WO2000018750A9 - Chelates comprising chinoid groups as photoinitiators - Google Patents

Chelates comprising chinoid groups as photoinitiators

Info

Publication number
WO2000018750A9
WO2000018750A9 PCT/US1999/022590 US9922590W WO0018750A9 WO 2000018750 A9 WO2000018750 A9 WO 2000018750A9 US 9922590 W US9922590 W US 9922590W WO 0018750 A9 WO0018750 A9 WO 0018750A9
Authority
WO
WIPO (PCT)
Prior art keywords
photoinitiator
group
alkyl group
photoinitiators
present
Prior art date
Application number
PCT/US1999/022590
Other languages
French (fr)
Other versions
WO2000018750A2 (en
WO2000018750A8 (en
WO2000018750A3 (en
Inventor
Ronald Sinclair Nohr
John Gavin Macdonald
Original Assignee
Kimberly Clark Co
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 Kimberly Clark Co filed Critical Kimberly Clark Co
Priority to BRPI9914123-0A priority Critical patent/BR9914123B1/en
Priority to AU13098/00A priority patent/AU1309800A/en
Priority to PL99366326A priority patent/PL366326A1/en
Priority to JP2000572210A priority patent/JP2003533548A/en
Priority to CA002353685A priority patent/CA2353685A1/en
Priority to DE69930948T priority patent/DE69930948T2/en
Priority to EP99956500A priority patent/EP1117698B1/en
Priority to ES99956500T priority patent/ES2263291T3/en
Priority to SK417-2001A priority patent/SK4172001A3/en
Publication of WO2000018750A2 publication Critical patent/WO2000018750A2/en
Publication of WO2000018750A3 publication Critical patent/WO2000018750A3/en
Publication of WO2000018750A8 publication Critical patent/WO2000018750A8/en
Publication of WO2000018750A9 publication Critical patent/WO2000018750A9/en

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D295/00Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/04Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms
    • C07D295/12Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly or doubly bound nitrogen atoms
    • C07D295/135Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly or doubly bound nitrogen atoms with the ring nitrogen atoms and the substituent nitrogen atoms separated by carbocyclic rings or by carbon chains interrupted by carbocyclic rings
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00Processes of polymerisation
    • C08F2/46Polymerisation initiated by wave energy or particle radiation
    • C08F2/48Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising 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
    • C09D11/02Printing inks
    • C09D11/10Printing inks based on artificial resins
    • C09D11/101Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing

Definitions

  • the present invention relates to novel photoinitiators and methods for generating a reactive species using the photoinitiators.
  • the present invention further relates to methods of polymerizing or photocuring polymerizable material using the above-mentioned photoinitiators.
  • the photoinitiators of the present invention find particular utility in photocurable inks as used in ink jet printers or on a printing press with and without nitrogen blanketing.
  • polymers have served essential needs in society. For many years, these needs were filled by natural polymers. More recently, synthetic polymers have played an increasingly greater role, particularly since the beg vning of the 20th century.
  • Especially useful polymers are those prepared by an addition polymerization mechanism, i.e., free radical chain polymerization of unsaturated monomers, and include, by way of example only, coatings and adhesives.
  • chain polymerization is initiated by a reactive species, which often is a free radical.
  • the source of the free radicals is termed an initiator or photoinitiator.
  • Improvements in free radical chain polymerization have focused both on (1) more reactive monomer and pre- polymer materials and (2) the photoinitiator. Whether a particular unsaturated monomer can be converted to a polymer requires structural, thermodynamic, and kinetic feasibility. Even when all three exist, kinetic feasibility is achieved in many cases only with a specific type of photoinitiator. Moreover, the photoinitiator can have a significant effect on reaction rate which, in turn, may determine the commercial success or failure of a particular polymerization process or product.
  • a free radical-generating photoinitiator may generate free radicals in several different ways. For example, the thermal, homolytic dissociation of an initiator typically directly yields two free radicals per initiator molecule.
  • a photoinitiator i.e., an initiator which absorbs light energy, may produce free radicals by one of three pathways:
  • the photoinitiator undergoes excitation by energy absorption with subsequent decomposition into one or more radicals
  • the photoinitiator undergoes excitation and the excited species interacts with a second compound (by either energy transfer or a redox reaction) to form free radicals from the latter and /or former compound(s); or (3) the photoinitiator undergoes an electron transfer to produce a radical cation and a radical anion.
  • Radiation-drying printing includes, for example, off-set prmting operations, such as on a Heidelberg press, flexographic printing, and flat-bed printing.
  • Commercially available photoinitiator systems have a number of shortcomings. First, most of the commercially available photoinitiator systems require a relatively large amount of photoinitiator in the ink composition to fully cure/dry the ink composition. This leads to undesirable extractables within the ink composition.
  • X 2 is a conjugated system such as one or more aryl groups or substituted aryl groups
  • Zj is -O, -S, an alkyl group having from one to six carbon atoms, an ester moiety, a ketone moiety, an amine moiety, an imine moiety, an ether moiety, an aryl or substituted aryl group, a metal or non- metal, or a metal or non-metal containing group, such as a zinc-containing group or a boron-containing group, respectively
  • M is an alkyl group, a substituted alkyl group, or forms a five-member ring with Z .
  • photoinitiators are produced having a desired absorption maximum, which substantially corresponds to an emission band of a radiation source and selectively varies from less than about 222 nm to greater than about 445 nm.
  • the present invention is directed to the above- described photoinitiators, compositions containing the same, and methods for generating a reactive species which includes providing one or more of the photoinitiators and irradiating the one or more photoinitiators.
  • One of the main advantages of the photoinitiators of the present invention is that they efficiently generate one or more reactive species under extremely low energy lamps, such as excimer lamps and mercury lamps, as compared to prior art photoinitiators.
  • the photoinitiators of the present invention also efficiently generate one or more reactive species in air or in a nitrogen atmosphere. Unlike many prior photoinitiators, the photoinitiators of the present invention are not sensitive to oxygen.
  • the photoinitiators of the present invention are as much as ten times faster than the best prior art photoinitiators.
  • the present invention is further directed to a method of efficiently generating a reactive species by matching a photoinitiator having an absorption maximum to an emission band of a radiation source, which corresponds to the absorption maximum. By adjusting the substituents of the photoinitiator, one can shift the absorption maximum of the photoinitiator from less than about 222 nm to greater than 445 nm.
  • the present invention is also directed to methods of using the above-described photoinitiators to polymerize and /or photocure a polymerizable material.
  • the photoinitiators of the present invention result in rapid curing times in comparison to the curing times of prior art photoinitiators, even with relatively low output lamps.
  • the present invention includes a method of polymerizing an polymerizable material by exposing the polymerizable material to radiation in the presence of the efficacious wavelength specific photoinitiator composition described above. When an unsaturated oligomer/ monomer mixture is employed, curing is accomplished.
  • the present invention further includes a film and a method for producing a film, by drawing an admixture of polymerizable material and one or more photoinitiators of the present invention, into a film and irradiating the film with an amount of radiation sufficient to polymerize the composition.
  • the admixture may be drawn into a film on a nonwoven web or on a fiber, thereby providing a polymer- coated nonwoven web or fiber, and a method for producing the same.
  • the present invention is also directed to an adhesive composition comprising a polymerizable material admixed with one or more photoinitiators of the present invention.
  • the present invention includes a laminated structure comprising at least two layers bonded together with the above-described adhesive composition, in which at least one layer is a nonwoven web or film. Accordingly, the present invention provides a method of lammating a structure wherein a structure having at least two layers with the above-described adhesive composition between the layers is irradiated to polymerize the adhesive composition.
  • the present invention is further directed to a method of printing, wherein the method comprises incorporating one or more photoinitiators of the present invention into an ink composition; printing the ink onto a substrate; and drying the ink with a source of radiation.
  • the present invention is directed to energy-efficient, reactive, photoinitiators and methods for utilizing the same. More particularly, the present invention is directed to new photoinitiators having the following general formula:
  • X comprises a conjugated system such as one or more aryl groups or substituted aryl groups
  • Z is -O, -S, an alkyl group having from one to six carbon atoms, an ester moiety, a ketone moiety, an amine moiety, an imine moiety, an ether moiety, an aryl or substituted aryl group, a metal or non-metal, or a metal or non-metal containing group, such as a zinc-containing group or a boron-containing group, respectively
  • M comprises an alkyl group, a substituted alkyl group, or forms a five-member ring with Z ⁇ .
  • the present invention is further directed to a method of efficiently generating a reactive species by matching a photoinitiator having an absorption maximum to an emission band of a radiation source, which corresponds to the absorption maximum.
  • a photoinitiator having an absorption maximum to an emission band of a radiation source, which corresponds to the absorption maximum.
  • the present invention also includes a method of polymerizing a polymerizable material by exposing the polymerizable material to electromagnetic radiation in the presence of one or more of the photoinitiators described above. Further, the present invention is directed to a film and a method for producing a film, by drawing an admixture of polymerizable material and one or more of the photoinitiators described above, into a film and irradiating the film with an amount of electromagnetic radiation sufficient to polymerize the admixture.
  • the present invention is further directed to an adhesive composition comprising a polymerizable material admixed and one or more photoinitiators of the present invention.
  • the present invention includes a laminated structure comprising at least two layers bonded together with the above-described adhesive composition.
  • the present invention further provides a method of laminating a structure wherein a structure having at least two layers with the above-described adhesive composition between the layers is irradiated with appropriate electromagnetic radiation to polymerize the adhesive composition.
  • reactive species is used herein to mean any chemically reactive species including, but not limited to, free-radicals, cations, anions, nitrenes, and carbenes. Illustrated below are examples of several of such species.
  • carbenes include, for example, methylene or carbene, dichlorocarbene, diphenylcarbene, alkylcarbonyl-carbenes, siloxycarbenes, and dicarbenes.
  • nitrenes include, also by way of example, nitrene, alkyl nitrenes, and aryl nitrenes.
  • Cations include, by way of illustration, a proton; primary, secondary, and tertiary alkyl carbocations, such as methyl cation, ethyl cation, propyl cation, f-butyl cation, f-pentyl cation, -hexyl cation; allylic cations; benzylic cations; aryl cations, such as triphenyl cation; cyclopropylmethyl cations; methoxymethyl cation; triarylsulphonium cations; and acyl cations.
  • Cations also include those formed from various metal salts, such as tetra-n-butylammonium tetrahaloaurate(III) salts; sodium tetrachloroaurate(III); vanadium tetrachloride; and silver, copper(I) and (II), and thallium(I) triflates.
  • metal salts such as tetra-n-butylammonium tetrahaloaurate(III) salts; sodium tetrachloroaurate(III); vanadium tetrachloride; and silver, copper(I) and (II), and thallium(I) triflates.
  • anions include, by way of example, alkyl anions, such as ethyl anion, ⁇ -propyl anion, isobutyl anion, and neopentyl anion; cycloalkyl anions, such as cyclopropyl anion, cyclobutyl anion, and cyclopentyl anion; allylic anions; benzylic anions; aryl cations; and sulfur- or phosphorus-containing alkyl anions.
  • alkyl anions such as ethyl anion, ⁇ -propyl anion, isobutyl anion, and neopentyl anion
  • cycloalkyl anions such as cyclopropyl anion, cyclobutyl anion, and cyclopentyl anion
  • allylic anions such as cyclopropyl anion, cyclobutyl anion, and cyclopentyl anion
  • benzylic anions
  • organometallic photoinitiators include titanocenes, fluorinated diaryltitanocenes, iron arene complexes, manganese decacarbonyl, and methylcyclopentadienyl manganese tricarbonyl.
  • Organometallic photoinitiators generally produce free radicals or cations.
  • quantum yield is used herein to indicate the efficiency of a photochemical process. More particularly quantum yield is a measure of the probability that a particular molecule will absorb a quantum of light during its interaction with a photon. The term expresses the number of photochemical events per photon absorbed.
  • quantum yields may vary from zero (no absorption) to 1.
  • polymerization is used herein to mean the combining, e.g. covalent bonding, of a number of smaller molecules, such as monomers, to form large molecules, i.e., macromolecules or polymers.
  • the monomers may be combined to form only linear macromolecules or they may be combined to form three-dimensional macromolecules, commonly referred to as crosslinked polymers.
  • curing means the polymerization of functional oligomers and monomers, or even polymers, into a crosslinked polymer network.
  • curing is the polymerization of unsaturated monomers or oligomers in the presence of crosslinking agents.
  • unsaturated monomer “functional oligomer”
  • crosslinking agent is used herein with their usual meanings and are well understood by those having ordinary skill in the art. The singular form of each is intended to include both the singular and the plural, i.e., one or more of each respective material.
  • unsaturated polymerizable material is meant to include any unsaturated material capable of undergoing polymerization.
  • the term encompasses unsaturated monomers, oligomers, and crosslinking agents.
  • the singular form of the term is intended to include both the singular and the plural.
  • the term "fiber” as used herein denotes a threadlike structure.
  • the fibers used in the present invention may be any fibers known in the art.
  • the term "nonwoven web” as used herein denotes a web-like matter comprised of one or more overlapping or interconnected fibers in a nonwoven manner. It is to be understood that any nonwoven fibers known in the art may be used in the present invention.
  • the present invention is directed to new photoinitiators having the following general formula:
  • X is a conjugated system such as one or more aryl groups or substituted aryl groups
  • Z ⁇ is -O, -S, an alkyl group having from one to six carbon atoms, an ester moiety, a ketone moiety, an amine moiety, an imine moiety, an ether moiety, an aryl or substituted aryl group, a metal or non- metal, or a metal or non-metal containing group, such as a zinc-containing group or a boron-containing group, respectively
  • M ⁇ is an alkyl group, a substituted alkyl group, or forms a five-member ring with Z ⁇ .
  • X ⁇ comprises
  • R 6 and R 7 each independently represent hydrogen, an alkyl group having from one to six carbon atoms, an alkoxy group having from one to six carbon atoms, or a halogen-substituted alkyl group; and wherein ⁇ ⁇ and y 2 each independently represent a hydrogen, an alkyl group having from one to six carbon atoms, an aryl group,
  • X 3 represents a hydrogen, an alkyl or substituted alkyl group, or an aryl or substituted aryl group.
  • Other suitable X : groups include, but are not limited to, the following:
  • R 6 and R 7 each independently represent a methyl group, an ethyl group, an isopropyl group, a methoxy group, an ethoxy group, or a trifluoromethyl group.
  • M comprises a tertiary alkyl group having the following formula:
  • y 3 , y 4 and y 5 each independently represent a hydrogen, an alkyl group having from one to six carbon atoms, a tertiary amine group, an aryl group, or a substituted aryl group.
  • the photoinitiator has the following structure:
  • a calcium ion forms a five member ring, which includes the oxygen atom ("Z-,") and the electron-rich nitrogen atom.
  • Z-, oxygen atom
  • an arrow represents a coordinate covalent bond between an electron- rich nitrogen atom and a metal or non-metal cation.
  • Other suitable cations include, but are not limited to, beryllium, magnesium, strontium, barium, zinc, aluminum, and copper (II).
  • Z in the above-described general formula comprises an ester moiety.
  • photoinitiators include, but are not limited to, photoinitiators having the following structure:
  • the -C(0)CH 3 group (“Z ⁇ ") may be substituted with other groups including, but not limited to, -CH 3 , -BF 3 and phenyl groups.
  • the photoinitiators of the present invention have the following general formula:
  • X is as defined above;
  • Z 2 is a metal or non-metal cation, such as Zn 2+ , Ca 2+ , or boron, or a salt thereof, or -C(0)R, which forms a covalent bond with the oxygen atom;
  • R, R l R 2 , R , and R 4 are each independently a hydrogen atom, an alkyl or substituted alkyl group, or an aryl or substituted aryl group.
  • R ⁇ and R 2 may form one or more aromatic rings with X : .
  • Photoinitiators having the above formula include, but are not limited to, the following photoinitiators:
  • R ⁇ , R 12 , R 3 , and R 14 are each independently a hydrogen atom; an alkyl group or substituted alkyl group.
  • the photoinitiator has the following structure:
  • the photoinitiator has the following structure:
  • the calcium atom forms a five member ring, which includes the oxygen atom and the electron-rich nitrogen atom.
  • other salts may be used instead of the calcium chloride.
  • suitable salts include, but are not limited to, salts containing beryllium, magnesium, strontium, barium, zinc, aluminum, scandium, and copper (II).
  • another photoinitiator of the present invention may have the following structure:
  • R lr R 2 , and X 1 of the above-described general formula form one or more aromatic rings to form a photoinitiator having the structure below:
  • Z 2 , R 3 , and R 4 are substituents as defined above and y n and y 12 are each independently represent a hydrogen; an alkyl group having from one to six carbon atoms; an aryl group;
  • the present invention is further directed to novel photoinitiators having the following general formula:
  • Y is -O- or -N(R 5 )-;
  • Zg is a metal or nonmetal cation or a salt containing the cation;
  • X l7 R lr R 2 , R 3 , R 4 , and R 5 are as defined above.
  • Suitable Z 3 groups include, but are not limited to, metals and metal salts containing Cd, Hg, Zn, Al, Ga, In, Tl, Sc, Ge, Pb, Si, Ti, Sn, and Zr, as well as, nonmetals and nonmetal salts containing boron and phosphorus.
  • Z 3 comprises a chloride-containing salt such as zinc chloride, zinc benzyl chloride, or boron chloride.
  • "R" comprises hydrogen, a methyl group, an ethyl group, a propyl group, or a benzyl group.
  • the photoinitiator has the following structure:
  • X 4 comprises any nitrogen-containing group, which donates a pair of electrons to the nitrogen-carbon double bond
  • Ri, R 2 , R 3 , R-i, R ⁇ / and R 7 are as defined above.
  • the above photoinitiator has an absorption maximum of about 360 nm.
  • the photoinitiator has the following structure:
  • photoinitiators of the present invention have the following structure:
  • the photoinitiator has the following structure:
  • the absorption maximum of the photoinitiator shifts further to greater than about 410 nm.
  • other metal and nonmetal salts may be used in place of the metal and nonmetal chlorides.
  • the above photoinitiator may have the following structure:
  • the above-described photoinitiators of the present invention may be produced by the following reaction mechanism:
  • a first compound reacts with a metal or metal salt or a nonmetal or nonmetal salt, Z 3 , to produce a photoinitiator of the present invention, having a five- member ring containing a metal or nonmetal atom, at least one nitrogen atom, two carbon atoms, and possibly an oxygen atom.
  • the photoinitiators have the following general formula:
  • X ⁇ Y, R l R 2 , R 3 , R 4 , and R 5 are as defined above;
  • Z 4 is a metal or nonmetal atom; and
  • Z 5 and Z ⁇ are halogen- containing anions or form one or more rings with or without R 3 or R 4 .
  • the nitrogen atom donates its lone electron pair to metal or nonmetal atom, Z 4 , to form a five member ring.
  • Suitable , Z 4 groups include, but are not limited to, metals such as Cd,
  • Z 4 comprises Cd, Zn, Mg, Ti, boron or phosphorus. More desirably, Z 4 comprises Zn.
  • Suitable Z 5 and Z ⁇ groups include, but are not limited to, halogen- containing anions. Desirably, Z 5 and Zg each independently comprise fluorine, chlorine or bromine-containing anions. More desirably, Z 5 and Z 6 each independently comprise fluorine-containing anions. Even more desirably, Z 5 and Z 6 each independently comprise BF 4 , AsF 6 , PF 6 , or SbF 6 .
  • R lf R 2 , R 3 , and R 4 each independently comprise hydrogen, a methyl group, an ethyl group, a propyl group, or a benzyl group.
  • the photoinitiator has the following structure:
  • the photoinitiator has the following structure:
  • the photoinitiator of the present invention has the following structure:
  • the photoinitiator of the present invention has the following structure:
  • the above-described photoinitiators of the present invention may be produced by the following reaction mechanism:
  • a first compound reacts with a metal or nonmetal salt, Z 4 Z 5 Z 6 , to produce a photoinitiator of the present invention, having a five-member ring containing a metal or nonmetal atom, at least one nitrogen atom, two carbon atoms, and possibly an oxygen atom.
  • the present invention is further directed to novel photoinitiators having the following general structure:
  • Y 2 and Y 3 each independently represent -O- or - ⁇ (R 3 )(R 4 )-; and X ⁇ , Ri, R 2 , R 3 , R 4 , Z 4 , Z 5 , and 7_ are as defined above.
  • Y 3 represents -N(R 3 )(R 4 )- and Z 5 and ⁇ form two five member rings: one five member ring which includes Z 4 , Z 5 , and Z 6/ and one five member rings which includes with Z 4 , Z 6 and one of R 3 or R 4 .
  • the resulting photoinitiator has the following structure:
  • Z 5 , Zs and R 4 comprise any combination of carbon, nitrogen and oxygen atoms to form two five member rings.
  • Z 5 , Ze and R 4 may form two similar ring structures or two different ring structures. Also, each ring formed by Z 5 , Z 6 and R 4 may contain more than five ring members. In one embodiment of the present invention, the resulting photoinitiator has the following structure:
  • Xi, Y 2 , Ri, R2 R3 and Z4 are as defined above; and n 2 and n 2 each independently represent an integer from 1 to 5.
  • the resulting photoinitiator has the following structure:
  • Ri, R 2 , R3, R ⁇ R7/ ni, and n are as defined above.
  • Z 5 and Z ⁇ form a single ring.
  • the resulting photoinitiator has the following structure:
  • Z 5 and Z ⁇ comprise any combination of carbon, nitrogen and oxygen atoms to form a ring.
  • Z 5 and Z ⁇ form a five member ring so that the resulting photoinitiator has a dimeric structure.
  • One example of the resulting photoinitiator has the following structure:
  • photoinitiators of the present invention having the above-described structure include, but are not limited to, the following photoinitiators:
  • photoinitiators include, but are not limited to, the following photoinitiators:
  • Z 4 comprises boron or zinc in the dimeric structures above.
  • Z 4 comprises boron or zinc in the dimeric structures above.
  • the resulting photoinitiators are relatively stable at room temperature (from about 15°C to 25°C) and normal room humidity (from about 5% to 60%; desirably from 5% to 30%). However, upon exposure to radiation at an appropriate wavelength, the photoinitiators efficiently produce one or more reactive species.
  • the photoinitiators of the present invention have a high intensity of absorption.
  • the photoinitiators of the present invention have a molar extinction coefficient (absorptivity) greater than about 20,000 1 mole _1 cm-l.
  • the photoinitiators of the present invention have a molar extinction coefficient greater than about 25,000 1 mole-lcm "1 .
  • the present invention is further directed to a method of generating a reactive species.
  • the method of generating a reactive species involves generating a reactive species by exposing one or more of the above-described photoinitiators to radiation. The exposure of the photoinitiators to a radiation source triggers a photochemical process.
  • quantum yield is used herein to indicate the efficiency of a photochemical process. More particularly, quantum yield is a measure of the probability that a particular molecule (photoinitiator) will absorb a quantum of light during its interaction with a photon. The term expresses the number of photochemical events per photon absorbed. Thus, quantum yields may vary from zero (no absorption) to 1.
  • the photoinitiators of the present invention absorb photons having a relatively specific wavelength and transfers the absorbed energy to one or more excitable portions of the molecule.
  • the excitable portion of the molecule absorbs enough energy to cause a bond breakage, which generates one or more reactive species.
  • the efficiency with which a reactive species is generated with the photoinitiators of the present invention is significantly greater than that experienced with photoinitiators of the prior art as indicated by faster cure times.
  • the photoinitiators of the present invention desirably will have a quantum yield greater than about 0.8. More desirably, the quantum yield of the photoinitiators of the present invention will be greater than about 0.9.
  • the quantum yield of the photoinitiators of the present invention will be greater than about 0.95. Still more desirably, the quantum yield of the photoinitiators of the present invention will be greater than about 0.99, with the most desirable quantum yield being about 1.0.
  • Exposing the photoinitiators of the present invention to radiation results in the generation of one or more reactive species.
  • the photoinitiators may be employed in any situation where reactive species are required, such as for the polymerization of an unsaturated monomer and the curing of an unsaturated oligomer/ monomer mixture.
  • the unsaturated monomers and oligomers may be any of those known to one having ordinary skill in the art.
  • the polymerization and curing media also may contain other materials as desired, such as pigments, extenders, amine synergists, and such other additives as are well known to those having ordinary skill in the art.
  • examples of unsaturated monomers and oligomers include ethylene, propylene, vinyl chloride, isobutylene, styrene, isoprene, acrylonitrile, acrylic acid, methacylic acid, ethyl acrylate, methyl methacrylate, vinyl acrylate, allyl methacrylate, tripropylene glycol diacrylate, trimethylol propane ethoxylate acrylate, epoxy acrylates, such as the reaction product of a bisphenol A epoxide with acrylic acid; polyether acrylates, such as the reaction product of acrylic acid with an adipic acid/ hexanediol-based polyether, urethane acrylates, such as the reaction product of hydroxypropyl acrylate with diphenylmethane-4,4'-diisocyanate, and polybutadiene diacrylate oligomer.
  • the types of reactions that various reactive species enter into include, but are not limited to, addition reactions, including polymerization reactions; abstraction reactions; rearrangement reactions; elimination reactions, including decarboxylation reactions; oxidation-reduction (redox) reactions; substitution reactions; and conjugation/ deconjugation reactions.
  • addition reactions including polymerization reactions; abstraction reactions; rearrangement reactions; elimination reactions, including decarboxylation reactions; oxidation-reduction (redox) reactions; substitution reactions; and conjugation/ deconjugation reactions.
  • the present invention also comprehends a method of polymerizing a polymerizable material, such as an unsaturated monomer or epoxy compound, by exposing the polymerizable material to radiation in the presence of the effacious photoinitiators of the present invention described above.
  • a polymerizable material such as an unsaturated monomer or epoxy compound
  • the polymerizable material admixed with the photoinitiators of the present invention is to be admixed by means known in the art, and that the mixture will be irradiated with an amount of radiation sufficient to polymerize the material.
  • the amount of radiation sufficient to polymerize the material is readily determinable by one of ordinary skill in the art, and depends upon the identity and amount of photoinitiators, the identity and amount of the polymerizable material, the intensity and wavelength of the radiation, and the duration of exposure to the radiation.
  • one or more photoinitiators of the present invention are used to polymerize an epoxy resin. It is believed that the following reaction mechanism takes place in the presence of a hydrogen-donating compound, such as an alcohol, cumene or amine:
  • Reactive species, HZ 2 and/or FLZ 2 then react with an epoxy resin according to the following mechanism to produce a polyether:
  • the weak conjugate bases, Z ⁇ and/or Z 2 ⁇ which are non- nucleophilic, enable the polymerization reaction to take place, unlike other anions, which may prematurely terminate the polymerization reaction.
  • the present invention further includes a film and a method for producing a film, by drawing an admixture of a polymerizable material and one or more photoinitiators of the present invention, into a film and irradiating the film with an amount of radiation sufficient to polymerize the composition.
  • the polymerizable material is an unsaturated oligomer/monomer mixture
  • curing is accomplished. Any film thickness may be produced, as per the thickness of the admixture formed, so long as the admixture sufficiently polymerizes upon exposure to radiation.
  • the admixture may be drawn into a film on a nonwoven web or on a fiber, thereby providing a polymer- coated nonwoven web or fiber, and a method for producing the same.
  • the present invention also includes an adhesive composition comprising a polymerizable material admixed with one or more photoinitiators of the present invention.
  • the present invention includes a laminated structure comprising at least two layers bonded together with the above-described adhesive composition.
  • a laminate is produced wherein at least one layer is a cellulosic or polyolefin nonwoven web or film. Accordingly, the present invention provides a method of laminating a structure wherein a structure having at least two layers with the above-described adhesive composition between the layers is irradiated to polymerize the adhesive composition. When the unsaturated polymerizable material in the adhesive is an unsaturated oligomer/monomer mixture, the adhesive is irradiated to cure the composition.
  • any layers may be used in the laminates of the present invention, on the condition that at least one of the layers allows sufficient radiation to penetrate through the layer to enable the admixture to polymerize sufficiently.
  • any cellulosic or polyolefin nonwoven web or film known in the art may be used as one of the layers so long as they allow radiation to pass through.
  • the amount of radiation sufficient to polymerize the admixture is readily determinable by one of ordinary skill in the art, and depends upon the identity and amount of photoinitiator, the identity and amount of the polymerizable material, the thickness of the admixture, the identity and thickness of the layer, the intensity and wavelength of the radiation, and the duration of exposure to the radiation.
  • the radiation to which the photoinitiators of the present invention may be exposed generally will have a wavelength of from about 4 to about 1,000 nanometers.
  • the radiation may be ultraviolet radiation, including near ultraviolet and far or vacuum ultraviolet radiation; visible radiation; and near infrared radiation.
  • the radiation will have a wavelength of from about 100 to about 900 nanometers. More desirably, the radiation will have a wavelength of from about 100 to 700 nanometers.
  • the radiation will be ultraviolet radiation having a wavelength of from about 4 to about 400 nanometers. More desirably, the radiation will have a wavelength of from about 100 to about 420 nanometers, and even more desirably will have a wavelength of from 320 to about 420 nanometers.
  • the radiation desirably will be incoherent, pulsed ultraviolet radiation from a dielectric barrier discharge excimer lamp or radiation from a mercury lamp.
  • Excimers are unstable excited-state 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.
  • the dielectric barrier excimers in general emit in the range of from about 125 nm to about 500 nm, depending upon the excimer gas mixture.
  • Dielectric barrier discharge excimer lamps (also referred to hereinafter as “excimer lamp”) are 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. 16671674 (1990); and E. Eliasson and U. Kogelschatz, "UV Excimer Radiation from Dielectric- Barrier Discharges.” Appl. Phys. B. 46, pp. 299-303 (1988).
  • Excimer lamps were developed by ABB Infocom Ltd., Lenzburg, Switzerland, and at the present time are available from Heraeus Noblelight GmbH, Kleinostheim, Germany.
  • the excimer lamp emits incoherent, pulsed ultraviolet radiation.
  • Such radiation has a relatively narrow bandwidth, i.e., the half width is of the order of approximately 5 to 100 nanometers.
  • the radiation will have a half width of the order of approximately 5 to 50 nanometers, and more desirably will have a half width of the order of 5 to 25 nanometers.
  • the half width will be of the order of approximately 5 to 15 nanometers.
  • the ultraviolet radiation emitted from an excimer lamp can be emitted in a plurality of wavelengths, wherein one or more of the wavelengths within the band are emitted at a maximum intensity. Accordingly, a plot of the wavelengths in the band against the intensity for each wavelength in the band produces a bell curve.
  • the "half width" of the range of ultraviolet radiation emitted by an excimer lamp is defined as the width of the bell curve at 50% of the maximum height of the bell curve.
  • excimer lamp 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 and the claims.
  • excimer lamp radiation is essentially monochromatic.
  • excimer lamps are highly desirable for use in the present invention, the source of radiation used with the photoinitiators of the present invention may be any radiation source known to those of ordinary skill in the art.
  • a mercury lamp with a D-bulb which produces radiation having an emission peak of about 360 nm is used to produce free radicals from the above-described photoinitiators.
  • This radiation source is particularly useful when matched with one or more photoinitiators of the present invention having an absorption maximum of about 360 nanometers, corresponding to the emission peak of the mercury lamp.
  • Other specialty doped lamps which emit radiation at about 420 nm, may be used with photoinitiators of the present invention which have an absorption maximum at about 420 nm.
  • One lamp, the V-bulb available from Fusion Systems is another suitable lamp for use in the present invention.
  • specialty lamps having a specific emission band may be manufactured for use with one or more specific photoinitiators of the present invention.
  • New lamp technology provides the following potential advantages:
  • the photoinitiators of the present invention As a result of the photoinitiators of the present invention absorbing radiation in the range of about 250 to about 390 nanometers, some of the photoinitiators of the present invention will generate one or more reactive species upon exposure to sunlight. Accordingly, these photoinitiators of the present invention provides a method for the generation of reactive species that does not require the presence of a special light source.
  • the photoinitiators of the present invention enable the production of adhesive and coating compositions that consumers can apply to a desired object and polymerize or cure upon exposure to sunlight. These photoinitiators also enable numerous industry applications wherein polymerizable materials may be polymerized merely upon exposure to sunlight. Therefore, depending upon how the photoinitiator is designed, the photoinitiator of the present invention can eliminate the cost of purchasing and maintaining light sources in numerous industries wherein such light sources are necessary without the photoinitiators of the present invention.
  • the effective tuning of the photoinitiators of the present invention for a specific wavelength band permits the photoinitiators of the present invention to more efficiently utilize the target radiation in the emission spectrum of the radiating source corresponding to the "tuned" wavelength band, even though the intensity of such radiation may be much lower than, for example, radiation from a narrow band emitter, such as an excimer lamp.
  • a narrow band emitter such as an excimer lamp.
  • the effectiveness of the photoinitiators of the present invention is not necessarily dependent upon the availability or use of a narrow wavelength band radiation source.
  • the above-described photoinitiators of the present invention may be incorporated into ink compositions.
  • one or more of the photoinitiators are incorporated into an ink jet ink composition for use on ink jet ink printers.
  • the ink composition may be used on commercially available ink jet printing machines alone or in combination with a radiation source in series with the ink jet printing machine for instantaneous curing of the ink jet ink composition.
  • Any radiation source known to those of ordinary skill in the art may be used to cure the ink jet ink composition.
  • one of the above-described radiation sources is used to cure the ink composition.
  • a further use of the above-described photoinitiators of the present invention involves the incorporation of one or more of the photoinitiators into an ink composition for use on a radiation-drying printing press.
  • Radiation-drying printing refers to any printing method which utilizes radiation as a drying means. Radiation- drying printing includes, for example, off-set printing operations, such as on a Heidelberg press, flexographic printing, and flat-bed printing.
  • the photoinitiators of the present invention enable increased press output due to the photoreactivity of the photoinitiators. Further, the increased output may be obtained while using a minimal amount of photoinitiator and a low energy light source. In one embodiment of the present invention, complete curing at an output rate of 10,000 printed sheets per hour may be obtained using a 50 W cold lamp as the light source.
  • the amount of photoinitiator added to the ink composition, adhesive composition or resin is less than about 4.0 wt% of the total weight of the composition. More desirably, the amount of photoinitiator added to the composition is from about 0.25 to about 3.0 wt% of the total weight of the composition. Most desirably, the amount of photoinitiator added to the composition is from about 0.25 to about 2.0 wt% of the total weight of the composition.
  • a major advantage of the photoinitiators of the present invention is that they enable rapid curing times of ink compositions, adhesive compositions and/or resins in comparison to the curing times of prior art photoinitiators.
  • Ink compositions containing the photoinitiators of the present invention possess rapid curing times from 5-10 times faster than the curing times of ink compositions containing the best known photoinitiators.
  • the use of the photoinitiators of the present invention in ink compositions, adhesive compositions or resins for printing presses enables print speeds, which were at one time thought to be unobtainable.
  • the printed sheet output is greater than 6,000 sheets per hour. More desirably, the printed sheet output is greater than 8,000 sheets per hour. Most desirably, the printed sheet output is greater than
  • Ciba Geigy photoinitiator 369 (CGI 369) in the form of a powder was added to a 1 g sample of red flexo ink (Gamma Graphics). The mixture was exposed to UV radiation while positioned within an FTIR machine to monitor the decrease in carbon-carbon double bonds within the mixture. The curing rate was measured.
  • Flexo Resin A mixture of ⁇ mberly Clark's photoinitiator, having the following structure, in the form of a powder was added to a 1 g sample of red flexo ink (Gamma Graphics).
  • the mixture was exposed to UV radiation while positioned within an FTIR machine to monitor the decrease in carbon- carbon double bonds within the mixture.
  • the curing rate was measured.
  • the photoinitiator had a curing rate relative to the CGI 369 photoinitiator of greater than 220%.
  • zinc chloride containing water was heated under an argon gas atmosphere to produce zinc chloride free of water.
  • Into a 250 ml, three-necked, round- bottom flask fitted with condenser, argon gas inlet, and bubbler outlet was placed 2.6 g ( 0.019 mole) of ZnCl 2 .
  • the flask was continuously flushed with argon while the ZnCl 2 was heated with a propane torch.
  • the ZnCl 2 was heated for about 15 minutes until it melted. Heating was continued for about ten minutes and then the ZnCl 2 was allowed to cool under an argon atmosphere.
  • the product was ground to form a powder, still under an argon atmosphere.
  • zinc chloride containing water was heated under an argon gas atmosphere to produce zinc chloride free of water.
  • Into a 1-liter, three-necked flask was placed 7.4 g ( 0.05 mole) of ZnCl 2 .
  • the flask was continuously flushed with argon while the ZnCl 2 was heated with a propane torch.
  • the ZnCl 2 was heated until it liquified. Heating was continued for about ten minutes and then the ZnCl 2 was allowed to cool.
  • the product was ground to form a powder, still under an argon atmosphere.
  • the resulting modified-369 compound had the following structure:
  • the yellow solid was found to have a similar retention time and UV absorption compared to IRGACURE® 369. However, the cure rate of a resin containing the yellow solid was 3 to 5 times faster than the cure rate of an identical resin containing the IRGACURE® 369 photoinitiator.
  • the flask was continuously flushed with argon and cooled in an ice bath. Into the flask was added 38.8 g (0.0275 mole) of boron trifluoride etherate. The reaction was carried out in the dark and stirred at 0°C for about 10 hours.
  • Zn-containing photoinitiator Two lots of Zn-containing photoinitiator were prepared as in Examples 2-5 above. The lots were designated Z1029 and Z106. Offset printing trials were performed at the Institute for Surface Modification (Leipzig, Germany) using Gerber Schmidt highly pigmented black ink compositions. The photoinitiator was added to the ink composition and mixed using a high speed vortex mixer. After mixing for about 15 minutes, the temperature was measured to be about 60 °C. Similar ink compositions were prepared using IRGACURE® 369.
  • a sheet-fed offset press manufactured by Heidelberg Press, Model No. GT052 was used to print sheets using the above ink compositions.
  • the press ran up to 8,000 sheets per hour.
  • the curing took place in a nitrogen atmosphere or in air.
  • the results of the printing test are given below in Table 1.
  • photoinitiator systems of the present invention consistently provided better cure than IRGACURE® 369 alone.
  • the photoinitiators of the present invention provided good cure results in a nitrogen atmosphere, as well as, in air.
  • zinc tetrafluoroborate available from Aldrich
  • a vacuum oven (0.01 mm Hg)
  • the dried solid and ether were mixed to form a 0.5M solution of zinc tetrafluoroborate in ether.
  • IRGACURE® 369 available from Ciba Geigy having the following structure
  • CYRACURE® UVR-6110 cycloaliphatic diepoxide, available from Union Carbide
  • a magnetic stirrer Into the beaker was added 0.1 g of the photoinitiator produced from Example 1, which was allowed to dissolved over a period of 2 minutes.
  • 2.5 g of UCAR- VAGH vinyl chloride-vinyl acetate-vinyl alcohol terpolymer, available from Union Carbide
  • UCAR- VAGH vinyl chloride-vinyl acetate-vinyl alcohol terpolymer, available from Union Carbide
  • Example 15 Into a 1-liter, three-necked round-bottom flask was placed 15.0 g (0.05 mole) of l-(2,6-dimethoxy-4- morpholinophenyl)-2-methylpropan-l-one produced in Example 13 and 150 ml. of glacial acetic acid. Hydrogen bromide gas was bubbled through the mixture for about 40 minutes. The product was then used in the next step, disclosed in Example 15.
  • Example 14 Into a 1 -liter, three-necked round-bottom flask was placed 19.1 g (0.05 mole) of the product produced in Example 14. The mixture was chilled to 5°C. To the chilled mixture was added dropwise 8.0 g of Br 2 over a period of about one hour. The mixture was then stirred for about one hour. The solvent was removed under vacuum to yield a pale yellow/orange solid. The yield of the final product was 20.9 g of product (92%).
  • a sample containing 0.1 g of the photoinitiator produced in Example 19 and 1.0 g of a red flexographic resin was prepared. A drop of the resin sample was drawn down on a white panel. The thin film was exposed to a 50W excimer lamp (308 nm). The resin fully cured after 4 flashes

Abstract

The present invention is directed to new, energy-efficient, photoinitiators having general formula (I) wherein X1 is a conjugated system such as one or more aryl groups or substituted aryl groups; Z1 is -O, -S, an alkyl group having from one to six carbon atoms, an ester moiety, a ketone moiety, an amine moiety, an imine moiety, an ether moiety, an aryl or substituted aryl group, a metal or non-metal, or a metal or non-metal containing group, such as a zinc-containing group or a boron-containing group, respectively; and M1 is an alkyl group, a substituted alkyl group, or forms a five member ring with Z1. The present invention is also directed to a method of generating a reactive species, which includes exposing one or more photoinitiators to radiation to form one or more reactive species. Also described are methods of polymerizing polymerizable materials, methods of curing an unsaturated oligomer/monomer mixture, and methods of laminating using the photoinitiators of the present invention. In addition, the present invention is directed to ink compositions, adhesive compositions and resins, and methods of printing using the above-described photoinitiators.

Description

CHELATES COMPRISING CHINOID GROUPS AS PHOTOINITIATORS
Technical Field
The present invention relates to novel photoinitiators and methods for generating a reactive species using the photoinitiators. The present invention further relates to methods of polymerizing or photocuring polymerizable material using the above-mentioned photoinitiators. The photoinitiators of the present invention find particular utility in photocurable inks as used in ink jet printers or on a printing press with and without nitrogen blanketing.
Background of the Invention
Polymers have served essential needs in society. For many years, these needs were filled by natural polymers. More recently, synthetic polymers have played an increasingly greater role, particularly since the beg vning of the 20th century. Especially useful polymers are those prepared by an addition polymerization mechanism, i.e., free radical chain polymerization of unsaturated monomers, and include, by way of example only, coatings and adhesives. In fact, the majority of commercially significant processes are based on free-radical chemistry. That is, chain polymerization is initiated by a reactive species, which often is a free radical. The source of the free radicals is termed an initiator or photoinitiator. Improvements in free radical chain polymerization have focused both on (1) more reactive monomer and pre- polymer materials and (2) the photoinitiator. Whether a particular unsaturated monomer can be converted to a polymer requires structural, thermodynamic, and kinetic feasibility. Even when all three exist, kinetic feasibility is achieved in many cases only with a specific type of photoinitiator. Moreover, the photoinitiator can have a significant effect on reaction rate which, in turn, may determine the commercial success or failure of a particular polymerization process or product.
A free radical-generating photoinitiator may generate free radicals in several different ways. For example, the thermal, homolytic dissociation of an initiator typically directly yields two free radicals per initiator molecule. A photoinitiator, i.e., an initiator which absorbs light energy, may produce free radicals by one of three pathways:
(1) the photoinitiator undergoes excitation by energy absorption with subsequent decomposition into one or more radicals;
(2) the photoinitiator undergoes excitation and the excited species interacts with a second compound (by either energy transfer or a redox reaction) to form free radicals from the latter and /or former compound(s); or (3) the photoinitiator undergoes an electron transfer to produce a radical cation and a radical anion.
While any free radical chain polymerization process should avoid the presence of species which may prematurely terminate the polymerization reaction, prior photoinitiators present special problems. For example, absorption of the light by the reaction medium may limit the amount of energy available for absorption by the photoinitiator. Also, the often competitive and complex kinetics involved may have an adverse effect on the reaction rate. Moreover, some commercially available radiation sources, such as medium and high pressure mercury and xenon lamps, may emit over a wide wavelength range, thus producing individual emission bands of relatively low intensity. Many photoinitiators only absorb over a small portion of the emission spectra and, as a consequence, much of the lamps' radiation remains unused. In addition, most known photoinitiators have only moderate "quantum yields" (generally less than 0.4) at these wavelengths, indicating that the conversion of light radiation to radical formation can be more efficient.
Many commercially available photoinitiators, including IRGACURE® 369, are presently used in ink compositions to accelerate ink drying in "radiation-drying printing/' As used herein, the term "radiation-drying printing'' refers to any prmting method which utilizes radiation as a drying means. Radiation-drying printing includes, for example, off-set prmting operations, such as on a Heidelberg press, flexographic printing, and flat-bed printing. Commercially available photoinitiator systems have a number of shortcomings. First, most of the commercially available photoinitiator systems require a relatively large amount of photoinitiator in the ink composition to fully cure/dry the ink composition. This leads to undesirable extractables within the ink composition. Second, most of the commercially available photoinitiator systems require a high energy radiation source to induce photocuring. Moreover, even with the high energy radiation source, often the cure results are unsatisfactory. Third, many commercially available photoinitiator systems are highly reactive to oxygen and must be used under a nitrogen blanket. Fourth, even with a large amount of photoinitiator and a high energy light source, the commercially available photoinitiator systems require a dry/cure time only accomplished by multiple passes, as many as 15 passes, under a light source, which significantly limits the output of a radiation-drying printing press.
What is needed in the art is a new class of energy- efficient photoinitiators having unsurpassed photoreactivity even when exposed to a low energy light source, such as a
50 W excimer cold lamp. What is also needed in the art is a new class of energy-efficient photoinitiators that may be cured in air, as well as, a nitrogen atmosphere. Further, what is needed in the art is a class of photoinitiators having unsurpassed photoreactivity, for use in the radiation-drying printing industry, which will significantly increase the output of a radiation-drying printing press due to reduction in ink drying/curing time.
Summary of the Invention
The present invention addresses some of the difficulties and problems discussed above by the discovery of energy-efficient photoinitiators having the following general formula:
Figure imgf000005_0001
wherein X2 is a conjugated system such as one or more aryl groups or substituted aryl groups; Zj is -O, -S, an alkyl group having from one to six carbon atoms, an ester moiety, a ketone moiety, an amine moiety, an imine moiety, an ether moiety, an aryl or substituted aryl group, a metal or non- metal, or a metal or non-metal containing group, such as a zinc-containing group or a boron-containing group, respectively; and M: is an alkyl group, a substituted alkyl group, or forms a five-member ring with Z . By selecting particular "Xi", "Z ', and "M ' groups, photoinitiators are produced having a desired absorption maximum, which substantially corresponds to an emission band of a radiation source and selectively varies from less than about 222 nm to greater than about 445 nm.
The present invention is directed to the above- described photoinitiators, compositions containing the same, and methods for generating a reactive species which includes providing one or more of the photoinitiators and irradiating the one or more photoinitiators. One of the main advantages of the photoinitiators of the present invention is that they efficiently generate one or more reactive species under extremely low energy lamps, such as excimer lamps and mercury lamps, as compared to prior art photoinitiators. The photoinitiators of the present invention also efficiently generate one or more reactive species in air or in a nitrogen atmosphere. Unlike many prior photoinitiators, the photoinitiators of the present invention are not sensitive to oxygen. Further, the photoinitiators of the present invention are as much as ten times faster than the best prior art photoinitiators. The present invention is further directed to a method of efficiently generating a reactive species by matching a photoinitiator having an absorption maximum to an emission band of a radiation source, which corresponds to the absorption maximum. By adjusting the substituents of the photoinitiator, one can shift the absorption maximum of the photoinitiator from less than about 222 nm to greater than 445 nm.
The present invention is also directed to methods of using the above-described photoinitiators to polymerize and /or photocure a polymerizable material. The photoinitiators of the present invention result in rapid curing times in comparison to the curing times of prior art photoinitiators, even with relatively low output lamps. The present invention includes a method of polymerizing an polymerizable material by exposing the polymerizable material to radiation in the presence of the efficacious wavelength specific photoinitiator composition described above. When an unsaturated oligomer/ monomer mixture is employed, curing is accomplished. The present invention further includes a film and a method for producing a film, by drawing an admixture of polymerizable material and one or more photoinitiators of the present invention, into a film and irradiating the film with an amount of radiation sufficient to polymerize the composition. The admixture may be drawn into a film on a nonwoven web or on a fiber, thereby providing a polymer- coated nonwoven web or fiber, and a method for producing the same.
The present invention is also directed to an adhesive composition comprising a polymerizable material admixed with one or more photoinitiators of the present invention. Similarly, the present invention includes a laminated structure comprising at least two layers bonded together with the above-described adhesive composition, in which at least one layer is a nonwoven web or film. Accordingly, the present invention provides a method of lammating a structure wherein a structure having at least two layers with the above-described adhesive composition between the layers is irradiated to polymerize the adhesive composition. The present invention is further directed to a method of printing, wherein the method comprises incorporating one or more photoinitiators of the present invention into an ink composition; printing the ink onto a substrate; and drying the ink with a source of radiation. These and other features and advantages of the present invention will become apparent after a review of the following detailed description of the disclosed embodiments and the appended claims. Detailed Description of the Invention
The present invention is directed to energy-efficient, reactive, photoinitiators and methods for utilizing the same. More particularly, the present invention is directed to new photoinitiators having the following general formula:
Figure imgf000008_0001
wherein X: comprises a conjugated system such as one or more aryl groups or substituted aryl groups; Z: is -O, -S, an alkyl group having from one to six carbon atoms, an ester moiety, a ketone moiety, an amine moiety, an imine moiety, an ether moiety, an aryl or substituted aryl group, a metal or non-metal, or a metal or non-metal containing group, such as a zinc-containing group or a boron-containing group, respectively; and M: comprises an alkyl group, a substituted alkyl group, or forms a five-member ring with Zλ.
The present invention is further directed to a method of efficiently generating a reactive species by matching a photoinitiator having an absorption maximum to an emission band of a radiation source, which corresponds to the absorption maximum. By adjusting the substituents of the photoinitiator, one can shift the absorption maximum of the photoinitiator from less than about 222 nm to greater than 445 nm.
The present invention also includes a method of polymerizing a polymerizable material by exposing the polymerizable material to electromagnetic radiation in the presence of one or more of the photoinitiators described above. Further, the present invention is directed to a film and a method for producing a film, by drawing an admixture of polymerizable material and one or more of the photoinitiators described above, into a film and irradiating the film with an amount of electromagnetic radiation sufficient to polymerize the admixture.
The present invention is further directed to an adhesive composition comprising a polymerizable material admixed and one or more photoinitiators of the present invention. Similarly, the present invention includes a laminated structure comprising at least two layers bonded together with the above-described adhesive composition. The present invention further provides a method of laminating a structure wherein a structure having at least two layers with the above-described adhesive composition between the layers is irradiated with appropriate electromagnetic radiation to polymerize the adhesive composition.
Definitions
As used herein, the term "reactive species" is used herein to mean any chemically reactive species including, but not limited to, free-radicals, cations, anions, nitrenes, and carbenes. Illustrated below are examples of several of such species. Examples of carbenes include, for example, methylene or carbene, dichlorocarbene, diphenylcarbene, alkylcarbonyl-carbenes, siloxycarbenes, and dicarbenes. Examples of nitrenes include, also by way of example, nitrene, alkyl nitrenes, and aryl nitrenes. Cations (sometimes referred to as carbocations or carbonium ions) include, by way of illustration, a proton; primary, secondary, and tertiary alkyl carbocations, such as methyl cation, ethyl cation, propyl cation, f-butyl cation, f-pentyl cation, -hexyl cation; allylic cations; benzylic cations; aryl cations, such as triphenyl cation; cyclopropylmethyl cations; methoxymethyl cation; triarylsulphonium cations; and acyl cations. Cations also include those formed from various metal salts, such as tetra-n-butylammonium tetrahaloaurate(III) salts; sodium tetrachloroaurate(III); vanadium tetrachloride; and silver, copper(I) and (II), and thallium(I) triflates. Examples of anions (sometimes referred to as carbanions) include, by way of example, alkyl anions, such as ethyl anion, π-propyl anion, isobutyl anion, and neopentyl anion; cycloalkyl anions, such as cyclopropyl anion, cyclobutyl anion, and cyclopentyl anion; allylic anions; benzylic anions; aryl cations; and sulfur- or phosphorus-containing alkyl anions. Finally, examples of organometallic photoinitiators include titanocenes, fluorinated diaryltitanocenes, iron arene complexes, manganese decacarbonyl, and methylcyclopentadienyl manganese tricarbonyl. Organometallic photoinitiators generally produce free radicals or cations. As used herein, the term "quantum yield" is used herein to indicate the efficiency of a photochemical process. More particularly quantum yield is a measure of the probability that a particular molecule will absorb a quantum of light during its interaction with a photon. The term expresses the number of photochemical events per photon absorbed.
Thus, quantum yields may vary from zero (no absorption) to 1.
As used herein, the term "polymerization" is used herein to mean the combining, e.g. covalent bonding, of a number of smaller molecules, such as monomers, to form large molecules, i.e., macromolecules or polymers. The monomers may be combined to form only linear macromolecules or they may be combined to form three-dimensional macromolecules, commonly referred to as crosslinked polymers.
As used herein, the term "curing" means the polymerization of functional oligomers and monomers, or even polymers, into a crosslinked polymer network. Thus, curing is the polymerization of unsaturated monomers or oligomers in the presence of crosslinking agents. As used herein, the terms "unsaturated monomer," "functional oligomer," and "crosslinking agent" are used herein with their usual meanings and are well understood by those having ordinary skill in the art. The singular form of each is intended to include both the singular and the plural, i.e., one or more of each respective material.
As used herein, the term "unsaturated polymerizable material" is meant to include any unsaturated material capable of undergoing polymerization. The term encompasses unsaturated monomers, oligomers, and crosslinking agents. Again, the singular form of the term is intended to include both the singular and the plural.
As used herein, the term "fiber" as used herein denotes a threadlike structure. The fibers used in the present invention may be any fibers known in the art. As used herein, the term "nonwoven web" as used herein denotes a web-like matter comprised of one or more overlapping or interconnected fibers in a nonwoven manner. It is to be understood that any nonwoven fibers known in the art may be used in the present invention.
Photoinitiators
The present invention is directed to new photoinitiators having the following general formula:
Figure imgf000011_0001
wherein X is a conjugated system such as one or more aryl groups or substituted aryl groups; Z^ is -O, -S, an alkyl group having from one to six carbon atoms, an ester moiety, a ketone moiety, an amine moiety, an imine moiety, an ether moiety, an aryl or substituted aryl group, a metal or non- metal, or a metal or non-metal containing group, such as a zinc-containing group or a boron-containing group, respectively; and Mλ is an alkyl group, a substituted alkyl group, or forms a five-member ring with Zλ. In one embodiment of the present invention, Xλ comprises
Figure imgf000012_0001
or
Figure imgf000012_0002
wherein R6 and R7 each independently represent hydrogen, an alkyl group having from one to six carbon atoms, an alkoxy group having from one to six carbon atoms, or a halogen-substituted alkyl group; and wherein γλ and y2 each independently represent a hydrogen, an alkyl group having from one to six carbon atoms, an aryl group,
Figure imgf000012_0003
or
Figure imgf000012_0004
wherein X3 represents a hydrogen, an alkyl or substituted alkyl group, or an aryl or substituted aryl group. Other suitable X: groups include, but are not limited to, the following:
Figure imgf000013_0001
Figure imgf000013_0002
or
Figure imgf000013_0003
Desirably, R6 and R7 each independently represent a methyl group, an ethyl group, an isopropyl group, a methoxy group, an ethoxy group, or a trifluoromethyl group.
In a further embodiment of the present invention, M: comprises a tertiary alkyl group having the following formula:
Y3 Y4
wherein y3 , y4 and y5 each independently represent a hydrogen, an alkyl group having from one to six carbon atoms, a tertiary amine group, an aryl group, or a substituted aryl group.
In one embodiment of the present invention, the photoinitiator has the following structure:
Figure imgf000014_0001
In the above structure, a calcium ion forms a five member ring, which includes the oxygen atom ("Z-,") and the electron-rich nitrogen atom. As used herein, an arrow represents a coordinate covalent bond between an electron- rich nitrogen atom and a metal or non-metal cation. It should be understood that other cations may be used instead of the calcium ion. Other suitable cations include, but are not limited to, beryllium, magnesium, strontium, barium, zinc, aluminum, and copper (II).
In a further embodiment, Z in the above-described general formula comprises an ester moiety. Examples of such photoinitiators include, but are not limited to, photoinitiators having the following structure:
Figure imgf000015_0001
or
Figure imgf000015_0002
In the above photoinitiators, it should be noted that the -C(0)CH3 group ("Zη") may be substituted with other groups including, but not limited to, -CH3, -BF3 and phenyl groups.
In yet a further embodiment, the photoinitiators of the present invention have the following general formula:
Figure imgf000015_0003
wherein X is as defined above; Z2 is a metal or non-metal cation, such as Zn2+, Ca2+, or boron, or a salt thereof, or -C(0)R, which forms a covalent bond with the oxygen atom; and R, Rl R2, R , and R4 are each independently a hydrogen atom, an alkyl or substituted alkyl group, or an aryl or substituted aryl group. In a further embodiment, Rτ and R2 may form one or more aromatic rings with X:.
Photoinitiators having the above formula include, but are not limited to, the following photoinitiators:
Figure imgf000016_0001
and
Figure imgf000016_0002
One photoinitiator of particular interest, having the above general formula, is shown below:
Figure imgf000016_0003
wherein Rπ, R12, R 3, and R14 are each independently a hydrogen atom; an alkyl group or substituted alkyl group.
In one embodiment of the present invention, the photoinitiator has the following structure:
Figure imgf000017_0001
In a further embodiment of the present invention, the photoinitiator has the following structure:
Figure imgf000017_0002
In the above structure, the calcium atom forms a five member ring, which includes the oxygen atom and the electron-rich nitrogen atom. It should be understood that other salts may be used instead of the calcium chloride. Other suitable salts include, but are not limited to, salts containing beryllium, magnesium, strontium, barium, zinc, aluminum, scandium, and copper (II). For example, another photoinitiator of the present invention may have the following structure:
Figure imgf000018_0001
In a further embodiment of the present invention, Rlr R2, and X1 of the above-described general formula form one or more aromatic rings to form a photoinitiator having the structure below:
Figure imgf000018_0002
wherein Z2, R3, and R4, are substituents as defined above and yn and y12 are each independently represent a hydrogen; an alkyl group having from one to six carbon atoms; an aryl group;
Figure imgf000018_0003
or
X,N wherein X3 is defined above.
The present invention is further directed to novel photoinitiators having the following general formula:
Figure imgf000019_0001
wherein Y is -O- or -N(R5)-; Zg is a metal or nonmetal cation or a salt containing the cation; and Xl7 Rlr R2, R3, R4, and R5 are as defined above. Suitable Z3 groups include, but are not limited to, metals and metal salts containing Cd, Hg, Zn, Al, Ga, In, Tl, Sc, Ge, Pb, Si, Ti, Sn, and Zr, as well as, nonmetals and nonmetal salts containing boron and phosphorus. Desirably, Z3 comprises a chloride-containing salt such as zinc chloride, zinc benzyl chloride, or boron chloride. Desirably, "R" comprises hydrogen, a methyl group, an ethyl group, a propyl group, or a benzyl group. Ln one embodiment of the present invention, the photoinitiator has the following structure:
Figure imgf000019_0002
wherein X4 comprises any nitrogen-containing group, which donates a pair of electrons to the nitrogen-carbon double bond; and Ri, R2, R3, R-i, Rό/ and R7 are as defined above. The above photoinitiator has an absorption maximum of about 360 nm. In a further embodiment of the present invention, the photoinitiator has the following structure:
Figure imgf000020_0001
wherein X , Ri, R2, R3, R4, Rό and R7 are as defined above. By replacing the zinc chloride with boron chloride, the absorption maximum of the photoinitiator shifts to about
410 nm.
Other photoinitiators of the present invention have the following structure:
Figure imgf000020_0002
wherein X4, Ri, R2, R3, R4 Rs, Rό/ and R7 are as defined above. In one embodiment of the present invention, the photoinitiator has the following structure:
Figure imgf000021_0001
wherein X4, Ri, R2, R3, R4/ Rs, Rό/ and R7 are as defined above. By replacing the oxygen atom with a nitrogen atom in the five member ring, the absorption maximum of the photoinitiator shifts further to greater than about 410 nm. It should be noted that other metal and nonmetal salts may be used in place of the metal and nonmetal chlorides. For example, the above photoinitiator may have the following structure:
Figure imgf000021_0002
The above-described photoinitiators of the present invention may be produced by the following reaction mechanism:
Figure imgf000021_0003
wherein a first compound reacts with a metal or metal salt or a nonmetal or nonmetal salt, Z3, to produce a photoinitiator of the present invention, having a five- member ring containing a metal or nonmetal atom, at least one nitrogen atom, two carbon atoms, and possibly an oxygen atom.
In a further embodiment of the present invention, the photoinitiators have the following general formula:
Figure imgf000022_0001
wherein Xυ Y, Rl R2, R3, R4, and R5 are as defined above; Z4 is a metal or nonmetal atom; and Z5 and Z^ are halogen- containing anions or form one or more rings with or without R3 or R4. In the above photoinitiator structure, the nitrogen atom donates its lone electron pair to metal or nonmetal atom, Z4, to form a five member ring. Suitable , Z4 groups include, but are not limited to, metals such as Cd,
Hg, Zn, Mg, Al, Ga, In, Tl, Sc, Ge, Pb, Si, Ti, Sn and Zr, as well as, nonmetals such as boron and phosphorus. Desirably, Z4 comprises Cd, Zn, Mg, Ti, boron or phosphorus. More desirably, Z4 comprises Zn. Suitable Z5 and Z^ groups include, but are not limited to, halogen- containing anions. Desirably, Z5 and Zg each independently comprise fluorine, chlorine or bromine-containing anions. More desirably, Z5 and Z6 each independently comprise fluorine-containing anions. Even more desirably, Z5 and Z6 each independently comprise BF4 , AsF6 , PF6 , or SbF6 .
Desirably, Rlf R2, R3, and R4 each independently comprise hydrogen, a methyl group, an ethyl group, a propyl group, or a benzyl group. In one embodiment of the present invention, the photoinitiator has the following structure:
Figure imgf000023_0001
wherein Xv Y, Ri, R , R3, R4, Z5, and Z6 are as defined above. In a further embodiment of the present invention, the photoinitiator has the following structure:
Figure imgf000023_0002
wherein X4, Ri, R2, R3, R4/ R5/ Rό/ R7/ Z5, and Z_ are as defined above. Other photoinitiators of the present invention have the following structure:
Figure imgf000023_0003
wherein X4, Ri, R2, R3/ R4 R5/ Rό/ R7/ Z5, and ^ are as defined above.
In yet a further embodiment, the photoinitiator of the present invention has the following structure:
Figure imgf000024_0001
wherein Z5 and Z^ are as defined above. In a further embodiment of the present invention, the photoinitiator of the present invention has the following structure:
Figure imgf000024_0002
The above-described photoinitiators of the present invention may be produced by the following reaction mechanism:
Figure imgf000025_0001
wherein a first compound reacts with a metal or nonmetal salt, Z4Z5Z6, to produce a photoinitiator of the present invention, having a five-member ring containing a metal or nonmetal atom, at least one nitrogen atom, two carbon atoms, and possibly an oxygen atom.
The present invention is further directed to novel photoinitiators having the following general structure:
Figure imgf000025_0002
wherein Y2 and Y3 each independently represent -O- or -Ν(R3)(R4)-; and Xλ, Ri, R2, R3, R4, Z4, Z5, and 7_ are as defined above. In one embodiment of the present invention,
Y3 represents -N(R3)(R4)- and Z5 and ^ form two five member rings: one five member ring which includes Z4, Z5, and Z6/ and one five member rings which includes with Z4, Z6 and one of R3 or R4. The resulting photoinitiator has the following structure:
Figure imgf000026_0001
wherein Z5, Zs and R4 comprise any combination of carbon, nitrogen and oxygen atoms to form two five member rings.
It should be noted that Z5, Ze and R4 may form two similar ring structures or two different ring structures. Also, each ring formed by Z5, Z6 and R4 may contain more than five ring members. In one embodiment of the present invention, the resulting photoinitiator has the following structure:
Figure imgf000026_0002
wherein Xi, Y2, Ri, R2 R3 and Z4 are as defined above; and n2 and n2 each independently represent an integer from 1 to 5. Desirably, the resulting photoinitiator has the following structure:
Figure imgf000027_0001
wherein Ri, R2, R3, Rό R7/ ni, and n are as defined above.
In a further embodiment of the present invention, Z5 and Zό form a single ring. The resulting photoinitiator has the following structure:
Figure imgf000027_0002
wherein Z5 and Zβ comprise any combination of carbon, nitrogen and oxygen atoms to form a ring. In one embodiment of the present invention, Z5 and Z^ form a five member ring so that the resulting photoinitiator has a dimeric structure. One example of the resulting photoinitiator has the following structure:
Figure imgf000028_0001
wherein Xi, Y2, Y3, Z4, Ri and R2 are as defined above.
Other photoinitiators of the present invention having the above-described structure include, but are not limited to, the following photoinitiators:
Figure imgf000028_0002
and
Figure imgf000029_0001
wherein Xi, Z4, R and R are as defined above. Other desirable photoinitiators include, but are not limited to, the following photoinitiators:
Figure imgf000029_0002
and
Figure imgf000029_0003
wherein Z4, Rlr R2, R3, R , R6 and R7 are as defined above. Desirably, Z4 comprises boron or zinc in the dimeric structures above. It should be understood that the above dimeric structures are only examples of suitable dimeric structures for the photoinitiators of the present invention. Any combination of ' ", "Z", "Y", and "R" groups may be used to form suitable dimeric structures for the photoinitiators of the present invention.
The resulting photoinitiators are relatively stable at room temperature (from about 15°C to 25°C) and normal room humidity (from about 5% to 60%; desirably from 5% to 30%). However, upon exposure to radiation at an appropriate wavelength, the photoinitiators efficiently produce one or more reactive species. The photoinitiators of the present invention have a high intensity of absorption. For example, the photoinitiators of the present invention have a molar extinction coefficient (absorptivity) greater than about 20,000 1 mole_1cm-l. As a further example, the photoinitiators of the present invention have a molar extinction coefficient greater than about 25,000 1 mole-lcm"1.
Method of Generating a Reactive Species and Applications
Therefor
The present invention is further directed to a method of generating a reactive species. The method of generating a reactive species involves generating a reactive species by exposing one or more of the above-described photoinitiators to radiation. The exposure of the photoinitiators to a radiation source triggers a photochemical process. As stated above, the term "quantum yield" is used herein to indicate the efficiency of a photochemical process. More particularly, quantum yield is a measure of the probability that a particular molecule (photoinitiator) will absorb a quantum of light during its interaction with a photon. The term expresses the number of photochemical events per photon absorbed. Thus, quantum yields may vary from zero (no absorption) to 1. The photoinitiators of the present invention absorb photons having a relatively specific wavelength and transfers the absorbed energy to one or more excitable portions of the molecule. The excitable portion of the molecule absorbs enough energy to cause a bond breakage, which generates one or more reactive species. The efficiency with which a reactive species is generated with the photoinitiators of the present invention is significantly greater than that experienced with photoinitiators of the prior art as indicated by faster cure times. For example, the photoinitiators of the present invention desirably will have a quantum yield greater than about 0.8. More desirably, the quantum yield of the photoinitiators of the present invention will be greater than about 0.9. Even more desirably, the quantum yield of the photoinitiators of the present invention will be greater than about 0.95. Still more desirably, the quantum yield of the photoinitiators of the present invention will be greater than about 0.99, with the most desirable quantum yield being about 1.0. Exposing the photoinitiators of the present invention to radiation results in the generation of one or more reactive species. Thus, the photoinitiators may be employed in any situation where reactive species are required, such as for the polymerization of an unsaturated monomer and the curing of an unsaturated oligomer/ monomer mixture. The unsaturated monomers and oligomers may be any of those known to one having ordinary skill in the art. In addition, the polymerization and curing media also may contain other materials as desired, such as pigments, extenders, amine synergists, and such other additives as are well known to those having ordinary skill in the art.
By way of illustration only, examples of unsaturated monomers and oligomers include ethylene, propylene, vinyl chloride, isobutylene, styrene, isoprene, acrylonitrile, acrylic acid, methacylic acid, ethyl acrylate, methyl methacrylate, vinyl acrylate, allyl methacrylate, tripropylene glycol diacrylate, trimethylol propane ethoxylate acrylate, epoxy acrylates, such as the reaction product of a bisphenol A epoxide with acrylic acid; polyether acrylates, such as the reaction product of acrylic acid with an adipic acid/ hexanediol-based polyether, urethane acrylates, such as the reaction product of hydroxypropyl acrylate with diphenylmethane-4,4'-diisocyanate, and polybutadiene diacrylate oligomer. The types of reactions that various reactive species enter into include, but are not limited to, addition reactions, including polymerization reactions; abstraction reactions; rearrangement reactions; elimination reactions, including decarboxylation reactions; oxidation-reduction (redox) reactions; substitution reactions; and conjugation/ deconjugation reactions.
Accordingly, the present invention also comprehends a method of polymerizing a polymerizable material, such as an unsaturated monomer or epoxy compound, by exposing the polymerizable material to radiation in the presence of the effacious photoinitiators of the present invention described above. When an unsaturated oligomer /monomer mixture is employed in place of an unsaturated monomer, curing is accomplished. It is to be understood that the polymerizable material admixed with the photoinitiators of the present invention is to be admixed by means known in the art, and that the mixture will be irradiated with an amount of radiation sufficient to polymerize the material. The amount of radiation sufficient to polymerize the material is readily determinable by one of ordinary skill in the art, and depends upon the identity and amount of photoinitiators, the identity and amount of the polymerizable material, the intensity and wavelength of the radiation, and the duration of exposure to the radiation. In one embodiment of the present invention, one or more photoinitiators of the present invention are used to polymerize an epoxy resin. It is believed that the following reaction mechanism takes place in the presence of a hydrogen-donating compound, such as an alcohol, cumene or amine:
HZ, and/or HZ-,
Figure imgf000033_0001
Reactive species, HZ2 and/or FLZ2, then react with an epoxy resin according to the following mechanism to produce a polyether:
Figure imgf000033_0002
Figure imgf000034_0001
The weak conjugate bases, Z{ and/or Z2 ~ , which are non- nucleophilic, enable the polymerization reaction to take place, unlike other anions, which may prematurely terminate the polymerization reaction.
Polymer Films, Coated Fibers and Webs, and Adhesive Compositions
The present invention further includes a film and a method for producing a film, by drawing an admixture of a polymerizable material and one or more photoinitiators of the present invention, into a film and irradiating the film with an amount of radiation sufficient to polymerize the composition. When the polymerizable material is an unsaturated oligomer/monomer mixture, curing is accomplished. Any film thickness may be produced, as per the thickness of the admixture formed, so long as the admixture sufficiently polymerizes upon exposure to radiation. The admixture may be drawn into a film on a nonwoven web or on a fiber, thereby providing a polymer- coated nonwoven web or fiber, and a method for producing the same. Any method known in the art of drawing the admixture into a film may be used in the present invention. The amount of radiation sufficient to polymerize the material is readily determinable by one of ordinary skill in the art, and depends upon the identity and amount of photoinitiator, the identity and amount of the polymerizable material, the thickness of the admixture, the intensity and wavelength of the radiation, and duration of exposure to the radiation. The present invention also includes an adhesive composition comprising a polymerizable material admixed with one or more photoinitiators of the present invention. Similarly, the present invention includes a laminated structure comprising at least two layers bonded together with the above-described adhesive composition. In one embodiment of the present invention, a laminate is produced wherein at least one layer is a cellulosic or polyolefin nonwoven web or film. Accordingly, the present invention provides a method of laminating a structure wherein a structure having at least two layers with the above-described adhesive composition between the layers is irradiated to polymerize the adhesive composition. When the unsaturated polymerizable material in the adhesive is an unsaturated oligomer/monomer mixture, the adhesive is irradiated to cure the composition.
It is to be understood that any layers may be used in the laminates of the present invention, on the condition that at least one of the layers allows sufficient radiation to penetrate through the layer to enable the admixture to polymerize sufficiently. Accordingly, any cellulosic or polyolefin nonwoven web or film known in the art may be used as one of the layers so long as they allow radiation to pass through. Again, the amount of radiation sufficient to polymerize the admixture is readily determinable by one of ordinary skill in the art, and depends upon the identity and amount of photoinitiator, the identity and amount of the polymerizable material, the thickness of the admixture, the identity and thickness of the layer, the intensity and wavelength of the radiation, and the duration of exposure to the radiation. The radiation to which the photoinitiators of the present invention may be exposed generally will 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 radiation; and near infrared radiation. Desirably, the radiation will have a wavelength of from about 100 to about 900 nanometers. More desirably, the radiation will have a wavelength of from about 100 to 700 nanometers. Desirably, the radiation will be ultraviolet radiation having a wavelength of from about 4 to about 400 nanometers. More desirably, the radiation will have a wavelength of from about 100 to about 420 nanometers, and even more desirably will have a wavelength of from 320 to about 420 nanometers. The radiation desirably will be incoherent, pulsed ultraviolet radiation from a dielectric barrier discharge excimer lamp or radiation from a mercury lamp.
Excimers are unstable excited-state 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. The dielectric barrier excimers in general emit in the range of from about 125 nm to about 500 nm, depending upon the excimer gas mixture.
Dielectric barrier discharge excimer lamps (also referred to hereinafter as "excimer lamp") are 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. 16671674 (1990); and E. Eliasson and U. Kogelschatz, "UV Excimer Radiation from Dielectric- Barrier Discharges." Appl. Phys. B. 46, pp. 299-303 (1988). Excimer lamps were developed by ABB Infocom Ltd., Lenzburg, Switzerland, and at the present time are available from Heraeus Noblelight GmbH, Kleinostheim, Germany. The excimer lamp emits incoherent, pulsed ultraviolet radiation. Such radiation has a relatively narrow bandwidth, i.e., the half width is of the order of approximately 5 to 100 nanometers. Desirably, the radiation will have a half width of the order of approximately 5 to 50 nanometers, and more desirably will have a half width of the order of 5 to 25 nanometers. Most desirably, the half width will be of the order of approximately 5 to 15 nanometers.
The ultraviolet radiation emitted from an excimer lamp can be emitted in a plurality of wavelengths, wherein one or more of the wavelengths within the band are emitted at a maximum intensity. Accordingly, a plot of the wavelengths in the band against the intensity for each wavelength in the band produces a bell curve. The "half width" of the range of ultraviolet radiation emitted by an excimer lamp is defined as the width of the bell curve at 50% of the maximum height of the bell curve.
The emitted radiation of an excimer lamp is incoherent and pulsed, the frequency of the pulses being dependent upon the frequency of the alternating current power supply which typically is in the range of from about 20 to about 300 kHz. An excimer lamp 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 and the claims. Thus, in comparison 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 essentially monochromatic. Although excimer lamps are highly desirable for use in the present invention, the source of radiation used with the photoinitiators of the present invention may be any radiation source known to those of ordinary skill in the art. In a further embodiment of the present invention, a mercury lamp with a D-bulb, which produces radiation having an emission peak of about 360 nm is used to produce free radicals from the above-described photoinitiators. This radiation source is particularly useful when matched with one or more photoinitiators of the present invention having an absorption maximum of about 360 nanometers, corresponding to the emission peak of the mercury lamp. Other specialty doped lamps, which emit radiation at about 420 nm, may be used with photoinitiators of the present invention which have an absorption maximum at about 420 nm. One lamp, the V-bulb available from Fusion Systems, is another suitable lamp for use in the present invention. In addition, specialty lamps having a specific emission band may be manufactured for use with one or more specific photoinitiators of the present invention. New lamp technology provides the following potential advantages:
(a) substantially single wavelength output;
(b) unique wavelength output; (c) high intensity; and
(d) absence of radiation trapping.
As a result of the photoinitiators of the present invention absorbing radiation in the range of about 250 to about 390 nanometers, some of the photoinitiators of the present invention will generate one or more reactive species upon exposure to sunlight. Accordingly, these photoinitiators of the present invention provides a method for the generation of reactive species that does not require the presence of a special light source. The photoinitiators of the present invention enable the production of adhesive and coating compositions that consumers can apply to a desired object and polymerize or cure upon exposure to sunlight. These photoinitiators also enable numerous industry applications wherein polymerizable materials may be polymerized merely upon exposure to sunlight. Therefore, depending upon how the photoinitiator is designed, the photoinitiator of the present invention can eliminate the cost of purchasing and maintaining light sources in numerous industries wherein such light sources are necessary without the photoinitiators of the present invention.
The effective tuning of the photoinitiators of the present invention for a specific wavelength band permits the photoinitiators of the present invention to more efficiently utilize the target radiation in the emission spectrum of the radiating source corresponding to the "tuned" wavelength band, even though the intensity of such radiation may be much lower than, for example, radiation from a narrow band emitter, such as an excimer lamp. For example, it may be desirable to utilize an excimer lamp, or other radiation emission source, that emits radiation having a wavelength of approximately 360 nm or 420 nm with the photoinitiators of the present invention. However, the effectiveness of the photoinitiators of the present invention is not necessarily dependent upon the availability or use of a narrow wavelength band radiation source.
Use of the Above-Described Photoinitiators in an Ink Composition
The above-described photoinitiators of the present invention may be incorporated into ink compositions. In one embodiment of the present invention, one or more of the photoinitiators are incorporated into an ink jet ink composition for use on ink jet ink printers. The ink composition may be used on commercially available ink jet printing machines alone or in combination with a radiation source in series with the ink jet printing machine for instantaneous curing of the ink jet ink composition. Any radiation source known to those of ordinary skill in the art may be used to cure the ink jet ink composition. Desirably, one of the above-described radiation sources is used to cure the ink composition.
Use of the Above-Described Photoinitiators in Other
Radiation-Drying Printing Process
A further use of the above-described photoinitiators of the present invention involves the incorporation of one or more of the photoinitiators into an ink composition for use on a radiation-drying printing press. As discussed above,
"radiation-drying printing" refers to any printing method which utilizes radiation as a drying means. Radiation- drying printing includes, for example, off-set printing operations, such as on a Heidelberg press, flexographic printing, and flat-bed printing.
The photoinitiators of the present invention enable increased press output due to the photoreactivity of the photoinitiators. Further, the increased output may be obtained while using a minimal amount of photoinitiator and a low energy light source. In one embodiment of the present invention, complete curing at an output rate of 10,000 printed sheets per hour may be obtained using a 50 W cold lamp as the light source.
Any of the above-described photoinitiators may be used in the printing processes disclosed herein. Desirably, the amount of photoinitiator added to the ink composition, adhesive composition or resin is less than about 4.0 wt% of the total weight of the composition. More desirably, the amount of photoinitiator added to the composition is from about 0.25 to about 3.0 wt% of the total weight of the composition. Most desirably, the amount of photoinitiator added to the composition is from about 0.25 to about 2.0 wt% of the total weight of the composition.
A major advantage of the photoinitiators of the present invention is that they enable rapid curing times of ink compositions, adhesive compositions and/or resins in comparison to the curing times of prior art photoinitiators. Ink compositions containing the photoinitiators of the present invention possess rapid curing times from 5-10 times faster than the curing times of ink compositions containing the best known photoinitiators. The use of the photoinitiators of the present invention in ink compositions, adhesive compositions or resins for printing presses enables print speeds, which were at one time thought to be unobtainable. For example, in an open air printing process using a Heidelberg print press and a 50 W excimer cold lamp for photocuring, desirably the printed sheet output is greater than 6,000 sheets per hour. More desirably, the printed sheet output is greater than 8,000 sheets per hour. Most desirably, the printed sheet output is greater than
10,000 sheets per hour.
The present invention is further described by the examples which follow. Such examples, however, are not to be construed as limiting in any way either the spirit or the scope of the present invention. In the examples, all parts are by weight, unless stated otherwise.
COMPARATIVE EXAMPLE 1 Photocuring of CGI 369 in Red Flexo Resin
A mixture of Ciba Geigy photoinitiator 369 (CGI 369) in the form of a powder was added to a 1 g sample of red flexo ink (Gamma Graphics). The mixture was exposed to UV radiation while positioned within an FTIR machine to monitor the decrease in carbon-carbon double bonds within the mixture. The curing rate was measured.
EXAMPLE 1
Photocuring of One of KC's New Photoinitiators in Red
Flexo Resin A mixture of αmberly Clark's photoinitiator, having the following structure, in the form of a powder was added to a 1 g sample of red flexo ink (Gamma Graphics).
Figure imgf000042_0001
The mixture was exposed to UV radiation while positioned within an FTIR machine to monitor the decrease in carbon- carbon double bonds within the mixture. The curing rate was measured. The photoinitiator had a curing rate relative to the CGI 369 photoinitiator of greater than 220%.
EXAMPLE 2
Method of Forming a l-(p -fluorophenyl) -2- dimethylamine- ethanone Intermediate to a Photoinitiator of the Present
Invention The following reaction was carried out as detailed below:
Figure imgf000042_0002
Into a three-necked round-bottom flask was placed 200 ml of anhydrous diethyl ether with stirrer bar and bubbler inlet. The ether was cooled to 0°C. Dimethyl amine was bubbled into the solvent for 1 hour to make a saturated solution. Into the flask was placed 10.0 g (0.046 mole) of 1- p-fluorophenacyl bromide dissolved in 50 ml of ether over a period of about 20 minutes. The temperature of the mixture was kept at 0°C for about 4 hours and then allowed to raise to room temperature overnight. The reaction mixture was then filtered to remove the dimethyl amine hydroxide and the solvent to yield a yellow oil. The oil was pumped in a vacuum oven and used in further examples without further purification. The final product was l-(p-fluorophenyl)-2- dimethylamine-ethanone and the yield of the reaction was 7.5 g of oil (94%).
EXAMPLE 3 Method of Forming a l-(p-fluorophenyl)-2-dimethylamine- 2-methyl-propanone Intermediate to a Photoinitiator of the Present Invention
The following reaction was carried out as detailed below:
Figure imgf000043_0001
Into a 1-liter, round-bottom flask was placed 5.0 g (0.028 mole) of the l-(p-fluorophenyl)-2-dimethylamine- ethanone compound of Example 1, 8.6 g (0.062 mole) of methyl iodide, and 330 ml of acetonitrile. The reaction mixture was stirred for about 4 hours. The solvent was then removed and replaced with 300 ml of water and 7.3 g of a 34 wt% solution of sodium hydroxide (0.07 mole). The reaction mixture was then heated at about 55°C to 60°C for about 1 hour. On cooling, the reaction mixture was extracted with ether, and dried over magnesium sulfate. The solvent was removed under reduced pressure to yield an oil which was pumped in the vacuum oven. The product crystallized in a refrigerator overnight. The final product was measured to be 4.1 g of l-(p-fluorophenyl)-2-dimethylamine-2-methyl- propanone and the yield was found to be about 71%.
EXAMPLE 4 Method of Forming a Piperazine-Containing Intermediate to a Photoinitiator of the Present Invention
The following reaction was carried out as detailed below:
Figure imgf000044_0001
Into a 250 ml, round-bottom flask was placed 1.4 g
(0.01 mole) of potassium carbonate, 2.0 g of the product from Example 2, 0.86 g (0.01 mole) of piperazine, and 20 ml of N,N-dimethylformamide (DMF). The mixture was flushed with argon for about 20 minutes prior to heating at reflux. The reaction mixture was heated at reflux for about
16 hours. HPLC indicated a 80% conversion to the desired product shown below (This was the only compound having a 325 nm UV absorption peak.) The crude product was recrystallized from ethanol to yield a pale yellow solid. The yield of the reaction was 1.8 g of l-piperazine-2- dimethylamine-2-methyl-propanone (69%) .
EXAMPLE 5 Method of Forming a Zn-Containing Photoinitiator of the
Present Invention The following reaction was carried out as detailed below:
Figure imgf000045_0001
In order to form one of the photoinitiators of the present invention, zinc chloride containing water was heated under an argon gas atmosphere to produce zinc chloride free of water. Into a 250 ml, three-necked, round- bottom flask fitted with condenser, argon gas inlet, and bubbler outlet was placed 2.6 g ( 0.019 mole) of ZnCl2. The flask was continuously flushed with argon while the ZnCl2 was heated with a propane torch. The ZnCl2 was heated for about 15 minutes until it melted. Heating was continued for about ten minutes and then the ZnCl2 was allowed to cool under an argon atmosphere. The product was ground to form a powder, still under an argon atmosphere.
The resulting ZnCl2, 80 ml of benzene, and 8 g of the 1 - morpholino-2-dimethylamine-2-methyl-propanone produced in Example 4 were heated at reflux for about 12 hours in an argon atmosphere. The solution was then cooled and filtered. The solvent was removed under reduced pressure to yield a yellow powder. The powder was pumped in a vacuum oven at ambient temperature to yield 6.9 g of photoinitiator (yield 79%) having the structure above.
Samples of the yellow solid were mixed into offset black resins (GERBER-SCHMIDT GmbH, Frankfurt, Germany) at 2.0 wt% based on the total weight of the resin. The resins were drawn down into a thin film and exposed to an excimer lamp (308 nm). The resins fully cured after 1-2 flashes (0.05 seconds /flash). The control prepared with IRGACURE® 369 (available from Ciba Geigy) took 6-8 flashes and was still not fully cured.
EXAMPLE 6 Method of Forming a New Zn-Containing Photoinitiator
In order to form one of the photoinitiators of the present invention, zinc chloride containing water was heated under an argon gas atmosphere to produce zinc chloride free of water. Into a 1-liter, three-necked flask was placed 7.4 g ( 0.05 mole) of ZnCl2. The flask was continuously flushed with argon while the ZnCl2 was heated with a propane torch. The ZnCl2 was heated until it liquified. Heating was continued for about ten minutes and then the ZnCl2 was allowed to cool. The product was ground to form a powder, still under an argon atmosphere.
The resulting ZnCl2, 200 ml of benzene, and 20 g (0.05 mole) of IRGACURE® 369 (available from Ciba Geigy) having the following structure
Figure imgf000046_0001
were heated at reflux for about 12 hours in an argon atmosphere. The solution was then cooled and filtered. The solvent was removed under reduced pressure.
The resulting modified-369 compound had the following structure:
Figure imgf000047_0001
The yellow solid was found to have a similar retention time and UV absorption compared to IRGACURE® 369. However, the cure rate of a resin containing the yellow solid was 3 to 5 times faster than the cure rate of an identical resin containing the IRGACURE® 369 photoinitiator.
Samples of the yellow solid were mixed into offset and flexo resins (GERBER-SCHMIDT GmbH, Frankfurt, Germany) at 2.0 and 3.0 wt% based on the total weight of the resin. The resins were printed onto white plates and exposed to an excimer lamp (308 nm) or a mercury lamp (360 nm). The resins rapidly cured.
EXAMPLE 7
Method of Forming a New BF ^-Containing Photoinitiator Into a 1-liter, three-necked flask was placed 100 g
(0.275 mole) of IRGACURE® 369 and 500 ml of dry benzene.
The flask was continuously flushed with argon and cooled in an ice bath. Into the flask was added 38.8 g (0.0275 mole) of boron trifluoride etherate. The reaction was carried out in the dark and stirred at 0°C for about 10 hours.
A yellow precipitate formed and was filtered. The solvent was removed under reduced pressure to yield 82.1 g (69% yield) of a yellow solid. HPLC indicated a different retention time and a UV absorption at about 415 nm.
Samples of the yellow solid were mixed into offset and flexo resins at 2.0 and 3.0 wt% based on the total weight of the resin. The resins were rapidly cured when printed onto white plates and exposed to a Fusion Systems 'V Bulb (420 nm).
EXAMPLE 8 Method of Forming a New BCl3-Containing Photoinitiator
Into a 1 -liter, three-necked flask was placed 10 g (0.027 mole) of IRGACURE® 369 and 50 ml of dry benzene. The flask was continuously flushed with argon and cooled in an ice bath. Into the flask was added 3.16 g (0.027 mole) of boron trichloride in xylene. The reaction was stirred overnight at 0°C for about 10 hours.
A yellow precipitate formed and was filtered. The solvent was removed under reduced pressure to yield 11.2 g (86% yield) of a yellow solid. HPLC indicated a retention time and a UV absorption similar to IRGACURE® 369.
Samples of the yellow solid were mixed into offset resins at 2.0 wt% based on the total weight of the resin. The resins were rapidly cured when drawn down onto white plates and exposed to an excimer lamp (308 nm).
EXAMPLE 9 Offset Printing Using Photoinitiators of the Present
Invention Two lots of Zn-containing photoinitiator were prepared as in Examples 2-5 above. The lots were designated Z1029 and Z106. Offset printing trials were performed at the Institute for Surface Modification (Leipzig, Germany) using Gerber Schmidt highly pigmented black ink compositions. The photoinitiator was added to the ink composition and mixed using a high speed vortex mixer. After mixing for about 15 minutes, the temperature was measured to be about 60 °C. Similar ink compositions were prepared using IRGACURE® 369.
A sheet-fed offset press manufactured by Heidelberg Press, Model No. GT052, was used to print sheets using the above ink compositions. The press ran up to 8,000 sheets per hour. The curing took place in a nitrogen atmosphere or in air. The results of the printing test are given below in Table 1.
Figure imgf000049_0001
Figure imgf000050_0002
*** Test was run in air, as opposed to a nitrogen atmosphere.
As shown in Table 1, photoinitiator systems of the present invention consistently provided better cure than IRGACURE® 369 alone. The photoinitiators of the present invention provided good cure results in a nitrogen atmosphere, as well as, in air.
EXAMPLE 10 Method of Forming a New Cationic Photoinitiator
In order to form one of the photoinitiators of the present invention, zinc tetrafluoroborate (available from Aldrich) was heated overnight at 50 °C in a vacuum oven (0.01 mm Hg) to produce zinc tetrafluoroborate free of water. The dried solid and ether were mixed to form a 0.5M solution of zinc tetrafluoroborate in ether.
Four grams (0.01 mole) of IRGACURE® 369 (available from Ciba Geigy) having the following structure
Figure imgf000050_0001
was dissolved in 100 ml of ether (anhydrous) in a three- necked round bottom flask fitted with stirrer bar, argon gas bubbler, and condenser. To this solution was added, via a syringe, 21.5 ml of the 0.5M Zn(BF4)2 ether solution over 10 minutes. The clear solution turned cloudy. A white precipitate formed over a period of an hour. The white precipitate was filtered on a Buckner funnel and washed with 100 ml of anhydrous ether. The powder was then pumped in a vacuum for over an hour at room temperature.
The resulting compound had the following structure:
Figure imgf000051_0001
EXAMPLE 11 Curing Process Using a Cationic Photoinitiator
In a beaker 8.5 g of CYRACURE® UVR-6110 (cycloaliphatic diepoxide, available from Union Carbide) was heated to 50°C while stirring with a magnetic stirrer. Into the beaker was added 0.1 g of the photoinitiator produced from Example 1, which was allowed to dissolved over a period of 2 minutes. Into the beaker, 2.5 g of UCAR- VAGH (vinyl chloride-vinyl acetate-vinyl alcohol terpolymer, available from Union Carbide) was slowly added while stirring resulting in a clear solution after about 3 minutes. A drop of the mixture was drawn down onto a metal plate. The film was exposed to a medium pressure mercury arc lamp. The film immediately went from being tacky to fully cured.
EXAMPLE 12 Method of Forming a l-(2,6-dimethoxy-4-fluorophenyl)-2- methylpropan-1-one Intermediate to a Photoinitiator of the
Present Invention The following reaction was carried out as detailed below:
Figure imgf000052_0001
Into a 1-liter, three-necked round-bottom flask was placed 20.0 g (0.13 mole) of l,3-dimethoxy-5-fluorobenzene, 13.6 g (0.0.13 mole) of 2-methylpropanoyl chloride, and 100 ml of nitrobenzene. The mixture was flushed with argon and an equal molar amount of A1C13 (17.2 g) was added to the reaction mixture while stirring at 5°C. The mixture was stirred at a temperature of 5°C for about 1 hour after the addition of the A1C13. The reaction mixture was then mixed with about 100 ml of distilled water and extracted with dichloromethane. The organic layer was washed with NaHC03 solution, salt water, and then dried. The solvent was removed by vacuum to yield the final product, l-(2,6- dimethoxy-4-fluorophenyl)-2-methylpropan-l-one. The yield of the reaction was 22.8 g of product (77%). EXAMPLE 13 Method of Forming a Morpholino -Containing Intermediate to a Photoinitiator of the Present Invention The following reaction was carried out as detailed below:
Figure imgf000053_0001
Into a 1-liter, three-necked round-bottom flask was placed 15.0 g (0.07 mole) of l-(2,6-dimethoxy-4- fluorophenyl)-2-methylpropan-l-one produced in Example
12, 5.8 g (0.07 mole) of morpholine, and 19.0 g (0.14 mole) of K2COs in 100 ml. of dimethvlsulf oxide (DMSO). The mixture was flushed with argon and heated to reflux overnight. The reaction mixture was cooled and then mixed with about 100 ml of distilled water and extracted with dichloromethane. The organic layer was washed with NaHC03 solution, salt water, and then dried. The solvent was removed by vacuum to yield the final product, l-(2,6- dimethoxy-4-morpholinophenyl)-2-methylpropan-l-one. The yield of the reaction was 18.1 g of product (88%).
EXAMPLE 14
Method of Forming a Morpholino -Containing Bromide Salt Intermediate to a Photoinitiator of the Present Invention
The following reaction was carried out as detailed below:
Figure imgf000054_0001
Into a 1-liter, three-necked round-bottom flask was placed 15.0 g (0.05 mole) of l-(2,6-dimethoxy-4- morpholinophenyl)-2-methylpropan-l-one produced in Example 13 and 150 ml. of glacial acetic acid. Hydrogen bromide gas was bubbled through the mixture for about 40 minutes. The product was then used in the next step, disclosed in Example 15.
EXAMPLE 15 Method of Forming a Morpholino -Containing Bromide- Containing Salt Intermediate to a Photoinitiator of the
Present Invention The following reaction was carried out as detailed below:
Figure imgf000054_0002
Into a 1 -liter, three-necked round-bottom flask was placed 19.1 g (0.05 mole) of the product produced in Example 14. The mixture was chilled to 5°C. To the chilled mixture was added dropwise 8.0 g of Br2 over a period of about one hour. The mixture was then stirred for about one hour. The solvent was removed under vacuum to yield a pale yellow/orange solid. The yield of the final product was 20.9 g of product (92%).
EXAMPLE 16
Method of Forming a Morpholino-Containing Bromide- Containing Salt Intermediate to a Photoinitiator of the
Present Invention The following reaction was carried out as detailed below:
+ H2N(CH2)2NH(CH2)2NH2
Figure imgf000055_0001
Figure imgf000055_0002
Into a 1-liter, three-necked round-bottom flask was placed 15.0 g (0.03 mole) of the product produced in Example 17, 3.1 g (0.03 mole) of diethylenetriamine, 8.2 g (0.06 mole) of K2C03, and 100 ml. of toluene. The mixture was heated at reflux overnight. The solvent was removed under vacuum to yield a yellow solid. The yield of the final product was 8.7 g of product (74%). EXAMPLE 17 Method of Forming a Zn-complex Photoinitiator of the
Present Invention The following reaction was carried out as detailed below:
Figure imgf000056_0001
ether/toluene
Figure imgf000056_0002
Into a 1 -liter, three-necked round-bottom flask was placed 5.0 g (0.013 mole) of the product produced in Example 18 and 50 ml. of toluene. To the mixture was slowly added 1.72 g (0.013 mole) of Zn(OEt2) 2C12 in ether (i.e., 21 ml. of a 0.6M solution of Zn(OEt2) 2C12 in ether). The reaction materials were stored for about one hour at room temperature. The solvent was removed under vacuum to yield a yellow solid. The yield of the final product was 5.4 g of product (96%). EXAMPLE 18
Testing of Zn-Containing Photoinitiator of the Present
Invention in a Red Flexographic Resin
A sample containing 0.1 g of the photoinitiator produced in Example 19 and 1.0 g of a red flexographic resin was prepared. A drop of the resin sample was drawn down on a white panel. The thin film was exposed to a 50W excimer lamp (308 nm). The resin fully cured after 4 flashes
(0.01 seconds /flash).
While the specification has been described in detail with respect to specific embodiments thereof, it will be appreciated that those skilled in the art, upon attaining an understanding of the foregoing, may readily conceive of alterations to, variations of, and equivalents to these embodiments. Accordingly, the scope of the present invention should be assessed as that of the appended claims and any equivalents thereto.

Claims

ClaimsWhat is claimed is:
1. A photoinitiator having the following formula:
^
X, =C
\
M,
wherein Xλ comprises a conjugated system of one or more aryl groups or substituted aryl groups; Zλ comprises -O, -S, an alkyl group having from one to six carbon atoms, an ester moiety, a ketone moiety, an amine moiety, an imine moiety, an ether moiety, an aryl or substituted aryl group, a metal or non-metal, or a metal or non-metal contaming group; and M1 comprises an alkyl group, a substituted alkyl group, or forms a five-member ring with Zλ.
2. The photoinitiator of Claim 1, wherein X1 comprises
Figure imgf000058_0001
Figure imgf000059_0001
or
Figure imgf000059_0002
wherein R6 and R7 each independently represent hydrogen, an alkyl group having from one to six carbon atoms, an alkoxy group having from one to six carbon atoms, or a halogen-substituted alkyl group; and wherein y-, and y2 each independently represent a hydrogen, an alkyl group having from one to six carbon atoms, an aryl group,
Q
or
Figure imgf000059_0003
wherein X3 represents a hydrogen, an alkyl or substituted alkyl group, or an aryl or substituted aryl group.
3. The photoinitiator of Claim 1, wherein M^ comprises a tertiary alkyl group having the following formula:
Figure imgf000060_0001
wherein y3 , y4 and y5 each independently represent a hydrogen, an alkyl group having from one to six carbon atoms, a tertiary amine group, an aryl group, or a substituted aryl group.
4. The photoinitiator of Claim 1, wherein Mλ and Z1 form a five-member ring.
5. The photoinitiator of Claim 4, wherein the photoinitiator has the following structure:
Figure imgf000060_0002
wherein Z2 is a metal or non-metal atom, a metal or non- metal containing salt, or -C(0)R, which forms a covalent bond with the oxygen atom; R, R3 and R4 are each independently a hydrogen atom, an alkyl or substituted alkyl group, or an aryl or substituted aryl group; and R^ and R2 are each independently a hydrogen atom, an alkyl or substituted alkyl group, or an aryl or substituted aryl group, or form one or more aromatic rings with Xv
6. The photoinitiator of Claim 5, wherein Rl R2, and X-i form a photoinitiator having the structure below:
Figure imgf000061_0001
wherein yπ and y12 are each independently represent a hydrogen, an alkyl group having from one to six carbon atoms, an aryl group,
Figure imgf000061_0002
or
Figure imgf000061_0003
wherein X3 represents a hydrogen, an alkyl or substituted alkyl group, or an aryl or substituted aryl group.
7. The photoinitiator of Claim 5, wherein the photoinitiator comprises
Figure imgf000062_0001
or
Figure imgf000062_0002
or
Figure imgf000062_0003
or
Figure imgf000063_0001
8. The photoinitiator of Claim 4, wherein the photoinitiator has the following structure:
Figure imgf000063_0002
wherein Y is -O- or -N(R5)-; Z3 is a metal or nonmetal cation or a salt containing the cation; R3 and R4 are each independently a hydrogen atom, an alkyl or substituted alkyl group, or an aryl or substituted aryl group; and R1 and R2 are each independently a hydrogen atom, an alkyl or substituted alkyl group, or an aryl or substituted aryl group, or form one or more aromatic rings with X1.
9. The photoinitiator of Claim 4, wherein the photoinitiator has the following structure:
Figure imgf000064_0001
wherein Y2 and Y3 each independently represent -O- or -N(R3)(R4)-; R3, and R4 are each independently a hydrogen atom, an alkyl or substituted alkyl group, or an aryl or substituted aryl group; R^ and R2 are each independently a hydrogen atom, an alkyl or substituted alkyl group, or an aryl or substituted aryl group or form one or more aromatic rings with X^ Z4 is a metal or nonmetal atom; and Z5 and Z6 are halogen-containing anions or form one or more rings with or without R3 or R4.
10. The photoinitiator of Claim 9, wherein Z4 comprises Cd, Hg, Zn, Mg, Al, Ga, In, TI, Sc, Ge, Pb, Si, Ti, Sn, Zr, boron or phosphorus.
11. The photoinitiator of Claim 9, wherein Z5 and Z6 each independently comprise fluorine, chlorine or bromine- containing anions.
12. The photoinitiator of Claim 9, wherein the photoinitiator comprises
Figure imgf000065_0001
wherein R6 and R7 each independently represent hydrogen, an alkyl group having from one to six carbon atoms, an alkoxy group having from one to six carbon atoms, or a halogen-substituted alkyl group.
13. The photoinitiator of Claim 9, wherein the photoinitiator has the following structure:
Figure imgf000065_0002
wherein X4 comprises any nitrogen-containing group, which donates a pair of electrons to the nitrogen-carbon double bond; and R6 and R7 each independently represent hydrogen, an alkyl group having from one to six carbon atoms, an alkoxy group having from one to six carbon atoms, or a halogen-substituted alkyl group.
14. The photoinitiator of Claim 8, wherein the photoinitiator has the following structure:
Figure imgf000066_0001
wherein X4 comprises any nitrogen-containing group, which donates a pair of electrons to the nitrogen-carbon double bond; and R6 and R7 each independently represent hydrogen, an alkyl group having from one to six carbon atoms, an alkoxy group having from one to six carbon atoms, or a halogen-substituted alkyl group.
15. The photoinitiator of Claim 9, wherein the photoinitiator has the following structure:
Figure imgf000066_0002
Figure imgf000066_0003
Figure imgf000067_0001
or
Figure imgf000067_0002
16. A method of generating a reactive species, comprising: irradiating the canonic photoinitiator of Claim 1 with radiation.
17. A method of polymerizing a polymerizable material, comprising: irradiating an admixture of a polymerizable material and the photoinitiator of Claim 1.
PCT/US1999/022590 1998-09-28 1999-09-28 Chelates comprising chinoid groups as photoinitiators WO2000018750A2 (en)

Priority Applications (9)

Application Number Priority Date Filing Date Title
BRPI9914123-0A BR9914123B1 (en) 1998-09-28 1999-09-28 photoinitiators and applications therefor.
AU13098/00A AU1309800A (en) 1998-09-28 1999-09-28 Novel photoinitiators and applications therefor
PL99366326A PL366326A1 (en) 1998-09-28 1999-09-28 Novel photoinitiators and applications therefor
JP2000572210A JP2003533548A (en) 1998-09-28 1999-09-28 Chelates containing quinoid groups as photopolymerization initiators
CA002353685A CA2353685A1 (en) 1998-09-28 1999-09-28 Chelates comprising chinoid groups as photoinitiators
DE69930948T DE69930948T2 (en) 1998-09-28 1999-09-28 CHELATE WITH CHINOIDS GROUPS AS PHOTOINITIATORS
EP99956500A EP1117698B1 (en) 1998-09-28 1999-09-28 Chelates comprising chinoid groups as photoinitiators
ES99956500T ES2263291T3 (en) 1998-09-28 1999-09-28 CHEATS THAT INCLUDE QUINOID GROUPS AS PHOTOINIATORS.
SK417-2001A SK4172001A3 (en) 1998-09-28 1999-09-28 Chelates comprising chinoid groups as photoinitiators

Applications Claiming Priority (10)

Application Number Priority Date Filing Date Title
US10215398P 1998-09-28 1998-09-28
US60/102,153 1998-09-28
US11195098P 1998-12-11 1998-12-11
US60/111,950 1998-12-11
US12130299P 1999-02-23 1999-02-23
US60/121,302 1999-02-23
US12493999P 1999-03-18 1999-03-18
US60/124,939 1999-03-18
US13263099P 1999-05-05 1999-05-05
US60/132,630 1999-05-05

Publications (4)

Publication Number Publication Date
WO2000018750A2 WO2000018750A2 (en) 2000-04-06
WO2000018750A3 WO2000018750A3 (en) 2000-08-03
WO2000018750A8 WO2000018750A8 (en) 2000-09-28
WO2000018750A9 true WO2000018750A9 (en) 2001-07-26

Family

ID=27537029

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1999/022590 WO2000018750A2 (en) 1998-09-28 1999-09-28 Chelates comprising chinoid groups as photoinitiators

Country Status (12)

Country Link
US (1) US6265458B1 (en)
EP (1) EP1117698B1 (en)
JP (1) JP2003533548A (en)
AT (1) ATE323725T1 (en)
AU (1) AU1309800A (en)
BR (1) BR9914123B1 (en)
CA (1) CA2353685A1 (en)
DE (1) DE69930948T2 (en)
ES (1) ES2263291T3 (en)
PL (1) PL366326A1 (en)
SK (1) SK4172001A3 (en)
WO (1) WO2000018750A2 (en)

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BR0109086A (en) * 2000-03-10 2003-06-03 Novartis Ag Reactive Polymers
EP1351946A2 (en) 2000-09-01 2003-10-15 Icos Corporation Materials and methods to potentiate cancer treatment
EP2236488A1 (en) 2001-03-30 2010-10-06 The Arizona Board of Regents on behalf of the University of Arizona Materials, methods and uses for photochemical generation of acids and/or radical species
JP2004043433A (en) * 2002-04-26 2004-02-12 Kitai Kagi Kofun Yugenkoshi Morpholinoketone derivative and its use
US20040029044A1 (en) * 2002-08-08 2004-02-12 3M Innovative Properties Company Photocurable composition
EP1660473A2 (en) 2003-03-24 2006-05-31 Luitpold Pharmaceuticals, Inc. Xanthones, thioxanthones and acridinones as dna-pk inhibitors
KR100529371B1 (en) * 2003-07-29 2005-11-21 주식회사 엘지화학 Catalyst precursor resin composition and preparation method of light-penetrating electro-magnetic interference shielding material using the same
US7262229B2 (en) * 2004-05-03 2007-08-28 Flint Group Ink for excimer curing
GB2420117A (en) * 2004-11-10 2006-05-17 Sun Chemical Ltd Piperazino based multi-functional photoinitiators
US8063115B2 (en) 2006-11-23 2011-11-22 Agfa Graphics Nv Radiation curable compositions
EP1927632B1 (en) * 2006-11-23 2010-08-18 Agfa Graphics N.V. Novel radiation curable compositions
CN101139436B (en) * 2007-10-18 2010-05-19 吉林大学 Amine imines zinc catalyst and preparation method and use thereof

Family Cites Families (757)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2809189A (en) 1957-10-08 Method of producing stabilized
CA517364A (en) 1955-10-11 H. Von Glahn William Stabilized diazonium salts and process of effecting same
CA465495A (en) 1950-05-30 Z. Lecher Hans Stabilization of colouring compositions containing diazonium salts
US2381145A (en) 1945-08-07 Stable diazo salt preparation
CA465499A (en) 1950-05-30 American Cyanamid Company Stabilization of printing pastes containing diazonium salts
US2628959A (en) 1953-02-17 Process for making stabilized
CA461082A (en) 1949-11-15 Jozsef Biro Laszlo Writing paste
CA460268A (en) 1949-10-11 L. Walsh William Stable diazonium salt preparation and process of preparing same
CA537687A (en) 1957-03-05 J. Leavitt Julian Stable solutions of mixtures of naphthols and stabilized diazo compounds
US2237885A (en) 1941-04-08 Stable diazo compounds
CA779239A (en) 1968-02-27 General Electric Company Information recording
CA458808A (en) 1949-08-09 L. Gardner Frank Cleat assembly for athletic shoes
CA465496A (en) 1950-05-30 Z. Lecher Hans Stabilization of colouring compositions containing diazonium salts
CA552565A (en) 1958-02-04 Scalera Mario Stabilization of copperized azo dyestuffs
CA463021A (en) 1950-02-07 Streck Clemens Stable diazo salt preparation and process of preparing them
CA463022A (en) 1950-02-07 General Aniline And Film Corporation Stable diazo salt preparation
CA571792A (en) 1959-03-03 Ciba Limited Process for printing textiles and printing preparations therefor
CA483214A (en) 1952-05-13 General Aniline And Film Corporation Diazo amino printing colors
US2185153A (en) 1939-12-26 Stable ice color producing
US582853A (en) 1897-05-18 Adolf feer
CA413257A (en) 1943-06-15 Albert Genest Homer Hat bat shrinking and felting machine
US1325971A (en) 1919-12-23 Kazue akashi
US3248337A (en) 1966-04-26 Composite reducing agent for use in the textile industry
US2612495A (en) 1952-09-30 Process of effecting same
US1876880A (en) 1932-09-13 Othmab dbapal
US2171976A (en) 1939-09-05 Process of manufacturing stabilized
US3123647A (en) 1964-03-03 Certificate of correction
US575228A (en) 1897-01-12 Moritz von gallois
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.
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
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
GB1184054A (en) 1966-04-05 1970-03-11 Agfa Gevaert Nv Thermographic Recording Processes and Materials
US3528814A (en) 1966-04-29 1970-09-15 Agfa Gevaert Ag Sensitization of light-sensitive polymers
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
US3565753A (en) 1967-07-17 1971-02-23 Ncr Co Capsule-cellulose fiber units and products made therewith
SE312870B (en) 1967-07-17 1969-07-28 Asea Ab
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
US3595657A (en) 1968-10-03 1971-07-27 Little Inc A Non-silver direct positive dye bleachout system using indigoid dyes and colorless 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
US3595659A (en) 1968-10-03 1971-07-27 Little Inc A Non-silver direct positive dye bleachout system using indigoid dyes and colored activators
US3595658A (en) 1968-10-03 1971-07-27 Little Inc A Non-silver direct positive dye bleachout system using polymethine 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
US3647467A (en) 1969-05-22 1972-03-07 Du Pont Hexaarylbiimidazole-heterocyclic compound compositions
US3697280A (en) 1969-05-22 1972-10-10 Du Pont Hexaarylbiimidazole-selected aromatic hydrocarbon 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
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
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
US3926641A (en) 1971-11-18 1975-12-16 Sun Chemical Corp Photopolymerizable compositions comprising polycarboxysubstituted benzophenone reaction products
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
US3904562A (en) 1973-01-31 1975-09-09 Sherwin Williams Co Organic pigments encapsulated with vinylpyrrolidone polymer
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
US4181807A (en) 1974-11-30 1980-01-01 Ciba-Geigy Corporation Polymerizable esters derived from a glycidyl ether of a phenolic unsaturated ketone
US4179577A (en) 1974-11-30 1979-12-18 Ciba-Geigy Corporation Polymerisable esters derived from a phenolic unsaturated ketone
GB1489419A (en) 1974-11-30 1977-10-19 Ciba Geigy Ag Polymerisable esters
JPS5442617B2 (en) 1974-12-28 1979-12-15
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
US4065315A (en) * 1976-04-26 1977-12-27 Dynachem Corporation Phototropic dye system and photosensitive compositions containing the same
US4132562A (en) 1976-08-06 1979-01-02 Marion Darrah And Joseph Y. Houghton, Co-Trustees Intrachromospheruloid/inorganic pigment compositions and processes for producing same
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
US4189323A (en) * 1977-04-25 1980-02-19 Hoechst Aktiengesellschaft Radiation-sensitive copying composition
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
US4212970A (en) * 1977-11-28 1980-07-15 Fuji Photo Film Co., Ltd. 2-Halomethyl-5-vinyl-1,3,4-oxadiazole compounds
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
JPS5482234A (en) 1977-12-14 1979-06-30 Fuji Photo Film Co Ltd Photostabilizing method for organic base material
JPS5482385A (en) 1977-12-14 1979-06-30 Fuji Photo Film Co Ltd Stabilizing method for organic basic substance to light
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
US4234106A (en) * 1978-12-01 1980-11-18 Pullman Incorporated Fuel delivery system for a furnace or kiln
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
US4336323A (en) 1979-12-07 1982-06-22 Minnesota Mining And Manufacturing Company Decolorizable imaging system
US4370401A (en) 1979-12-07 1983-01-25 Minnesota Mining And Manufacturing Company Light sensitive, thermally developable 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
EP0040177B1 (en) 1980-05-13 1983-07-20 Ciba-Geigy Ag Process for the preparation of benzene or naphthalene alkenyl carboxylic acid derivatives
EP0041043B1 (en) 1980-05-13 1983-11-09 Ciba-Geigy Ag Process for the preparation of derivatives of alkenyl benzene or alkenyl naphthalene
US4343891A (en) 1980-05-23 1982-08-10 Minnesota Mining And Manufacturing Company Fixing of tetra (hydrocarbyl) borate salt imaging systems
US4307182A (en) 1980-05-23 1981-12-22 Minnesota Mining And Manufacturing Company Imaging systems with tetra(aliphatic) borate salts
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
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
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
US4401470A (en) 1981-03-30 1983-08-30 Mobil Oil Corporation Intaglio printing ink and method of employing the same
US4372582A (en) 1981-03-30 1983-02-08 Minnesota Mining And Manufacturing Company Stabilizer for electron doner-acceptor carbonless copying systems
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
US4822714A (en) 1981-11-12 1989-04-18 The Mead Corporation Transfer imaging system
US4399209A (en) 1981-11-12 1983-08-16 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
JPS5971048A (en) * 1982-10-18 1984-04-21 Mitsubishi Chem Ind Ltd Photopolymerizable photosensitive composition
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
JPS5978339A (en) * 1982-10-28 1984-05-07 Fuji Photo Film Co Ltd Photopolymerizable composition
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
JPS59148784A (en) * 1983-02-10 1984-08-25 Konishiroku Photo Ind Co Ltd Free radical generator
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
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
DE3333450A1 (en) * 1983-09-16 1985-04-11 Hoechst Ag, 6230 Frankfurt CARBONYL METHYLENE HETEROCYCLES CONTAINING TRIHALOGEN METHYL GROUPS, METHOD FOR THE PRODUCTION THEREOF AND LIGHT-SENSITIVE MIXTURE THAT CONTAINS THESE COMPOUNDS
US4702996A (en) 1983-09-28 1987-10-27 General Electric Company Method of enhancing the contrast of images and materials therefor
DE3337024A1 (en) * 1983-10-12 1985-04-25 Hoechst Ag, 6230 Frankfurt LIGHT SENSITIVE COMPOUNDS HAVING TRICHLORMETHYL GROUPS, METHOD FOR THE PRODUCTION THEREOF AND LIGHT SENSITIVE MIXTURE CONTAINING THESE COMPOUNDS
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
JPS60159742A (en) * 1984-01-30 1985-08-21 Fuji Photo Film Co Ltd Photopolymerizable composition
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
JPS6131490A (en) * 1984-07-24 1986-02-13 Mitsubishi Chem Ind Ltd Liquid crystal composittion
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
IT1187703B (en) 1985-07-23 1987-12-23 Lamberti Fratelli Spa SUBSTITUTED BENZOPHENONES AND THEIR LIQUID MIXTURES, SUITABLE FOR USE AS PHOTOPOLYMERIZATION INITIATORS
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
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
US4716097A (en) * 1986-02-03 1987-12-29 E. I. Du Pont De Nemours And Company Increased photopolymer photospeed employing yellow light preexposure
US4716093A (en) * 1986-03-17 1987-12-29 E. I. Du Pont De Nemours And Company Solvent developable photoresist composition and process of use
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
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
CA1323949C (en) * 1987-04-02 1993-11-02 Michael C. Palazzotto Ternary photoinitiator system for addition polymerization
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
US4945121A (en) 1987-08-18 1990-07-31 Koh-I-Noor Radiograph, Inc. Thermosetting dyed latex colorant dispersions
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
US5008302A (en) * 1987-12-01 1991-04-16 Ciba-Geigy Corporation Titanocenes, the use thereof, and N-substituted pyrroles
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
JPH0753469B2 (en) 1987-12-29 1995-06-07 新王子製紙株式会社 Inkjet recording sheet and manufacturing method thereof
EP0327763A3 (en) * 1988-02-08 1991-11-06 Minnesota Mining And Manufacturing Company Colored salts of polymeric sulfonate polyanions and dye cations, and light-absorbing coatings made therewith
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
US5202213A (en) 1988-08-31 1993-04-13 Canon Kabushiki Kaisha Developer with surface treated silicic acid for developing electrostatic image
US5030248A (en) 1988-08-31 1991-07-09 Sandoz Ltd. Dyeing method
US5034526A (en) 1988-09-07 1991-07-23 Minnesota Mining And Manufacturing Company Halomethyl-1,3,5-triazines containing a sensitizer moiety
US5187045A (en) 1988-09-07 1993-02-16 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
DE3832032A1 (en) * 1988-09-21 1990-03-22 Hoechst Ag PHOTOPOLYMERIZABLE MIXTURE AND RECORDING MATERIAL MANUFACTURED THEREOF
US5098793A (en) 1988-09-29 1992-03-24 Uop Cyclodextrin films on solid substrates
DE3833437A1 (en) 1988-10-01 1990-04-05 Basf Ag RADIATION SENSITIVE MIXTURES AND THEIR USE
DE3833438A1 (en) 1988-10-01 1990-04-05 Basf Ag RADIATION SENSITIVE MIXTURES AND THEIR USE
JP2547626B2 (en) 1988-10-07 1996-10-23 富士写真フイルム株式会社 Method for producing monomer
JPH02100048A (en) 1988-10-07 1990-04-12 Fuji Photo Film Co Ltd Silver halide color photographic sensitive material
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
EP0373573B1 (en) 1988-12-14 1994-06-22 Ciba-Geigy Ag Recording material for ink jet printing
JP2604453B2 (en) 1988-12-14 1997-04-30 積水化学工業株式会社 Acrylic adhesive tape
US5098477A (en) 1988-12-14 1992-03-24 Ciba-Geigy Corporation Inks, particularly for ink 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
US5230982A (en) 1989-03-09 1993-07-27 The Mead Corporation Photoinitiator compositions containing disulfides and photohardenable compositions containing the same
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
US5068371A (en) * 1989-06-01 1991-11-26 Ciba-Geigy Corporation Novel nitrogen-containing titanocenes, and the use thereof
EP0401165B1 (en) * 1989-06-01 1994-11-30 Ciba-Geigy Ag New oxygen-containing titanocenes and their use
DE59005996D1 (en) * 1989-06-01 1994-07-14 Ciba Geigy Process for the preparation of titanocenes with o, o'-difluoroaryl ligands.
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
US5068140A (en) 1989-08-02 1991-11-26 Xerox Corporation Transparencies
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
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
US5292458A (en) * 1990-04-10 1994-03-08 Seiko Instruments Inc. Method of producing photosensitive microcapsules
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.
RU1772118C (en) 1990-02-19 1992-10-30 В. П. Чуев, М. М. Асимов, О. Д. Каменева, В. М. Никитченко, С. Н. Коваленко и А. Н. Рубинов Method for synthesis of water-soluble form of coumarine derivative
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
US5384186A (en) 1990-05-09 1995-01-24 The Proctor & Gamble Company Non-destructive carriers for cyclodextrin complexes
US5139687A (en) 1990-05-09 1992-08-18 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
US5153105A (en) 1990-06-18 1992-10-06 Minnesota Mining And Manufacturing Company Thermally developable light sensitive imageable layers containing photobleachable dyes
US5153104A (en) 1990-06-18 1992-10-06 Minnesota Mining And Manufacturing Company Thermally developable light-sensitive layers containing photobleachable sensitizers
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
TW207021B (en) 1990-07-23 1993-06-01 Showa Denko Kk
JP3244288B2 (en) 1990-07-23 2002-01-07 昭和電工株式会社 Near infrared decolorable recording material
US5277965A (en) 1990-08-01 1994-01-11 Xerox Corporation Recording sheets
US5089374A (en) 1990-08-20 1992-02-18 Eastman Kodak Company Novel bis-onium salts and the use thereof as photoinitiators
US5281261A (en) 1990-08-31 1994-01-25 Xerox Corporation Ink compositions containing modified pigment particles
JP3019381B2 (en) 1990-08-31 2000-03-13 ソニー株式会社 Optical recording medium
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
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
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
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
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
US5141556A (en) 1991-06-13 1992-08-25 E. I. Du Pont De Nemours And Company Penetrants for aqueous ink jet inks
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
JPH05169839A (en) * 1991-12-20 1993-07-09 Mitsubishi Kasei Corp Infrared heating type thermal transfer recording sheet
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
US5193854A (en) 1992-02-28 1993-03-16 Babn Technologies Inc. Tamper-resistant article and method of authenticating the same
JP2845389B2 (en) 1992-03-10 1999-01-13 大日精化工業株式会社 Colored composition for thermal transfer recording
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
US5268027A (en) 1992-12-22 1993-12-07 E. I. Du Pont De Nemours And Company Alkylpolyol ethers as cosolvents for ink jet inks
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
US5426164A (en) 1992-12-24 1995-06-20 The Dow Chemical Company Photodefinable polymers containing perfluorocyclobutane groups
EP0605840A3 (en) 1992-12-25 1994-12-14 Mitsubishi Paper Mills Ltd Ink jet recording sheet.
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.
JPH06248193A (en) 1993-02-25 1994-09-06 Ensuiko Sugar Refining Co Ltd Crocetin-containing pigment
JPH06248194A (en) 1993-02-25 1994-09-06 Ensuiko Sugar Refining Co Ltd Coloring matter containing quercetin
US5677067A (en) 1993-03-02 1997-10-14 Mitsubishi Paper Mills Limited Ink jet recording sheet
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
DE69406731T2 (en) 1993-07-30 1998-03-26 Canon Kk The recording element, the ink jet recording method using the same, printing and dispersion thus obtained, and the method for producing the recording element using the dispersion
CA2120838A1 (en) 1993-08-05 1995-02-06 Ronald Sinclair Nohr Solid colored composition mutable by ultraviolet radiation
US5773182A (en) 1993-08-05 1998-06-30 Kimberly-Clark Worldwide, Inc. Method of light stabilizing a colorant
US5645964A (en) 1993-08-05 1997-07-08 Kimberly-Clark Corporation Digital information recording media and method of using same
US5681380A (en) 1995-06-05 1997-10-28 Kimberly-Clark Worldwide, Inc. Ink for ink jet printers
US5700850A (en) 1993-08-05 1997-12-23 Kimberly-Clark Worldwide Colorant compositions and colorant stabilizers
US5721287A (en) 1993-08-05 1998-02-24 Kimberly-Clark Worldwide, Inc. Method of mutating a colorant by irradiation
US5733693A (en) 1993-08-05 1998-03-31 Kimberly-Clark Worldwide, Inc. Method for improving the readability of data processing forms
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
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
US5506079A (en) 1994-02-28 1996-04-09 Ricoh Company, Ltd. Magnetic composition, magnetic toner and ink containing the magnetic composition
JPH07290818A (en) 1994-03-04 1995-11-07 Mitsubishi Paper Mills Ltd Ink jet recording tack sheet
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
US5883161A (en) 1994-06-23 1999-03-16 Cellresin Technologies, Llc Moisture barrier material comprising a thermoplastic and a compatible cyclodextrin derivative
US5501902A (en) 1994-06-28 1996-03-26 Kimberly Clark Corporation Printable material
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
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
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
US5811199A (en) 1995-06-05 1998-09-22 Kimberly-Clark Worldwide, Inc. Adhesive compositions containing a photoreactor composition
US5747550A (en) 1995-06-05 1998-05-05 Kimberly-Clark Worldwide, Inc. Method of generating a reactive species and polymerizing an unsaturated polymerizable material
US5786132A (en) 1995-06-05 1998-07-28 Kimberly-Clark Corporation Pre-dyes, mutable dye compositions, and methods of developing a color
US5798015A (en) 1995-06-05 1998-08-25 Kimberly-Clark Worldwide, Inc. Method of laminating a structure with adhesive 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
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
BR9606811A (en) 1995-11-28 2000-10-31 Kimberly Clark Co Enhanced dye stabilizers
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
US5558965A (en) * 1995-12-21 1996-09-24 Hewlett-Packard Company Diiminoquinilidines as electron transport agents in electrophotographic elements
US5795985A (en) 1996-03-05 1998-08-18 Ciba Specialty Chemicals Corporation Phenyl alkyl ketone substituted by cyclic amine and a process for the preparation thereof
US5891229A (en) 1996-03-29 1999-04-06 Kimberly-Clark Worldwide, Inc. Colorant stabilizers
DE19618607C2 (en) 1996-05-09 1999-07-08 Schoeller Felix Jun Foto Recording material for ink jet printing processes
US5709976A (en) 1996-06-03 1998-01-20 Xerox Corporation Coated papers
KR100517535B1 (en) 1996-09-13 2006-05-09 다이닛뽄 잉크 앤드 케미칼즈, 인코포레이티드 Process for producing jet ink and colored particulate dispersion for jet ink
US6060215A (en) * 1997-03-31 2000-05-09 Hitachi, Ltd. Photosensitive resin composition and application of its photosensitivity
JP3134072B2 (en) 1997-05-13 2001-02-13 三洋化成工業株式会社 Dispersant for pearlescent pigments
US5939238A (en) * 1998-06-02 1999-08-17 Morton International, Inc. Photoimageable composition having improved photoinitiator system

Also Published As

Publication number Publication date
JP2003533548A (en) 2003-11-11
EP1117698B1 (en) 2006-04-19
ES2263291T3 (en) 2006-12-01
AU1309800A (en) 2000-04-17
ATE323725T1 (en) 2006-05-15
WO2000018750A2 (en) 2000-04-06
WO2000018750A8 (en) 2000-09-28
WO2000018750A3 (en) 2000-08-03
SK4172001A3 (en) 2001-11-06
US6265458B1 (en) 2001-07-24
DE69930948D1 (en) 2006-05-24
PL366326A1 (en) 2005-01-24
DE69930948T2 (en) 2006-09-07
CA2353685A1 (en) 2000-04-06
BR9914123B1 (en) 2010-11-30
EP1117698A2 (en) 2001-07-25
BR9914123A (en) 2002-06-18

Similar Documents

Publication Publication Date Title
US6486227B2 (en) Zinc-complex photoinitiators and applications therefor
US6780896B2 (en) Stabilized photoinitiators and applications thereof
EP0767803B1 (en) Method of generating a reactive species and applications therefor
US5747550A (en) Method of generating a reactive species and polymerizing an unsaturated polymerizable material
US5798015A (en) Method of laminating a structure with adhesive containing a photoreactor composition
US5849411A (en) Polymer film, nonwoven web and fibers containing a photoreactor composition
US6265458B1 (en) Photoinitiators and applications therefor
US5811199A (en) Adhesive compositions containing a photoreactor composition
US5739175A (en) Photoreactor composition containing an arylketoalkene wavelength-specific sensitizer
JP2003533548A6 (en) Chelates containing quinoid groups as photopolymerization initiators
US3926640A (en) Photopolymerizable compositions comprising benzophenone reaction products
KR100711692B1 (en) Chelates Comprising Chinoid Groups As Photoinitiators
US6277897B1 (en) Photoinitiators and applications therefor
US6294698B1 (en) Photoinitiators and applications therefor
US6071979A (en) Photoreactor composition method of generating a reactive species and applications therefor
MXPA01002683A (en) Novel photoinitiators and applications therefor
JPS61197614A (en) Curable resin composition
US6008268A (en) Photoreactor composition, method of generating a reactive species, and applications therefor
WO1999054363A1 (en) Novel photoinitiators and applications therefor
MXPA00010170A (en) Novel photoinitiators and applications therefor
MXPA00001253A (en) Novel photoinitiators and applications therefor

Legal Events

Date Code Title Description
ENP Entry into the national phase

Ref document number: 2000 13098

Country of ref document: AU

Kind code of ref document: A

AK Designated states

Kind code of ref document: A2

Designated state(s): AE AL AM AT AU AZ BA BB BG BR BY CA CH CN CR CU CZ DE DK DM EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MD MG MK MN MW MX NO NZ PL PT RO RU SD SE SG SI SK SL TJ TM TR TT TZ UA UG UZ VN YU ZA ZW

AL Designated countries for regional patents

Kind code of ref document: A2

Designated state(s): GH GM KE LS MW SD SL SZ TZ UG ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE BF BJ CF CG CI CM GA GN GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
AK Designated states

Kind code of ref document: A3

Designated state(s): AE AL AM AT AU AZ BA BB BG BR BY CA CH CN CR CU CZ DE DK DM EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MD MG MK MN MW MX NO NZ PL PT RO RU SD SE SG SI SK SL TJ TM TR TT TZ UA UG UZ VN YU ZA ZW

AL Designated countries for regional patents

Kind code of ref document: A3

Designated state(s): GH GM KE LS MW SD SL SZ TZ UG ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE BF BJ CF CG CI CM GA GN GW ML MR NE SN TD TG

AK Designated states

Kind code of ref document: C1

Designated state(s): AE AL AM AT AU AZ BA BB BG BR BY CA CH CN CR CU CZ DE DK DM EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MD MG MK MN MW MX NO NZ PL PT RO RU SD SE SG SI SK SL TJ TM TR TT TZ UA UG UZ VN YU ZA ZW

AL Designated countries for regional patents

Kind code of ref document: C1

Designated state(s): GH GM KE LS MW SD SL SZ TZ UG ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE BF BJ CF CG CI CM GA GN GW ML MR NE SN TD TG

CFP Corrected version of a pamphlet front page
CR1 Correction of entry in section i

Free format text: PAT. BUL. 14/2000 UNDER (30) ADD "60/124939 18.03.99 US"

REG Reference to national code

Ref country code: DE

Ref legal event code: 8642

WWE Wipo information: entry into national phase

Ref document number: 200101664

Country of ref document: ZA

WWE Wipo information: entry into national phase

Ref document number: PA/a/2001/002683

Country of ref document: MX

ENP Entry into the national phase

Ref document number: 2353685

Country of ref document: CA

Ref document number: 2353685

Country of ref document: CA

Kind code of ref document: A

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
WWE Wipo information: entry into national phase

Ref document number: 4172001

Country of ref document: SK

Ref document number: IN/PCT/2001/415/CHE

Country of ref document: IN

WWE Wipo information: entry into national phase

Ref document number: 1020017003875

Country of ref document: KR

ENP Entry into the national phase

Ref document number: 2000 572210

Country of ref document: JP

Kind code of ref document: A

WWE Wipo information: entry into national phase

Ref document number: 1999956500

Country of ref document: EP

WWP Wipo information: published in national office

Ref document number: 1999956500

Country of ref document: EP

AK Designated states

Kind code of ref document: C2

Designated state(s): AE AL AM AT AU AZ BA BB BG BR BY CA CH CN CR CU CZ DE DK DM EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MD MG MK MN MW MX NO NZ PL PT RO RU SD SE SG SI SK SL TJ TM TR TT TZ UA UG UZ VN YU ZA ZW

AL Designated countries for regional patents

Kind code of ref document: C2

Designated state(s): GH GM KE LS MW SD SL SZ TZ UG ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE BF BJ CF CG CI CM GA GN GW ML MR NE SN TD TG

COP Corrected version of pamphlet

Free format text: PAGES 57-66, CLAIMS, REPLACED BY NEW PAGES 57-66; DUE TO LATE TRANSMITTAL BY THE RECEIVING OFFICE

WWP Wipo information: published in national office

Ref document number: 1020017003875

Country of ref document: KR

WWG Wipo information: grant in national office

Ref document number: 1999956500

Country of ref document: EP

WWR Wipo information: refused in national office

Ref document number: 1020017003875

Country of ref document: KR