CA2412607C - Novel photoinitiators and applications therefor - Google Patents
Novel photoinitiators and applications therefor Download PDFInfo
- Publication number
- CA2412607C CA2412607C CA2412607A CA2412607A CA2412607C CA 2412607 C CA2412607 C CA 2412607C CA 2412607 A CA2412607 A CA 2412607A CA 2412607 A CA2412607 A CA 2412607A CA 2412607 C CA2412607 C CA 2412607C
- Authority
- CA
- Canada
- Prior art keywords
- carbon atoms
- alkyl group
- photoinitiator
- photoinitiators
- present
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
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- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- JUHDUIDUEUEQND-UHFFFAOYSA-N methylium Chemical compound [CH3+] JUHDUIDUEUEQND-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000004573 morpholin-4-yl group Chemical group N1(CCOCC1)* 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
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- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 0.000 description 1
- WTXMTPLATLKWQS-UHFFFAOYSA-N propane Chemical compound CC[CH2+] WTXMTPLATLKWQS-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
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- 230000007017 scission Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229940080262 sodium tetrachloroaurate Drugs 0.000 description 1
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- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 description 1
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- JTJFQBNJBPPZRI-UHFFFAOYSA-J vanadium tetrachloride Chemical compound Cl[V](Cl)(Cl)Cl JTJFQBNJBPPZRI-UHFFFAOYSA-J 0.000 description 1
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Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
- G03F7/029—Inorganic compounds; Onium compounds; Organic compounds having hetero atoms other than oxygen, nitrogen or sulfur
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
- C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
Abstract
The present invention is directed to new, energy-efficient, photoinitiators having the following formula: whrein Z each independlently represent the formula (II) wherein R1, R2, R3 and R4 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; R5, R6, R7 and R8 each independently represent an alkyl group having from one to six carbon atoms, an aryl group, or a halogen-substituted alkyl group having from one to six carbon atoms; wherein R9 represents (R10)2O or (R10)3N, wherein R10 represents H or an alkyl group having from one to eight carbon atoms; and wherein R11 represents H, an alkyl group having from one to eight carbon atoms, a benzyl group or an aralkyl group. The present invention is also directed to a method of generating a reactive species, 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
NOVEL PHOTOINITIATORS
AND APPLICATIONS THEREFOR
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 beginning 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
AND APPLICATIONS THEREFOR
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 beginning 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
2 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
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 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. 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
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 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. 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
4 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:
R2 O ZnL _ R3 (Rii)2N\ SC Z
A
wherein Z each independently represents O N= O +N= O
S +N=
or wherein R1, R2, R3 and R4 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; R5, R6, R7 and R8 each independently represent an alkyl group having from one to six carbon atoms, an aryl group, a phenyl-substituted alkyl group having from one to six carbon atoms, or a halogen-substituted alkyl group having from one to six
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:
R2 O ZnL _ R3 (Rii)2N\ SC Z
A
wherein Z each independently represents O N= O +N= O
S +N=
or wherein R1, R2, R3 and R4 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; R5, R6, R7 and R8 each independently represent an alkyl group having from one to six carbon atoms, an aryl group, a phenyl-substituted alkyl group having from one to six carbon atoms, or a halogen-substituted alkyl group having from one to six
5 carbon atoms; wherein R9 represents (R10)20 or (R,o)3N; wherein R10 represents H or an alkyl group having from one to eight carbon atoms;
and wherein Rl I r ?resents H, an alkyl group having from one to eight carbon atoms, oenzyl group or an aralkyl group. By selecting particular "R" 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 290 nm to greater than about 350 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 290 nm to greater than about 350 nm.
The present invention is also directed to methods of using the above-described photoinitiators to polymerize and/or
and wherein Rl I r ?resents H, an alkyl group having from one to eight carbon atoms, oenzyl group or an aralkyl group. By selecting particular "R" 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 290 nm to greater than about 350 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 290 nm to greater than about 350 nm.
The present invention is also directed to methods of using the above-described photoinitiators to polymerize and/or
6 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 a 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 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.
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
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 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.
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
7 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:
i Rs\/R6 /C", R9 Z==(:
R, 0' Z.Q- R3 t (R11) 2 N\ / Z
wherein Z each independently represents O +N- O +N=, O
S +N
or wherein R1, R2, R3 and R4 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; R5, R6, R7 and R.8 each independently represent an alkyl group having from one to six carbon atoms, an aryl group, a phenyl-substituted alkyl group having from one to six carbon atoms, or a halogen-substituted alkyl group having from one to six carbon atoms; wherein R9 represents (R1Q)20 or (R10)3N;
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:
i Rs\/R6 /C", R9 Z==(:
R, 0' Z.Q- R3 t (R11) 2 N\ / Z
wherein Z each independently represents O +N- O +N=, O
S +N
or wherein R1, R2, R3 and R4 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; R5, R6, R7 and R.8 each independently represent an alkyl group having from one to six carbon atoms, an aryl group, a phenyl-substituted alkyl group having from one to six carbon atoms, or a halogen-substituted alkyl group having from one to six carbon atoms; wherein R9 represents (R1Q)20 or (R10)3N;
8 wherein R10 represents H or an alkyl group having from one to eight carbon atoms; and wherein R11 represents H, an alkyl group having from one to eight carbon atoms, a benzyl group or an aralkyl group.
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. 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,
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. 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,
9 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, t-butyl cation, t-pentyl cation, t-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, n-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 5 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,"
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, t-butyl cation, t-pentyl cation, t-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, n-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 5 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,"
10 "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:
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:
11 Rs\ Rb /C-~" .. R9 Z=C
(Ru)2N--~' Z
A
Rg wherein Z each independently represents 0 +N O +N=, O
131 \+N'-, or wherein Ri, R2, R3 and R4 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; R5, R6, R7 and R8 each independently represent an alkyl group having from one to six carbon atoms, an aryl group, a phenyl-substituted alkyl group having from one to six carbon atoms, or a halogen-substituted alkyl group having from one to six carbon atoms; wherein R9 represents (RIO)20 or (R10)3N; wherein RIO represents H or an alkyl group having from one to eight carbon atoms; and wherein RI I represents H, an alkyl group having from one to eight carbon atoms, a benzyl group or an aralkyl group.
(Ru)2N--~' Z
A
Rg wherein Z each independently represents 0 +N O +N=, O
131 \+N'-, or wherein Ri, R2, R3 and R4 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; R5, R6, R7 and R8 each independently represent an alkyl group having from one to six carbon atoms, an aryl group, a phenyl-substituted alkyl group having from one to six carbon atoms, or a halogen-substituted alkyl group having from one to six carbon atoms; wherein R9 represents (RIO)20 or (R10)3N; wherein RIO represents H or an alkyl group having from one to eight carbon atoms; and wherein RI I represents H, an alkyl group having from one to eight carbon atoms, a benzyl group or an aralkyl group.
12 Photoinitiators having the above formula include, but are not limited to, the following photoinitiators: R5 \ / OH2 O N C/C\NHa O-- Zn2+
O
HN C N O
2..\
A
O
HN C N O
2..\
A
13 H3~ /CH3 OH2 O N ~=& CSCNH
O-- Zn2+
,C N \O
/ _ +\J
O~
O N C~C\NH
O Zn2+
O
C N O
H2N--, C
and
O-- Zn2+
,C N \O
/ _ +\J
O~
O N C~C\NH
O Zn2+
O
C N O
H2N--, C
and
14 Ph(CH2)2 (CH2)2Ph O N C /C~
O-- Zn?+ _ O HN \C=C)=+N Ph(CH2)2 (CH2)2Ph wherein R5, R6, R7, R8 and R9 are as described above.
The photoinitiators of the present invention may be associated with a variety of counterions. Suitable counterions possess a negative charge distribution, which is spread over a large anion, resulting in a diffused charge rather than a point charge. Examples of suitable counterions include, but are not limited to, tetraphenylboron, tetrachoroboron, tetrafluoroboron, hexafluorophosphate, and perchlorate. Desirably, the counterion comprises tetraphenylboron or tetrafluoroboron. More desirably, the counterion comprises tetrafluoroboron.
In one embodiment of the present invention, a photoinitiator system comprises the following photoinitiator and counterions:
H3~ CH3 OH2 C\ ..
0Zn 2 C
HzN',,~' O~
The above-described photoinitiators of the present invention may be produced by the following reaction mechanism, shown for when R11 is hydrogen and Z is NC4H4O:
R
O C\ C'~ NH2 + \-/ C~ ~ / NHz R1 R5 \ R6 R3 R/ \ R8 + Zn- containing compound or complex X
RI R5\ OR6 Rv O C\ Hz RZ O n2+ R3 H2N lC ~\O
R -wherein one or more compounds react with the Zn-containing compound or complex to produce a photoinitiator of the present invention and one or more anions (X-). Suitable Zn-containing compounds or complexes include, but are not limited to, Zn(OEt2)2C12, Zn(H20)6(BF4)2, and Zn(H20)6(BPh4)2. In the above mechanism, the use of a particular Zn-containing compound or complex results in a particular R9 group and anions as shown in the table below:
Zn-containing Resulting R9 Resulting Anions Compound or Group Complex Zn(OEt2)2C12 OEt2 Cl Zn(H20)6(BF4)2 H2O BF4 Zn(H20)6(BPh4)2 H2O BPh4 It should be understood that the above examples of suitable photoinitiators are only a few of the possible photoinitiators encompassed by the present invention. Any combination of photoinitiator having selected "R" groups and any of the above-mentioned counterions may be used in combination to form a photoinitiator system of the present invention. Further, the above reaction mechanism is only one example of many possible reaction mechanisms, which may include a variety of reactants, resulting in 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-lcm-1. As a further example, the photoinitiators of the present invention have a molar extinction coefficient greater than about 25,000 1 mole-1cm 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 O.S. 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 1Ø
In one embodiment of the present invention, the photoinitiators of the present invention are exposed to radiation at a desired wavelength, resulting in the generation of one or more reactive species, wherein an electron-donating solvent is used to generate one or more reactive species. Any solvent capable of donating an electron to the photoinitiators of the present invention may be used to generate one or more reactive species. Suitable electron-donating solvents include, but are not limited to, acrylates, methacylates, vinyl esters, enamines, and a combination thereof. Desirably, the electron-donating solvent comprises acrylic acid.
It is believed that the interaction between the photoinitiator of the present invention and the electron-donating solvent takes place as shown by the following reaction mechanism:
Donation of electron e H~C_\ HCC OH
iC-OH /C
O O
e-H
H\+
C-C
H C-OH
As shown above, donation of an electron from the electron-donating solvent generates a cationic free radical.
Electron Interaction With Photo initiator:
H3~ /CH3 OH2 O Zn2+
O
C N O
/\
e \ / OH2 C
O N o C/ 2 Zn -O
C N O
H2N / - +' j The introduction of the electron into the structure of the 5 photoinitiator results in the formation of a carbon-carbon double bond and cleavage of the carbon-nitrogen bond. The end result is a nitrogen-containing free radical.
The above mechanism generates a combination of free radicals, one of which is a cationic free radical and one of which is nitrogen radical species. In conventional electron transfer systems, an initiator generates a radical cation, which starts the polymerization process, and a radical anion, which is a chain terminator (i.e., stops polymerization). However, the method of generating a reactive species of the present invention generates a radical cation and a nitrogen radical species, both of which start the polymerization process, and neither of which act as a chain terminator (i.e., stop polymerization).
Exposing the photoinitiators of the present invention to radiation results in the generation of one or more reactive species as discussed above. 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 herein. 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.
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 is further directed to coatings comprising a polymerizable material admixed with one or more photoinitiators of the present invention. The coatings may be applied to a substrate and then exposed to an amount of radiation sufficient to polymerize the polymerizable material of the coating.
Any substrate may be used in the practice of the present invention.
Particular applications of interest include, but are not limited to, coatings on textiles, coatings on fabrics, coatings on textile fibers, and coatings on optical fibers.
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 290 to about 320 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., 5 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 10 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
O-- Zn?+ _ O HN \C=C)=+N Ph(CH2)2 (CH2)2Ph wherein R5, R6, R7, R8 and R9 are as described above.
The photoinitiators of the present invention may be associated with a variety of counterions. Suitable counterions possess a negative charge distribution, which is spread over a large anion, resulting in a diffused charge rather than a point charge. Examples of suitable counterions include, but are not limited to, tetraphenylboron, tetrachoroboron, tetrafluoroboron, hexafluorophosphate, and perchlorate. Desirably, the counterion comprises tetraphenylboron or tetrafluoroboron. More desirably, the counterion comprises tetrafluoroboron.
In one embodiment of the present invention, a photoinitiator system comprises the following photoinitiator and counterions:
H3~ CH3 OH2 C\ ..
0Zn 2 C
HzN',,~' O~
The above-described photoinitiators of the present invention may be produced by the following reaction mechanism, shown for when R11 is hydrogen and Z is NC4H4O:
R
O C\ C'~ NH2 + \-/ C~ ~ / NHz R1 R5 \ R6 R3 R/ \ R8 + Zn- containing compound or complex X
RI R5\ OR6 Rv O C\ Hz RZ O n2+ R3 H2N lC ~\O
R -wherein one or more compounds react with the Zn-containing compound or complex to produce a photoinitiator of the present invention and one or more anions (X-). Suitable Zn-containing compounds or complexes include, but are not limited to, Zn(OEt2)2C12, Zn(H20)6(BF4)2, and Zn(H20)6(BPh4)2. In the above mechanism, the use of a particular Zn-containing compound or complex results in a particular R9 group and anions as shown in the table below:
Zn-containing Resulting R9 Resulting Anions Compound or Group Complex Zn(OEt2)2C12 OEt2 Cl Zn(H20)6(BF4)2 H2O BF4 Zn(H20)6(BPh4)2 H2O BPh4 It should be understood that the above examples of suitable photoinitiators are only a few of the possible photoinitiators encompassed by the present invention. Any combination of photoinitiator having selected "R" groups and any of the above-mentioned counterions may be used in combination to form a photoinitiator system of the present invention. Further, the above reaction mechanism is only one example of many possible reaction mechanisms, which may include a variety of reactants, resulting in 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-lcm-1. As a further example, the photoinitiators of the present invention have a molar extinction coefficient greater than about 25,000 1 mole-1cm 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 O.S. 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 1Ø
In one embodiment of the present invention, the photoinitiators of the present invention are exposed to radiation at a desired wavelength, resulting in the generation of one or more reactive species, wherein an electron-donating solvent is used to generate one or more reactive species. Any solvent capable of donating an electron to the photoinitiators of the present invention may be used to generate one or more reactive species. Suitable electron-donating solvents include, but are not limited to, acrylates, methacylates, vinyl esters, enamines, and a combination thereof. Desirably, the electron-donating solvent comprises acrylic acid.
It is believed that the interaction between the photoinitiator of the present invention and the electron-donating solvent takes place as shown by the following reaction mechanism:
Donation of electron e H~C_\ HCC OH
iC-OH /C
O O
e-H
H\+
C-C
H C-OH
As shown above, donation of an electron from the electron-donating solvent generates a cationic free radical.
Electron Interaction With Photo initiator:
H3~ /CH3 OH2 O Zn2+
O
C N O
/\
e \ / OH2 C
O N o C/ 2 Zn -O
C N O
H2N / - +' j The introduction of the electron into the structure of the 5 photoinitiator results in the formation of a carbon-carbon double bond and cleavage of the carbon-nitrogen bond. The end result is a nitrogen-containing free radical.
The above mechanism generates a combination of free radicals, one of which is a cationic free radical and one of which is nitrogen radical species. In conventional electron transfer systems, an initiator generates a radical cation, which starts the polymerization process, and a radical anion, which is a chain terminator (i.e., stops polymerization). However, the method of generating a reactive species of the present invention generates a radical cation and a nitrogen radical species, both of which start the polymerization process, and neither of which act as a chain terminator (i.e., stop polymerization).
Exposing the photoinitiators of the present invention to radiation results in the generation of one or more reactive species as discussed above. 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 herein. 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.
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 is further directed to coatings comprising a polymerizable material admixed with one or more photoinitiators of the present invention. The coatings may be applied to a substrate and then exposed to an amount of radiation sufficient to polymerize the polymerizable material of the coating.
Any substrate may be used in the practice of the present invention.
Particular applications of interest include, but are not limited to, coatings on textiles, coatings on fabrics, coatings on textile fibers, and coatings on optical fibers.
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 290 to about 320 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., 5 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 10 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
15 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 20 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 25 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.
Method of Forming a 1 -(p fluorophenyl)-2-bromo propan-1-one Intermediate to a Photoinitiator of the Present Invention The following reaction was carried out as detailed below:
F OC- CH2CH3 + Br2 F C- CH(Br)CH3 OC
Into a three-necked round-bottom flask was placed 10.0 g (0.07 mole) of K2C03 in 150 ml of carbon tetrachloride with stirrer bar. The mixture was cooled to about 0 C. Into the flask was added 40.0 g (0.28 mole) of 1-(p-fluorophenyl)propan-1-one.
Bromine was slowly added to the mixture over a period of about minutes. The temperature of the mixture was allowed to rise to 30 room temperature over a period of about 60 minutes.
The reaction mixture was filtered and the solvent was removed under reduced pressure on a rotovaporator. The final product was used without further purification.
Method of Forming a 1-(p fluorophenyl)-2-bromo-2-methyl-propan-l -one Intermediate to a Photoinitiator of the Present Invention 10 The following reaction was carried out as detailed below:
F-{ ( ) }- C- CH(Br)CH3 + CH3I CH3C ~ F IC- C(Br)(CH3)2 NaOH
Into a three-necked round-bottom flask was placed 200 ml of acetonitrile with stirrer bar. Into the flask was added 50.0 g (0.22 mole) of 1 -(p-fluorophenyl)-2-bromo-propan- 1 -one from 15 Example 1 and 31.2 g (0.22 mole) of methyl iodine while stirring at room temperature. The mixture was stirred for about 12 hours.
The solvent was reduced by half and 17.6 g (0.44 mole) of NaOH
was added to the mixture. The mixture was heated to a range of about 50 to 60 C for a period of about 30 minutes. After cooling, 20 200 ml. of water was added to the mixture. The mixture was then extracted with ether (2 X 70 ml.), dried over MgSO4, and filtered.
The solvent was then removed to yield a product, which was used without further purification.
Method of Forming a 1=(p fluorophenyl)-2-amino-2-methyl-propan-1-one Intermediate to a Photoinitiator of the Present Invention 30 The following reaction was carried out as detailed below:
1 ether ICI
F \~ C- C(Br)(cH3)2 + NH3 0'C F O C- C( 2)(CH3)2 Into a three-necked round-bottom flask was placed 200 ml of ether with stirrer bar. Into the flask was added 45.0 g (0.19 mole) of 1-(p-fluorophenyl)-2-bromo-2-methyl-propan- l -one from Example 2. The mixture was cooled to about 0 C. Into the flask was bubbled ammonia gas for 2 hours, aster which was bubbled argon gas to flush away any excess ammonia. The solvent was then removed on the rotovaporator. The resulting product was used without further purification.
Method of Forming a Morpholino-Containing Intermediate to a Photoinitiator of the Present Invention The following reaction was carried out as detailed below:
F C- C(NH2)(CH3)2 + HN O
DMSO
C(NH2)(CH3)2 Into a 1-liter, three-necked round-bottom flask was placed 25.0 g (0.144 mole) of 1-(p-fluorophenyl)-2-amino-2-methyl-propan-1-one from Example 3, 12.5 g (0.144 mole) of morpholine, and 20.0 g (0.15 mole) of K2C03 in 100 ml. of dimethylsulfoxide (DMSO). The mixture was flushed with argon and heated to reflux (160 C) for about 12 hours under an argon atmosphere.
The reaction mixture was cooled and filtered. The solvent was mixed with about 200 g of ice and extracted with dichloromethane. The organic layer was washed with 50 ml of a saturated salt solution, dried over MgSO4, and then filtered. The solvent was removed by vacuum to yield 24.2 g of product (actual yield 68%).
The resulting product was found to have a Xmax (CH3CN) value of 314 net, which indicated the presence of the 1-(morpholino)-2-amino-2-methyl-propan-l-one compound.
Method of Forming a Zn-complex Photoinitiator of the Present Invention The following reaction was carried out as detailed below:
Into a 250 ml, three-necked round-bottom flask was placed O N C- C(NH2)(CH3)2 + Zn(112O)X(BF4)2 1,4-dioxane O N C~C\NH2 O. Zn2+
C N O
H2N / +\, A
2.0 g (8.3 mmole) of zinctetrafluoroborate (Street Chemical Company, Newburyport, MA), 4.1 g (16.6 mmole) of the morpholino-containing product of Example 4, 30 ml of water, and 30 ml of 1,4-dioxane. The mixture, was stirred and heated to reflux. The color of the mixture changed from bright yellow to dull yellow after about 50 minutes. HPLC indicated that all of the starting materials converted to product. The starting material had an UV value, X. (CH3CN), of 314 nm, while the product had an UV value, X. (CH3CN), of 356 nm.
The solvent was removed and pumped under a vacuum (0.01 mm Hg) for about 16 hours at room temperature. The yield of the final product was 4.1 g of product (68%).
Testing of Zn-Containing Photoinitiator of the Present Invention in a Red Flexographic Resin A sample containing 2 wt% of the photoinitiator produced in Example 5 and 98 W16. of a red flexographic resin was prepared by mixing the components at about 50 C in an aluminum pan. A drop of the resin sample was drawn down on a white panel using a zero-draw down bar. The thin film was exposed to a 50W
excimer lamp (308 nm). The resin fully cured after 3 flashes (0.05 seconds/flash).
The ultraviolet radiation emitted from an excimer lamp can 20 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 25 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.
Method of Forming a 1 -(p fluorophenyl)-2-bromo propan-1-one Intermediate to a Photoinitiator of the Present Invention The following reaction was carried out as detailed below:
F OC- CH2CH3 + Br2 F C- CH(Br)CH3 OC
Into a three-necked round-bottom flask was placed 10.0 g (0.07 mole) of K2C03 in 150 ml of carbon tetrachloride with stirrer bar. The mixture was cooled to about 0 C. Into the flask was added 40.0 g (0.28 mole) of 1-(p-fluorophenyl)propan-1-one.
Bromine was slowly added to the mixture over a period of about minutes. The temperature of the mixture was allowed to rise to 30 room temperature over a period of about 60 minutes.
The reaction mixture was filtered and the solvent was removed under reduced pressure on a rotovaporator. The final product was used without further purification.
Method of Forming a 1-(p fluorophenyl)-2-bromo-2-methyl-propan-l -one Intermediate to a Photoinitiator of the Present Invention 10 The following reaction was carried out as detailed below:
F-{ ( ) }- C- CH(Br)CH3 + CH3I CH3C ~ F IC- C(Br)(CH3)2 NaOH
Into a three-necked round-bottom flask was placed 200 ml of acetonitrile with stirrer bar. Into the flask was added 50.0 g (0.22 mole) of 1 -(p-fluorophenyl)-2-bromo-propan- 1 -one from 15 Example 1 and 31.2 g (0.22 mole) of methyl iodine while stirring at room temperature. The mixture was stirred for about 12 hours.
The solvent was reduced by half and 17.6 g (0.44 mole) of NaOH
was added to the mixture. The mixture was heated to a range of about 50 to 60 C for a period of about 30 minutes. After cooling, 20 200 ml. of water was added to the mixture. The mixture was then extracted with ether (2 X 70 ml.), dried over MgSO4, and filtered.
The solvent was then removed to yield a product, which was used without further purification.
Method of Forming a 1=(p fluorophenyl)-2-amino-2-methyl-propan-1-one Intermediate to a Photoinitiator of the Present Invention 30 The following reaction was carried out as detailed below:
1 ether ICI
F \~ C- C(Br)(cH3)2 + NH3 0'C F O C- C( 2)(CH3)2 Into a three-necked round-bottom flask was placed 200 ml of ether with stirrer bar. Into the flask was added 45.0 g (0.19 mole) of 1-(p-fluorophenyl)-2-bromo-2-methyl-propan- l -one from Example 2. The mixture was cooled to about 0 C. Into the flask was bubbled ammonia gas for 2 hours, aster which was bubbled argon gas to flush away any excess ammonia. The solvent was then removed on the rotovaporator. The resulting product was used without further purification.
Method of Forming a Morpholino-Containing Intermediate to a Photoinitiator of the Present Invention The following reaction was carried out as detailed below:
F C- C(NH2)(CH3)2 + HN O
DMSO
C(NH2)(CH3)2 Into a 1-liter, three-necked round-bottom flask was placed 25.0 g (0.144 mole) of 1-(p-fluorophenyl)-2-amino-2-methyl-propan-1-one from Example 3, 12.5 g (0.144 mole) of morpholine, and 20.0 g (0.15 mole) of K2C03 in 100 ml. of dimethylsulfoxide (DMSO). The mixture was flushed with argon and heated to reflux (160 C) for about 12 hours under an argon atmosphere.
The reaction mixture was cooled and filtered. The solvent was mixed with about 200 g of ice and extracted with dichloromethane. The organic layer was washed with 50 ml of a saturated salt solution, dried over MgSO4, and then filtered. The solvent was removed by vacuum to yield 24.2 g of product (actual yield 68%).
The resulting product was found to have a Xmax (CH3CN) value of 314 net, which indicated the presence of the 1-(morpholino)-2-amino-2-methyl-propan-l-one compound.
Method of Forming a Zn-complex Photoinitiator of the Present Invention The following reaction was carried out as detailed below:
Into a 250 ml, three-necked round-bottom flask was placed O N C- C(NH2)(CH3)2 + Zn(112O)X(BF4)2 1,4-dioxane O N C~C\NH2 O. Zn2+
C N O
H2N / +\, A
2.0 g (8.3 mmole) of zinctetrafluoroborate (Street Chemical Company, Newburyport, MA), 4.1 g (16.6 mmole) of the morpholino-containing product of Example 4, 30 ml of water, and 30 ml of 1,4-dioxane. The mixture, was stirred and heated to reflux. The color of the mixture changed from bright yellow to dull yellow after about 50 minutes. HPLC indicated that all of the starting materials converted to product. The starting material had an UV value, X. (CH3CN), of 314 nm, while the product had an UV value, X. (CH3CN), of 356 nm.
The solvent was removed and pumped under a vacuum (0.01 mm Hg) for about 16 hours at room temperature. The yield of the final product was 4.1 g of product (68%).
Testing of Zn-Containing Photoinitiator of the Present Invention in a Red Flexographic Resin A sample containing 2 wt% of the photoinitiator produced in Example 5 and 98 W16. of a red flexographic resin was prepared by mixing the components at about 50 C in an aluminum pan. A drop of the resin sample was drawn down on a white panel using a zero-draw down bar. The thin film was exposed to a 50W
excimer lamp (308 nm). The resin fully cured after 3 flashes (0.05 seconds/flash).
Claims (20)
1. A photoinitiator having the general formula:
wherein Z each independently represents wherein R1, R2, R3 and R4 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 having from one to six carbon atoms; R5, R6, R7 and R8 each independently represent an alkyl group having from one to six carbon atoms, an aryl group, a phenyl-substituted alkyl group having from one to six carbon atoms, or a halogen-substituted alkyl group having from one to six carbon atoms; wherein R9 represents (R10)2O or (R10)3N;
wherein R10 represents H or an alkyl group having from one to eight carbon atoms; and wherein R11 represents H, an alkyl group having from one to eight carbon atoms, a benzyl group or an aralkyl group.
wherein Z each independently represents wherein R1, R2, R3 and R4 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 having from one to six carbon atoms; R5, R6, R7 and R8 each independently represent an alkyl group having from one to six carbon atoms, an aryl group, a phenyl-substituted alkyl group having from one to six carbon atoms, or a halogen-substituted alkyl group having from one to six carbon atoms; wherein R9 represents (R10)2O or (R10)3N;
wherein R10 represents H or an alkyl group having from one to eight carbon atoms; and wherein R11 represents H, an alkyl group having from one to eight carbon atoms, a benzyl group or an aralkyl group.
2. The photoinitiator of Claim 1, wherein the photoinitiator comprises:
3. The photoinitiator , of Claim 1, wherein the photoinitiator is associated with one or more counterions.
4. The photoinitiator of Claim 3, wherein the one or more counterions comprise tetraphenylboron, tetrachloroboron, tetrafluoroboron, hexafluorophosphate, perchlorate, or a combination thereof.
5. The photoinitiator of Claim 4, wherein the one or more counterions comprise tetraphenylboron or tetrafluoroboron.
6. The photoinitiator of Claim 3, wherein the photoinitiator and the one or more counterions comprise
7. A method of generating a reactive species, comprising:
irradiating the photoinitiator of Claim 1 with radiation.
irradiating the photoinitiator of Claim 1 with radiation.
8. A method of polymerizing a polymerizable material, comprising:
irradiating an admixture of a polymerizable material and the photoinitiator of Claim 1.
irradiating an admixture of a polymerizable material and the photoinitiator of Claim 1.
9. A method of generating a reactive species, comprising:
irradiating a photoinitiator according to any one of claims 1 to 6 with radiation, wherein at least one cationic free radical and at least one nitrogen radial species are generated.
irradiating a photoinitiator according to any one of claims 1 to 6 with radiation, wherein at least one cationic free radical and at least one nitrogen radial species are generated.
10. The method of generating a reactive species of Claim 9, wherein the photoinitiator has the general formula:
wherein Z each independently represent wherein R1, R2, R3 and R4 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 having from one to six carbon atoms; R5, R6, R7 and R8 each independently represent an alkyl group having from one to six carbon atoms, an aryl group, a phenyl-substituted alkyl group having from one to six carbon atoms, or a halogen-substituted alkyl group having from one to six carbon atoms; wherein R9 represents (R10)2O or (R10)3N;
wherein R10 represents H or an alkyl group having from one to eight carbon atoms; and wherein R11 represents H, an alkyl group having from one to eight carbon atoms, a benzyl group or an aralkyl group.
wherein Z each independently represent wherein R1, R2, R3 and R4 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 having from one to six carbon atoms; R5, R6, R7 and R8 each independently represent an alkyl group having from one to six carbon atoms, an aryl group, a phenyl-substituted alkyl group having from one to six carbon atoms, or a halogen-substituted alkyl group having from one to six carbon atoms; wherein R9 represents (R10)2O or (R10)3N;
wherein R10 represents H or an alkyl group having from one to eight carbon atoms; and wherein R11 represents H, an alkyl group having from one to eight carbon atoms, a benzyl group or an aralkyl group.
11. The method of generating a reactive species of Claim 10, wherein the photoinitiator comprises:
12. The method of generating a reactive species of Claim 10, wherein the photoinitiator is associated with one or more counterions.
13. The method of generating a reactive species of Claim 12, wherein the one or more counterions comprise tetraphenylboron, tetrachloroboron, tetrafluoroboron, hexafluorophosphate, perchlorate, or a combination thereof.
14. The method of generating a reactive species of Claim 13, wherein the one or more counterions comprise tetraphenylboron or tetrafluoroboron.
15. The method of generating a reactive species of Claim 12, wherein the photoinitiator and the one or more counterions comprise
16. A photoreactive composition comprising at least one photoinitiator according to any one of claims 1 to 6 and at least one counterion, wherein the composition is capable of generating at least one cationic free radical and at least one nitrogen radical species.
17. The photoreactive composition of Claim 16, wherein the photoinitiator having the general formula:
wherein Z each independently represent wherein R1, R2, R3 and R4 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 having from one to six carbon atoms; R5, R6, R7 and R8 each independently represent an alkyl group having from one to six carbon atoms, an aryl group, a phenyl-substituted alkyl group having from one to six carbon atoms, or a halogen-substituted alkyl group having from one to six carbon atoms; wherein R9 represents (R10)2O or (R10)3N;
wherein R10 represents H or an alkyl group having from one to eight carbon atoms; and wherein R11 represents H, an alkyl group having from one to eight carbon atoms, a benzyl group or an aralkyl group.
wherein Z each independently represent wherein R1, R2, R3 and R4 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 having from one to six carbon atoms; R5, R6, R7 and R8 each independently represent an alkyl group having from one to six carbon atoms, an aryl group, a phenyl-substituted alkyl group having from one to six carbon atoms, or a halogen-substituted alkyl group having from one to six carbon atoms; wherein R9 represents (R10)2O or (R10)3N;
wherein R10 represents H or an alkyl group having from one to eight carbon atoms; and wherein R11 represents H, an alkyl group having from one to eight carbon atoms, a benzyl group or an aralkyl group.
18. The photoreactive composition of Claim 16, wherein the photoinitiator comprises:
19. The photoreactive composition of Claim 16, wherein the at least one counterion comprises tetraphenylboron, tetrachloroboron, tetrafluoroboron, hexafluorophosphate, perchlorate, or a combination thereof
20. The photoreactive composition of Claim 16, wherein the composition comprises
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Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
ATE527119T1 (en) * | 2002-07-01 | 2011-10-15 | Inca Digital Printers Ltd | PRESSURE APPARATUS AND METHOD |
GB2396331A (en) * | 2002-12-20 | 2004-06-23 | Inca Digital Printers Ltd | Curing ink |
US8409618B2 (en) | 2002-12-20 | 2013-04-02 | Kimberly-Clark Worldwide, Inc. | Odor-reducing quinone compounds |
EP1572467B1 (en) * | 2002-12-20 | 2019-10-23 | Inca Digital Printers Limited | Curing |
US6780896B2 (en) | 2002-12-20 | 2004-08-24 | Kimberly-Clark Worldwide, Inc. | Stabilized photoinitiators and applications thereof |
US7666410B2 (en) | 2002-12-20 | 2010-02-23 | Kimberly-Clark Worldwide, Inc. | Delivery system for functional compounds |
US7262229B2 (en) * | 2004-05-03 | 2007-08-28 | Flint Group | Ink for excimer curing |
FR2876983B1 (en) * | 2004-10-22 | 2007-02-16 | Eads Space Transp Sa Sa | RIGIDIFICATION OF INFLATABLE DEPLOYMENT STRUCTURES ESPECIALLY FOR SPATIAL USE |
US7763061B2 (en) | 2004-12-23 | 2010-07-27 | Kimberly-Clark Worldwide, Inc. | Thermal coverings |
KR101297917B1 (en) * | 2005-08-30 | 2013-08-27 | 어드밴스드 테크놀러지 머티리얼즈, 인코포레이티드 | Boron ion implantation using alternative fluorinated boron precursors, and formation of large boron hydrides for implantation |
US20100112795A1 (en) * | 2005-08-30 | 2010-05-06 | Advanced Technology Materials, Inc. | Method of forming ultra-shallow junctions for semiconductor devices |
US7935538B2 (en) | 2006-12-15 | 2011-05-03 | Kimberly-Clark Worldwide, Inc. | Indicator immobilization on assay devices |
US7785496B1 (en) | 2007-01-26 | 2010-08-31 | Clemson University Research Foundation | Electrochromic inks including conducting polymer colloidal nanocomposites, devices including the electrochromic inks and methods of forming same |
US8052829B2 (en) * | 2007-10-26 | 2011-11-08 | Dymax Corporation | Photopolymerizable compositions containing an oxonol dye |
US20090157024A1 (en) * | 2007-12-14 | 2009-06-18 | Kimberly-Clark Worldwide, Inc. | Hydration Test Devices |
US8134042B2 (en) | 2007-12-14 | 2012-03-13 | Kimberly-Clark Worldwide, Inc. | Wetness sensors |
US8222476B2 (en) | 2008-10-31 | 2012-07-17 | Kimberly-Clark Worldwide, Inc. | Absorbent articles with impending leakage sensors |
US20110021011A1 (en) | 2009-07-23 | 2011-01-27 | Advanced Technology Materials, Inc. | Carbon materials for carbon implantation |
US8138071B2 (en) * | 2009-10-27 | 2012-03-20 | Advanced Technology Materials, Inc. | Isotopically-enriched boron-containing compounds, and methods of making and using same |
US8062965B2 (en) * | 2009-10-27 | 2011-11-22 | Advanced Technology Materials, Inc. | Isotopically-enriched boron-containing compounds, and methods of making and using same |
US8598022B2 (en) | 2009-10-27 | 2013-12-03 | Advanced Technology Materials, Inc. | Isotopically-enriched boron-containing compounds, and methods of making and using same |
TWI386983B (en) | 2010-02-26 | 2013-02-21 | Advanced Tech Materials | Method and apparatus for enhanced lifetime and performance of ion source in an ion implantation system |
US8779383B2 (en) | 2010-02-26 | 2014-07-15 | Advanced Technology Materials, Inc. | Enriched silicon precursor compositions and apparatus and processes for utilizing same |
US8623292B2 (en) | 2010-08-17 | 2014-01-07 | Kimberly-Clark Worldwide, Inc. | Dehydration sensors with ion-responsive and charged polymeric surfactants |
US9205392B2 (en) | 2010-08-30 | 2015-12-08 | Entegris, Inc. | Apparatus and method for preparation of compounds or intermediates thereof from a solid material, and using such compounds and intermediates |
TWI583442B (en) | 2011-10-10 | 2017-05-21 | 恩特葛瑞斯股份有限公司 | B2f4 manufacturing process |
KR20220025123A (en) | 2012-02-14 | 2022-03-03 | 엔테그리스, 아이엔씨. | Carbon dopant gas and co-flow for implant beam and source life performance |
SG11201601015RA (en) | 2013-08-16 | 2016-03-30 | Entegris Inc | Silicon implantation in substrates and provision of silicon precursor compositions therefor |
WO2016138331A1 (en) | 2015-02-27 | 2016-09-01 | Kimberly-Clark Worldwide, Inc. | Absorbent article leakage assessment system |
KR102099784B1 (en) | 2017-04-05 | 2020-04-10 | 킴벌리-클라크 월드와이드, 인크. | Absorbent article leak detection clothing and absorbent article leak detection method using the same |
Family Cites Families (359)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CA461082A (en) | 1949-11-15 | Jozsef Biro Laszlo | Writing paste | |
CA779239A (en) | 1968-02-27 | General Electric Company | Information recording | |
US28789A (en) | 1860-06-19 | Boiler foe | ||
CA458808A (en) | 1949-08-09 | L. Gardner Frank | Cleat assembly for athletic shoes | |
US1325971A (en) | 1919-12-23 | Kazue akashi | ||
CA571792A (en) | 1959-03-03 | Ciba Limited | Process for printing textiles and printing preparations therefor | |
US3123647A (en) | 1964-03-03 | Certificate of correction | ||
US28225A (en) | 1860-05-08 | Improvement in apparatus for defecating cane-juice | ||
CA93103A (en) | 1905-04-18 | 1905-05-16 | George Nikel | Elevator bucket |
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 |
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 |
DE503314C (en) | 1929-07-30 | 1930-07-29 | I G Farbenindustrie Akt Ges | Layers of fading paint |
BE369421A (en) | 1929-09-09 | |||
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 |
US2049005A (en) | 1932-01-04 | 1936-07-28 | Gaspar Bela | Color-photographic bleach out dyestuff layers |
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 |
BE417861A (en) | 1935-05-04 | |||
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 |
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 | |||
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 |
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 |
NL54339C (en) | 1939-11-20 | |||
US2312751A (en) | 1940-05-08 | 1943-03-02 | Standard Oil Dev Co | Preparation of unsaturated ketones |
GB600451A (en) | 1940-11-06 | 1948-04-09 | American Cyanamid Co | Direct dye planographic printing compositions |
US2346090A (en) | 1942-08-19 | 1944-04-04 | Eastman Kodak Co | Photographic bleach-out layer |
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 |
US2647080A (en) | 1950-06-30 | 1953-07-28 | Du Pont | Light-stabilized photopolymerization of acrylic esters |
DE903529C (en) | 1951-09-01 | 1954-02-08 | Kalle & Co Ag | Photosensitive layers |
US2732301A (en) | 1952-10-15 | 1956-01-24 | Chxcxch | |
BE529607A (en) | 1953-06-18 | |||
BE540426A (en) | 1953-07-13 | |||
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 |
US2936241A (en) | 1957-05-16 | 1960-05-10 | Sperry Rand Corp | Non-printing indicia ink |
US2940853A (en) | 1958-08-21 | 1960-06-14 | Eastman Kodak Co | Azide sensitized resin photographic resist |
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 |
IT649406A (en) | 1960-03-24 | |||
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 |
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 |
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 |
US3300314A (en) | 1963-02-01 | 1967-01-24 | Eastman Kodak Co | Nonsilver, light-sensitive photographic elements |
US3284205A (en) | 1963-09-17 | 1966-11-08 | Horizons Inc | Benzotriazole and heterocyclic ketimide activators for leuco compounds |
NL125868C (en) | 1964-01-29 | |||
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 |
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 |
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 |
US3488269A (en) | 1965-09-15 | 1970-01-06 | Technical Operations Inc | Labile hydrogen initiators for visible light photopolymerization |
US3502476A (en) | 1965-10-20 | 1970-03-24 | Konishiroku Photo Ind | Light-sensitive photographic materials |
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 |
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 |
US3607863A (en) | 1967-02-28 | 1971-09-21 | Dyckerhoff Zementwerke Ag | Clathrate compounds |
SE312870B (en) | 1967-07-17 | 1969-07-28 | Asea Ab | |
US3642472A (en) | 1967-08-30 | 1972-02-15 | Holotron Corp | Bleaching of holograms |
US3574624A (en) | 1968-02-08 | 1971-04-13 | Eastman Kodak Co | Photographic elements containing dithiolium salts |
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 |
DE1769854C3 (en) | 1968-07-26 | 1982-08-19 | Bayer Ag, 5090 Leverkusen | Photoinitiators and processes for photopolymerization |
US3595658A (en) | 1968-10-03 | 1971-07-27 | Little Inc A | Non-silver direct positive dye bleachout system using polymethine dyes and colored activators |
US3595659A (en) | 1968-10-03 | 1971-07-27 | Little Inc A | Non-silver direct positive dye bleachout system using indigoid dyes and colored activators |
US3595657A (en) | 1968-10-03 | 1971-07-27 | Little Inc A | Non-silver direct positive dye bleachout system using indigoid dyes and colorless activators |
US3595655A (en) | 1968-10-03 | 1971-07-27 | Little Inc A | Non-silver direct positive dyes bleachout system using polymethine dyes and colorless activators |
US3914166A (en) | 1968-11-06 | 1975-10-21 | Bayer Ag | Butyric acid derivatives as novel photosensitizers |
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 |
BE757961A (en) * | 1969-10-24 | 1971-04-01 | Ici Ltd | METHODS FOR SAVING AN IMAGE |
US3695879A (en) | 1970-04-20 | 1972-10-03 | Ibm | Hologram life extension |
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 |
NL7113828A (en) | 1970-10-15 | 1972-04-18 | ||
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 | ||
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 |
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 |
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 |
US3933682A (en) | 1973-01-31 | 1976-01-20 | Sun Chemical Corporation | Photopolymerization co-initiator systems |
JPS5148516B2 (en) | 1973-02-07 | 1976-12-21 | ||
US3915824A (en) | 1973-03-30 | 1975-10-28 | Scm Corp | Uv and laser curing of the polymerizable binder |
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 | ||
GB1469641A (en) | 1973-09-20 | 1977-04-06 | Agfa Gevaert | 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 |
US3984248A (en) | 1974-02-19 | 1976-10-05 | Eastman Kodak Company | Photographic polymeric film supports containing photobleachable o-nitroarylidene dyes |
US3988154A (en) | 1974-02-19 | 1976-10-26 | Eastman Kodak Company | Photographic supports and elements utilizing photobleachable omicron-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 |
GB1489419A (en) | 1974-11-30 | 1977-10-19 | Ciba Geigy Ag | Polymerisable esters |
US4179577A (en) | 1974-11-30 | 1979-12-18 | Ciba-Geigy Corporation | Polymerisable esters derived from a phenolic unsaturated ketone |
US4181807A (en) | 1974-11-30 | 1980-01-01 | Ciba-Geigy Corporation | Polymerizable esters derived from a glycidyl ether of a phenolic unsaturated ketone |
JPS5442617B2 (en) | 1974-12-28 | 1979-12-15 | ||
DE2500520A1 (en) | 1975-01-08 | 1976-07-15 | Schickedanz Willi | METHOD OF MAKING COLOR COPIES |
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 |
JPS5299776A (en) | 1976-02-18 | 1977-08-22 | Hitachi Ltd | Radiation sensitive high polymeric material |
US4144156A (en) | 1976-04-14 | 1979-03-13 | Basf Aktiengesellschaft | Manufacture of unsymmetric monoacetals of aromatic 1,2-diketones employable as photoiniatiators |
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 |
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 |
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 |
US4141807A (en) | 1977-03-01 | 1979-02-27 | Stauffer Chemical Company | Photopolymerizable composition stabilized with nitrogen-containing aromatic compounds |
DE2722264C2 (en) | 1977-05-17 | 1984-06-28 | Merck Patent Gmbh, 6100 Darmstadt | Use of substituted oxyalkylphenones as photosensitizers |
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 |
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 |
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 |
US4345011A (en) | 1978-01-30 | 1982-08-17 | Eastman Kodak Company | Color imaging devices and color filter arrays using photo-bleachable dyes |
US4199420A (en) | 1978-04-06 | 1980-04-22 | Stauffer Chemical Company | Alkoxymethylbenzophenones as photoinitiators for photopolymerizable compositions and process based thereon |
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 |
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 |
JPS5550001A (en) | 1978-10-06 | 1980-04-11 | Fuji Photo Film Co Ltd | Photo-polymerizable composition |
JPS5577742A (en) | 1978-12-08 | 1980-06-11 | Fuji Photo Film Co Ltd | Photosensitive composition |
JPS5592370A (en) | 1978-12-29 | 1980-07-12 | Nissan Chem Ind Ltd | Phenoxypyridine derivative and its preparation |
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 |
JPS55133032A (en) | 1979-04-03 | 1980-10-16 | Ricoh Co Ltd | Photosensitive composition |
US4289844A (en) | 1979-06-18 | 1981-09-15 | Eastman Kodak Company | Photopolymerizable compositions featuring novel co-initiators |
JPS566236A (en) | 1979-06-28 | 1981-01-22 | Fuji Photo Film Co Ltd | Photosensitive material and pattern forming method using it |
JPS5664335A (en) | 1979-10-29 | 1981-06-01 | Fuji Photo Film Co Ltd | Photosensitive composition |
JPS5677189A (en) | 1979-11-30 | 1981-06-25 | Fuji Photo Film Co Ltd | Recording material |
US4370401A (en) | 1979-12-07 | 1983-01-25 | Minnesota Mining And Manufacturing Company | Light sensitive, thermally developable imaging system |
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 |
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 |
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 |
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 |
EP0040177B1 (en) | 1980-05-13 | 1983-07-20 | Ciba-Geigy Ag | Process for the preparation of benzene or naphthalene alkenyl carboxylic acid derivatives |
US4307182A (en) | 1980-05-23 | 1981-12-22 | Minnesota Mining And Manufacturing Company | Imaging systems with tetra(aliphatic) borate salts |
US4343891A (en) | 1980-05-23 | 1982-08-10 | Minnesota Mining And Manufacturing Company | Fixing of tetra (hydrocarbyl) borate salt imaging systems |
JPS56167139A (en) | 1980-05-27 | 1981-12-22 | Daikin Ind Ltd | Sensitive material |
JPS5720734A (en) | 1980-07-15 | 1982-02-03 | Fuji Photo Film Co Ltd | Heat developing photosensitive material |
US4416961A (en) | 1980-09-11 | 1983-11-22 | Eastman Kodak Company | Color imaging devices and color filter arrays using photo-bleachable dyes |
DE3041153A1 (en) | 1980-10-31 | 1982-06-16 | Bayer Ag, 5090 Leverkusen | METHOD FOR IMPROVING THE LIGHT FASTNESS OF POLYAMIDE COLORS |
US4369283A (en) | 1981-03-06 | 1983-01-18 | E. I. Du Pont De Nemours & Company | High solids can coating composition containing epoxy, acrylic and aminoplast resins |
US4372582A (en) | 1981-03-30 | 1983-02-08 | Minnesota Mining And Manufacturing Company | Stabilizer for electron doner-acceptor carbonless copying systems |
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 |
EP0088050B1 (en) | 1982-02-26 | 1986-09-03 | Ciba-Geigy Ag | Coloured photo-hardenable composition |
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 |
EP0108037B1 (en) | 1982-10-01 | 1989-06-07 | Ciba-Geigy Ag | Propiophenone derivatives as photoinitiators in the photopolymerization |
US4447521A (en) | 1982-10-25 | 1984-05-08 | Minnesota Mining And Manufacturing Company | Fixing of tetra(hydrocarbyl)borate salt imaging systems |
US4450227A (en) | 1982-10-25 | 1984-05-22 | Minnesota Mining And Manufacturing Company | Dispersed imaging systems with tetra (hydrocarbyl) borate salts |
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 |
US4559371A (en) | 1983-02-18 | 1985-12-17 | Ciba Geigy Corporation | Photocurable colored compositions employing alpha-amino phenone initiator |
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 |
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. |
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 |
US4702996A (en) | 1983-09-28 | 1987-10-27 | General Electric Company | Method of enhancing the contrast of images and materials therefor |
JPS6083029A (en) | 1983-10-13 | 1985-05-11 | Mitsui Toatsu Chem Inc | Optical recording medium |
GB8333853D0 (en) | 1983-12-20 | 1984-02-01 | Ciba Geigy Ag | Production of images |
US4571377A (en) | 1984-01-23 | 1986-02-18 | Battelle Memorial Institute | Photopolymerizable composition containing a photosensitive donor and photoinitiating acceptor |
JPH0697339B2 (en) | 1984-02-02 | 1994-11-30 | 富士写真フイルム株式会社 | Photopolymerizable composition |
GB8402937D0 (en) | 1984-02-03 | 1984-03-07 | Ciba Geigy Ag | Production of images |
US4701402A (en) | 1984-02-13 | 1987-10-20 | Minnesota Mining And Manufacturing Company | Oxidative imaging |
US4620875A (en) | 1984-04-10 | 1986-11-04 | Ricoh Company, Ltd. | Aqueous ink composition |
US4534838A (en) | 1984-04-16 | 1985-08-13 | Loctite Corporation | Siloxane polyphotoinitiators of the substituted acetophenone type |
US4745042A (en) | 1984-04-19 | 1988-05-17 | Matsushita Electric Industrial Co., Ltd. | Water-soluble photopolymer and method of forming pattern by use of the same |
JPS60264279A (en) | 1984-06-13 | 1985-12-27 | Fuji Photo Film Co Ltd | Recording material |
JPS612771A (en) | 1984-06-14 | 1986-01-08 | Taoka Chem Co Ltd | Ink composition |
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 |
US4632891A (en) | 1984-10-04 | 1986-12-30 | Ciba-Geigy Corporation | Process for the production of images |
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 |
JPS61101568A (en) | 1984-10-23 | 1986-05-20 | Ricoh Co Ltd | Water based ink |
US4565769A (en) | 1984-11-21 | 1986-01-21 | E. I. Du Pont De Nemours And Company | Polymeric sensitizers for photopolymer composition |
IE56890B1 (en) | 1984-12-30 | 1992-01-15 | Scully Richard L | Photosensitive composition for direct positive colour photograph |
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 |
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 |
US4772541A (en) | 1985-11-20 | 1988-09-20 | The Mead Corporation | Photohardenable compositions containing a dye borate complex and photosensitive materials employing the same |
DE3650107T2 (en) | 1985-11-20 | 1995-05-24 | Mead Corp | Ionic dyes. |
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 |
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 |
US4925770A (en) | 1986-05-20 | 1990-05-15 | Director General Of Agency Of Industrial Science And Technology | Contrast-enhancing agent for photolithography |
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 |
US4711802A (en) | 1986-08-14 | 1987-12-08 | E. I. Du Pont De Nemours And Company | Aqueous ink for use on fluorocarbon surfaces |
JPH0610727B2 (en) | 1986-09-17 | 1994-02-09 | 富士写真フイルム株式会社 | Photoresponsive material |
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 |
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 |
US4902725A (en) | 1986-12-22 | 1990-02-20 | General Electric Company | Photocurable acrylic coating composition |
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 |
ES2054861T3 (en) | 1987-03-26 | 1994-08-16 | Ciba Geigy Ag | NEW ALPHA-AMINO ACETOPHENONES AS PHOTO INITIATORS. |
US4766050A (en) | 1987-03-27 | 1988-08-23 | The Mead Corporation | Imaging system with integral cover sheet |
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 |
US4853037A (en) | 1987-10-30 | 1989-08-01 | Hewlett-Packard Company | Low glycol inks for plain paper printing |
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 |
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 |
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 |
US5187045A (en) | 1988-09-07 | 1993-02-16 | Minnesota Mining And Manufacturing Company | Halomethyl-1,3,5-triazines containing a sensitizer moiety |
US5034526A (en) | 1988-09-07 | 1991-07-23 | Minnesota Mining And Manufacturing Company | Halomethyl-1,3,5-triazines containing a sensitizer moiety |
DE3830914A1 (en) | 1988-09-10 | 1990-03-22 | Hoechst Ag | PHOTOPOLYMERIZABLE MIXTURE, RECORDING MATERIAL MADE THEREOF, AND METHOD FOR PRODUCING COPIES |
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 |
EP0368327B1 (en) | 1988-11-11 | 1995-02-15 | Fuji Photo Film Co., Ltd. | Light-sensitive composition |
US5045435A (en) | 1988-11-25 | 1991-09-03 | Armstrong World Industries, Inc. | Water-borne, alkali-developable, photoresist coating compositions and their preparation |
US5185236A (en) | 1988-12-09 | 1993-02-09 | Fuji Photo Film Co., Ltd. | Full color recording materials and a method of forming colored images |
JP2604453B2 (en) | 1988-12-14 | 1997-04-30 | 積水化学工業株式会社 | Acrylic adhesive tape |
US4954416A (en) | 1988-12-21 | 1990-09-04 | Minnesota Mining And Manufacturing Company | Tethered sulfonium salt photoinitiators for free radical polymerization |
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 |
US5230982A (en) | 1989-03-09 | 1993-07-27 | The Mead Corporation | Photoinitiator compositions containing disulfides and photohardenable compositions containing the same |
EP0388837B1 (en) * | 1989-03-21 | 1996-04-10 | Ciba-Geigy Ag | Initiators for cationically polymerisable materials |
KR900014930A (en) | 1989-03-27 | 1990-10-25 | 로레인 제이. 프란시스 | Dye borate photoinitiator and photocurable composition containing same |
EP0425429B1 (en) | 1989-08-25 | 1995-02-22 | Ciba-Geigy Ag | Light stabilised inks |
US5362916A (en) | 1989-09-06 | 1994-11-08 | Tropix, Inc. | Synthesis of mercaptaryl or hydroxyaryl enol ether alkali metal salts |
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 |
JPH03155554A (en) | 1989-11-14 | 1991-07-03 | Japan Synthetic Rubber Co Ltd | Radiation sensitive resin composition |
US5026425A (en) | 1989-12-11 | 1991-06-25 | Hewlett-Packard Company | Waterfastness of DB-168 ink by cation substitution |
JP2632066B2 (en) | 1990-04-06 | 1997-07-16 | 富士写真フイルム株式会社 | Positive image forming method |
US5053320A (en) | 1990-04-16 | 1991-10-01 | Richard L. Scully | Direct dry negative color printing process and composition |
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 |
US5187049A (en) | 1990-07-16 | 1993-02-16 | Minnesota Mining And Manufacturing Company | Photosensitive thermally developed compositions |
JP3244288B2 (en) | 1990-07-23 | 2002-01-07 | 昭和電工株式会社 | Near infrared decolorable recording material |
TW207021B (en) | 1990-07-23 | 1993-06-01 | Showa Denko Kk | |
US5089374A (en) | 1990-08-20 | 1992-02-18 | Eastman Kodak Company | Novel bis-onium salts and the use thereof as photoinitiators |
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 |
US5224197A (en) | 1990-09-06 | 1993-06-29 | The United States Of America As Represented By The Secretary Of The Air Force | Integrated optics using photodarkened polystyrene |
US5208136A (en) | 1990-09-06 | 1993-05-04 | The United States Of America As Represented By The Secretary Of The Air Force | Fabricating of integrated optics |
JP2642776B2 (en) | 1990-09-10 | 1997-08-20 | 三田工業株式会社 | Information recording medium and information recording method |
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 |
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 |
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 |
EP0542286B1 (en) | 1991-11-14 | 1996-07-17 | Showa Denko Kabushikikaisha | Decolorizable toner |
DE4142956C2 (en) | 1991-12-24 | 1996-08-14 | Du Pont Deutschland | Bleachable antihalation system for photographic materials |
US5219703A (en) | 1992-02-10 | 1993-06-15 | Eastman Kodak Company | Laser-induced thermal dye transfer with bleachable near-infrared absorbing sensitizers |
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 |
US5344483A (en) | 1992-03-30 | 1994-09-06 | Porelon, Inc. | High-density, low-viscosity ink for use in ink jet printers |
US5503664A (en) | 1992-05-20 | 1996-04-02 | 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 |
US5296275A (en) | 1992-07-01 | 1994-03-22 | Xytronyx, Inc. | Phototranschromic ink |
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 |
JP3176444B2 (en) | 1992-10-01 | 2001-06-18 | 株式会社リコー | Aqueous ink and recording method using the same |
DE4234222A1 (en) | 1992-10-10 | 1994-04-14 | Cassella Ag | Water-soluble sulfur dyes, their preparation and use |
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 |
US5426164A (en) | 1992-12-24 | 1995-06-20 | The Dow Chemical Company | Photodefinable polymers containing perfluorocyclobutane groups |
US5455074A (en) | 1992-12-29 | 1995-10-03 | Kimberly-Clark Corporation | Laminating method and products made thereby |
US5330860A (en) | 1993-04-26 | 1994-07-19 | E. I. Du Pont De Nemours And Company | Membrane and electrode structure |
US5721287A (en) | 1993-08-05 | 1998-02-24 | Kimberly-Clark Worldwide, Inc. | Method of mutating a colorant by irradiation |
US5506079A (en) | 1994-02-28 | 1996-04-09 | Ricoh Company, Ltd. | Magnetic composition, magnetic toner and ink containing the magnetic composition |
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 |
US5476540A (en) | 1994-10-05 | 1995-12-19 | Hewlett Packard Corporation | Gel-forming inks for use in the alleviation of bleed |
US5849411A (en) | 1995-06-05 | 1998-12-15 | Kimberly-Clark Worldwide, Inc. | Polymer film, nonwoven web and fibers containing a photoreactor composition |
US5798015A (en) | 1995-06-05 | 1998-08-25 | Kimberly-Clark Worldwide, Inc. | Method of laminating a structure with adhesive 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 |
US5811199A (en) | 1995-06-05 | 1998-09-22 | Kimberly-Clark Worldwide, Inc. | Adhesive compositions containing a photoreactor composition |
GB9515304D0 (en) | 1995-07-26 | 1995-09-20 | Ilford Ag | Azo dyes |
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 |
JP3206439B2 (en) | 1996-06-28 | 2001-09-10 | 東海興業株式会社 | Molding manufacturing method and apparatus |
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 |
TW452575B (en) | 1996-12-06 | 2001-09-01 | Ciba Sc Holding Ag | New Α-aminoacetophenone photoinitiators and photopolymerizable compositions comprising these photoinitiators |
-
2001
- 2001-06-19 AU AU2001269905A patent/AU2001269905A1/en not_active Abandoned
- 2001-06-19 MX MXPA02012011A patent/MXPA02012011A/en active IP Right Grant
- 2001-06-19 EP EP01948460A patent/EP1297022B1/en not_active Expired - Lifetime
- 2001-06-19 US US09/884,896 patent/US6486227B2/en not_active Expired - Lifetime
- 2001-06-19 JP JP2002505857A patent/JP2004501987A/en not_active Abandoned
- 2001-06-19 KR KR1020027017284A patent/KR100772772B1/en active IP Right Grant
- 2001-06-19 DE DE60121588T patent/DE60121588T2/en not_active Expired - Lifetime
- 2001-06-19 AT AT01948460T patent/ATE333471T1/en not_active IP Right Cessation
- 2001-06-19 WO PCT/US2001/019525 patent/WO2002000735A1/en active IP Right Grant
- 2001-06-19 CA CA2412607A patent/CA2412607C/en not_active Expired - Fee Related
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MXPA02012011A (en) | 2003-04-22 |
DE60121588D1 (en) | 2006-08-31 |
JP2004501987A (en) | 2004-01-22 |
WO2002000735A1 (en) | 2002-01-03 |
US20020099111A1 (en) | 2002-07-25 |
AU2001269905A1 (en) | 2002-01-08 |
ATE333471T1 (en) | 2006-08-15 |
EP1297022A1 (en) | 2003-04-02 |
US6486227B2 (en) | 2002-11-26 |
CA2412607A1 (en) | 2002-01-03 |
DE60121588T2 (en) | 2006-11-16 |
EP1297022B1 (en) | 2006-07-19 |
KR100772772B1 (en) | 2007-11-01 |
KR20030011359A (en) | 2003-02-07 |
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