# US 2013/0158148 A1 · Photosensitive silicone resin composition > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 2013/0158148 A1 - Document ID: US20130158148A1 - Status: Published application - Kind: A1 - Application number: 13/816,657 - Filed: 2011-06-15 - Published: 2013-06-20 - Earliest claimed: 2010-08-13 - Assignees: Asahi Kasei E-Materials Corporation - Inventors: Natsumi Tsugane; Hideo Saito; Toru Kusakabe; Motonori Nakamichi - Web page: https://patentgrep.com/patent/US20130158148A1 ## CPC - C08L 83/00: Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers - C08F 299/08: from polysiloxanes - C08K 5/0025: {Crosslinking or vulcanising agents; including accelerators} - C08K 9/06: with silicon-containing compounds - G03F 7/0757: {Macromolecular compounds containing Si-O, Si-C or Si-N bonds (G03F7/0752 takes precedence)} - C08G 77/14: containing silicon bound to oxygen-containing groups - C08G 77/20: containing silicon bound to unsaturated aliphatic groups - G03F 7/0047: {characterised by additives for obtaining a metallic or ceramic pattern, e.g. by firing} - C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06) - C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS - C08K: Use of inorganic or non-macromolecular organic substances as compounding ingredients (paints, inks, varnishes, dyes, polishes, adhesives C09) - 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) - C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS ## Abstract Provided is a resin composition which gives a cured product of a photocurable resin having excellent crack resistance even when formed into a thick film, and capable of maintaining a low coefficient of linear thermal expansion, low thermal weight loss, and a low cure shrinkage. This photosensitive silicone resin composition comprises (A) a silica particle-containing condensation reaction product and (B) a photopolymerization initiator, and is characterized in that the silica particle-containing condensation reaction product (A) is a condensation reaction product of a polysiloxane compound (a) comprising a hydrolytic condensation product of one or more silane compounds represented by the following general formula (1): R1n1SiX14-n1 (wherein R1, n1 and X1 are defined in the claims) and/or the silane compound, and silica particles (b), and has a terminal structure Si—O—Y (wherein Y is defined in the claims) which satisfies the following formula (2): 0<[Si—O—SiR33]/([Si—O—R2]+[Si—O—SiR33])≦1 (wherein, R2 and R3 are defined in the claims), and has a photopolymerizable functional group. ## Claims ### Claim 1 A photosensitive silicone resin composition comprising (A) a silica particle-containing condensation reaction product and (B) a photopolymerization initiator, wherein: the silica particle-containing condensation reaction product (A) is a condensation reaction product of polysiloxane compound (a), composed of a hydrolytic condensation product of one or more types of silane compounds represented by the following general formula (1): R1n1SiX14-n1 (1) (wherein, R1 represents a hydrogen atom or organic group containing 1 to 20 carbon atoms, n1 represents an integer of 0 to 3, X1 represents a group selected from the group consisting of a hydroxyl group, halogen atom, alkoxy group having 1 to 6 carbon atoms and acetoxy group having 1 to 6 carbon atoms, and n1, R1 and X1 may each be the same or different in the case a plurality thereof is present) and/or the silane compound, and silica particles (b), a terminal structure Si—O—Y of the condensation reaction product (A) (wherein, Y represents R2 or SiR33, R2 and R3 represent hydrogen atoms or organic groups having 1 to 20 carbon atoms, and the plurality of R3 may each be the same or different) satisfies the following formula (2): 0<[Si—O—SiR33]/([Si—O—R2]+[Si—O—SiR33])≦1 (2) (wherein, R2 and R3 are as previously described), and the condensation reaction product (A) has a photopolymerizable functional group. ### Claim 2 (depends on 1) The photosensitive silicone resin composition according to claim 1, wherein the photopolymerizable functional group equivalent of the photosensitive silicone resin composition is 0.5 mmol/g to 4.5 mmol/g. ### Claim 3 (depends on 1) The photosensitive silicone resin composition according to claim 1, wherein the [Si—O—SiR33] in formula (2) is derived from one or more types of a silicon compound (c) represented by the following general formula (3): R33 SiX2 (3) (wherein, R3 is the same as defined in formula (2), X2 represents a group selected from the group consisting of a hydroxyl group, halogen atom, alkoxy group having 1 to 6 carbon atoms and acetoxy group having 1 to 6 carbon atoms, and the plurality of R3 present may be the same or different), or the following general formula (4): R33SiNHSiR33 (4) (wherein, R3 is the same as defined in formula (2), and the plurality of R3 present may be the same or different). ### Claim 4 (depends on 1) The photosensitive silicone resin composition according to claim 1, wherein the silica particle-containing condensation reaction product (A) is a condensation reaction product of the polysiloxane compound (a) composed of a hydrolytic condensation product of one or more types of silane compounds represented by general formula (1), or the polysiloxane compound (a) and the silane compound, and the silica particles (b). ### Claim 5 (depends on 1) The photosensitive silicone resin composition according to claim 1, wherein the [Si—O—SiR33] in formula (2) is obtained by reacting a condensation reaction product of the polysiloxane compound (a) and/or the silane compound and the silica particles (b), with the silicon compound (c). ### Claim 6 (depends on 1) The photosensitive silicone resin composition according to claim 1, further comprising a compound (C) having a photopolymerizable functional group in a molecule thereof. ### Claim 7 (depends on 1) The photosensitive silicone resin composition according to claim 1, further comprising (D) an antioxidant and/or ultraviolet absorber. ### Claim 8 (depends on 7) The photosensitive silicone resin composition according to claim 7, comprising 100 parts by weight of the silica particle-containing condensation reaction product (A), 0.01 parts by weight to 50 parts by weight of the photopolymerization initiator (B), 0 parts by weight to 900 parts by weight of the compound (C) having a photopolymerizable function group in a molecule thereof, and 0 parts by weight to 50 parts by weight of the antioxidant and/or ultraviolet absorber (D). ### Claim 9 (depends on 3) The photosensitive silicone resin composition according to claim 3, wherein the photopolymerizable function group in the silica particle-containing condensation reaction product (A) is derived from the polysiloxane compound (a) and/or the silicon compound (c). ### Claim 10 (depends on 6) The photosensitive silicone resin composition according to claim 6, wherein the photopolymerizable functional group in the silica particle-containing condensation reaction product (A) and/or the compound (C) having a photopolymerizable functional group in a molecule thereof is at least one type selected from the group consisting of a (meth)acryloyl group, styryl group, norborneyl group, epoxy group and mercapto group. ### Claim 11 (depends on 3) The photosensitive silicone resin composition according to claim 3, wherein the amount of the silica particles (b) in 100% by weight of the silica particle-containing condensation reaction product (A) is 1% by weight to 80% by weight, and the total amount of the polysiloxane compound (a) and the silicon compound (c) is 20% by weight to 99% by weight. ### Claim 12 (depends on 1) The photosensitive silicone resin composition according to claim 1, wherein the molar ratio {component M/(component M+component D+component T+component Q)}×100 of a component M to the total number of moles of the component M, a component D, a component T and a component Q in the silica particle-containing condensation reaction product (A) excluding the silica particles (b) is 1 mol % to 50 mol %. ### Claim 13 (depends on 1) The photosensitive silicone resin composition according to claim 1, wherein the polysiloxane compound (a) contains a product obtained as a hydrolytic condensation product of a silane compound in which at least n1 of the silane compound represented by general formula (1) is 1. ### Claim 14 (depends on 1) The photosensitive silicone resin composition according to claim 1, wherein the polysiloxane compound (a) contains a product obtained as a hydrolytic condensation product of a silane compound in which at least n1 in the silane compound represented by general formula (1) is 1, and a silane compound in which n1 is 2. ### Claim 15 (depends on 1) The photosensitive silicone resin composition according to claim 1, the ratio of the number of bonds that form siloxane bonds with silicon in the silica particle-containing condensation reaction product (A) to the total number of bonds that respectively form the siloxane bonds, direct bonds with hydroxyl groups and direct bonds with hydrolyzable groups is 40 mol % to 100 mol %. ### Claim 16 (depends on 1) The photosensitive silicone resin composition according to claim 1, wherein the silica particles (b) are produced from an alkoxysilane by a wet method. ### Claim 17 (depends on 1) The photosensitive silicone resin composition according to claim 1, wherein the mean primary particle diameter of the silica particles (b) is 1 nm to 20 nm. ### Claim 18 (depends on 3) The photosensitive silicone resin composition according to claim 3, wherein the silicon compound (c) is a silicon compound in which X2 in the silicon compound represented by general formula (3) is a halogen atom. ### Claim 19 (depends on 6) The photosensitive silicone resin composition according to claim 6, wherein the photopolymerizable functional group in the silica particle-containing condensation reaction product (A) and/or the compound (C) having a photopolymerizable functional group in a molecule thereof is a (meth)acryloyl group and/or styryl group. ### Claim 20 (depends on 6) The photosensitive silicone resin composition according to claim 6, wherein the photopolymerizable functional group in the silica particle-containing condensation reaction product (A) and/or the compound (C) having a photopolymerizable functional group in a molecule thereof is an epoxy group and/or mercapto group. ### Claim 21 (depends on 1) The photosensitive silicone resin composition according to claim 1, wherein the photopolymerization initiator (B) is a photoradical polymerization initiator. ### Claim 22 (depends on 6) The photosensitive silicone resin composition according to claim 6, wherein at least one type of the compound (C) having a photopolymerizable functional group in a molecule thereof contains one or more carbon rings and/or heterocycles in a molecule thereof. ### Claim 23 A production process of a photosensitive silicone resin composition, comprising the following steps: a first step for obtaining a polysiloxane compound (a) by hydrolytically condensing one or more types of silane compounds represented by the following general formula (1): R1n1SiX14-n1 (1) (wherein, R1 represents a hydrogen atom or organic group containing 1 to 20 carbon atoms, n1 represents an integer of 0 to 3, X1 represents a group selected from the group consisting of a halogen atom, alkoxy group having 1 to 6 carbon atoms and acetoxy group having 1 to 6 carbon atoms, and n1, R1 and X1 may each be the same or different in the case a plurality thereof is present), a second step for obtaining a condensation reaction product by condensing the resulting polysiloxane compound (a) and/or the silane compound with silica particles (b), a third step for obtaining a silica particle-containing condensation reaction product (A) by condensing the resulting condensation reaction product with a silicon compound (c) represented by the following general formula (3): R33SiX2 (3) (wherein, R3 represents a hydrogen atom or organic group containing 1 to 20 carbon atoms, X2 represents a group selected from the group consisting of a hydroxyl group, halogen atom, alkoxy group having 1 to 6 carbon atoms and acetoxy group having 1 to 6 carbon atoms, and the plurality of R3 present may be the same or different), or the following general formula (4): R33SiNHSiR33 (4) (wherein, R3 is the same as defined in general formula (3)), and a fourth step for mixing the resulting silica particle-containing condensation reaction product (A) with a photopolymerization initiator (B). ### Claim 24 A production process of a photosensitive silicone resin composition, comprising the following steps: a first step for obtaining a polysiloxane compound (a) by hydrolytically condensing a silane compound at least including a silane compound represented by the following general formula (1): R1n1SiX14-n1 (1) (wherein, R1 represents a hydrogen atom or organic group containing 1 to 20 carbon atoms, n1 represents an integer of 0 to 3, X1 represents a group selected from the group consisting of a hydroxyl group, halogen atom, alkoxy group having 1 to 6 carbon atoms and acetoxy group having 1 to 6 carbon atoms, and n1, R1 and X1 may each be the same or different in the case a plurality thereof is present) in which n1 is 3, a second step for obtaining a condensation reaction product by condensing the resulting polysiloxane compound (a) and/or the silane compound with silica particles (b), a third step for obtaining a silica particle-containing condensation reaction product (A) by condensing the resulting condensation reaction product at with a silane compound at least including a silane compound represented by the following general formula (1): R1n1SiX14-n1 (1) (wherein, R1 represents a hydrogen atom or organic group containing 1 to 20 carbon atoms, n1 represents an integer of 0 to 3, X1 represents a group selected from the group consisting of a hydroxyl group, halogen atom, alkoxy group having 1 to 6 carbon atoms and acetoxy group having 1 to 6 carbon atoms, and n1, R1 and X1 may each be the same or different in the case a plurality thereof is present) in which n1 is 1 or 2, and a fourth step for mixing the resulting silica particle-containing condensation reaction product (A) with a photopolymerization initiator (B). ### Claim 25 (depends on 23) The process according to claim 23, wherein in the first step, one or more types of silane compounds represented by general formula (1) are hydrolytically condensed under acidic conditions in an aqueous alcohol solution. ### Claim 26 (depends on 23) The process according to claim 23, wherein in the second step, a condensation reaction product is obtained by condensing 20% by weight to 99% by weight of the polysiloxane compound (a) and 1% by weight to 80% by weight of the silica particles (b) in an aqueous solution of an alcohol having 1 to 4 carbon atoms, at a pH of 5 to 9, and at 50° C. to 100° C. (1 atm). ### Claim 27 (depends on 23) The process according to claim 23, wherein in the second step, after adding at least one type of solvent having a boiling point of 100° C. to 200° C. (1 atm) selected from the group consisting of an alcohol, ketone, ester, ether and hydrocarbon solvent to the condensation reaction product obtained by condensing the polysiloxane compound (a) and the silica particles (b), the water content of the condensation reaction product is adjusted to 0.001% by weight to 5% by weight by distilling off the added solvent component by distillation. ### Claim 28 (depends on 23) The process according to claim 23, wherein in the third step, after adding at least one type of solvent selected from the group consisting of an alcohol, ketone, ester, ether and hydrocarbon solvent to the condensation reaction product obtained by condensing the polysiloxane compound (a) and the silica particles (b), the silicon compound (c) represented by general formula (3) is reacted with a scavenger in the form of an organic base in an amount 0.5 times to 3 times the number of moles of the silicon compound (c) followed by removing the organic salt formed by washing with an aqueous solution to obtain the silica particle-containing condensation reaction product (A), or after adding at least one type of solvent selected from the group consisting of an alcohol, ketone, ester, ether and hydrocarbon solvent to the condensation reaction product obtained by condensing the polysiloxane compound (a) and the silica particles (b), the silicon compound (c) represented by general formula (3) is allowed to react to obtain the silica particle-containing condensation reaction product (A). ### Claim 29 (depends on 23) The process according to claim 23, wherein in the third step, after reacting the silicon compound (c) with the condensation reaction product obtained by condensing the polysiloxane compound (a) and the silica particles (b), the solvent component in the reaction product is distilled off to obtain the silica particle-containing condensation reaction product (A). ### Claim 30 (depends on 23) The process according to claim 23, wherein in the fourth step, a compound (C) having a photopolymerizable functional group in a molecule thereof and/or an antioxidant and/or ultraviolet absorber (D) are further mixed. ### Claim 31 (depends on 1) A production process of a cured product of a photosensitive silicon resin composition, comprising: a step for irradiating the photosensitive silicone resin composition according to claim 1 with light having a dominant wavelength of 200 nm to 500 nm. ### Claim 32 (depends on 31) A cured product obtained according to the process according to claim 31. ### Claim 33 (depends on 31) The process according to claim 31, further comprising a step for baking at 130° C. to 300° C. ### Claim 34 (depends on 33) A cured product obtained according to the process according to claim 33. ### Claim 35 (depends on 31) A plastic lens produced according to the process according to claim 31. ### Claim 36 (depends on 31) A replica material produced according to the process according to claim 31. ### Claim 37 (depends on 31) A surface coating material produced according to the process according to claim 31.