# US 2018/0024434 A1 · Tetracarboxylic acid diester compound, polyimide precursor polymer and method for producing the same, negative photosensitive resin composition, patterning process, and method for forming cured film > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 2018/0024434 A1 - Document ID: US20180024434A1 - Status: Published application - Kind: A1 - Application number: 15/616,237 - Filed: 2017-06-07 - Published: 2018-01-25 - Earliest claimed: 2016-07-25 - Assignees: Shin-Etsu Chemical Co., Ltd. - Applicants: Shin-Etsu Chemical Co., Ltd. - Inventors: Katsuya TAKEMURA; Hiroyuki URANO; Masashi IIO; Masayoshi SAGEHASHI; Koji HASEGAWA - Web page: https://patentgrep.com/patent/US20180024434A1 ## CPC - G03F 7/0387: {Polyamides or polyimides} - C07C 69/76: Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring - C07C 69/80: Phthalic acid esters - C08G 73/1007: {from tetracarboxylic acids or derivatives and diamines} - C08G 73/1042: {Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds} - C08G 73/121: {Preparatory processes from unsaturated precursors and polyamines} - C08G 73/123: {the unsaturated precursors comprising halogen-containing substituents} - C08G 73/127: {containing oxygen in the form of ether bonds in the main chain} - G03F 7/0045: {with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors} - G03F 7/0046: {with perfluoro compounds, e.g. for dry lithography (G03F7/0048 takes precedence)} - G03F 7/031: Organic compounds not covered by group G03F7/029 - G03F 7/037: the binders being polyamides or polyimides - G03F 7/038: Macromolecular compounds which are rendered insoluble or differentially wettable (G03F7/075 takes precedence; macromolecular azides G03F7/012; macromolecular diazonium compounds G03F7/021) - G03F 7/0385: {using epoxidised novolak resin} - G03F 7/0388: {with ethylenic or acetylenic bands in the side chains of the photopolymer} - G03F 7/162: {Coating on a rotating support, e.g. using a whirler or a spinner} - G03F 7/168: {Finishing the coated layer, e.g. drying, baking, soaking} - G03F 7/2004: {characterised by the use of a particular light source, e.g. fluorescent lamps or deep UV light} - G03F 7/325: {Non-aqueous compositions} - G03F 7/38: Treatment before imagewise removal, e.g. prebaking {(G03F7/265 takes precedence)} - G03F 7/40: Treatment after imagewise removal, e.g. baking - 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) - C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS - C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS ## Abstract The present invention provides a tetracarboxylic acid diester compound shown by the following general formula (1), wherein X1 represents a tetravalent organic group; and R1 represents a group shown by the following general formula (2), Y1nRf)k (2) wherein the dotted line represents a bond; Y1 represents an organic group with a valency of k+1; Rf represents a linear, branched, or cyclic alkyl group having 1 to 20 carbon atoms or an aromatic group in which a part or all of hydrogen atoms is/are substituted with a fluorine atom(s); “k” represents 1, 2, or 3; and “n” represents 0 or 1. There can be provided a tetracarboxylic acid diester compound that can give a polyimide precursor polymer soluble in a safe organic solvent widely used as a solvent of a composition, and usable as a base resin of a negative photosensitive resin composition. ## Claims ### Claim 1 A tetracarboxylic acid diester compound shown by the following general formula (1), wherein X1 represents a tetravalent organic group; and R1 represents a group shown by the following general formula (2), Y1nRf)k (2) wherein the dotted line represents a bond; Y1 represents an organic group with a valency of k+1; Rf represents a linear, branched, or cyclic alkyl group having 1 to 20 carbon atoms or an aromatic group in which a part or all of hydrogen atoms is/are substituted with a fluorine atom(s); “k” represents 1, 2, or 3; and “n” represents 0 or 1. ### Claim 2 (depends on 1) The tetracarboxylic acid diester compound according to claim 1, wherein Y1 in the general formula (2) is a linear or branched divalent organic group having 1 to 6 carbon atoms. ### Claim 3 (depends on 1) The tetracarboxylic acid diester compound according to claim 1, wherein R1 in the general formula (1) is an organic group selected from groups shown by the following general formulae (3), (4), (5), and (6), wherein the dotted line represents a bond; Rf is as defined above; Ra and Rb represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms; Y2 and Y3 represent a linear or branched alkylene group having 1 to 6 carbon atoms; n1 represents an integer of 0 to 6; n2 represents an integer of 1 to 6; n3 represents an integer of 0 to 6; n4 represents an integer of 1 to 6; n5 represents an integer of 0 to 6; n6 represents 0 or 1; and n7 represents an integer of 0 to 6. ### Claim 4 (depends on 2) The tetracarboxylic acid diester compound according to claim 2, wherein R1 in the general formula (1) is an organic group selected from groups shown by the following general formulae (3), (4), (5), and (6), wherein the dotted line represents a bond; Rf is as defined above; Ra and Rb represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms; Y2 and Y3 represent a linear or branched alkylene group having 1 to 6 carbon atoms; n1 represents an integer of 0 to 6; n2 represents an integer of 1 to 6; n3 represents an integer of 0 to 6; n4 represents an integer of 1 to 6; n5 represents an integer of 0 to 6; n6 represents 0 or 1; and n7 represents an integer of 0 to 6. ### Claim 5 (depends on 1) The tetracarboxylic acid diester compound according to claim 1, wherein R1 in the general formula (1) is a group shown by the following general formula (3-1), —CH2—CH2—Rf (3-1) wherein the dotted line represents a bond; and Rf is as defined above. ### Claim 6 (depends on 2) The tetracarboxylic acid diester compound according to claim 2, wherein R1 in the general formula (1) is a group shown by the following general formula (3-1), —CH2—CH2—Rf (3-1) wherein the dotted line represents a bond; and Rf is as defined above. ### Claim 7 (depends on 3) The tetracarboxylic acid diester compound according to claim 3, wherein R1 in the general formula (1) is a group shown by the following general formula (3-1), —CH2—CH2—Rf (3-1) wherein the dotted line represents a bond; and Rf is as defined above. ### Claim 8 (depends on 4) The tetracarboxylic acid diester compound according to claim 4, wherein R1 in the general formula (1) is a group shown by the following general formula (3-1), —CH2—CH2—Rf (3-1) wherein the dotted line represents a bond; and Rf is as defined above. ### Claim 9 A polyimide precursor polymer comprising a structural unit shown by the following general formula (7), wherein X1 represents a tetravalent organic group; X2 represents a divalent organic group; and R1 represents a group shown by the following general formula (2), Y1nRf)k (2) wherein the dotted line represents a bond; Y1 represents an organic group with a valency of k+1; Rf represents a linear, branched, or cyclic alkyl group having 1 to 20 carbon atoms or an aromatic group in which a part or all of hydrogen atoms is/are substituted with a fluorine atom(s); “k” represents 1, 2, or 3; and “n” represents 0 or 1. ### Claim 10 (depends on 9) The polyimide precursor polymer according to claim 9, further comprising a structural unit shown by the following general formula (8), wherein X2 is as defined above; X3 represents a tetravalent organic group that is the same as or different from X1; and R2 and R3 independently represent a hydrogen atom, a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms, or an organic group shown by the following general formula (9), provided that at least one of R2 and R3 is an organic group shown by the general formula (9), wherein the dotted line represents a bond; R4 represents a hydrogen atom or an organic group having 1 to 3 carbon atoms; R5 and R6 independently represent a hydrogen atom or an organic group having 1 to 3 carbon atoms; and “m” represents an integer of 2 to 10. ### Claim 11 (depends on 9) A method for producing the polyimide precursor polymer according to claim 9, comprising reacting a tetracarboxylic acid diester compound shown by the following general formula (1) with a diamine shown by the following general formula (10), wherein X1 and R1 are as defined above, H2N—X2—NH2 (10) wherein X2 is as defined above. ### Claim 12 (depends on 10) A method for producing the polyimide precursor polymer according to claim 10, comprising reacting a tetracarboxylic acid diester compound shown by the following general formula (1) with a diamine shown by the following general formula (10) and a tetracarboxylic acid diester compound shown by the following general formula (11), wherein X1 and R1 are as defined above, H2N—X2—NH2 (10) wherein X2 is as defined above, wherein X3, R2, and R3 are as defined above. ### Claim 13 (depends on 10) A negative photosensitive resin composition comprising: (A) the polyimide precursor polymer according to claim 10; (B) a photo-radical initiator; and (D) a solvent. ### Claim 14 (depends on 9) A negative photosensitive resin composition comprising: (A′) the polyimide precursor polymer according to claim 9; (B) a photo-radical initiator; (C) a crosslinking agent having two or more photo-polymerizable unsaturated linking groups per molecule; and (D) a solvent. ### Claim 15 (depends on 10) A negative photosensitive resin composition comprising: (A′) the polyimide precursor polymer according to claim 10; (B) a photo-radical initiator; (C) a crosslinking agent having two or more photo-polymerizable unsaturated linking groups per molecule; and (D) a solvent. ### Claim 16 (depends on 9) A negative photosensitive resin composition comprising: (A′) the polyimide precursor polymer according to claim 9; (B′) a photo acid generator; (C′) one or two or more crosslinking agents selected from an amino condensate modified with formaldehyde or formaldehyde-alcohol, a phenol compound having on average two or more methylol groups or alkoxymethylol groups per molecule, a polyhydric phenol compound in which a hydrogen atom of a phenolic hydroxyl group is substituted with a glycidyl group, a polyhydric phenol compound in which a hydrogen atom of a phenolic hydroxyl group is substituted with a substituent shown by the following formula (C-1), and a compound containing two or more nitrogen atoms having a glycidyl group as shown by the following formula (C-2), wherein the dotted line represents a bond, Rc represents a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms, and “s” represents 1 or 2; and (D) a solvent. ### Claim 17 (depends on 10) A negative photosensitive resin composition comprising: (A′) the polyimide precursor polymer according to claim 10; (B′) a photo acid generator; (C′) one or two or more crosslinking agents selected from an amino condensate modified with formaldehyde or formaldehyde-alcohol, a phenol compound having on average two or more methylol groups or alkoxymethylol groups per molecule, a polyhydric phenol compound in which a hydrogen atom of a phenolic hydroxyl group is substituted with a glycidyl group, a polyhydric phenol compound in which a hydrogen atom of a phenolic hydroxyl group is substituted with a substituent shown by the following formula (C-1), and a compound containing two or more nitrogen atoms having a glycidyl group as shown by the following formula (C-2), wherein the dotted line represents a bond, Rc represents a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms, and “s” represents 1 or 2; and (D) a solvent. ### Claim 18 (depends on 13) A patterning process comprising: (1) applying the negative photosensitive resin composition according to claim 13 onto a substrate to form a photosensitive material film; (2) exposing the photosensitive material film to a high energy beam having a wavelength of 190 to 500 nm or an electron beam via a photomask after a heat treatment; and (3) performing development with a developer of an organic solvent. ### Claim 19 (depends on 18) The patterning process according to claim 18, further comprising performing post-exposure bake between the exposing step and the development step. ### Claim 20 (depends on 18) A method for forming a cured film, comprising baking a film having a pattern formed by the patterning process according to claims 18 at 100 to 300° C. and post-curing the film.