# US 2015/0147533 A1 · Photocurable Resin Composition for Imprinting, Production Method and Structure Thereof > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 2015/0147533 A1 - Document ID: US20150147533A1 - Status: Published application - Kind: A1 - Application number: 14/402,490 - Filed: 2013-05-15 - Published: 2015-05-28 - Earliest claimed: 2012-05-25 - Assignees: Soken Chemical & Engineering Co., Ltd. - Applicants: Soken Chemical & Engineering Co., Ltd. - Inventors: Hiroko Yamada; Yasuo Suto; Yukihiro Miyazawa - Web page: https://patentgrep.com/patent/US20150147533A1 ## CPC - C08F 22/10: Esters - B29C 59/005: {characterised by the choice of material} - B29C 59/026: {of layered or coated substantially flat surfaces} - C08F 2/50: with sensitising agents - G03F 7/0002: {Lithographic processes using patterning methods other than those involving the exposure to radiation, e.g. by stamping} - Y10T 428/24612: Composite web or sheet - C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS - B29C: SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING (making preforms B29B11/00; making laminated products by combining previously unconnected layers which become one product whose layers will remain together B32B37/00 - B32B41/00) - 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) - Y10T: TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION ## Abstract Provided is a photocurable resin composition in which curing shrinkage in photo-imprinting is suppressed, and capable of producing by photo-imprinting a structure which has high surface hardness and in which the occurrence of yellowing is suppressed even when irradiated with e.g., ultraviolet ray. The photocurable resin composition includes a (meth)acrylic monomer (A) and a photoinitiator (B), wherein the photoinitiator (B) has a combination of an alkylphenone-based photoinitiator (B1) and an acylphosphine oxide-based photoinitiator (B2), wherein a blending weight ratio (B1:B2) of the alkylphenone-based photoinitiator (B1) to the acylphosphine oxide-based photoinitiator (B2) is in the range of 1:99 to 90:10. ## Claims ### Claim 1 A photocurable resin composition for imprinting comprising a (meth)acrylic monomer (A) and a photoinitiator (B), wherein the photoinitiator (B) comprises a combination of an alkylphenone-based photoinitiator (B1) and an acylphosphine oxide-based photoinitiator (B2), wherein a blending weight ratio (B1:B2) of the alkylphenone-based photoinitiator (B1) to the acylphosphine oxide-based photoinitiator (B2) is in the range of 1:99 to 90:10. ### Claim 2 (depends on 1) The photocurable resin composition for imprinting according to claim 1, wherein with respect to 100 parts by weight of the (meth)acrylic monomer (A), the alkylphenone-based photoinitiator (B1) is contained at 0.01 to 20 parts by weight and the acylphosphine oxide-based photoinitiator (B2) is contained at 0.01 to 20 parts by weight. ### Claim 3 (depends on 1) The photocurable resin composition for imprinting according to claim 1, wherein the alkylphenone-based photoinitiator (B1) is at least one kind selected from the group consisting of 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propane-1-one, 1-[4 (2 hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-propane-1-one; and 2-hydroxy-1-{[4-(2-hydroxy-2-methyl-propionyl)-benzyl]phenyl}-2-methyl-propane-1-one. ### Claim 4 (depends on 1) The photocurable resin composition for imprinting according to claim 1, wherein the acylphosphine oxide-based photoinitiator (B2) is at least one kind selected from the group consisting of 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide. ### Claim 5 (depends on 4) The photocurable resin composition for imprinting according to claim 4, wherein the alkylphenone-based photoinitiator (B1) is 1-hydroxy-cyclohexyl-phenyl-ketone and the acylphosphine oxide-based photoinitiator (B2) is bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, and wherein a blending weight ratio (B1:B2) of the alkylphenone-based photoinitiator (B1) to the acylphosphine oxide-based photoinitiator (B2) is in the range of 10:90 to 70:30. ### Claim 6 (depends on 1) A method for producing a structure having a surface on which a fine pattern is formed, comprising: (I) a step of applying, on a substrate, the photocurable resin composition for imprinting according to claim 1, (II) a step of bringing a master mold having a surface on which a fine pattern is formed into contact with the photocurable resin composition for imprinting applied on the substrate, (III) a step of applying light to the photocurable resin composition for imprinting provided between the substrate and the master mold to cure the photocurable resin composition for imprinting, and (IV) a step of releasing the master mold from the photocurable resin composition for imprinting that has been cured. ### Claim 7 (depends on 1) A method for producing a structure having a surface on which a fine pattern is formed, comprising: (I) a step of dropwise adding the photocurable resin composition for imprinting according to claim 1 on a master mold having a surface on which a fine pattern is formed, (II) a step of covering a surface of the photocurable resin composition for imprinting with a substrate, (III) a step of applying light to the photocurable resin composition for imprinting provided between the substrate and the master mold to cure the photocurable resin composition for imprinting, and (IV) a step of releasing the master mold from the photocurable resin composition for imprinting that has been cured. ### Claim 8 (depends on 6) A structure obtained by the production method according to claim 6. ### Claim 9 (depends on 8) The structure according to claim 8, which has a fine pattern with a shrinkage factor of not more than 10% with respect to the fine pattern of the master mold. ### Claim 10 (depends on 8) The structure according to claim 8, wherein a value obtained by subtracting a YI value of the structure before irradiated with light at 18,000 mJ/cm2 from a YI value of the structure after irradiated with light at 18,000 mJ/cm2 is 0.0 to 3.0. ### Claim 11 (depends on 8) The structure according to claim 8, which has a surface hardness of 3B to 3H in terms of pencil hardness in accordance with JIS K5600 5-4. ### Claim 12 (depends on 8) The structure according to claim 8, wherein the structure is an imprinting mold. ### Claim 13 (depends on 8) The structure according to claim 8, wherein the structure is an antireflection film. ### Claim 14 (depends on 8) The structure according to claim 8, wherein the structure is a diffusion film. ### Claim 15 (depends on 2) The photocurable resin composition for imprinting according to claim 2, wherein the alkylphenone-based photoinitiator (B1) is at least one kind selected from the group consisting of 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propane-1-one, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-propane-1-one; and 2-hydroxy-1-{[4-(2-hydroxy-2-methyl-propionyl)-benzyl]phenyl}-2-methyl-propane-1-one. ### Claim 16 (depends on 2) The photocurable resin composition for imprinting according to claim 2, wherein the acylphosphine oxide-based photoinitiator (B2) is at least one kind selected from the group consisting of: 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide. ### Claim 17 (depends on 2) A method for producing a structure having a surface on which a fine pattern is formed, comprising: (I) a step of applying, on a substrate, the photocurable resin composition for imprinting according to claim 2, (II) a step of bringing a master mold having a surface on which a fine pattern is formed into contact with the photocurable resin composition for imprinting applied on the substrate, (III) a step of applying light to the photocurable resin composition for imprinting provided between the substrate and the master mold to cure the photocurable resin composition for imprinting, and (IV) a step of releasing the master mold from the photocurable resin composition for imprinting that has been cured. ### Claim 18 (depends on 2) A method for producing a structure having a surface on which a fine pattern is formed, comprising: (I) a step of dropwise adding the photocurable resin composition for imprinting according to claim 2 on a master mold having a surface on which a fine pattern is formed, (II) a step of covering a surface of the photocurable resin composition for imprinting with a substrate, (III) a step of applying light to the photocurable resin composition for imprinting provided between the substrate and the master mold to cure the photocurable resin composition for imprinting, and (IV) a step of releasing the master mold from the photocurable resin composition for imprinting that has been cured. ### Claim 19 (depends on 7) A structure obtained by the production method according to claim 7. ### Claim 20 (depends on 9) The structure according to claim 9, wherein a value obtained by subtracting a YI value of the structure before irradiated with light at 18,000 mJ/cm2 from a YI value of the structure after irradiated with light at 18,000 mJ/cm2 is 0.0 to 3.0.