# US 2019/0169211 A1 · Novel tetracarboxylic dianhydride, polyimide resin and method for producing the same, photosensitive resin compositions, patterning process, method for forming cured film, interlayer insulating film, surface protective film, and electronic parts > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 2019/0169211 A1 - Document ID: US20190169211A1 - Status: Published application - Kind: A1 - Application number: 16/196,281 - Filed: 2018-11-20 - Published: 2019-06-06 - Earliest claimed: 2017-12-05 - Assignees: Shin-Etsu Chemical Co., Ltd. - Applicants: Shin-Etsu Chemical Co., Ltd. - Inventors: Hiroyuki URANO; Hiroki TAKANO; Masashi IIO; Katsuya TAKEMURA; Kazuya HONDA - Web page: https://patentgrep.com/patent/US20190169211A1 ## CPC - C07F 7/0814: {said ring is substituted at a C ring atom by Si} - C08G 73/1007: {from tetracarboxylic acids or derivatives and diamines} - C08G 73/1039: {comprising halogen-containing substituents} - C08G 73/1042: {Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds} - C08G 73/1046: {Polyimides containing oxygen in the form of ether bonds in the main chain} - C08G 73/1053: {with oxygen only in the tetracarboxylic moiety} - C08G 73/106: {containing silicon} - C08G 73/1078: {wholly aromatic in the diamino moiety} - C08G 73/1085: {Polyimides with diamino moieties or tetracarboxylic segments containing heterocyclic moieties} - C08G 77/045: {containing less than 25 silicon atoms} - C08G 77/46: containing polyether sequences - C09D 179/08: Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors - G03F 7/0233: {characterised by the polymeric binders or the macromolecular additives other than the macromolecular quinonediazides} - 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 7/0387: {Polyamides or polyimides} - G03F 7/039: Macromolecular compounds which are photodegradable, e.g. positive electron resists (G03F7/075 takes precedence; macromolecular quinonediazides G03F7/023) - G03F 7/0757: {Macromolecular compounds containing Si-O, Si-C or Si-N bonds (G03F7/0752 takes precedence)} - G03F 7/16: Coating processes; Apparatus therefor (applying coatings to base materials in general B05; applying photosensitive compositions to base for photographic purposes G03C1/74) - G03F 7/20: Exposure; Apparatus therefor (photographic printing apparatus for making copies G03B27/00) - G03F 7/322: {Aqueous alkaline compositions} - C07F: ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM (metal-containing porphyrins C07D487/22) - C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS - C09D: COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR (cosmetics A61K; processes for applying liquids or other fluent materials to surfaces, in general, B05D; staining wood B27K5/02; glazes or vitreous enamels C03C; natural resins, French polish, drying-oils, driers, turpentine, per se, C09F; polishing compositions other than French polish, ski waxes C09G; adhesives or use of materials as adhesives C09J; materials for sealing or packing joints or covers C09K3/10; materials for stopping leaks C09K3/12; processes for the electrolytic or electrophoretic production of coatings C25D) - 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) ## Abstract The present invention has been made in view of the circumstances herein. An object of the present invention is to provide: a tetracarboxylic dianhydride which can lead to a polyimide usable as a base resin of a photosensitive resin composition capable of forming a fine pattern and obtaining high resolution without impairing excellent characteristics such as mechanical strength and adhesiveness; a polyimide resin obtained by using the tetracarboxylic dianhydride; and a method for producing the polyimide resin. The tetracarboxylic dianhydride is shown by the following general formula (1). ## Claims ### Claim 1 A tetracarboxylic dianhydride shown by the following general formula (1), wherein Z represents a linear or branched divalent hydrocarbon group having 4 to 100 carbon atoms optionally containing an oxygen atom therein; R1 to R4 each represent an identical or different monovalent hydrocarbon group having 1 to 8 carbon atoms; R5 represents a trivalent organic group; and “n” represents an integer of 1 to 100. ### Claim 2 (depends on 1) The tetracarboxylic dianhydride according to claim 1, wherein R5 in the general formula (1) is shown by the following general formula (2) or (3), wherein R6 represents a carbon atom or an oxygen atom, and wherein R7 represents a linear or branched alkylene group or alkenylene group having 3 to 15 carbon atoms. ### Claim 3 (depends on 1) The tetracarboxylic dianhydride according to claim 1, wherein Z in the general formula (1) is a divalent organic group shown by the following general formula (4), CH2mOR15—OlCH2m (4) wherein R15 represents a linear or branched alkylene group having 2 to 15 carbon atoms; “1” represents an integer of 1 to 50; and “m” represents an integer of 2 to 15. ### Claim 4 A polyimide resin comprising a structural unit shown by the following general formula (5), wherein Z represents a linear or branched divalent hydrocarbon group having 4 to 100 carbon atoms optionally containing an oxygen atom therein; R1 to R4 each represent an identical or different monovalent hydrocarbon group having 1 to 8 carbon atoms; R5 represents a trivalent organic group; “n” represents an integer of 1 to 100; and X represents a divalent organic group. ### Claim 5 (depends on 4) The polyimide resin according to claim 4, wherein X in the general formula (5) is a divalent organic group shown by the following general formula (6), wherein “f” represents 0 or 1; Y represents a divalent bonding group; and f=0 represents direct bonding without a bonding group. ### Claim 6 (depends on 5) The polyimide resin according to claim 5, wherein Y in the general formula (6) is a divalent group shown by the following formula (7) or (8), ### Claim 7 (depends on 4) A method for producing the polyimide resin according to claim 4, the method comprising reacting a tetracarboxylic dianhydride shown by the following general formula (1) with a diamine shown by the following general formula (9), wherein Z represents a linear or branched divalent hydrocarbon group having 4 to 100 carbon atoms optionally containing an oxygen atom therein; R1 to R4 each represent an identical or different monovalent hydrocarbon group having 1 to 8 carbon atoms; R5 represents a trivalent organic group; and “n” represents an integer of 1 to 100, N2N—X—NH2 (9) wherein X is as defined above. ### Claim 8 (depends on 4) A positive type photosensitive resin composition comprising: (A) the polyimide resin according to claim 4; (B) a photosensitive agent which generates an acid by light to increase a dissolution rate in an aqueous alkaline solution and is a compound having a quinonediazide structure; and (D) a solvent. ### Claim 9 (depends on 4) A positive type photosensitive resin composition comprising: (A) the polyimide resin according to claim 4; (B) a photosensitive agent which generates an acid by light to increase a dissolution rate in an aqueous alkaline solution and is a compound having a quinonediazide structure; (C) at least one of a crosslinking agent(s) selected from an amino condensate modified by formaldehyde or formaldehyde-alcohol, a phenol compound having two or more methylol groups or alkoxymethylol groups in one molecule on average, a compound in which a hydrogen atom of a hydroxyl group of a polyvalent phenol is substituted by a glycidyl group or a group having a glycidyl group, a compound in which a hydrogen atom of a hydroxyl group of a polyvalent phenol is substituted by a substituent shown by the following formula (C-1), and a compound containing two or more groups each shown by the following formula (C-2) or (C-2′), wherein a 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 10 (depends on 4) A negative type photosensitive resin composition comprising: (A′) the polyimide resin according to claim 4; (B′) a photoacid generator; (C′) at least one of a crosslinking agent(s) selected from an amino condensate modified by formaldehyde or formaldehyde-alcohol, a phenol compound having two or more methylol groups or alkoxymethylol groups in one molecule on average, a compound in which a hydrogen atom of a hydroxyl group of a polyvalent phenol is substituted by a glycidyl group or a group having a glycidyl group, a compound in which a hydrogen atom of a hydroxyl group of a polyvalent phenol is substituted by a substituent shown by the following formula (C-1), and a compound containing two or more groups each shown by the following formula (C-2) or (C-2′), wherein a 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 11 (depends on 8) A patterning process comprising the steps of: (1) coating the positive type photosensitive resin composition according to claim 8 onto a substrate to form a film of a photosensitive material; (2) after heat treatment, exposing the film of the photosensitive material by a high energy beam with a wavelength of 190 to 500 nm or an electron beam through a photomask; and (3) developing the film using a developing solution of an aqueous alkaline solution. ### Claim 12 (depends on 9) A patterning process comprising the steps of: (1) coating the positive type photosensitive resin composition according to claim 9 onto a substrate to form a film of a photosensitive material; (2) after heat treatment, exposing the film of the photosensitive material by a high energy beam with a wavelength of 190 to 500 nm or an electron beam through a photomask; and (3) developing the film using a developing solution of an aqueous alkaline solution. ### Claim 13 (depends on 10) A patterning process comprising the steps of: (I) coating the negative type photosensitive resin composition according to claim 10 onto a substrate to form a film of a photosensitive material; (II) after heat treatment, exposing the film of the photosensitive material by a high energy beam with a wavelength of 190 to 500 nm or an electron beam through a photomask; and (III) developing the film using a developing solution of an aqueous alkaline solution. ### Claim 14 (depends on 13) The patterning process according to claim 13, further comprising a heating step after the exposure between the step (II) and the step (III). ### Claim 15 (depends on 11) A method for forming a cured film, comprising heating and post-curing the patterned film obtained by the patterning process according to claim 11, at a temperature of 100 to 300° C. ### Claim 16 (depends on 12) A method for forming a cured film, comprising heating and post-curing the patterned film obtained by the patterning process according to claim 12, at a temperature of 100 to 300° C. ### Claim 17 (depends on 13) A method for forming a cured film, comprising heating and post-curing the patterned film obtained by the patterning process according to claim 13, at a temperature of 100 to 300° C. ### Claim 18 (depends on 8) An interlayer insulating film comprising a cured film in which the positive type photosensitive resin composition according to claim 8 has cured. ### Claim 19 (depends on 8) A surface protective film comprising a cured film in which the positive type photosensitive resin composition according to claim 8 has cured. ### Claim 20 (depends on 18) An electronic part comprising the interlayer insulating film according to claim 18.