy-substituted benzophenone
US3765896A (en) 1971-11-22 1973-10-16 Eastman Kodak Co Photographic element containing a light sensitive photobleachant and a colored stable 2-amino-aryl-7-oxyl-3-oxide-2-imidazoline free radical
US3729313A (en) 1971-12-06 1973-04-24 Minnesota Mining & Mfg Novel photosensitive systems comprising diaryliodonium compounds and their use
US3801329A (en) 1971-12-17 1974-04-02 Union Carbide Corp Radiation curable coating compositions
USRE28789E (en) 1972-01-25 1976-04-27 E. I. Du Pont De Nemours And Company Photopolymerizable compositions containing cyclic cis-α-dicarbonyl compounds and selected sensitizers
US3928264A (en) 1972-02-11 1975-12-23 Monsanto Co Polymeric ultraviolet light stabilizers prepared from phenol-formaldehyde condensates
US3800439A (en) 1972-05-04 1974-04-02 Scan Tron Corp Test scoring apparatus
US3844790A (en) 1972-06-02 1974-10-29 Du Pont Photopolymerizable compositions with improved resistance to oxygen inhibition
FR2189417B1 (en) 1972-06-23 1978-06-30 Sandoz Sa
JPS5034966B2 (en) 1972-07-24 1975-11-12
US3914165A (en) 1972-09-18 1975-10-21 Desoto Inc Radiation curable non-gelled michael addition reaction products
US4012256A (en) 1972-09-25 1977-03-15 Keuffel & Esser Company Photo-imaging utilizing alkali-activated photopolymerizable compositions
US4056665A (en) 1972-10-26 1977-11-01 Owens-Illinois, Inc. Composition and process
US3933682A (en) 1973-01-31 1976-01-20 Sun Chemical Corporation Photopolymerization co-initiator systems
JPS5148516B2 (en) 1973-02-07 1976-12-21
US3915824A (en) 1973-03-30 1975-10-28 Scm Corp Uv and laser curing of the polymerizable binder
US3876496A (en) 1973-05-14 1975-04-08 Ernesto B Lozano Method and means for protecting documents
US4251622A (en) 1973-05-25 1981-02-17 Nippon Paint Co., Ltd. Photo-sensitive composition for dry formation of image
FR2235907A1 (en) 1973-07-06 1975-01-31 Union Carbide Corp Aryl diakoxy methyl ketone prepn. - from alkyl nitrite, aryl methyl ketone and alkanol, used as photo-sensitisers in polymer hardening
JPS5041536A (en) 1973-08-03 1975-04-16
US4067892A (en) 1973-08-23 1978-01-10 Beecham Group Limited Substituted (4-carboxyphenoxy) phenyl alkane compounds
GB1469641A (en) * 1973-09-20 1977-04-06 Agfa Gevaert Stabilization of photosensitive recording material
US4039332A (en) 1973-09-20 1977-08-02 Agfa-Gevaert N.V. Stabilization of photosensitive recording material
US4022674A (en) 1973-10-11 1977-05-10 Sun Chemical Corporation Photopolymerizable compounds and compositions comprising the product of the reaction of a monomeric ester and a polycarboxy-substituted benzophenone
US3960685A (en) 1973-11-12 1976-06-01 Sumitomo Chemical Company, Limited Photosensitive resin composition containing pullulan or esters thereof
US3919323A (en) 1974-08-08 1975-11-11 Sandoz Ag Acyl substituted dibenzylethers
US3978132A (en) 1973-12-06 1976-08-31 Sandoz, Inc. Acyl benzyl ethers
GB1494191A (en) 1973-12-17 1977-12-07 Lilly Industries Ltd Preparation of alpha-acyloxy aldehydes and ketones
US3988154A (en) 1974-02-19 1976-10-26 Eastman Kodak Company Photographic supports and elements utilizing photobleachable omicron-nitroarylidene dyes
US3984248A (en) 1974-02-19 1976-10-05 Eastman Kodak Company Photographic polymeric film supports containing photobleachable o-nitroarylidene dyes
US4058400A (en) 1974-05-02 1977-11-15 General Electric Company Cationically polymerizable compositions containing group VIa onium salts
US4043819A (en) 1974-06-11 1977-08-23 Ciba-Geigy Ag Photo-polymerizable material for the preparation of stable polymeric images and process for making them by photopolymerization in a matrix
US4017652A (en) 1974-10-23 1977-04-12 Ppg Industries, Inc. Photocatalyst system and ultraviolet light curable coating compositions containing the same
US4179577A (en) 1974-11-30 1979-12-18 Ciba-Geigy Corporation Polymerisable esters derived from a phenolic unsaturated ketone
US4181807A (en) 1974-11-30 1980-01-01 Ciba-Geigy Corporation Polymerizable esters derived from a glycidyl ether of a phenolic unsaturated ketone
GB1489419A (en) 1974-11-30 1977-10-19 Ciba Geigy Ag Polymerisable esters
DE2500520A1 (en) 1975-01-08 1976-07-15 Schickedanz Willi METHOD OF MAKING COLOR COPIES
ES434175A1 (en) 1975-01-27 1976-12-01 Genaro Salcedo Allende Process for obtaining materials having low content of soluble elements for multiple applications
US4024324A (en) 1975-07-17 1977-05-17 Uop Inc. Novel polyolefin composition of matter
GB1525159A (en) 1975-10-27 1978-09-20 Fuji Photo Film Co Ltd Desensitization of colour developer
JPS5265425A (en) 1975-11-24 1977-05-30 Minnesota Mining & Mfg Image forming composition
JPS5274406A (en) 1975-12-05 1977-06-22 Dainippon Toryo Kk Ink for ink jet recording
US4126412A (en) 1975-12-29 1978-11-21 Monsanto Company Method for stabilizing brightened modacrylic fibers
JPS5299776A (en) 1976-02-18 1977-08-22 Hitachi Ltd Radiation sensitive high polymeric material
US4105572A (en) 1976-03-31 1978-08-08 E. I. Du Pont De Nemours And Company Ferromagnetic toner containing water-soluble or water-solubilizable resin(s)
US4144156A (en) 1976-04-14 1979-03-13 Basf Aktiengesellschaft Manufacture of unsymmetric monoacetals of aromatic 1,2-diketones employable as photoiniatiators
DE2714978A1 (en) 1976-04-15 1977-10-27 Sandoz Ag COLORING PROCESS
JPS5928323B2 (en) 1976-08-12 1984-07-12 富士写真フイルム株式会社 Photopolymerizable composition
US4048034A (en) 1976-08-27 1977-09-13 Uop Inc. Photopolymerization using an alpha-aminoacetophenone
JPS5994B2 (en) 1976-09-14 1984-01-05 富士写真フイルム株式会社 photosensitive composition
US4100047A (en) 1976-10-12 1978-07-11 Mobil Oil Corporation Ultraviolet curable aqueous coatings
US4054719A (en) 1976-11-23 1977-10-18 American Cyanamid Company Phenacyl ester photosensitizers for radiation-curable coatings
US4085062A (en) 1976-11-24 1978-04-18 Givaudan Corporation N,N'-bis-aromaticformamidines useful as sunscreening agents
JPS5928326B2 (en) 1976-12-02 1984-07-12 富士写真フイルム株式会社 Photopolymerizable composition
CH603767A5 (en) 1976-12-27 1978-08-31 Sandoz Ag Spray dried basic dyes
JPS6026122B2 (en) 1977-01-20 1985-06-21 富士写真フイルム株式会社 Photopolymerizable composition
DE2708188C2 (en) 1977-02-25 1979-02-08 Bayer Ag, 5090 Leverkusen Stabilization of anionic indole dyes
US4141807A (en) 1977-03-01 1979-02-27 Stauffer Chemical Company Photopolymerizable composition stabilized with nitrogen-containing aromatic compounds
US4190671A (en) 1977-03-17 1980-02-26 Biorex Laboratories Limited Chalcone derivatives
DE2722264C2 (en) 1977-05-17 1984-06-28 Merck Patent Gmbh, 6100 Darmstadt Use of substituted oxyalkylphenones as photosensitizers
US4114028A (en) 1977-05-26 1978-09-12 Sealectro Corporation Optical punched card reader
US4111699A (en) 1977-06-06 1978-09-05 Eastman Kodak Company O-nitro-o-azaarylidene photobleachable dyes and photographic elements utilizing them
US4110112A (en) 1977-06-23 1978-08-29 Neste Oy Photosensitive material containing 2,3-di(2,3-diiodopropoxy)-propyl cellulose and uses thereof
US4250096A (en) 1977-10-14 1981-02-10 Ciba-Geigy Corporation 3- and 4-Azidophthalic acid derivatives
JPS5462987A (en) 1977-10-28 1979-05-21 Fuji Photo Film Co Ltd Stabilizing method for organic basic substance to light
JPS5469580A (en) 1977-11-15 1979-06-04 Fuji Photo Film Co Ltd Stabilizing method for organic basic substance to light
JPS5472780A (en) 1977-11-22 1979-06-11 Fuji Photo Film Co Ltd Stabilizing method for organic basic substance to light
JPS5474728A (en) 1977-11-28 1979-06-15 Fuji Photo Film Co Ltd Photosensitive composition
JPS5928328B2 (en) 1977-11-29 1984-07-12 富士写真フイルム株式会社 Photopolymerizable composition
JPS5482385A (en) 1977-12-14 1979-06-30 Fuji Photo Film Co Ltd Stabilizing method for organic basic substance to light
JPS5482234A (en) 1977-12-14 1979-06-30 Fuji Photo Film Co Ltd Photostabilizing method for organic base material
JPS5482386A (en) 1977-12-15 1979-06-30 Fuji Photo Film Co Ltd Stabilizing method for organic basic substance to light
US4391867A (en) 1977-12-16 1983-07-05 E. I. Du Pont De Nemours & Co. Polyvinyl butyral ink formulation
US4318791A (en) 1977-12-22 1982-03-09 Ciba-Geigy Corporation Use of aromatic-aliphatic ketones as photo sensitizers
JPS6054197B2 (en) 1978-01-05 1985-11-29 富士写真フイルム株式会社 color developing ink
US4345011A (en) 1978-01-30 1982-08-17 Eastman Kodak Company Color imaging devices and color filter arrays using photo-bleachable dyes
US4245018A (en) 1978-01-30 1981-01-13 Fuji Photo Film Co., Ltd. Method for stabilizing organic substrate materials including photographic dye images to light and a color diffusion transfer material
EP0003884A3 (en) 1978-02-23 1979-09-19 Imperial Chemical Industries Plc Alpha-beta unsaturated ketone derivatives useful as herbicides
CH623447B (en) 1978-03-06 Sandoz Ag PROCESS FOR COLORING ACETALIZED PVC / PVA TEXTILES WITH DISPERSION DYES.
FR2420522A1 (en) 1978-03-20 1979-10-19 Unicler ACID (M-BENZOYL-PHENOXY) -2 PROPIONIC DERIVATIVES AND THEIR APPLICATIONS AS MEDICINAL PRODUCTS
US4199420A (en) 1978-04-06 1980-04-22 Stauffer Chemical Company Alkoxymethylbenzophenones as photoinitiators for photopolymerizable compositions and process based thereon
JPS54136581A (en) 1978-04-14 1979-10-23 Fuji Photo Film Co Ltd Stabilizing method for organic basic substance to light
JPS54136582A (en) 1978-04-17 1979-10-23 Fuji Photo Film Co Ltd Stabilizing method for organic basic substance to light
US4162162A (en) 1978-05-08 1979-07-24 E. I. Du Pont De Nemours And Company Derivatives of aryl ketones and p-dialkyl-aminoarylaldehydes as visible sensitizers of photopolymerizable compositions
JPS54152091A (en) 1978-05-22 1979-11-29 Fuji Photo Film Co Ltd Photopolymerizable composition
GB2025942A (en) 1978-05-31 1980-01-30 Sori Soc Rech Ind Phenoxyalkylcarboxylic acids
EP0007468B1 (en) 1978-07-13 1982-04-07 Ciba-Geigy Ag Compositions photodurcissables
JPS6053300B2 (en) 1978-08-29 1985-11-25 富士写真フイルム株式会社 Photosensitive resin composition
DE2839129C2 (en) 1978-09-08 1982-06-03 Chemische Fabrik Stockhausen GmbH, 4150 Krefeld Process for improving the lightfastness of leathers dyed in the usual way
DE2842862A1 (en) 1978-10-02 1980-04-10 Boehringer Mannheim Gmbh METHOD FOR DETERMINING ION, POLAR AND / OR LIPOPHILE SUBSTANCES IN LIQUIDS
JPS5550001A (en) 1978-10-06 1980-04-11 Fuji Photo Film Co Ltd Photo-polymerizable composition
JPS5577742A (en) 1978-12-08 1980-06-11 Fuji Photo Film Co Ltd Photosensitive composition
JPS5592370A (en) 1978-12-29 1980-07-12 Nissan Chem Ind Ltd Phenoxypyridine derivative and its preparation
US4300123A (en) 1979-01-02 1981-11-10 Westinghouse Electric Corp. Optical reading system
US4270130A (en) 1979-01-08 1981-05-26 Eastman Kodak Company Thermal deformation record device with bleachable dye
DE2902293A1 (en) 1979-01-22 1980-07-31 Henkel Kgaa COATING MATERIAL FOR THE BACK OF PAPER TO BE GLUED
JPS55102538A (en) 1979-01-30 1980-08-05 Kawasaki Kasei Chem Ltd Preparation of p-n-alkyl benzoate
CH640361A5 (en) 1979-02-01 1983-12-30 Landis & Gyr Ag Device for thermal clear machine readable optical markers.
CA1160880A (en) 1979-02-02 1984-01-24 Keith E. Whitmore Imaging with nonplanar support elements
US4197080A (en) 1979-02-14 1980-04-08 Eastman Kodak Company Radiation-cleavable nondiffusible compounds and photographic elements and processes employing them
US4258367A (en) 1979-03-29 1981-03-24 Whittaker Corporation Light sensitive jet inks
JPS55133032A (en) 1979-04-03 1980-10-16 Ricoh Co Ltd Photosensitive composition
JPS55152750A (en) 1979-05-17 1980-11-28 Fuji Photo Film Co Ltd Stabilization of organic substrate substance against light
US4289844A (en) 1979-06-18 1981-09-15 Eastman Kodak Company Photopolymerizable compositions featuring novel co-initiators
US4426153A (en) 1979-06-21 1984-01-17 Ibm Corporation Apparatus for the reduction of image intensity variations in a continuously variable reducing copier
JPS566236A (en) 1979-06-28 1981-01-22 Fuji Photo Film Co Ltd Photosensitive material and pattern forming method using it
US4288631A (en) 1979-09-05 1981-09-08 General Electric Company UV Stabilizers, coating compositions and composite structures obtained therefrom
US4256493A (en) 1979-10-04 1981-03-17 Dai Nippon Tokyo Co., Ltd. Jet ink composition
US4349617A (en) 1979-10-23 1982-09-14 Fuji Photo Film Co., Ltd. Function separated type electrophotographic light-sensitive members and process for production thereof
US4292154A (en) 1979-11-07 1981-09-29 Gelman Sciences, Inc. Buffer composition and method for the electrophoretic separation of proteins
JPS5677189A (en) 1979-11-30 1981-06-25 Fuji Photo Film Co Ltd Recording material
US4370401A (en) 1979-12-07 1983-01-25 Minnesota Mining And Manufacturing Company Light sensitive, thermally developable imaging system
US4336323A (en) 1979-12-07 1982-06-22 Minnesota Mining And Manufacturing Company Decolorizable imaging system
US4373020A (en) 1979-12-07 1983-02-08 Minnesota Mining And Manufacturing Company Decolorizable imaging system
US4460676A (en) 1980-02-21 1984-07-17 Fabel Warren M Non-impact single and multi-ply printing method and apparatus
DE3008411A1 (en) 1980-03-05 1981-09-10 Merck Patent Gmbh, 6100 Darmstadt NEW AROMATIC-ALIPHATIC KETONES, THEIR USE AS PHOTOINITIATORS AND PHOTOPOLYMERIZABLE SYSTEMS CONTAINING SUCH KETONES
US4373017A (en) 1980-03-05 1983-02-08 Konishiroku Photo Industry Co., Ltd. Photosensitive compound and photosensitive material containing it
US4276211A (en) 1980-03-10 1981-06-30 Troy Chemical Corporation Stabilization composition for coating composition
DE3010148A1 (en) 1980-03-15 1981-09-24 Merck Patent Gmbh, 6100 Darmstadt NEW MIXTURES BASED ON AROMATIC-ALIPHATIC KETONES, THEIR USE AS PHOTOINITIATORS AND PHOTOPOLYMERIZABLE SYSTEMS CONTAINING SUCH MIXTURES
US4268667A (en) 1980-04-21 1981-05-19 E. I. Du Pont De Nemours And Company Derivatives of aryl ketones based on 9,10-dihydro-9,10-ethanoanthracene and p-dialkyl-aminoaryl aldehydes as visible sensitizers for photopolymerizable compositions
US4351893A (en) 1980-12-31 1982-09-28 E. I. Du Pont De Nemours And Company Derivatives of aryl ketones as visible sensitizers of photopolymerizable compositions
EP0041043B1 (en) 1980-05-13 1983-11-09 Ciba-Geigy Ag Process for the preparation of derivatives of alkenyl benzene or alkenyl naphthalene
EP0040177B1 (en) 1980-05-13 1983-07-20 Ciba-Geigy Ag Process for the preparation of benzene or naphthalene alkenyl carboxylic acid derivatives
US4343891A (en) 1980-05-23 1982-08-10 Minnesota Mining And Manufacturing Company Fixing of tetra (hydrocarbyl) borate salt imaging systems
US4302606A (en) 1980-05-23 1981-11-24 Gaf Corporation 2-Hydroxy,alkoxy,methylolbenzophenone intermediate compounds for the manufacture of improved copolymerizable ultraviolet light absorber compounds
US4307182A (en) 1980-05-23 1981-12-22 Minnesota Mining And Manufacturing Company Imaging systems with tetra(aliphatic) borate salts
JPS56167139A (en) 1980-05-27 1981-12-22 Daikin Ind Ltd Sensitive material
JPS575771A (en) 1980-06-13 1982-01-12 Fuji Photo Film Co Ltd Formation of colored image by ink jetting method
JPS5720734A (en) 1980-07-15 1982-02-03 Fuji Photo Film Co Ltd Heat developing photosensitive material
HU181733B (en) 1980-08-07 1983-11-28 Chinoin Gyogyszer Es Vegyeszet Process for preparing sorbents containing cyclodextrin on cellulose base
US4416961A (en) 1980-09-11 1983-11-22 Eastman Kodak Company Color imaging devices and color filter arrays using photo-bleachable dyes
JPS5774372A (en) 1980-10-27 1982-05-10 Seiko Epson Corp Fluid ink for printer
DE3041153A1 (en) 1980-10-31 1982-06-16 Bayer Ag, 5090 Leverkusen METHOD FOR IMPROVING THE LIGHT FASTNESS OF POLYAMIDE COLORS
DE3169463D1 (en) 1980-12-22 1985-04-25 Unilever Nv Composition containing a photo-activator for improved bleaching
JPS57107879A (en) 1980-12-25 1982-07-05 Mitsubishi Paper Mills Ltd Preparation of recording paper
US4500335A (en) 1980-12-30 1985-02-19 Texas A&M University Composition of matter and method of use for nitrogen fertilization
US4369283A (en) 1981-03-06 1983-01-18 E. I. Du Pont De Nemours & Company High solids can coating composition containing epoxy, acrylic and aminoplast resins
US4372582A (en) 1981-03-30 1983-02-08 Minnesota Mining And Manufacturing Company Stabilizer for electron doner-acceptor carbonless copying systems
US4401470A (en) 1981-03-30 1983-08-30 Mobil Oil Corporation Intaglio printing ink and method of employing the same
US4350753A (en) 1981-06-15 1982-09-21 Polychrome Corporation Positive acting composition yielding pre-development high visibility image after radiation exposure comprising radiation sensitive diazo oxide and haloalkyl-s-triazine with novolak and dyestuff
JPS57207065A (en) 1981-06-17 1982-12-18 Seiko Epson Corp Ink jet recorder
DE3126433A1 (en) 1981-07-04 1983-01-13 Merck Patent Gmbh, 6100 Darmstadt Novel mixtures based on substituted dialkoxyacetophenones, their use as photoinitiators, and photopolymerisable systems containing such mixtures
US4508570A (en) 1981-10-21 1985-04-02 Ricoh Company, Ltd. Aqueous ink for ink-jet printing
JPS5872139A (en) 1981-10-26 1983-04-30 Tokyo Ohka Kogyo Co Ltd Photosensitive material
US4399209A (en) 1981-11-12 1983-08-16 The Mead Corporation Transfer imaging system
US4822714A (en) 1981-11-12 1989-04-18 The Mead Corporation Transfer imaging system
US4425424A (en) 1982-04-08 1984-01-10 Eastman Kodak Company Dye-forming compositions
US4495041A (en) 1982-04-15 1985-01-22 Mobil Oil Corporation Photochemical process using shape-selective photoassisted heterogenous catalyst compositions
JPS5936174A (en) 1982-08-23 1984-02-28 Ricoh Co Ltd Water-based ink for ink jet recording
US5135940A (en) 1982-09-23 1992-08-04 Merck Frosst Canada, Inc. Leukotriene antagonists
EP0108037B1 (en) 1982-10-01 1989-06-07 Ciba-Geigy Ag Propiophenone derivatives as photoinitiators in the photopolymerization
US4450227A (en) 1982-10-25 1984-05-22 Minnesota Mining And Manufacturing Company Dispersed imaging systems with tetra (hydrocarbyl) borate salts
US4447521A (en) 1982-10-25 1984-05-08 Minnesota Mining And Manufacturing Company Fixing of tetra(hydrocarbyl)borate salt imaging systems
JPS5980475A (en) 1982-10-29 1984-05-09 Ricoh Co Ltd Aqueous ink composition
US5108874A (en) 1982-11-01 1992-04-28 Microsi, Inc. Composite useful in photolithography
JPH0718087B2 (en) 1982-12-07 1995-03-01 コモンウエルス・サイエンテイフィック・アンド・インダストリアル・リサーチ・オーガニゼーション Method of protecting wool, dyed wool, silk, nylon or a blend thereof from light deterioration and wool protected from light degradation, dyed wool, silk, nylon or a blend thereof
US4523924A (en) 1982-12-20 1985-06-18 Ciba-Geigy Corporation Process for the preparation of stable aqueous solutions of water-soluble reactive dyes by membrane separation
JPS59133235A (en) 1983-01-21 1984-07-31 Kanebo Ltd Zeolite particle-containing polymer and its production
GB2136590B (en) 1983-03-15 1986-01-02 Minnesota Mining & Mfg Dye-bleach materials and process
US4510392A (en) 1983-04-08 1985-04-09 E. I. Du Pont De Nemours And Company Autoradiogram marking process
DE3415033C2 (en) 1983-04-20 1986-04-03 Hitachi Chemical Co., Ltd. 4'-Azidobenzal-2-methoxyacetophenone, process for its preparation and photosensitive composition containing it
US4567171A (en) 1983-04-21 1986-01-28 Ciba-Geigy Corporation Stable, concentrated, liquid dispersions of anionic dyestuffs
GB8311252D0 (en) 1983-04-26 1983-06-02 Ciba Geigy Ag Photocrosslinking process
FI81916C (en) 1983-05-09 1990-12-10 Vickers Plc FOER STRAOLNING KAENSLIG SKIVA.
DE3417782A1 (en) 1983-05-23 1984-11-29 Sandoz-Patent-GmbH, 7850 Lörrach COLORING TOOLS
JPS59219270A (en) 1983-05-30 1984-12-10 Wako Pure Chem Ind Ltd Method and reagent for stabilization of tetrazolium salt with cyclodextrin
EP0127797B1 (en) 1983-06-03 1987-06-16 F. HOFFMANN-LA ROCHE & CO. Aktiengesellschaft Labelled molecules for fluorescence immunoassays and processes and intermediates for their preparation
US4475999A (en) 1983-06-06 1984-10-09 Stauffer Chemical Company Sensitization of glyoxylate photoinitiators
US4595745A (en) 1983-06-27 1986-06-17 Ube Industries, Ltd. Organic solvent-soluble photosensitive polyamide resin
JPS6020622U (en) 1983-07-15 1985-02-13 アルプス電気株式会社 DC constant voltage output circuit device
DE3326640A1 (en) 1983-07-23 1985-01-31 Basf Ag, 6700 Ludwigshafen METHOD FOR IMPROVING THE LIGHT FASTNESS OF COLORING WITH ACID OR METAL COMPLEX DYES ON POLYAMIDE
US4707161A (en) 1983-07-23 1987-11-17 Basf Aktiengesellschaft Lightfastness of dyeings obtained with acid dyes or metal complex dyes on polyamides: treatment with copper hydroxamates
US4702996A (en) 1983-09-28 1987-10-27 General Electric Company Method of enhancing the contrast of images and materials therefor
JPS6083029A (en) 1983-10-13 1985-05-11 Mitsui Toatsu Chem Inc Optical recording medium
US4707425A (en) 1983-11-18 1987-11-17 Mitsui Toatsu Chemicals, Incorporated Optical recording method and media therefor
GB8333853D0 (en) 1983-12-20 1984-02-01 Ciba Geigy Ag Production of images
JPH0630950B2 (en) 1983-12-29 1994-04-27 日本製紙株式会社 Sheet for recording aqueous ink and method for producing the same
US4571377A (en) 1984-01-23 1986-02-18 Battelle Memorial Institute Photopolymerizable composition containing a photosensitive donor and photoinitiating acceptor
JPH0697339B2 (en) 1984-02-02 1994-11-30 富士写真フイルム株式会社 Photopolymerizable composition
GB8402937D0 (en) 1984-02-03 1984-03-07 Ciba Geigy Ag Production of images
US4701402A (en) 1984-02-13 1987-10-20 Minnesota Mining And Manufacturing Company Oxidative imaging
US4620875A (en) 1984-04-10 1986-11-04 Ricoh Company, Ltd. Aqueous ink composition
US4534838A (en) 1984-04-16 1985-08-13 Loctite Corporation Siloxane polyphotoinitiators of the substituted acetophenone type
US4745042A (en) 1984-04-19 1988-05-17 Matsushita Electric Industrial Co., Ltd. Water-soluble photopolymer and method of forming pattern by use of the same
JPS60264279A (en) 1984-06-13 1985-12-27 Fuji Photo Film Co Ltd Recording material
JPS612771A (en) 1984-06-14 1986-01-08 Taoka Chem Co Ltd Ink composition
US4763966A (en) 1984-07-16 1988-08-16 Fuji Photo Film Co., Ltd. Infrared absorbent
JPH0755582B2 (en) 1984-07-27 1995-06-14 株式会社リコー Two-color thermosensitive recording label
US4632895A (en) 1984-08-23 1986-12-30 Minnesota Mining And Manufacturing Company Diffusion or sublimation transfer imaging system
US4663275A (en) 1984-09-04 1987-05-05 General Electric Company Photolithographic method and combination including barrier layer
US4617380A (en) 1984-09-11 1986-10-14 Ciba-Geigy Corporation Process for the preparation of concentrated stable liquid dye solutions of CI Direct Yellow 11 utilizing an extended surface silica filter aid during a desalting procedure
US4524122A (en) 1984-09-26 1985-06-18 Eastman Kodak Company Substituted 4-nitrophenylazo-1-naphthol cyan dyes having improved light stability
US4632891A (en) 1984-10-04 1986-12-30 Ciba-Geigy Corporation Process for the production of images
JPS61101568A (en) 1984-10-23 1986-05-20 Ricoh Co Ltd Water based ink
JPS61101574A (en) 1984-10-23 1986-05-20 Ricoh Co Ltd Water based ink
JPS61101572A (en) 1984-10-23 1986-05-20 Ricoh Co Ltd Water based ink
US4790565A (en) 1984-10-24 1988-12-13 Steed Signs Pty., Limited Game
JPH068390B2 (en) 1984-11-19 1994-02-02 住友化学工業株式会社 Reactive dye liquid composition and dyeing or printing method using the same
US4565769A (en) 1984-11-21 1986-01-21 E. I. Du Pont De Nemours And Company Polymeric sensitizers for photopolymer composition
DE3565136D1 (en) 1984-12-21 1988-10-27 Ciba Geigy Ag Process for the photochemical stabilisation of synthetic fibrous materials containing polyamide fibres
IE56890B1 (en) 1984-12-30 1992-01-15 Scully Richard L Photosensitive composition for direct positive colour photograph
US4672041A (en) 1985-02-22 1987-06-09 Beckman Instruments, Inc. Method and stable diazo reagent for detecting bilirubin
JPH0613653B2 (en) 1985-02-26 1994-02-23 株式会社リコー Aqueous ink composition
JPH0710620B2 (en) 1985-03-28 1995-02-08 株式会社リコー Two-color thermosensitive recording label
EP0196901A3 (en) 1985-03-29 1988-10-19 Taoka Chemical Co., Ltd Copper phthalocyanine compound and aqueous ink composition comprising the same
DE3512179A1 (en) 1985-04-03 1986-12-04 Merck Patent Gmbh, 6100 Darmstadt PHOTO INITIATORS FOR PHOTOPOLYMERIZATION IN AQUEOUS SYSTEMS
JPS61238874A (en) 1985-04-17 1986-10-24 Ricoh Co Ltd Water-based ink composition
JPH0621930B2 (en) 1985-05-01 1994-03-23 富士写真フイルム株式会社 Photoresponsive material
DE3563462D1 (en) 1985-05-09 1988-07-28 Ciba Geigy Ag Process for the photochemical stabilisation of undyed and dyed polyamide fibrous material and its mixtures
US4668533A (en) 1985-05-10 1987-05-26 E. I. Du Pont De Nemours And Company Ink jet printing of printed circuit boards
US4720450A (en) 1985-06-03 1988-01-19 Polaroid Corporation Thermal imaging method
CA1270089A (en) 1985-08-01 1990-06-05 Masami Kawabata Photopolymerizable composition
US4786586A (en) 1985-08-06 1988-11-22 Morton Thiokol, Inc. Radiation curable coating for photographic laminate
US4622286A (en) 1985-09-16 1986-11-11 E. I. Du Pont De Nemours And Company Photoimaging composition containing admixture of leuco dye and 2,4,5-triphenylimidazolyl dimer
JPH0615673B2 (en) * 1985-10-25 1994-03-02 三菱電機株式会社 Method for producing dye inclusion compound
JPS62102241A (en) 1985-10-30 1987-05-12 Tokyo Ohka Kogyo Co Ltd Photosensitive composition
DE3650107T2 (en) 1985-11-20 1995-05-24 Mead Corp Ionic dyes.
US4772541A (en) 1985-11-20 1988-09-20 The Mead Corporation Photohardenable compositions containing a dye borate complex and photosensitive materials employing the same
JPS62174741A (en) 1986-01-24 1987-07-31 Fuji Photo Film Co Ltd Method for stabilizing organic base body material to light
DE3609320A1 (en) 1986-03-20 1987-09-24 Basf Ag PHOTOCHROME SYSTEM, LAYERS MADE THEREOF AND THEIR USE
EP0239376A3 (en) 1986-03-27 1988-05-11 Gec-Marconi Limited Contrast enhanced photolithography
US4755450A (en) 1986-04-22 1988-07-05 Minnesota Mining And Manufacturing Company Spectral sensitizing dyes in photopolymerizable systems
US4775386A (en) 1986-05-05 1988-10-04 Ciba-Geigy Corporation Process for photochemical stabilization of undyed and dyed polyamide fibre material and blends thereof with other fibres: copper complex and light stabilizer treatment
US4895880A (en) 1986-05-06 1990-01-23 The Mead Corporation Photocurable compositions containing photobleachable ionic dye complexes
US4849320A (en) 1986-05-10 1989-07-18 Ciba-Geigy Corporation Method of forming images
US4772291A (en) 1986-05-12 1988-09-20 Japan Liquid Crystal Co., Ltd. Process for the preparation of densely colored pellet for synthetic resins
US4925770A (en) 1986-05-20 1990-05-15 Director General Of Agency Of Industrial Science And Technology Contrast-enhancing agent for photolithography
IT207808Z2 (en) 1986-06-03 1988-02-15 Promosint & Contractors Srl QUICK DISCHARGE VALVE PROVIDED WITH PISTON SHUTTER WITH INTERNAL GUIDE
US4988561A (en) 1986-06-17 1991-01-29 J. M. Huber Corporation Paper coated with synthetic alkali metal aluminosilicates
US4721531A (en) 1986-07-08 1988-01-26 Plasticolors, Inc. Pigment dispersions exhibiting improved compatibility in polyurethane systems
US4724021A (en) 1986-07-23 1988-02-09 E. I. Du Pont De Nemours And Company Method for making porous bottom-layer dielectric composite structure
US5002993A (en) 1986-07-25 1991-03-26 Microsi, Inc. Contrast enhancement layer compositions, alkylnitrones, and use
DE3625355A1 (en) 1986-07-26 1988-02-04 Basf Ag BENZOPHENONETHER ESTER AND A METHOD FOR IMPROVING THE LIGHT-FASTNESS OF POLYESTER TESTS USING BENZOPHENONETHER ESTERS
US5190565A (en) 1986-07-28 1993-03-02 Allied-Signal Inc. Sulfonated 2-(2'-hydroxyaryl)-2H-benzotriazoles and/or sulfonated aromatic formaldehyde condensates and their use to improve stain resistance and dye lightfasteness
US4874391A (en) 1986-07-29 1989-10-17 Ciba-Geigy Corporation Process for photochemical stabilization of polyamide fiber material and mixtures thereof with other fibers: water-soluble copper complex dye and light-stabilizer
US4752341A (en) 1986-08-11 1988-06-21 Pq Corporation Pigment system for paper
US4711802A (en) 1986-08-14 1987-12-08 E. I. Du Pont De Nemours And Company Aqueous ink for use on fluorocarbon surfaces
US4933265A (en) 1986-09-01 1990-06-12 Fuji Photo Film Co., Ltd. Process for forming direct positive color image
JPH0610727B2 (en) 1986-09-17 1994-02-09 富士写真フイルム株式会社 Photoresponsive material
US4727824A (en) 1986-09-22 1988-03-01 Personal Pet Products Partnership Absorbent composition, method of making and using same
DE3632530A1 (en) 1986-09-25 1988-04-07 Basf Ag METHOD FOR PRODUCING ALPHA BETA UNSATURATED KETONES
US4800149A (en) 1986-10-10 1989-01-24 The Mead Corporation Photohardenable compositions containing a dye borate complex and photosensitive materials employing the same
DE3637717A1 (en) 1986-11-05 1988-05-11 Hoechst Ag LIGHT-SENSITIVE MIXTURE, THIS RECORDING MATERIAL AND METHOD FOR PRODUCING POSITIVE OR NEGATIVE RELIEF COPIES USING THIS MATERIAL
US4746735A (en) 1986-11-21 1988-05-24 The Dow Chemical Company Regiospecific aryl nitration of meso-substituted tetraarylporphyrins
US4952478A (en) 1986-12-02 1990-08-28 Canon Kabushiki Kaisha Transfer recording medium comprising a layer changing its transferability when provided with light and heat
GB8628807D0 (en) 1986-12-02 1987-01-07 Ecc Int Ltd Clay composition
US4902725A (en) 1986-12-22 1990-02-20 General Electric Company Photocurable acrylic coating composition
JPS63190815A (en) 1987-02-04 1988-08-08 Hoou Kk Powdery hair dye composition
US4838938A (en) 1987-02-16 1989-06-13 Canon Kabushiki Kaisha Recording liquid and recording method by use thereof
US4926190A (en) 1987-02-18 1990-05-15 Ciba-Geigy Corporation Ink jet recording process using certain benzotriazole derivatives as light stabilizers
US4831068A (en) 1987-02-27 1989-05-16 Ciba-Geigy Corporation Process for improving the photochemical stability of dyeings on polyester fibre materials
DE3738567A1 (en) 1987-03-12 1988-09-22 Merck Patent Gmbh COREACTIVE PHOTOINITIATORS
US5028792A (en) 1987-03-19 1991-07-02 Xytronyx, Inc. System for the visualization of exposure to ultraviolet radiation
US4766050A (en) 1987-03-27 1988-08-23 The Mead Corporation Imaging system with integral cover sheet
US4853398A (en) 1987-04-13 1989-08-01 Eli Lilly And Company Leukotriene antagonists and use thereas
US4892941A (en) 1987-04-17 1990-01-09 Dolphin David H Porphyrins
US4952680A (en) 1987-04-23 1990-08-28 Basf Aktiengesellschaft Preparation of stable solutions of azo dyes of m-phenylenediamine by reaction with formic acid
DE3720850A1 (en) 1987-06-24 1989-01-05 Basf Ag METHOD FOR PRODUCING UNSATURED AND SATURATED KETONES
JPS649272A (en) 1987-07-01 1989-01-12 Nippon Kayaku Kk Non-flying granular dye
JPH07120036B2 (en) 1987-07-06 1995-12-20 富士写真フイルム株式会社 Photopolymerizable composition
WO1989001186A1 (en) 1987-07-28 1989-02-09 Nippon Kayaku Kabushiki Kaisha Photosensitive resin composition and color filter
US5196295A (en) 1987-07-31 1993-03-23 Microsi, Inc. Spin castable mixtures useful for making deep-UV contrast enhancement layers
DE3826046A1 (en) 1987-08-17 1989-03-02 Asea Brown Boveri METHOD FOR PRODUCING METAL LAYERS
US5180624A (en) 1987-09-21 1993-01-19 Jujo Paper Co., Ltd. Ink jet recording paper
US4803008A (en) 1987-09-23 1989-02-07 The Drackett Company Cleaning composition containing a colorant stabilized against fading
DE3732980A1 (en) 1987-09-30 1989-04-13 Basf Ag METHOD FOR IMPROVING THE LIGHT-FASTNESS OF POLYESTER TESTS USING BENZOPHENONETHER ESTERS AND NEW BENZOPHENONETHER ESTERS
US5025036A (en) 1987-10-01 1991-06-18 Hoffmann-La Roche Inc. Catechol carboxylic acids
US4950304A (en) 1987-10-02 1990-08-21 Ciba-Geigy Corporation Process for quenching or suppressing the fluorescence of substrates treated with fluorescent whitening agents
JP2604177B2 (en) 1987-10-05 1997-04-30 富士写真フイルム株式会社 Direct positive color image forming method
JPH01106053A (en) 1987-10-20 1989-04-24 Fuji Photo Film Co Ltd Direct positive color image forming method
US4853037A (en) 1987-10-30 1989-08-01 Hewlett-Packard Company Low glycol inks for plain paper printing
US4968596A (en) 1987-11-02 1990-11-06 Fuji Photo Film Co. Ltd. Method for forming a direct positive image
US4954380A (en) 1987-11-27 1990-09-04 Canon Kabushiki Kaisha Optical recording medium and process for production thereof
US5037726A (en) 1987-12-08 1991-08-06 Fuji Photo Film Co., Ltd. Method for forming a direct positive image from a material comprising a nucleation accelerator
US4812517A (en) 1987-12-28 1989-03-14 E. I. Du Pont De Nemours And Company Dispersants resistant to color change
JPH01174485A (en) * 1987-12-29 1989-07-11 Brother Ind Ltd Color developer
JPH0753469B2 (en) 1987-12-29 1995-06-07 新王子製紙株式会社 Inkjet recording sheet and manufacturing method thereof
US4813970A (en) 1988-02-10 1989-03-21 Crompton & Knowles Corporation Method for improving the lightfasteness of nylon dyeings using copper sulfonates
US5001330A (en) 1988-03-02 1991-03-19 National Computer Systems, Inc. Optically scanned document with fail-safe marking
JPH01223446A (en) 1988-03-03 1989-09-06 Fuji Photo Film Co Ltd Photoimage forming material and photoimage forming system using same
DE3807381A1 (en) 1988-03-07 1989-09-21 Hoechst Ag HETEROCYCLIC COMPOUNDS CONTAINING 4,6-BIS-TRICHLOROMETHYL-S-TRIAZIN-2-YL-GROUPS, PROCESS FOR THE PREPARATION THEREOF AND LIGHT-SENSITIVE MIXTURE CONTAINING THIS COMPOUND
US5106723A (en) 1988-03-10 1992-04-21 Microsi, Inc. Contrast enhancement layer compositions, alkylnitrones, and use
US5279652A (en) 1988-03-24 1994-01-18 Rainer Kaufmann Use of solids as antiblocking additives for marker liquids
JPH0735640B2 (en) 1988-04-18 1995-04-19 富士写真フイルム株式会社 Method for producing dyed polysaccharide
US4902787A (en) 1988-04-21 1990-02-20 North Carolina State University Method for producing lightfast disperse dyestuffs containing a build-in photostabilizer [molecule] compound
US4812139A (en) 1988-05-04 1989-03-14 Burlington Industries, Inc. Dyed polyester fabrics with improved lightfastness
EP0345212A1 (en) 1988-05-04 1989-12-06 Ciba-Geigy Ag Process to prevent yellowing of polyamide fibres finished with stain-proofing agents
DE3815622A1 (en) 1988-05-07 1989-11-16 Merck Patent Gmbh PHOTOINITIATOR DISPERSIONS
US5262276A (en) 1988-05-11 1993-11-16 Fuji Photo Film Co., Ltd. Light-sensitive compositions
DE3918105A1 (en) 1988-06-02 1989-12-14 Toyo Boseki PHOTOPOLYMERIZABLE COMPOSITION
US5003142A (en) 1988-06-03 1991-03-26 E. I. Du Pont De Nemours And Company Easy opening microwave pouch
ES2050274T3 (en) 1988-06-14 1994-05-16 Ciba Geigy Ag PROCEDURE FOR THE PHOTOCHEMICAL STABILIZATION OF UNDYED AND DYED POLYPROPYLENE FIBERS.
DE3921600C1 (en) 1988-07-02 1990-01-04 Asea Brown Boveri Ag, 6800 Mannheim, De
US4917956A (en) 1988-07-11 1990-04-17 Uop Method of preparing cyclodextrin-coated surfaces
DE3824486A1 (en) 1988-07-20 1990-02-08 Basf Ag METHOD FOR PRODUCING 4-ALKOXY-2-HYDROXYBENZOPHENONE-5-SULPHONIC ACIDS
DE3826947A1 (en) 1988-08-09 1990-02-22 Merck Patent Gmbh THIOXANTHON DERIVATIVES, THEIR USE AS PHOTOINITIATORS, PHOTOPOLYMERIZABLE BINDING SYSTEMS AND METHOD FOR THE PRODUCTION OF A RADIATION-COATED COATING
US4886774A (en) 1988-08-09 1989-12-12 Alfred Doi Ultraviolet protective overcoat for application to heat sensitive record materials
JPH0820734B2 (en) 1988-08-11 1996-03-04 富士写真フイルム株式会社 Photosensitive composition and photopolymerizable composition using the same
US5334455A (en) 1988-08-12 1994-08-02 Stamicarbon B.V. Free-radical curable compositions
US5153166A (en) 1988-08-18 1992-10-06 Trustees Of At Biochem Chromatographic stationary supports
US5030248A (en) 1988-08-31 1991-07-09 Sandoz Ltd. Dyeing method
US5202213A (en) 1988-08-31 1993-04-13 Canon Kabushiki Kaisha Developer with surface treated silicic acid for developing electrostatic image
US5187045A (en) 1988-09-07 1993-02-16 Minnesota Mining And Manufacturing Company Halomethyl-1,3,5-triazines containing a sensitizer moiety
US5034526A (en) 1988-09-07 1991-07-23 Minnesota Mining And Manufacturing Company Halomethyl-1,3,5-triazines containing a sensitizer moiety
DE3830914A1 (en) 1988-09-10 1990-03-22 Hoechst Ag PHOTOPOLYMERIZABLE MIXTURE, RECORDING MATERIAL MADE THEREOF, AND METHOD FOR PRODUCING COPIES
US5098793A (en) 1988-09-29 1992-03-24 Uop Cyclodextrin films on solid substrates
DE3833438A1 (en) 1988-10-01 1990-04-05 Basf Ag RADIATION SENSITIVE MIXTURES AND THEIR USE
DE3833437A1 (en) 1988-10-01 1990-04-05 Basf Ag RADIATION SENSITIVE MIXTURES AND THEIR USE
JPH02100048A (en) 1988-10-07 1990-04-12 Fuji Photo Film Co Ltd Silver halide color photographic sensitive material
JP2547626B2 (en) 1988-10-07 1996-10-23 富士写真フイルム株式会社 Method for producing monomer
CH676168A5 (en) 1988-10-10 1990-12-14 Asea Brown Boveri
US5026427A (en) 1988-10-12 1991-06-25 E. I. Dupont De Nemours And Company Process for making pigmented ink jet inks
EP0368327B1 (en) 1988-11-11 1995-02-15 Fuji Photo Film Co., Ltd. Light-sensitive composition
KR0139296B1 (en) 1988-11-21 1998-05-15 가와무라 시게꾸니 Chalcone derivatives and process for producing the same
US5045435A (en) 1988-11-25 1991-09-03 Armstrong World Industries, Inc. Water-borne, alkali-developable, photoresist coating compositions and their preparation
CH677846A5 (en) 1988-12-01 1991-06-28 Asea Brown Boveri
US5185236A (en) 1988-12-09 1993-02-09 Fuji Photo Film Co., Ltd. Full color recording materials and a method of forming colored images
US5098477A (en) 1988-12-14 1992-03-24 Ciba-Geigy Corporation Inks, particularly for ink printing
JP2604453B2 (en) 1988-12-14 1997-04-30 積水化学工業株式会社 Acrylic adhesive tape
EP0373573B1 (en) 1988-12-14 1994-06-22 Ciba-Geigy Ag Recording material for ink jet printing
US5096781A (en) 1988-12-19 1992-03-17 Ciba-Geigy Corporation Water-soluble compounds as light stabilizers
US4954416A (en) 1988-12-21 1990-09-04 Minnesota Mining And Manufacturing Company Tethered sulfonium salt photoinitiators for free radical polymerization
US5030243A (en) 1989-01-05 1991-07-09 Ciba-Geigy Corporation Process for the photochemical stabilization of undyed and dyeable artificial leather with a sterically hindered amine
JPH02289856A (en) 1989-01-18 1990-11-29 Fuji Photo Film Co Ltd Photosensitive and thermosensitive composition and recording material and image forming method using the same
US4985345A (en) 1989-02-02 1991-01-15 Ricoh Company, Ltd. Recording material
CH677292A5 (en) 1989-02-27 1991-04-30 Asea Brown Boveri
US4902299A (en) 1989-02-28 1990-02-20 E. I. Du Pont De Nemours And Company Nylon fabrics with cupric salt and oxanilide for improved dye-lightfastness
KR900014930A (en) 1989-03-27 1990-10-25 로레인 제이. 프란시스 Dye borate photoinitiator and photocurable composition containing same
CH677557A5 (en) 1989-03-29 1991-05-31 Asea Brown Boveri
US4933948A (en) 1989-05-30 1990-06-12 Eastman Kodak Company Dye laser solutions
JPH0323984A (en) 1989-06-20 1991-01-31 Seiji Kawashima Printed matter
US5023129A (en) 1989-07-06 1991-06-11 E. I. Du Pont De Nemours And Company Element as a receptor for nonimpact printing
US5328504A (en) 1989-08-09 1994-07-12 Seiko Epson Corporation Image recording ink
EP0425429B1 (en) 1989-08-25 1995-02-22 Ciba-Geigy Ag Light stabilised inks
DE59008830D1 (en) 1989-08-25 1995-05-11 Ciba Geigy Ag Light stabilized inks.
EP0417040A1 (en) 1989-09-06 1991-03-13 Ciba-Geigy Ag Dyeing process for wool
DE3930516A1 (en) 1989-09-13 1991-03-21 Riedel De Haen Ag BENZOPHENONETHER ESTER, METHOD FOR THE PRODUCTION THEREOF, AND THEIR USE FOR IMPROVING THE LIGHT STABILITY OF POLYESTER TESTS
US5098806A (en) 1989-09-22 1992-03-24 Board Of Regents, The University Of Texas System Photosensitive elements based on polymeric matrices of diacetylenes and spiropyrans and the use thereof as coatings to prevent document reproduction
US5176984A (en) 1989-10-25 1993-01-05 The Mead Corporation Photohardenable compositions containing a borate salt
US5028262A (en) 1989-11-02 1991-07-02 Eastman Kodak Company Stabilization of ink compositions
JPH03155554A (en) 1989-11-14 1991-07-03 Japan Synthetic Rubber Co Ltd Radiation sensitive resin composition
JP2830211B2 (en) 1989-11-17 1998-12-02 日本曹達株式会社 Method for producing β-hydroxyketones
US5026425A (en) 1989-12-11 1991-06-25 Hewlett-Packard Company Waterfastness of DB-168 ink by cation substitution
DE3941295A1 (en) 1989-12-14 1991-06-20 Basf Ag METHOD FOR COLORING POLYAMIDE SUBSTRATES
US4968813A (en) 1989-12-22 1990-11-06 Eastman Kodak Company Derivatives of 4H-thiopyran-1,1-dioxides
JP2740315B2 (en) * 1989-12-27 1998-04-15 中国パール販売株式会社 Aseptic cooking plate
US5069681A (en) 1990-01-03 1991-12-03 Ciba-Geigy Corporation Process for the photochemical stabilization of dyed polyamide fibres with foamed aqueous composition of copper organic complexes
US5202212A (en) 1990-01-16 1993-04-13 Mitsui Toatsu Chemicals, Inc. Toner composition for electrophotography
DE59105066D1 (en) 1990-01-19 1995-05-11 Ciba Geigy Ag Stabilization of dyeings on polyamide fibers.
NL9000268A (en) 1990-02-05 1991-09-02 Oce Nederland Bv Doped tin oxide powder, a process for its preparation, and its use in electrically conductive or anti-static coatings.
JPH03257463A (en) 1990-03-07 1991-11-15 Nippon Paint Co Ltd Toner and production thereof
JP2632066B2 (en) 1990-04-06 1997-07-16 富士写真フイルム株式会社 Positive image forming method
US5272201A (en) 1990-04-11 1993-12-21 E. I. Du Pont De Nemours And Company Amine-containing block polymers for pigmented ink jet inks
US5221334A (en) 1990-04-11 1993-06-22 E. I. Du Pont De Nemours And Company Aqueous pigmented inks for ink jet printers
US5085698A (en) 1990-04-11 1992-02-04 E. I. Du Pont De Nemours And Company Aqueous pigmented inks for ink jet printers
US5053320A (en) 1990-04-16 1991-10-01 Richard L. Scully Direct dry negative color printing process and composition
US5139687A (en) 1990-05-09 1992-08-18 The Proctor & Gamble Company Non-destructive carriers for cyclodextrin complexes
US5384186A (en) 1990-05-09 1995-01-24 The Proctor & Gamble Company Non-destructive carriers for cyclodextrin complexes
US5261953A (en) 1990-05-10 1993-11-16 Ciba-Geigy Corporation Inks
DE59104652D1 (en) 1990-05-10 1995-03-30 Ciba Geigy Ag Inks.
US5108505A (en) 1990-05-16 1992-04-28 Hewlett-Packard Company Waterfast inks via cyclodextrin inclusion complex
EP0485614B1 (en) 1990-05-21 1997-08-13 Toppan Printing Co., Ltd. Cyclodextrin derivative
CH680099A5 (en) 1990-05-22 1992-06-15 Asea Brown Boveri
DE59108599D1 (en) 1990-05-31 1997-04-17 Ciba Geigy Stabilization of dyeings on polyamide fibers
US5153104A (en) 1990-06-18 1992-10-06 Minnesota Mining And Manufacturing Company Thermally developable light-sensitive layers containing photobleachable sensitizers
US5153105A (en) 1990-06-18 1992-10-06 Minnesota Mining And Manufacturing Company Thermally developable light sensitive imageable layers containing photobleachable dyes
US5275646A (en) 1990-06-27 1994-01-04 Domino Printing Sciences Plc Ink composition
DE59106971D1 (en) 1990-07-12 1996-01-11 Ciba Geigy Ag Process for the photochemical and thermal stabilization of polyamide fiber materials.
US5187049A (en) 1990-07-16 1993-02-16 Minnesota Mining And Manufacturing Company Photosensitive thermally developed compositions
JP3244288B2 (en) 1990-07-23 2002-01-07 昭和電工株式会社 Near infrared decolorable recording material
TW207021B (en) 1990-07-23 1993-06-01 Showa Denko Kk
US5089374A (en) 1990-08-20 1992-02-18 Eastman Kodak Company Novel bis-onium salts and the use thereof as photoinitiators
JP3019381B2 (en) 1990-08-31 2000-03-13 ソニー株式会社 Optical recording medium
US5224197A (en) 1990-09-06 1993-06-29 The United States Of America As Represented By The Secretary Of The Air Force Integrated optics using photodarkened polystyrene
US5208136A (en) 1990-09-06 1993-05-04 The United States Of America As Represented By The Secretary Of The Air Force Fabricating of integrated optics
JP2642776B2 (en) 1990-09-10 1997-08-20 三田工業株式会社 Information recording medium and information recording method
EP0475905B1 (en) 1990-09-13 1998-01-14 Ciba SC Holding AG Photochemical stabilisation of wool
JPH04153079A (en) 1990-10-18 1992-05-26 Digital Sutoriimu:Kk Erasable and rewritable paper, printing ink and printing apparatus and erasing apparatus using them
US5296556A (en) 1990-10-30 1994-03-22 Union Camp Corporation Three-component curable resin compositions
JP2550775B2 (en) 1990-11-22 1996-11-06 富士ゼロックス株式会社 Carrier for magnetic brush developer
SE468054B (en) 1990-12-03 1992-10-26 Mo Och Domsjoe Ab PAPER AND PROCEDURES FOR PREPARING PAPER
EP0490819B1 (en) 1990-12-13 1995-09-13 Ciba-Geigy Ag Aqueous dispersion of slightly water soluble U.V. absorbers
US5254429A (en) 1990-12-14 1993-10-19 Anocoil Photopolymerizable coating composition and lithographic printing plate produced therefrom
JPH06504628A (en) 1990-12-20 1994-05-26 エクソン・ケミカル・パテンツ・インク UV/EB curable butyl copolymers for lithography and anti-corrosion coating applications
US5190710A (en) 1991-02-22 1993-03-02 The B. F. Goodrich Company Method for imparting improved discoloration resistance to articles
US5144964A (en) 1991-03-14 1992-09-08 Philip Morris Incorporated Smoking compositions containing a flavorant-release additive
FR2675347B1 (en) 1991-04-17 1994-09-02 Tabacs & Allumettes Ind PAPER CIGARETTE INCORPORATING A SMOKE MODIFYING AGENT.
EP0511166A1 (en) 1991-04-26 1992-10-28 Ciba-Geigy Ag Process for photochemical and thermic stabilization of polyamide fibre material with a fiberaffinitive copper complex and an oxalicacid diarylamide
US5271764A (en) 1992-02-12 1993-12-21 Xerox Corporation Ink compositions
US5286286A (en) 1991-05-16 1994-02-15 Xerox Corporation Colorless fast-drying ink compositions for printing concealed images detectable by fluorescence
US5302195A (en) 1991-05-22 1994-04-12 Xerox Corporation Ink compositions containing cyclodextrins
US5141797A (en) 1991-06-06 1992-08-25 E. I. Du Pont De Nemours And Company Ink jet paper having crosslinked binder
DE4118899C1 (en) 1991-06-08 1992-10-22 Degussa Ag, 6000 Frankfurt, De
US5141556A (en) 1991-06-13 1992-08-25 E. I. Du Pont De Nemours And Company Penetrants for aqueous ink jet inks
US5169438A (en) 1991-06-13 1992-12-08 E. I. Du Pont De Nemours And Company Aqueous ink jet inks containing cycloaliphatic diol pluggage inhibitors
US5160372A (en) 1991-06-13 1992-11-03 E. I. Du Pont De Nemours And Company Aqueous ink jet inks containing ester diol and amide diol cosolvents
JP3203694B2 (en) 1991-07-19 2001-08-27 東ソー株式会社 Manufacturing method of quartz glass
US5133803A (en) 1991-07-29 1992-07-28 Hewlett-Packard Company High molecular weight colloids which control bleed
DE4126461C2 (en) 1991-08-09 1994-09-29 Rainer Hoppe Dye-loaded inorganic molecular sieve, process for its preparation and its use
DE4127733A1 (en) 1991-08-22 1993-02-25 Basf Ag Graft polymers of natural substances containing saccharide structures or derivatives thereof and ethylenically unsaturated compounds and their use.
US5209814A (en) 1991-09-30 1993-05-11 E. I. Du Pont De Nemours And Company Method for diffusion patterning
US5205861A (en) 1991-10-09 1993-04-27 E. I. Du Pont De Nemours And Company Aqueous ink jet inks containing alkylene oxide condensates of certain nitrogen heterocyclic compounds as cosolvents
US5198330A (en) 1991-10-11 1993-03-30 Eastman Kodak Company Photographic element with optical brighteners having reduced migration
US5415976A (en) 1991-10-25 1995-05-16 Minnesota Mining And Manufacturing Company Aminoketone sensitizers for photopolymer compositions
US5455143A (en) 1991-10-25 1995-10-03 Minnesota Mining And Manufacturing Company Aminoketone sensitizers for aqueous soluble photopolymer compositions
US5202209A (en) 1991-10-25 1993-04-13 Xerox Corporation Toner and developer compositions with surface additives
SE9103140L (en) 1991-10-28 1993-04-29 Eka Nobel Ab HYDROPHOBERATED PAPER
US5180425A (en) 1991-11-05 1993-01-19 E. I. Du Pont De Nemours And Company Aqueous ink jet inks containing polyol/alkylene oxide condensates as cosolvents
US5224987A (en) 1991-11-12 1993-07-06 E. I. Du Pont De Nemours And Company Penetrants for aqueous ink jet inks
EP0542286B1 (en) 1991-11-14 1996-07-17 Showa Denko Kabushikikaisha Decolorizable toner
DE4142956C2 (en) 1991-12-24 1996-08-14 Du Pont Deutschland Bleachable antihalation system for photographic materials
DE4202038A1 (en) 1992-01-25 1993-07-29 Basf Ag USE OF A LIQUID CONTAINING IR DYES AS PRINTING INK
US5445651A (en) 1992-01-31 1995-08-29 The Procter & Gamble Company Detergent compositions inhibiting dye transfer in washing
US5271765A (en) 1992-02-03 1993-12-21 E. I. Du Pont De Nemours And Company Aqueous cationic dye-based ink jet inks
US5219703A (en) 1992-02-10 1993-06-15 Eastman Kodak Company Laser-induced thermal dye transfer with bleachable near-infrared absorbing sensitizers
US5541633A (en) 1992-02-12 1996-07-30 Xerox Corporation Ink jet printing of concealed images on carbonless paper
US5298030A (en) 1992-02-21 1994-03-29 Ciba-Geigy Corporation Process for the photochemical and thermal stabilization of undyed and dyed or printed polyester fiber materials
US5224476A (en) * 1992-02-24 1993-07-06 Duke University Method and apparatus for controlling fibrillation or tachycardia
US5193854A (en) 1992-02-28 1993-03-16 Babn Technologies Inc. Tamper-resistant article and method of authenticating the same
US5226957A (en) 1992-03-17 1993-07-13 Hewlett-Packard Company Solubilization of water-insoluble dyes via microemulsions for bleedless, non-threading, high print quality inks for thermal ink-jet printers
US5178420A (en) 1992-03-19 1993-01-12 Shelby Meredith E Reusable facsimile transmittal sheet and method
US5401562A (en) 1992-03-27 1995-03-28 Fuji Photo Film Co., Ltd. Paper material for photosensitive materials and method of producing the same
US5344483A (en) 1992-03-30 1994-09-06 Porelon, Inc. High-density, low-viscosity ink for use in ink jet printers
US5173112A (en) 1992-04-03 1992-12-22 E. I. Du Pont De Nemours And Company Nitrogen-containing organic cosolvents for aqueous ink jet inks
US5169436A (en) 1992-05-13 1992-12-08 E. I. Du Pont De Nemours And Company Sulfur-containing penetrants for ink jet inks
US5503664A (en) 1992-05-20 1996-04-02 Seiko Epson Corporation Ink compositions for ink jet printing
US5324349A (en) 1992-05-20 1994-06-28 Seiko Epson Corporation Ink compositions for ink jet printing
US5258274A (en) 1992-05-22 1993-11-02 Minnesota Mining And Manufacturing Company Thermal dye bleach construction sensitive to ultraviolet radiation
US5300403A (en) 1992-06-18 1994-04-05 International Business Machines Corporation Line width control in a radiation sensitive polyimide
US5256193A (en) 1992-06-25 1993-10-26 Xerox Corporation Porphyrin chromophore and dendrimer ink composition
US5372917A (en) 1992-06-30 1994-12-13 Kanzaki Paper Manufacturing Co., Ltd. Recording material
US5296275A (en) 1992-07-01 1994-03-22 Xytronyx, Inc. Phototranschromic ink
US5484816A (en) 1992-07-13 1996-01-16 Shiseido Company, Ltd. External skin treatment composition
US5270078A (en) 1992-08-14 1993-12-14 E. I. Du Pont De Nemours And Company Method for preparing high resolution wash-off images
US5310778A (en) 1992-08-25 1994-05-10 E. I. Du Pont De Nemours And Company Process for preparing ink jet inks having improved properties
EP0585679A1 (en) 1992-09-01 1994-03-09 Konica Corporation Method for forming a photographic color image
JP3151547B2 (en) 1992-09-07 2001-04-03 パイロットインキ株式会社 Aqueous ink composition for writing instruments
JP2602404B2 (en) 1992-09-08 1997-04-23 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー Aqueous ink composition
JP3176444B2 (en) 1992-10-01 2001-06-18 株式会社リコー Aqueous ink and recording method using the same
US5338822A (en) 1992-10-02 1994-08-16 Cargill, Incorporated Melt-stable lactide polymer composition and process for manufacture thereof
DE4234222A1 (en) 1992-10-10 1994-04-14 Cassella Ag Water-soluble sulfur dyes, their preparation and use
DE4236143A1 (en) 1992-10-26 1994-04-28 Bayer Ag Substrate with visible information protected against copying - prepd. with combination of adjacent fields of emitting and remitting colourants of almost same nuance when viewed without fluorescence
US5509957A (en) 1992-11-09 1996-04-23 Ciba-Geigy Corporation Ink compositions
US5489503A (en) 1992-12-03 1996-02-06 Ciba-Geigy Corp. UV absorbers
US5427415A (en) 1992-12-09 1995-06-27 Wallace Computer Services, Inc. Heat sensitive system and use thereof
DE69305308T2 (en) 1992-12-10 1997-03-20 Mitsubishi Paper Mills Ltd Inkjet recording sheet
US5372387A (en) 1992-12-15 1994-12-13 Wajda; Tadeusz Security device for document protection
US5292556A (en) 1992-12-22 1994-03-08 E. I. Du Pont De Nemours And Company Method for preparing negative-working wash-off relief images
US5250109A (en) 1992-12-22 1993-10-05 E. I. Du Pont De Nemours And Company Derivatives of polyoxyalkyleneamines as cosolvents for aqueous ink jet inks
US5268027A (en) 1992-12-22 1993-12-07 E. I. Du Pont De Nemours And Company Alkylpolyol ethers as cosolvents for ink jet inks
US5426164A (en) 1992-12-24 1995-06-20 The Dow Chemical Company Photodefinable polymers containing perfluorocyclobutane groups
US5455074A (en) 1992-12-29 1995-10-03 Kimberly-Clark Corporation Laminating method and products made thereby
US5302197A (en) 1992-12-30 1994-04-12 E. I. Du Pont De Nemours And Company Ink jet inks
GB9301451D0 (en) 1993-01-26 1993-03-17 Allied Colloids Ltd Production of filled paper
FR2700780B1 (en) 1993-01-28 1995-03-10 Novalis Fibres Filaments, fibers, pigmented threads for outdoor use.
JPH06248194A (en) 1993-02-25 1994-09-06 Ensuiko Sugar Refining Co Ltd Coloring matter containing quercetin
JPH06248193A (en) 1993-02-25 1994-09-06 Ensuiko Sugar Refining Co Ltd Crocetin-containing pigment
US5286288A (en) 1993-03-11 1994-02-15 Videojet Systems International, Inc. Hot melt inks for continuous jet printing
US5429628A (en) 1993-03-31 1995-07-04 The Procter & Gamble Company Articles containing small particle size cyclodextrin for odor control
JPH06287493A (en) 1993-04-07 1994-10-11 Canon Inc Ink and recording device using the same
KR0185765B1 (en) 1993-04-10 1999-04-15 가와다 미쓰구 Optical information medium and method for fabricating same
US5330860A (en) 1993-04-26 1994-07-19 E. I. Du Pont De Nemours And Company Membrane and electrode structure
DE4321376A1 (en) 1993-06-26 1995-01-05 Hoechst Ag Aqueous fine dispersion of an organophilic layered silicate
DE4322179C2 (en) 1993-07-03 1997-02-13 Schoeller Felix Jun Papier Recording material for ink jet printing processes
US5432274A (en) 1993-07-28 1995-07-11 National Research Council Of Canada Redox dye and method of preparation thereof using 2-hydroxypropyl-β-cyclodextrin and 1,1'-dimethylferrocene
US5645964A (en) 1993-08-05 1997-07-08 Kimberly-Clark Corporation Digital information recording media and method of using same
US5643356A (en) 1993-08-05 1997-07-01 Kimberly-Clark Corporation Ink for ink jet printers
US5865471A (en) 1993-08-05 1999-02-02 Kimberly-Clark Worldwide, Inc. Photo-erasable data processing forms
US5773182A (en) 1993-08-05 1998-06-30 Kimberly-Clark Worldwide, Inc. Method of light stabilizing a colorant
CA2120838A1 (en) 1993-08-05 1995-02-06 Ronald Sinclair Nohr Solid colored composition mutable by ultraviolet radiation
US5721287A (en) 1993-08-05 1998-02-24 Kimberly-Clark Worldwide, Inc. Method of mutating a colorant by irradiation
US5700850A (en) 1993-08-05 1997-12-23 Kimberly-Clark Worldwide Colorant compositions and colorant stabilizers
US5733693A (en) 1993-08-05 1998-03-31 Kimberly-Clark Worldwide, Inc. Method for improving the readability of data processing forms
BR9407181A (en) * 1993-08-05 1996-09-17 Kimberly Clark Co Colored composition process of its mutation electrophotographic process toner for the same substrate with image formed by colored and trans-absorbent composition of ultra violet radiation
US5681380A (en) 1995-06-05 1997-10-28 Kimberly-Clark Worldwide, Inc. Ink for ink jet printers
EP0639664A1 (en) 1993-08-16 1995-02-22 Basf Corporation Nylon fibers with improved dye washfastness and heat stability
DE4338486A1 (en) 1993-11-11 1995-08-10 Basf Ag Process for the production of recording materials for ink jet printers
EP0661598B1 (en) 1993-12-10 1998-09-16 Showa Denko Kabushiki Kaisha Decolorizable toner and a decolorizable toner production process
US5401303A (en) 1994-04-26 1995-03-28 E. I. Du Pont De Nemours And Company Aqueous inks having improved halo characteristics
JP3170415B2 (en) 1994-05-23 2001-05-28 シャープ株式会社 Electrostatic coupling input device
US5685754A (en) 1994-06-30 1997-11-11 Kimberly-Clark Corporation Method of generating a reactive species and polymer coating applications therefor
US5739175A (en) 1995-06-05 1998-04-14 Kimberly-Clark Worldwide, Inc. Photoreactor composition containing an arylketoalkene wavelength-specific sensitizer
US5474691A (en) 1994-07-26 1995-12-12 The Procter & Gamble Company Dryer-added fabric treatment article of manufacture containing antioxidant and sunscreen compounds for sun fade protection of fabrics
EP0699723A3 (en) 1994-08-31 1997-07-02 Canon Kk Ink-jet ink
US5476540A (en) 1994-10-05 1995-12-19 Hewlett Packard Corporation Gel-forming inks for use in the alleviation of bleed
JPH08230313A (en) 1994-12-12 1996-09-10 Arkwright Inc Polymer matrix coating for ink-jet medium
CO4560378A1 (en) * 1995-01-17 1998-02-10 Kimberly Clark Co STABILIZING COMPOSITION FOR DYES AND METHOD FOR STABILIZING A DYE IN THE LIGHT
US5580369A (en) 1995-01-30 1996-12-03 Laroche Industries, Inc. Adsorption air conditioning system
US5575891A (en) 1995-01-31 1996-11-19 The Procter & Gamble Company Soft tissue paper containing an oil and a polyhydroxy compound
US5643631A (en) 1995-03-17 1997-07-01 Minerals Tech Inc Ink jet recording paper incorporating novel precipitated calcium carbonate pigment
US5591489A (en) 1995-05-04 1997-01-07 Sequa Chemicals, Inc. Process for surface sizing paper or paperboard
US5798015A (en) 1995-06-05 1998-08-25 Kimberly-Clark Worldwide, Inc. Method of laminating a structure with adhesive containing a photoreactor composition
JP2001515524A (en) 1995-06-05 2001-09-18 キンバリー クラーク ワールドワイド インコーポレイテッド New pre-dye
US5747550A (en) 1995-06-05 1998-05-05 Kimberly-Clark Worldwide, Inc. Method of generating a reactive species and polymerizing an unsaturated polymerizable material
US5811199A (en) 1995-06-05 1998-09-22 Kimberly-Clark Worldwide, Inc. Adhesive compositions containing a photoreactor composition
US5849411A (en) 1995-06-05 1998-12-15 Kimberly-Clark Worldwide, Inc. Polymer film, nonwoven web and fibers containing a photoreactor composition
US5786132A (en) 1995-06-05 1998-07-28 Kimberly-Clark Corporation Pre-dyes, mutable dye compositions, and methods of developing a color
GB9515304D0 (en) 1995-07-26 1995-09-20 Ilford Ag Azo dyes
US5531821A (en) 1995-08-24 1996-07-02 Ecc International Inc. Surface modified calcium carbonate composition and uses therefor
US5855655A (en) 1996-03-29 1999-01-05 Kimberly-Clark Worldwide, Inc. Colorant stabilizers
US5782963A (en) 1996-03-29 1998-07-21 Kimberly-Clark Worldwide, Inc. Colorant stabilizers
US5709976A (en) 1996-06-03 1998-01-20 Xerox Corporation Coated papers
JP3206439B2 (en) 1996-06-28 2001-09-10 東海興業株式会社 Molding manufacturing method and apparatus
JP3134072B2 (en) 1997-05-13 2001-02-13 三洋化成工業株式会社 Dispersant for pearlescent pigments

Also Published As

Publication number Publication date
ZA965031B (en) 1997-02-26
JP2000506550A (en) 2000-05-30
MX9710016A (en) 1998-07-31
BR9609295A (en) 1999-05-18
ES2161357T3 (en) 2001-12-01
US6342305B1 (en) 2002-01-29
WO1997001605A1 (en) 1997-01-16
AR002608A1 (en) 1998-03-25
ATE206150T1 (en) 2001-10-15
US6033465A (en) 2000-03-07
AU5535296A (en) 1997-01-30
EP0846146A1 (en) 1998-06-10
EP0846146B1 (en) 2001-09-26

Similar Documents

Publication Publication Date Title
US5681380A (en) Ink for ink jet printers
US5643356A (en) Ink for ink jet printers
US5858586A (en) Digital information recording media and method of using same
US6066439A (en) Instrument for photoerasable marking
US5721287A (en) Method of mutating a colorant by irradiation
US5700850A (en) Colorant compositions and colorant stabilizers
US5773182A (en) Method of light stabilizing a colorant
CA2221565A1 (en) Novel colorants and colorant modifiers
EP1116708A1 (en) A method of dehydrating a tertiary alcohol
US6017471A (en) Colorants and colorant modifiers
CA2219463A1 (en) Temporary marking, ultraviolet radiation detection, and printing, all using photoerasable colorants
US6211383B1 (en) Nohr-McDonald elimination reaction
EP0799246B1 (en) Improved mutable composition
EP0830432A1 (en) Improved ink for ink jet printers
JP3590635B6 (en) New colorants and colorant modifiers

Legal Events

Date Code Title Description
EEER Examination request
FZDE Discontinued