# US 8,771,907 B2 · Positive photosensitive resin composition and method of forming cured film from the same > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 8,771,907 B2 - Document ID: US8771907B2 - Status: Granted - Kind: B2 - Application number: 12/891,558 - Filed: 2010-09-27 - Published: 2011-07-21 - Granted: 2014-07-08 - Earliest claimed: 2008-03-28 - Assignees: FUJIFILM Corporation - Applicants: Satoshi Takita - Inventors: Satoshi Takita - Web page: https://patentgrep.com/patent/US8771907B2 ## CPC - G03F 7/0392: {the macromolecular compound being present in a chemically amplified positive photoresist composition} - C08F 2/48: by ultraviolet or visible light - C08F 20/28: containing no aromatic rings in the alcohol moiety - C08F 216/1416: {Monomers containing oxygen in addition to the ether oxygen, e.g. allyl glycidyl ether} - C08F 220/26: Esters containing oxygen in addition to the carboxy oxygen - C08F 220/281: {and containing only one oxygen, e.g. furfuryl (meth)acrylate or 2-methoxyethyl (meth)acrylate} - C08F 220/325: {containing glycidyl radical, e.g. glycidyl (meth)acrylate} - C08F 212/08: Styrene - C08F 212/22: {Oxygen} - C08F 212/24: {Phenols or alcohols} - C08F 220/06: Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof - G03F 7/0045: {with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors} - G03F 7/40: Treatment after imagewise removal, e.g. baking - Y10T 428/24802: Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.] - 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 - Y10T: TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION ## Abstract According to one embodiment, a positive photosensitive resin composition includes a resin containing a specified acrylic acid besed-structural unit which generates a carboxyl group when its dissociative group is dissociated, which resin is insoluble in alkali or sparingly soluble in alkali but when its acid-dissociative group is dissociated, becomes soluble in alkali, a resin containing a structural unit derived from a radical-polymerizable monomer containing an epoxy group, a compound containing two or more epoxy groups in its molecule, provided that the resin containing the structural unit derived from a radical-polymerizable monomer containing an epoxy group is not included in this compound, and a compound that when exposed to actinic rays of 300 nm or longer wavelength, generates an acid. ## Claims ### Claim 1 A positive photosensitive resin composition comprising (A1) a resin containing any of structural units of general formula (1) below, which resin is insoluble in alkali or sparingly soluble in alkali but when its acid-dissociative group is dissociated, becomes soluble in alkali; (A2) a polymer or copolymer containing a structural unit derived from a radical-polymerizable monomer containing an epoxy group; (B) a compound containing two or more epoxy groups in its molecule, provided that the polymer or copolymer (A2) is not included in this compound; and (C) a compound that when exposed to actinic rays of 300 nm or longer wavelength, generates an acid, in which R1 represents a hydrogen atom, a methyl group, a halogen atom or a cyano group, each of R2 and R3 independently represents a hydrogen atom, or a linear alkyl group, provided that R2 and R3 are not simultaneously hydrogen atoms, and R4 represents a linear, branched or cyclic alkyl group or an aralkyl group, wherein the alkyl group is optionally subtituted with an alkoxy group having 1 to 5 carbon atoms or a halogen atom, provided that R2 and R4 may be linked to each other to thereby form a cyclic ether. ### Claim 2 (depends on 1) The positive photosensitive resin composition according to claim 1, wherein the component (A2) contains the structural unit derived from a radical-polymerizable monomer containing an epoxy group and any of structural units of general formula (1). ### Claim 3 (depends on 1) The positive photosensitive resin composition according to claim 1, wherein the radical-polymerizable monomer containing an epoxy group is 3,4-epoxycyclohexylmethyl acrylate or 3,4-epoxycyclohexylmethyl methacrylate. ### Claim 4 (depends on 1) The positive photosensitive resin composition according to claim 1, wherein the component (C) contains a compound containing any of oxime sulfonate groups of general formula (2) below, in which R5 represents an optionally substituted linear, branched or cyclic alkyl group or an optionally substituted aryl group. ### Claim 5 (depends on 1) The positive photosensitive resin composition according to claim 1, wherein the component (C) contains any of compounds of general formula (3) below, in which R5 represents an optionally substituted linear, branched or cyclic alkyl group or an optionally substituted aryl group, X represents an alkyl group, an alkoxy group or a halogen atom, and m is an integer of 0 to 3, provided that when m is 2 or 3, a plurality of X's may be identical to or different from each other. ### Claim 6 (depends on 1) The positive photosensitive resin composition according to claim 1, further comprising an adhesion aid (D). ### Claim 7 (depends on 1) A method of forming a cured film, comprising the steps of applying the positive photosensitive resin composition according to claim 1 to a substrate and drying the applied composition to thereby form a film; exposing the film through a mask to actinic rays of 300 nm or longer wavelength; developing the exposed film with an alkali developer to thereby form a pattern; and baking the formed pattern. ### Claim 8 (depends on 7) The method of forming a cured film according to claim 7, further comprising exposing the pattern on its entire surface after the development with an alkali developer to thereby form a pattern but before the baking of the formed pattern. ### Claim 9 (depends on 7) A cured film obtained by the method of claim 7. ### Claim 10 (depends on 1) The positive photosensitive resin composition according to claim 1, wherein the mass ratio of component (A1) to component (A2) is 30:70 to 70:30. ### Claim 11 (depends on 1) The positive photosensitive resin composition according to claim 1, wherein the number of carbon atoms of an alkyl group in R2 and R3 of general formula (1) is 1-6. ### Claim 12 A positive photosensitive resin composition comprising (A′) a resin containing not only any of structural units of general formula (1) below but also a structural unit containing a functional group capable of reacting with a carboxyl group to thereby form a covalent bond, which resin is insoluble in alkali or sparingly soluble in alkali but when its acid-dissociative group is dissociated, becomes soluble in alkali; (B) a compound containing two or more epoxy groups in its molecule, provided that the resin (A′) is not included in this compound; and (C) a compound that when exposed to actinic rays of 300 nm or longer wavelength, generates an acid, in which R1 represents a hydrogen atom, a methyl group, a halogen atom or a cyano group, each of R2 and R3 independently represents a hydrogen atom, or a linear alkyl group, provided that R2 and R3 are not simultaneously hydrogen atoms, and R4 represents a linear, branched or cyclic alkyl group or an aralkyl group, wherein the alkyl group is optionally subtituted with an alkoxy group or a halogen atom, provided that R2 and R4 may be linked to each other to thereby form a cyclic ether. ### Claim 13 (depends on 12) The positive photosensitive resin composition according to claim 12, wherein the functional group capable of reacting with a carboxyl group to thereby form a covalent bond, contained in the component (A′) is an epoxy group. ### Claim 14 (depends on 12) The positive photosensitive resin composition according to claim 12, wherein the structural unit containing a functional group capable of reacting with a carboxyl group to thereby from a covalent bond is the structural unit derived from 3,4-epoxycyclohexylmethyl acrylate or 3,4-epoxycyclohexylmethyl methacrylate. ### Claim 15 (depends on 12) The positive photosensitive resin composition according to claim 12, wherein the functional group capable of reacting with a carboxyl group to thereby form a covalent bond, contained in the component (A′) is an oxetane group. ### Claim 16 (depends on 12) The positive photosensitive resin composition according to claim 12, wherein the component (C) contains a compound containing any of oxime sulfonate groups of general formula (2) below, in which R5 represents an optionally substituted linear, branched or cyclic alkyl group or an optionally substituted aryl group. ### Claim 17 (depends on 12) The positive photosensitive resin composition according to claim 12, wherein the component (C) contains any of compounds of general formula (3) below, in which R5 represents an optionally substituted linear, branched or cyclic alkyl group or an optionally substituted aryl group, X represents an alkyl group, an alkoxy group or a halogen atom, and m is an integer of 0 to 3, provided that when m is 2 or 3, a plurality of X's may be identical to or different from each other. ### Claim 18 (depends on 12) The positive photosensitive resin composition according to claim 12, further comprising an adhesion aid (D). ### Claim 19 (depends on 12) A method of forming a cured film, comprising the steps of applying the positive photosensitive resin composition according to claim 12 to a substrate and drying the applied composition to thereby form a film; exposing the film through a mask to actinic rays of 300 nm or longer wavelength; developing the exposed film with an alkali developer to thereby form a pattern; and baking the formed pattern. ### Claim 20 (depends on 19) The method of forming a cured film according to claim 19, further comprising exposing the pattern on its entire surface after the development with an alkali developer to thereby form a pattern but before the baking of the formed pattern. ### Claim 21 (depends on 19) A cured film obtained by the method of claim 19. ### Claim 22 (depends on 1) The positive photosensitive resin composition according to claim 1, wherein at least one of component (A1) and component (A2) further contains a structural unit derived from acrylic acid or methacrylic acid.