# US 5,707,781 A · Photopolymerizable compositions having acyl or diacyl phosphine oxide and a fluorescent optical brightner > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 5,707,781 A - Document ID: US5707781A - Status: Granted - Kind: A - Application number: 08/435,560 - Filed: 1995-05-05 - Granted: 1998-01-13 - Earliest claimed: 1995-05-05 - Assignees: Bayer Aktiengesellschaft - Inventors: Wojciech A. Wilczak - Web page: https://patentgrep.com/patent/US5707781A ## CPC - G03F 3/10: Checking the colour or tonal value of separation negatives or positives - C08F 2/50: with sensitising agents - C08F 4/32: Organic compounds - C08F 257/02: on to polymers of styrene or alkyl-substituted styrenes - G03F 7/029: Inorganic compounds; Onium compounds; Organic compounds having hetero atoms other than oxygen, nitrogen or sulfur - Y10S 430/114: Initiator containing - Y10S 430/116: Redox or dye sensitizer - Y10S 430/134: Brightener containing - 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; (phototypographic composing devices B41B; photosensitive materials or processes for photographic purposes G03C; electrophotography, sensitive layers or processes therefor G03G) - C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS - Y10S: TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS ## Abstract The present invention relates a photopolymerizable composition which comprises: A) one or more ethylenically unsaturated, free-radical polymerizable monomers; B) one or more organic binders; and C) one or more photoinitiators, wherein the photoinitiator is an acyl or diacyl phosphine oxide, in combination with a fluorescent optical brightener; and a process for producing such a photopolymerizable composition. ## Claims ### Claim 1 A photopolymerizable composition which comprises: A) one or more ethylenically unsaturated, free-radical polymerizable monomers; B) one or more organic binders; and C) one or more photoinitiators, wherein the photoinitiator is an acyl or diacyl phosphine oxide, in combination with a fluorescent optical brightener selected from the group consisting of 2,2'-(thiophenediyl)-bis-(t-butyl benzoxazole); 2-(stibyl-4")-(naphtho-1',2',4,5)-1,2,3-triazole-2"-sulfonic acid phenyl ester; 7-(4'-chloro-6"-diethylamino-1',3',5'-triazine-4'-yl)amino-3-phenyl coumarin; wherein said optical brightener is present in an amount sufficient to enhance the photosensitivity of the acyl or diacyl phosphine oxide. ### Claim 2 (depends on 1) The composition of claim 1 comprising from about 20 weight percent to about 50 weight percent of the one or more ethylenically unsaturated, free-radical polymerizable monomers; from about 40 weight percent to about 70 weight percent of the one or more organic binders; and from about 5 weight percent to about 15 weight percent of the one or more photoinitiators. ### Claim 3 (depends on 1) The composition of claim 1 comprising from about 10 weight percent to about 60 weight percent of the one or more ethylenically unsaturated, free-radical polymerizable monomers. ### Claim 4 (depends on 1) The composition of claim 1 comprising from about 5 weight percent to about 70 weight percent of the one or more ethylenically unsaturated, free-radical polymerizable monomers. ### Claim 5 (depends on 1) The composition of claim 1 comprising from about 20 weight percent to about 80 weight percent of the one or more organic binders. ### Claim 6 (depends on 1) The composition of claim 1 comprising from about 30 weight percent to about 70 weight percent of the one or more organic binders. ### Claim 7 (depends on 1) The composition of claim 1 comprising from about 3 weight percent to about 20 weight percent of the one or more photoinitiators. ### Claim 8 (depends on 1) The composition of claim 1 comprising from about 1 weight percent to about 30 weight percent of the one or more photoinitiators. ### Claim 9 (depends on 1) The composition of claim 1 wherein the one or more ethylenically unsaturated, free-radical polymerizable monomers is an acrylate or methacrylate. ### Claim 10 (depends on 1) The composition of claim 1 wherein the one or more organic binders is selected from the group consisting of styrene/maleic anhydride copolymers and their half esters; acrylic polymers and copolymers; polyamides; polyvinyl pyrrolidones; cellulosic resins; phenolic resins; polyvinyl acetals; polyvinyl acetates and their copolymers; and mixtures thereof. ### Claim 11 (depends on 1) The composition of claim 1 wherein the acryl and diacyl phosphine oxide have the following formulas: ##STR2## where: R.sub.1 and R.sub.6 is a branched or unbranched alkyl of 1 to 18 carbon atoms, substituted or unsubstituted cycloalkyl of 5 or 6 carbon atoms, C.sub.6 -C.sub.18 aryl which is unsubstituted or substituted by a C.sub.1 -C.sub.18 alkyl or C.sub.1 -C.sub.18 alkoxy, or an S-containing or N-containing five-membered or six-membered heterocyclic radical, R.sub.1 and R.sub.6 being the same or different, R.sub.2 has the same meaning as R.sub.1, or is C.sub.1 -C.sub.18 alkoxy, C.sub.6 -C.sub.18 aryloxy or aralkoxy (C.sub.6 -C.sub.18 aryl, C.sub.1 -C.sub.18 alkyl), R.sub.1 and R.sub.2 being the same or different or together to form a ring; and R.sub.3, R.sub.4 and R.sub.5 are a tertiary alkyl of 4 to 18 carbon atoms, or a tertiary cycloalkyl of 5 or 6 carbon atoms, or is a C.sub.6 -C.sub.18 cycloalkyl, C.sub.6 -C.sub.18 aryl, or 5-membered or 6-membered heterocyclic radical containing S, N or O as heteroatoms which contain substituents A and B bonded at least to the two ring carbon atoms, capable of substitution, which are adjacent to the point of attachment to the carbonyl group of the R.sub.3 group, A and B being identical or different, and each being C.sub.1 -C.sub.18 alkyl, C.sub.1 -C.sub.18 alkoxy, C.sub.1 -C.sub.18 alkoxy, C.sub.1 -C.sub.18 alkyl C.sub.1 -C.sub.18 alkylthio, C.sub.6 -C.sub.18 cycloalkyl, C.sub.6 -C.sub.18 aryl or halogen, R.sub.3, R.sub.4 and R.sub.5 can be the same or different. ### Claim 12 A process for enhancing the photosensitivity of a photopolymerizable composition which composition comprises an admixture of: A) one or more ethylenically unsaturated, free-radical polymerizable monomers; B) one or more organic binders; and C) an acyl or diacyl phosphine oxide compound, the process comprising combining with said admixture a fluorescent optical brightener selected from the group consisting of 2,2'-(thiophenediyl)-bis-(t-butyl benzoxazole); 2-(stibyl-4")-(naphtho-1',2',4,5)-1,2,3-triazole-2"-sulfonic acid phenyl ester; 7-(4'-chloro-6"-diethylamino-1',3',5'-triazine-4'-yl)amino-3-phenyl coumarin; wherein said optical brightener is present in an amount sufficient to enhance the photosensitivity of the acyl or diacyl phosphine oxide. ### Claim 13 (depends on 12) The process of claim 12 comprising from about 20 weight percent to about 50 weight percent of the one or more ethylenically unsaturated, free-radical polymerizable monomers; from about 40 weight percent to about 70 weight percent of the one or more organic binders; and from about 5 weight percent to about 15 weight percent of the one or more photoinitiators. ### Claim 14 (depends on 12) The process of claim 12 comprising from about 10 weight percent to about 60 weight percent of the one or more ethylenically unsaturated, free-radical polymerizable monomers. ### Claim 15 (depends on 12) The process of claim 12 comprising from about 5 weight percent to about 70 weight percent of the one or more ethylenically unsaturated, free-radical polymerizable monomers. ### Claim 16 (depends on 12) The process of claim 12 comprising from about 20 weight percent to about 80 weight percent of the one or more organic binders. ### Claim 17 (depends on 12) The process of claim 12 comprising from about 30 weight percent to about 70 weight percent of the one or more organic binders. ### Claim 18 (depends on 12) The process of claim 12 comprising from about 3 weight percent to about 20 weight percent of the one or more photoinitiators. ### Claim 19 (depends on 12) The process of claim 12 comprising from about 1 weight percent to about 30 weight percent of the one or more photoinitiators. ### Claim 20 (depends on 12) The process of claim 12 wherein the one or more ethylenically unsaturated, free-radical polymerizable monomers is an acrylate or methacrylate. ### Claim 21 (depends on 12) The process of claim 12 wherein the one or more organic binders is selected from the group consisting of styrene/maleic anhydride copolymers and their half esters; acrylic polymers and copolymers; polyamides; polyvinyl pyrrolidones; cellulosic resins; phenolic resins; polyvinyl acetals; polyvinyl acetates and their copolymers; and mixtures thereof. ### Claim 22 (depends on 12) The process of claim 12 wherein the acyl and diacyl phosphine oxide has the following formulas: ##STR3## where: R.sub.1 and R.sub.6 is a branched or unbranched alkyl of 1 to 18 carbon atoms, substituted or unsubstituted cycloalkyl of 5 or 6 carbon atoms, C.sub.6 -C.sub.18 aryl which is unsubstituted or substituted by C.sub.1 -C.sub.18 alkyl or C.sub.1 -C.sub.18 alkoxy, or aryl S-containing or N-containing five-membered or six-membered heterocyclic radical, R.sub.1 and R.sub.6 being the same or different, R.sub.2 has the same meaning as R.sub.1, or is C.sub.1 -C.sub.18 alkoxy, C.sub.6 -C.sub.18 aryloxy or aralkoxy (C.sub.6 -C.sub.18 aryl, C.sub.1 -C.sub.18 alkyl), R.sub.1 and R.sub.2 being the same or different or together to form a ring, and R.sub.3, R.sub.4 and R.sub.5 are a tertiary alkyl of 4 to 18 carbon atoms, or a tertiary cycloalkyl of 5 or 6 carbon atoms, or is a C.sub.6 -C.sub.18 cycloalkyl, C.sub.6 -C.sub.18 aryl, or 5-membered or 6-membered heterocyclic radical containing S, N or O as heteroatoms which contain substituents A and B bonded at least to the two ring carbon atoms, capable of substitution, which are adjacent to the point of attachment to the carbonyl group of the R.sub.3 group, A and B being identical or different, and each being C.sub.1 -C.sub.18 alkyl, C.sub.1 -C.sub.18 alkoxy, C.sub.1 -C.sub.18 alkoxy, C.sub.1 -C.sub.18 alkyl, C.sub.1 -C.sub.18 alkylthio, C.sub.6 -C.sub.18 cycloalkyl, C.sub.6 -C.sub.18 aryl or halogen R.sub.3, R.sub.4 and R.sub.5 can be the same or different. ### Claim 23 A process for enhancing the photosensitivity of an acyl or diacyl phosphine oxide compound comprising combining with said acyl or diacyl phosphine oxide compound a fluorescent optical brightener selected from the group consisting of 2,2'-(thiophenediyl)-bis-(t-butyl benzoxazole); 2-(stibyl-4")-(naphtho-1',2',4,5)-1,2,3-triazole-2"-sulfonic acid phenyl ester; and 7-(4'-chloro-6"-diethylamino-1',3',5'-triazine-4'-yl)amino-3-phenyl coumarin, wherein said optical brightener is present in an amount sufficient to enhance the photosensitivity of the acyl or diacyl phosphine oxide.