Classifications

• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • 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
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/26—Processing photosensitive materials; Apparatus therefor
  • G03F7/40—Treatment after imagewise removal, e.g. baking
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
  • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
  • C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
  • C08G69/40—Polyamides containing oxygen in the form of ether groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
  • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
  • C08G73/1003—Preparatory processes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
  • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
  • C08G73/1003—Preparatory processes
  • C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
  • C08G73/1025—Preparatory processes from tetracarboxylic acids or derivatives and diamines polymerised by radiations
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
  • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
  • C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
  • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
  • C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
  • C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • 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
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • 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
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • 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
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
  • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • 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
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
  • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
  • G03F7/037—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polyamides or polyimides
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • 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
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
  • G03F7/0387—Polyamides or polyimides
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • 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
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
  • G03F7/0388—Macromolecular compounds which are rendered insoluble or differentially wettable with ethylenic or acetylenic bands in the side chains of the photopolymer
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • 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
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/20—Exposure; Apparatus therefor

Definitions

• the present invention provides a polyimide resin precursor, a method for producing the polyimide resin precursor, a photosensitive resin composition containing the polyimide resin precursor, a patterned resin film using the photosensitive resin precursor composition, and a method for producing a patterned polyimide resin film.
• Polyimide resins and polyamide resins have properties such as excellent heat resistance, mechanical strength, insulation, and low dielectric constant. For this reason, polyimide resins and polyamide resins are widely used as insulating materials and protective materials in various devices and electrical and electronic components such as electronic boards such as multilayer wiring boards.
• a composition with a specific structure having a constituent unit derived from 4,4'-bis(4-aminophenoxy)biphenyl has been developed as a composition capable of forming a resin film exhibiting good dielectric properties in a high frequency band.
• a photosensitive resin composition containing an aromatic polyamide resin and a photopolymerization initiator see Patent Document 1, Examples
• a polyimide precursor having an unsaturated double bond in the side chain and a specific amount of radical generation.
• a photosensitive resin composition containing a photopolymerization initiator having an oxime structure has been proposed.
• the present invention was made in view of the above problems, and includes a polyimide resin precursor that provides a polyimide resin having a low dielectric loss tangent and excellent chemical resistance, a method for producing the polyimide resin precursor, and a method for producing the polyimide resin precursor.
• the purpose of the present invention is to provide a photosensitive resin composition containing a polyimide resin (A) as a polymerizable resin, a patterned resin film using the photosensitive resin composition, and a method for producing a patterned polyimide resin film. do.
• the present inventors used a polymer of a diamine compound and a dicarboxylic acid which is a reaction product of tetracarboxylic dianhydride and alcohol as a polyimide resin precursor, It was discovered that the above problems could be solved by using a compound having a combination of a double bond or a methylol group and an ethylenically unsaturated double bond as the alcohol, and the present invention was completed. I ended up doing it. More specifically, the present invention provides the following.
• a first aspect of the present invention is a polyimide resin precursor in which a diamine compound and a dicarboxylic acid, which is a reaction product of tetracarboxylic dianhydride and alcohol, are polymerized
• the alcohol includes alcohol I, and may also include alcohol II
• Alcohol I has a combination of a secondary hydroxyl group and an ethylenically unsaturated double bond, or a combination of a methylol group and an ethylenically unsaturated double bond
• Alcohol II is a polyimide resin precursor that is another alcohol other than Alcohol I.
• a second aspect of the present invention is a method for producing a polyimide resin precursor, which comprises polymerizing a diamine compound and a dicarboxylic acid that is a reaction product of tetracarboxylic dianhydride and alcohol.
• the alcohol includes alcohol I, and may also include alcohol II, Alcohol I has a combination of a secondary hydroxyl group and an ethylenically unsaturated double bond, or a combination of a methylol group and an ethylenically unsaturated double bond, A method in which Alcohol II is another alcohol other than Alcohol I.
• a third aspect of the present invention comprises a polymerizable resin (A), a photoradical polymerization initiator (C), and a solvent (S), wherein the polymerizable resin (A) is the polyimide according to the first aspect.
• This is a photosensitive resin composition that is a resin precursor.
• a fourth aspect of the present invention includes applying the photosensitive resin composition according to the third aspect onto a substrate to form a coating film, positionally exposing the coating film to light, and exposing the photosensitive resin composition to light. Developing a patterned coating film.
• a fifth aspect of the present invention includes generating a polyimide resin derived from a polyimide resin precursor by heating the patterned resin film manufactured by the manufacturing method according to the fourth aspect. This is a method for manufacturing a patterned polyimide resin film.
• a polyimide resin precursor that provides a polyimide resin having a low dielectric loss tangent and excellent chemical resistance
• a method for producing the polyimide resin precursor and a polymerizable resin (A) containing the polyimide resin precursor.
• a photosensitive resin composition, a patterned resin film using the photosensitive resin composition, and a method for producing a patterned polyimide resin film can be provided.
• the polyimide resin precursor is a polymer of a diamine compound and a dicarboxylic acid.
• Dicarboxylic acid is a reaction product of tetracarboxylic dianhydride and alcohol.
• the above alcohols include Alcohol I and may also include Alcohol II.
• Alcohol I has a combination of a secondary hydroxyl group and an ethylenically unsaturated double bond, or a combination of a methylol group and an ethylenically unsaturated double bond.
• Alcohol II is an alcohol other than Alcohol I.
• the above polyimide resin precursor is cyclized by heating to produce a polyimide resin having a low dielectric loss tangent and excellent chemical resistance.
• the imide group concentration calculated by the following formula in the polyimide resin precursor is preferably 23% by mass or less, and more preferably 20% by mass or less. preferable.
• Imide group concentration (%) 140/ ⁇ (average molecular weight of units derived from the dicarboxylic acid) + (average molecular weight of units derived from the diamine compound) -18 ⁇ 2 ⁇ 100
• diamine compound diamine compounds conventionally used in the production of polyimide resins, polyamic acids, and polyamide resins can be used without particular limitation.
• the diamine compound is represented by the following formula (A2). H2NA1 - NH2 ... (A2) (In formula (A2), A 1 represents a divalent organic group.)
• a 1 is a divalent organic group.
• a 1 may have one or more substituents in addition to the two amino groups. Suitable examples of the substituent include a fluorine atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a fluorinated alkyl group having 1 to 6 carbon atoms, and a fluorinated alkyl group having 1 to 6 carbon atoms.
• a fluorinated alkoxy group, carboxy group, or hydroxy group of 1 or more and 6 or less is preferred.
• the substituent is a fluorinated alkyl group or a fluorinated alkoxy group, it is preferably a perfluoroalkyl group or a perfluoroalkoxy group.
• the lower limit of the number of carbon atoms in the organic group as A1 is preferably 2, more preferably 6, and the upper limit is preferably 50, more preferably 30.
• a 1 may be an aliphatic group.
• a 1 is preferably an organic group containing one or more aromatic rings.
• a 1 is an organic group containing one or more aromatic rings
• the organic group may be the aromatic group 1 itself, and the two or more aromatic groups may be an aliphatic hydrocarbon group or a halogenated aliphatic group. It may be a group bonded via a bond containing a group hydrocarbon group or a heteroatom such as an oxygen atom, a sulfur atom, or a nitrogen atom.
• the aromatic ring in A 1 that is bonded to the amino group is preferably a benzene ring.
• the ring bonded to the amino group in A 1 is a condensed ring containing two or more rings
• the ring bonded to the amino group in the condensed ring is preferably a benzene ring.
• the aromatic ring contained in A 1 may be an aromatic heterocycle.
• a 1 is an organic group containing an aromatic ring
• the organic group is represented by the following formulas (21) to ( It is preferable that it is at least one of the groups represented by 24).
• R 111 is a hydrogen atom, a fluorine atom, a carboxy group, a sulfonic acid group, a hydroxy group, an alkyl group having 1 to 4 carbon atoms, and a halogen having 1 to 4 carbon atoms. represents one selected from the group consisting of alkyl groups.
• Q 1 is a 9,9'-fluorenylidene group, or the formula : -C 6 H 4 -, -C 6 H 4 -C 6 H 4 -, -O-C 6 H 4 -C 6 H 4 -O-, -OC 6 H 4 -CO-C 6 H 4 -O-, -OC 6 H 4 -C(CH 3 ) 2 -C 6 H 4 -O-, -OCO -C 6 H 4 -COO-, -OCO-C 6 H 4 -C 6 H 4 -COO-, -OCO-, -O-, -CO-, -C(CF 3 ) 2 -, -C(CH 3 ) 2 -, -CH 2 -, -O-C 6 H 4 -SO 2 -C 6 H 4 -O-, -C(CH 3 ) 2 -C 6 H 4 -C(CH 3 ) 2 -, Consisting of groups
• -C 6 H 4 - in the example of Q 1 is a phenylene group.
• phenylene group m-phenylene group and p-phenylene group are preferable, and p-phenylene group is more preferable.
• -C 10 H 6 - is a naphthalenediyl group.
• the naphthalene diyl group include naphthalene-1,2-diyl group, naphthalene-1,4-diyl group, naphthalene-2,3-diyl group, naphthalene-2,6-diyl group, and naphthalene-2,7-diyl group.
• n is an integer of 1 or more, preferably an integer of 1 or more and 20 or less, more preferably an integer of 1 or more and 12 or less, and even more preferably an integer of 1 or more and 6 or less.
• n in formula (a2) is as explained for Q1 in formula (24).
• R 111 in formulas (21) to (24) is more preferably a hydrogen atom, a fluorine atom, a methyl group, an ethyl group, or a trifluoromethyl group, from the viewpoint of improving the electrical properties of the resin film formed. Particularly preferred are atoms or trifluoromethyl groups.
• Q 1 in formula (24) is -C 6 H 4 -C 6 H 4 -, -O-C 6 H 4 -C 6 H 4 from the viewpoint of electrical properties and mechanical properties of the resin film to be formed.
• Q 1 in formula (24) is -O-C 6 H 4 -C 6 H 4 -O-, -O-C 6 H 4 -C(CH 3 ) 2 -C 6 H 4 -O- is more preferable, and is represented by -O-C 6 H 4 -C 6 H 4 -O-, and -C 6 H 4 - A group in which both are p-phenylene groups is particularly preferred.
• the aromatic diamine compounds shown below can be suitably used. That is, the aromatic diamine compounds include p-phenylenediamine, m-phenylenediamine, 2,4-diaminotoluene, 4,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 3,4'-diaminobiphenyl, 1,5-diaminonaphthalene, 2,6-diaminonaphthalene, 9,10-diaminoanthracene, 9,10-bis(4-aminophenyl)anthracene, 4,4'-diamino-2,2'-bis(trifluoro methyl)biphenyl, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 4,4'-diamino
• a 1 a silicon atom-containing group which may have a chain aliphatic group and/or an aromatic ring can be employed.
• the groups shown below can typically be used.
• Specific examples of compounds having amino groups at both ends and a silicon atom-containing group include methylphenyl silicone modified with amino at both ends, dimethyl silicone modified with amino at both ends, and the like.
• Examples of the amino-modified methylphenyl silicone at both ends include X-22-1660B-3 (number average molecular weight of about 4,400) and X-22-9409 (number average molecular weight of about 1,300) manufactured by Shin-Etsu Chemical Co., Ltd. Can be mentioned.
• dimethyl silicone modified with amino at both terminals examples include X-22-161A (number average molecular weight of about 1,600), X-22-161B (number average molecular weight of about 3,000), and KF8012 (number average molecular weight of about 3,000) manufactured by Shin-Etsu Chemical Co., Ltd. (average molecular weight of about 4,400); BY16-835U (number average molecular weight of about 900) manufactured by Dow Corning Toray; and Silaplane FM3311 (number average molecular weight of approximately 1,000) manufactured by JNC.
• a diamine having an oxyalkylene group can also be preferably used as the diamine compound represented by formula (A2).
• Preferred examples of the oxyalkylene group include ethyleneoxy group, propyleneoxy group (-C(CH 3 )-CH 2 -O-, -CH 2 -C(CH 3 )-O-, or -CH 2 CH 2 CH 2 -O-).
• the diamine having an oxyalkylene group may contain a combination of two or more types of oxyalkylene groups. When the diamine having an oxyalkylene group contains two or more types of oxyalkylene groups, the two or more types of oxyalkylene groups may be contained in the diamine blockwise or randomly.
• the diamine having an oxyalkylene group preferably does not contain a cyclic group, and more preferably does not contain an aromatic group.
• Specific examples of diamines having an oxyalkylene group include Jeffamine (registered trademark) KH-511, Jeffamine (registered trademark) ED-600, Jeffamine (registered trademark) ED-900, and Jeffamine (registered trademark) ED-900, all manufactured by HUNTSUMAN.
• the diamine compound is expressed by the following formula (A1).
• a diamine compound (A-2) having the formula (A3) described below Selected from the group consisting of a diamine compound (A-1), a diamine compound (A-3) that does not fall under the diamine compound (A-2), and a dimer diamine compound (A-4), which has the partial structure shown below. It is preferable to include one or more of the following.
• the diamine compound (A-1) is a compound represented by the following formula (A1).
• X is an organic group having 1 or more and 100 or less carbon atoms.
• R a1 is a hydroxy group, a carboxy group, or a halogen atom.
• R a2 is an aliphatic group having 1 to 20 carbon atoms, a hydroxy group, a carboxy group, a sulfonic acid group, or a halogen atom.
• Ar is a phenyl group optionally substituted with R a2 or a naphthyl group optionally substituted with R a2 .
• ma1 is an integer from 0 to 10.
• ma2 is an integer from 0 to 7.
• ma3 is an integer from 1 to 10.
• Ar is a phenyl group which may be substituted with R a2 or a naphthyl group which may be substituted with R a2 .
• Ar is preferably a phenyl group or a naphthyl group. That is, in formula (A1), ma2 is preferably 0.
• R a2 is an aliphatic group having 1 to 20 carbon atoms, a hydroxy group, a carboxy group, a sulfonic acid group, or a halogen atom.
• the organic group as R a2 may contain a hetero atom such as O, N, S, P, B, Si, or a halogen atom.
• the number of carbon atoms in the aliphatic group as R a2 is preferably 1 or more and 12 or less, more preferably 1 or more and 6 or less.
• Aliphatic groups as R a2 include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, n-hexyl group.
• n-heptyl group n-octyl group, 2-ethylhexyl group, n-nonyl group, n-decyl group, n-undecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group chain alkyl groups such as n-heptadecyl group, n-octadecyl group, n-nonadecyl group, and n-icosyl group; vinyl group, 1-propenyl group, 2-n-propenyl group (allyl group), 1- Chain alkenyl groups such as n-butenyl group, 2-n-butenyl group, and 3-n-butenyl group; cycloalkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohex
• Chain alkyloxycarbonyl group formyloxy group, acetyloxy group, propionyloxy group, butanoyloxy group, pentanoyloxy group, hexanoyloxy group, heptanoyloxy group, octanoyloxy group, nonanoyloxy group, and decanoyl group It is an aliphatic acyloxy group such as an oxy group.
• ma3 is an integer from 1 to 10.
• the value of ma3 is not particularly limited as long as it is 1 or more and 10 or less, and is appropriately selected depending on the structure of X.
• the value of ma3 is preferably 1 or more and 4 or less, and more preferably 1 or 2.
• X is an organic group having 1 or more and 100 or less carbon atoms.
• the number of carbon atoms in the organic group as X is preferably 2 or more and 80 or less, more preferably 6 or more and 50 or less.
• the organic group as X may contain a heteroatom such as O, N, S, P, B, Si, or a halogen atom.
• two amino groups are each bonded to a carbon atom in the organic group as X.
• the organic group as X may be an aliphatic group, an aromatic group, or a combination of an aliphatic group and an aromatic group.
• the organic group as X may be a group bonded via a bond containing a heteroatom such as an oxygen atom, a sulfur atom, and a nitrogen atom.
• the aliphatic group may be a saturated aliphatic group or an unsaturated aliphatic group.
• the aliphatic group is preferably an aliphatic hydrocarbon group.
• the organic group as X is an aliphatic group
• the aliphatic group may be a chain or a cyclic group, or a combination of a chain aliphatic group and a cyclic aliphatic group. Good too.
• the chain aliphatic group may have a branch.
• the aliphatic group is preferably a group obtained by removing (ma1+ma3+2) hydrogen atoms from an alkylene group having 1 to 20 carbon atoms, and 1 to 16 carbon atoms
• a group obtained by removing (ma1+ma3+2) hydrogen atoms from the following alkylene group is more preferable, and a group obtained by removing (ma1+ma3+2) hydrogen atoms from an alkylene group having 1 to 12 carbon atoms is even more preferable.
• the groups composed of X, Ar, R a1 and R a2 in formula (A1) include the following formulas (11) to (15). ).
• formulas (11) to (15) Ar, R a1 , R a2 , ma1, ma2, and ma3 are the same as those in formula (A1).
• ma4 and ma5 are each independently an integer of 0 or more and 4 or less.
• ma6 and ma7 are each independently an integer of 0 or more and 4 or less.
• the sum of ma6 and ma7 is 1 or more and 8 or less.
• ma8, ma9, and ma10 are each independently an integer of 0 or more and 4 or less.
• the sum of ma8, ma9, and ma10 is 0 or more and 10 or less.
• ma11, ma12, and ma13 are each independently an integer of 0 or more and 4 or less.
• ma11, ma12, and ma13 is 1 or more and 10 or less.
• ma14 is an integer from 0 to 3.
• ma15 is an integer greater than or equal to 0 and less than or equal to 5.
• the sum of ma14 and ma15 is 0 or more and 8 or less.
• ma16 is an integer from 0 to 3.
• ma17 is an integer from 0 to 5.
• the sum of ma16 and ma17 is 1 or more and 8 or less.
• ma1 is preferably 0. Ma2 is preferably 0. Ma3 is preferably 1 or 2.
• ma1 is preferably 0. Ma2 is preferably 0. Ma3 is preferably 1 or 2.
• ma2 is preferably 0. Ma4 and ma5 are each preferably 0. Ma6 and ma7 are preferably 0, 1, or 2, respectively. The sum of ma6 and ma7 is 1 or more, and preferably 4 or less.
• ma2 is preferably 0. Ma8, ma9, and ma10 are each preferably 0. Ma11, ma12, and ma13 are each preferably 0, 1, or 2. The sum of ma11, ma12, and ma13 is 1 or more, and preferably 6 or less.
• ma2 is preferably 0. Ma14 and ma15 are each preferably 0. Ma16 and ma17 are preferably 0, 1, or 2, respectively. The sum of ma16 and ma17 is 1 or more, and preferably 4 or less.
• R a3 is a single bond or a divalent linking group.
• the divalent linking group is not a group containing an aromatic group.
• the number of carbon atoms in the linking group is preferably 1 or more and 20 or less, more preferably 1 or more and 12 or less, and even more preferably 1 or more and 6 or less.
• the aliphatic hydrocarbon group as a linking group may have one or more unsaturated bonds, may have a branch, and may include a ring structure.
• Specific examples of aliphatic hydrocarbon groups as linking groups include methylene group, ethane-1,2-diyl group (ethylene group), ethane-1,1-diyl group, propane-1,3-diyl group, and propane group.
• Suitable examples of the linking group include an alkylene group having 1 to 6 carbon atoms, an alkenylene group having 2 to 6 carbon atoms, an alkynylene group having 2 to 6 carbon atoms, and an alkylene group having 1 to 6 carbon atoms.
• Alkyleneoxy group alkenyleneoxy group having 2 to 6 carbon atoms, alkynyleneoxy group having 2 to 6 carbon atoms, alkylenethio group having 1 to 6 carbon atoms, alkenylene having 2 to 6 carbon atoms Thio group, alkynylenethio group having 2 to 6 carbon atoms, alkylene amino group having 1 to 6 carbon atoms, alkenylene amino group having 2 to 6 carbon atoms, alkynylene amino group having 2 to 6 carbon atoms , -CONH-, -NH-, -COO-, -O-, -CO-, -SO-, -SO 2 -, -S-, -OCONH-, and -OCOO-.
• the diamine compound (A-1) represented by the formula (A1) has the following formula (A1- A compound represented by 1) is preferable.
• R a1 , R a2 , Ar, ma1, ma2, and ma3 are the same as those in formula (A1).
• Y a1 is an organic group having 1 or more and 20 or less carbon atoms, or a single bond.
• Y a2 is an organic group having 1 or more and 20 or less carbon atoms.
• na1 is 0 or 1.
• na2 is 0 or 1.
• Ya1 is not a single bond.
• the organic group as Y a1 may contain a hetero atom such as O, N, S, P, B, Si, or a halogen atom.
• the organic group as Y a1 is preferably a hydrocarbon group.
• the hydrocarbon group as Y a1 may be an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a combination of an aliphatic hydrocarbon group and an aromatic hydrocarbon group.
• the hydrocarbon group as Y a1 is preferably an aromatic hydrocarbon group, and more preferably a phenylene group or a naphthalenediyl group.
• Preferred specific examples of the aromatic hydrocarbon group as Y a1 include p-phenylene group, m-phenylene group, o-phenylene, naphthalene-1,4-diyl group, naphthalene-1,2-diyl group, and naphthalene group.
• naphthalene-1,5-diyl group naphthalene-1,6-diyl group
• naphthalene-1,7-diyl group naphthalene-1,8-diyl group
• naphthalene-2,6-diyl group examples include diyl group, naphthalene-2,7-diyl group, and naphthalene-2,3-diyl group.
• aromatic hydrocarbon groups p-phenylene group and m-phenylene group are preferred, and p-phenylene group is more preferred.
• na2 is preferably 1, na1 and na2 are both 1, and Y a1 is more preferably an organic group.
• the structural unit represented by formula (A1-1) tends to be packed well. Therefore, it is thought that it is easy to obtain a polyimide resin precursor that provides a polyimide resin with excellent mechanical properties, thermal properties, electrical properties, etc.
• ma1 is preferably 0.
• Ma2 is preferably 0.
• Ma3 is preferably 1 or 2.
• diamine compound (A-1) represented by formula (A1) described above include the following compounds.
• the diamine compound (A-2) has a partial structure represented by the following formula (A2) and is a diamine compound that does not correspond to the diamine compound (A-1).
• R a3 and R a4 each independently represent an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a halogen atom.
• ma4 and ma5 are each independently an integer of 0 or more and 4 or less.
• the alkyl groups having 1 to 4 carbon atoms as R a3 and R a4 include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec- Examples include butyl group and tert-butyl group. Among these alkyl groups, methyl group and ethyl group are preferred, and methyl group is more preferred.
• the alkoxy group having 1 to 4 carbon atoms as R a3 and R a4 includes methoxy group, ethoxy group, n-propyloxy group, isopropyloxy group, n-butyloxy group, isobutyloxy group. , sec-butyloxy group, and tert-butyloxy group. Among these alkoxy groups, methoxy and ethoxy groups are preferred, and methoxy is more preferred.
• examples of the halogen atom as R a3 and R a4 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among these halogen atoms, chlorine atoms and bromine atoms are preferred.
• ma4 and ma5 are each independently an integer from 0 to 4. Since the diamine compound (A-2) is easily available, ma4 and ma5 are each preferably an integer of 0 or more and 2 or less, and 0 is more preferable.
• Examples of compounds suitable as the diamine compound (A2) include compounds represented by the following formula (A2-1).
• X 1 and X 2 are each independently selected from the group consisting of an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and a halogen atom. is an aromatic hydrocarbon group optionally substituted with one or more groups.
• R a3 , R a4 , ma4, and ma5 are the same as those in formula (A2).
• X 1 and X 2 in formula (A2-1) are each independently selected from the group consisting of an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and a halogen atom. It is a divalent aromatic hydrocarbon group which may be substituted with one or more groups. Examples of the alkyl group having 1 to 4 carbon atoms as a substituent include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, and tert-butyl group. Can be mentioned.
• alkyl groups methyl group and ethyl group are preferred, and methyl group is more preferred.
• alkoxy group having 1 to 4 carbon atoms as a substituent include methoxy group, ethoxy group, n-propyloxy group, isopropyloxy group, n-butyloxy group, isobutyloxy group, sec-butyloxy group, and tert- A butyloxy group is mentioned.
• methoxy and ethoxy groups are preferred, and methoxy is more preferred.
• the halogen atom as a substituent include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among these halogen atoms, chlorine atoms and bromine atoms are preferred.
• the number of carbon atoms in the aromatic hydrocarbon groups as X 1 and X 2 is not particularly limited, and is preferably 6 or more and 50 or less, more preferably 6 or more and 20 or less. Note that the number of carbon atoms in the above-mentioned aromatic hydrocarbon group does not include the number of carbon atoms in the substituents.
• the aromatic hydrocarbon groups as X 1 and X 2 include phenylene groups such as o-phenylene group, m-phenylene group, and p-phenylene group, naphthalene-1,4-diyl group, naphthalene-1,3 Naphthalenediyl groups such as -diyl group, naphthalene-2,6-diyl group, and naphthalene-2,7-diyl group, biphenyl-4,4'-diyl group, biphenyl-3,4'-diyl group, and biphenyl group.
• a biphenyldiyl group such as a -3,3'-diyl group is preferred.
• p-phenylene group p-phenylene group, m-phenylene group, naphthalene-1,4-diyl group, and biphenyl-4,4'-diyl group are preferred; ,4'-diyl group is more preferred, and p-phenylene group is even more preferred.
• diamine compound (A-2) represented by formula (A2) described above include the following compounds.
• the diamine compound (A-3) has a partial structure represented by the following formula (A3) and is a diamine compound that does not correspond to the diamine compound (A-1) or the diamine compound (A-2).
• R a5 and R a6 each independently represent an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a halogen atom.
• ma6 and ma7 are each independently an integer of 0 or more and 4 or less.
• R a7 and R a8 each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a halogenated alkyl group having 1 to 4 carbon atoms, or a phenyl group.
• R a7 and R a8 may be combined with each other to form a ring.
• the alkyl groups having 1 to 4 carbon atoms as R a5 and R a6 include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec- Examples include butyl group and tert-butyl group. Among these alkyl groups, methyl group and ethyl group are preferred, and methyl group is more preferred.
• the alkoxy group having 1 to 4 carbon atoms as R a5 and R a6 includes methoxy group, ethoxy group, n-propyloxy group, isopropyloxy group, n-butyloxy group, isobutyloxy group. , sec-butyloxy group, and tert-butyloxy group. Among these alkoxy groups, methoxy and ethoxy groups are preferred, and methoxy is more preferred.
• examples of the halogen atom as R a5 and R a6 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among these halogen atoms, chlorine atoms and bromine atoms are preferred.
• ma6 and ma7 are each independently an integer from 0 to 4. Since the diamine compound (A-3) is easily available, ma6 and ma7 are each preferably an integer of 0 or more and 2 or less, and 0 is more preferable.
• the alkyl groups having 1 to 4 carbon atoms as R a7 and R a8 include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec- Examples include butyl group and tert-butyl group.
• the halogenated alkyl group having 1 to 4 carbon atoms as R a7 and R a8 includes a chloromethyl group, a dichloromethyl group, a trichloromethyl group, a bromomethyl group, a dibromomethyl group, and a tribromomethyl group.
• R a7 and R a8 in formula (A3) hydrogen is used because the polyimide resin precursor has good solubility in organic solvents and the diamine compound (A-3) is easily available. Atom, methyl group, ethyl group, trifluoromethyl group, and phenyl group are preferred.
• R a7 and R a8 combine with each other to form a cycloalkylidene group having 5 or more carbon atoms and 8 or less carbon atoms, such as a cyclopentylidene group, a cyclohexylidene group, a cycloheptylidene group, and a cyclooctylidene group. It is also preferable to do so.
• Preferred specific examples of the partial structure represented by formula (A3) include the following structures.
• Examples of compounds suitable as the diamine compound (A-3) include compounds represented by the following formula (A3-1).
• X 3 and X 4 are each independently selected from the group consisting of an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and a halogen atom. is an aromatic hydrocarbon group optionally substituted with one or more groups.
• R a5 , R a6 , R a7 , R a8 , ma6, and ma7 are the same as those in formula (A3).
• X 3 and X 4 in formula (A3-1) are each independently selected from the group consisting of an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and a halogen atom. It is a divalent aromatic hydrocarbon group which may be substituted with one or more groups. Examples of the alkyl group having 1 to 4 carbon atoms as a substituent include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, and tert-butyl group. Can be mentioned.
• alkyl groups methyl group and ethyl group are preferred, and methyl group is more preferred.
• alkoxy group having 1 to 4 carbon atoms as a substituent include methoxy group, ethoxy group, n-propyloxy group, isopropyloxy group, n-butyloxy group, isobutyloxy group, sec-butyloxy group, and tert- A butyloxy group is mentioned.
• methoxy and ethoxy groups are preferred, and methoxy is more preferred.
• the halogen atom as a substituent include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among these halogen atoms, chlorine atoms and bromine atoms are preferred.
• the number of carbon atoms in the aromatic hydrocarbon group as X 3 and X 4 is not particularly limited, and is preferably 6 or more and 50 or less, more preferably 6 or more and 20 or less. Note that the number of carbon atoms in the above-mentioned aromatic hydrocarbon group does not include the number of carbon atoms in the substituents.
• aromatic hydrocarbon group as X 3 and Naphthalenediyl groups such as diyl group, naphthalene-2,6-diyl group, and naphthalene-2,7-diyl group, biphenyl-4,4'-diyl group, biphenyl-3,4'-diyl group, and biphenyl- Biphenyldiyl groups such as 3,3'-diyl groups are preferred.
• p-phenylene group p-phenylene group, m-phenylene group, naphthalene-1,4-diyl group, and biphenyl-4,4'-diyl group are preferred; A 4'-diyl group is more preferred, and a p-phenylene group is even more preferred.
• diamine compound (A-3) represented by formula (A3) described above include the following compounds.
• Dimer diamine compound (A-4) is also preferred as the diamine compound because it is easy to obtain a polyimide resin precursor that provides a polyimide resin with a low dielectric constant in a high frequency band and a low dielectric loss tangent.
• the dimer diamine compound (A-4) is a diamine compound in which two terminal carboxy groups of a dimer acid are substituted with aminomethyl groups or amino groups. Dimer acid is a known dibasic acid obtained by intermolecular polymerization reaction of unsaturated fatty acids. The industrial manufacturing process for producing dimer acids is largely standardized.
• a dimer acid is obtained by dimerizing an unsaturated fatty acid having 11 to 22 carbon atoms in the presence of a clay catalyst or the like.
• Industrially obtained dimer acids are mainly composed of dibasic acids having 36 carbon atoms obtained by dimerizing unsaturated fatty acids having 18 carbon atoms such as oleic acid, linoleic acid, and linolenic acid.
• Industrially obtained dimer acids contain arbitrary amounts of monomer acids with 18 carbon atoms, trimer acids with 54 carbon atoms, and other polymerized fatty acids with 20 to 54 carbon atoms, depending on the degree of purification. , may contain.
• the dimer diamine compound (A-4) a diamine compound represented by the following formula (31) is preferable. (31)
• e, f, g, and h are each integers of 0 or more. e+f is an integer of 6 or more and 17 or less. g+h is an integer of 8 or more and 19 or less.
• the wavy line portion means a carbon-carbon single bond or a carbon-carbon double bond.
• the diamine compound represented by formula (31) is preferably a compound represented by formula (32) below. (32)
• diamine compounds represented by the formula (31) include Versamine 551 (manufactured by BASF) and Priamine 1074 (manufactured by Croda Japan), which include the compound represented by the following formula (33), and the diamine compound represented by the formula (33) below.
• Examples include Versamine 552 (manufactured by BASF), Priamine 1073 (manufactured by Croda Japan), and Priamine 1075 (manufactured by Croda Japan), which contain the compound represented by (32).
• Such a commercially available dimer diamine compound (A-4) is usually a mixture containing multiple types of amine compounds. (33)
• a tetracarboxylic dianhydride represented by formula (34) can be obtained by reacting a diamine compound represented by formula (31) with an acid halide derived from trimellitic anhydride. It is also preferable to use a tetracarboxylic dianhydride represented by the following formula (34) as a raw material for producing a polyimide resin precursor.
• i, j, k, and l are each integers of 0 or more. i+j is an integer from 6 to 17. k+l is an integer of 8 or more and 19 or less.
• the wavy line portion means a carbon-carbon single bond or a carbon-carbon double bond.
• the ratio of the number of moles of the above compounds is preferably 10 mol% or more and 100 mol% or less, more preferably 15 mol% or more and 100 mol% or less, and even more preferably 20 mol% or more and 100 mol% or less.
• Dicarboxylic acid which is a reaction product of tetracarboxylic dianhydride and alcohol
• Dicarboxylic acid is a reaction product of tetracarboxylic dianhydride and alcohol.
• Alcohols are compounds that have a combination of a secondary hydroxyl group and an ethylenically unsaturated double bond, or a combination of a methylol group and an ethylenically unsaturated double bond.
• dicarboxylic acid means a dicarboxylic acid that is a reaction product of tetracarboxylic dianhydride and the above-mentioned alcohol. Tetracarboxylic dianhydride and alcohols will be explained below.
• the tetracarboxylic dianhydride is not particularly limited as long as the desired effect is not impaired.
• a tetracarboxylic dianhydride conventionally used in the production of polyamic acids and polyimide resins can be used.
• Examples of the tetracarboxylic dianhydride include a compound represented by the following formula (A3).
• a 2 is a tetravalent organic group having 6 or more and 50 or less carbon atoms.
• a 2 is a tetravalent organic group having 6 to 50 carbon atoms, and represents an acid anhydride group represented by two -CO-O-CO- in formula (A3).
• it may have one or more substituents.
• substituents include a fluorine atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a fluorinated alkyl group having 1 to 6 carbon atoms, and a fluorinated alkyl group having 1 to 6 carbon atoms.
• a fluorinated alkoxy group of 1 or more and 6 or less is preferred.
• the compound represented by formula (A3) may contain a carboxy group or a carboxylic acid ester group in addition to the acid anhydride group.
• the substituent is a fluorinated alkyl group or a fluorinated alkoxy group, it is preferably a perfluoroalkyl group or a perfluoroalkoxy group.
• the same can be said of one or more substituents that the aromatic group described below may have on the aromatic ring.
• the number of carbon atoms constituting A 2 is more preferably 8 or more, and even more preferably 12 or more. Further, the number of carbon atoms constituting A 2 is more preferably 40 or less, and even more preferably 30 or less.
• a 2 may be an aliphatic group, an aromatic group, or a combination of these structures.
• a 2 may contain a halogen atom, an oxygen atom, a nitrogen atom, and a sulfur atom in addition to a carbon atom and a hydrogen atom.
• a 2 contains an oxygen atom, nitrogen atom, or sulfur atom
• a 1 may include a group selected from N-, -COO-, -O-, -CO-, -SO-, -SO 2 -, -S-, and -S-S-, More preferably, the group selected from -O-, -CO-, -S-, and A 1 is included.
• the tetracarboxylic dianhydride represented by formula (A3) is an aliphatic tetracarboxylic dianhydride that has two dicarboxylic anhydride groups that bond to an aliphatic group, it does not bond to an aromatic group. It may also be an aromatic tetracarboxylic dianhydride having at least one dicarboxylic anhydride group. Note that the aromatic tetracarboxylic dianhydride preferably has two dicarboxylic anhydride groups bonded to the aromatic group.
• the aliphatic tetracarboxylic dianhydride may contain an alicyclic structure.
• the alicyclic structure may be polycyclic.
• Examples of aliphatic tetracarboxylic dianhydrides that do not have an alicyclic structure include 1,2,3,4-tetracarboxylic dianhydride (for example, Rikacid BT-100, manufactured by Shinnihon Chemical Co., Ltd.). Can be mentioned.
• Examples of the aliphatic tetracarboxylic dianhydride having an alicyclic structure include cyclobutanetetracarboxylic dianhydride, cyclopentane-1,2,3,4-tetracarboxylic dianhydride, and cyclohexane-1,2,4 , 5-tetracarboxylic dianhydride, norbornane-2-spiro- ⁇ -cyclopentanone- ⁇ '-spiro-2''-norbornane-5,5'',6,6''-tetracarboxylic dianhydride (e.g.
• aromatic tetracarboxylic dianhydride represented by formula (A3) and having two dicarboxylic anhydride groups bonded to an aromatic group examples include pyromellitic dianhydride, 1,4-bis(3 ,4-dicarboxyphenoxy)benzene dianhydride, 4,4'-oxydiphthalic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,3,3',4' -Biphenyltetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 2,2',3,3'-benzophenonetetracarboxylic dianhydride, 3,3', 4,4'-diphenylsulfonetetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfide tetracarboxylic dianhydride, trimellitic acid (3,4-
• 2,2-bis[4-(3,4-dicarboxyphenyloxy)phenyl]propane dianhydride is preferred because it easily forms a cured product with excellent electrical properties.
• ⁇ , ⁇ -bis(3,4-dicarboxyphenylcarbonyloxy)alkane dianhydride is a compound represented by the following formula (a1).
• n in formula (a1) which is the number of carbon atoms of the linear alkylene group in ⁇ , ⁇ -bis(3,4-dicarboxyphenylcarbonyloxy)alkane dianhydride, is an integer of 1 or more; 20 or less is preferable, and 2 or more and 12 or less are more preferable.
• Preferred specific examples of ⁇ , ⁇ -bis(3,4-dicarboxyphenylcarbonyloxy)alkane dianhydride include 1,2-bis(3,4-dicarboxyphenylcarbonyloxy)ethane dianhydride (e.g.
• the composition when a composition containing a polyimide resin precursor is used to suppress warping of a polyimide resin film formed using a composition containing a polyimide resin precursor, and when photosensitivity is imparted to a composition containing a polyimide resin precursor, the composition has good photolithographic properties.
• the aromatic tetracarboxylic dianhydride is biphenyltetracarboxylic dianhydride.
• biphenyltetracarboxylic dianhydride examples include 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 2,2' , 3,3'-biphenyltetracarboxylic dianhydride, and 3,3',4,4'-biphenyltetracarboxylic dianhydride is preferred.
• the aromatic tetracarboxylic dianhydride may also be, for example, a compound represented by the following formulas (a3-2) to (a3-4).
• R a01 , R a02 and R a03 each represent an aliphatic group optionally substituted with halogen, an oxygen atom, a sulfur atom, one or more It is either an aromatic group via a divalent element, or a divalent group constituted by a combination thereof.
• R a02 and R a03 may be the same or different. That is, R a01 , R a02 and R a03 may contain a carbon-carbon single bond, a carbon-oxygen-carbon ether bond, or a halogen element (fluorine, chlorine, bromine, iodine).
• Examples of the compound represented by formula (a3-2) include 2,2-bis(3,4-dicarboxyphenoxy)propane dianhydride, bis(3,4-dicarboxyphenoxy)methane dianhydride, 1, 1-bis(3,4-dicarboxyphenoxy)ethane dianhydride, 1,3-bis(3,4-dicarboxyphenoxy)benzene, 2,2-bis(3,4-dicarboxyphenoxy)hexafluoropropane Examples thereof include dianhydride, 1,4-bis(3,4-dicarboxyphenoxy)benzene dianhydride, and the like.
• R a04 and R a05 are either an aliphatic group which may be substituted with halogen, an aromatic group via one or more divalent elements, or a halogen. or a combination thereof.
• R a04 and R a05 may be the same or different.
• difluoropyromellitic dianhydride, dichloropyromellitic dianhydride, etc. can also be used.
• the polyimide resin precursor has a radically polymerizable group-containing group on its molecular chain in addition to the residue derived from the alcohol described above. Therefore, the tetravalent organic group A 2 in formula (A3) may be a group represented by the following formulas (a3-5) to (a3-7).
• R a01 , R a02 , and R a03 in formulas (a3-5) to (a3-7) are the same as those in formula (a3-2), formula (a3-3), and formula (a3-4) described above.
• R a01 , R a02 , and R a03 are the same as those in formula (a3-2), formula (a3-3), and formula (a3-4) described above.
• R a01 , R a02 , and R a03 In formula (a3-5), formula (a3-6), and formula (a3-7), R a06 is a radically polymerizable group-containing group. The radically polymerizable group-containing group will be described later.
• dicarboxylic acid is a reaction product of tetracarboxylic dianhydride and alcohol.
• Alcohols include alcohol I and may also include alcohol II.
• Alcohol I has a combination of a secondary hydroxyl group and an ethylenically unsaturated double bond, or a combination of a methylol group and an ethylenically unsaturated double bond.
• Alcohol II is an alcohol other than Alcohol I.
• a methylol group is defined as a secondary carbon atom, a tertiary carbon atom, a carbon atom that is bonded to one carbon atom and one heteroatom, or a bond that is bonded to two heteroatoms.
• a hydroxymethyl group bonded to a carbon atom in an aromatic ring is defined as a hydroxymethyl group bonded to a carbon atom in an aromatic ring, or a carbon atom in an aromatic ring.
• a hydroxyethyl group consists of a hydroxymethyl group and a methylene group.
• the hydroxymethyl group bonded to the primary carbon atom in the methylene group, which is included in the hydroxyethyl group does not fall under the methylol group. .
• the dicarboxylic acid has two carboxylic acid ester groups produced by the reaction of the carboxylic anhydride group and the above-mentioned alcohols.
• the ratio of the number of moles of the carboxylic acid ester group derived from alcohol I to the total number of moles of the aforementioned carboxylic ester groups in the dicarboxylic acid is preferably 50 mol% or more, more preferably 80 mol% or more, and 90 mol%. The above is more preferable.
• Alcohol I When producing Alcohol I, a mixture containing Alcohol I and Alcohol II may inevitably be produced due to the production method.
• Alcohols having meth)acryloyl groups or allyl groups may be produced as by-products.
• alcohol I has an ethylenically unsaturated double bond.
• an alkenyl group-containing group including an alkenyl group such as a vinyl group and an allyl group is preferable, and a (meth)acryloyl group-containing group is more preferable.
• the dicarboxylic acid has a residue containing an ethylenically unsaturated double bond derived from alcohol I. Therefore, the polyimide resin precursor also has a residue containing an ethylenically unsaturated double bond derived from alcohol I.
• Alcohol I may have a combination of two or more hydroxyl groups. Alcohol I may have a combination of a secondary hydroxyl group and a methylol group. Preferably, alcohol I has one secondary hydroxyl group or one methylol group.
• alcohol I is preferably a (meth)acrylate such as glycerin, trimethylolpropane, pentaerythritol, or dipentaerythritol.
• a (meth)acrylate such as glycerin, trimethylolpropane, pentaerythritol, or dipentaerythritol.
• Preferred specific examples of the alcohol I having two or more ethylenically unsaturated double bonds include glycerin-1,3-di(meth)acrylate, glycerin-1,2-di(meth)acrylate, and trimethylolpropane di(meth)acrylate.
• These compounds may have a combination of an acryloyl group and a methacryloyl group.
• alcohol I When alcohol I has one ethylenically unsaturated double bond, alcohol I is at least one selected from a compound represented by the following formula (1) and a compound represented by the following formula (2). Seeds are preferred.
• CH CR 1 -CO-O-R 2 -CHR 3 -OH (1)
• CH CR 1 -CO-OR 4 -CH 2 -OH (2)
• R 1 is a hydrogen atom or a methyl group.
• R 2 is a divalent organic group that is bonded to the oxygen atom in the ester bond via a C—O bond, and bonded to the carbon atom to which R 3 is bonded via a C—C bond.
• R 3 is a monovalent organic group that is bonded to the carbon atom to which R 3 is bonded through a C—C bond. R 2 and R 3 may be combined to form a ring.
• R 1 is a hydrogen atom or a methyl group.
• R 4 is a divalent organic group that is bonded to the oxygen atom in the ester bond via a C—O bond and bonded to the methylol group in formula (2) via a C—C bond.
• R 2 is a divalent organic group that is bonded to the oxygen atom in the ester bond via a C—O bond and bonded to the carbon atom to which R 3 is bonded via a C—C bond.
• the divalent organic group may be a group containing a halogen atom, and a heteroatom such as O, S, and N.
• the number of carbon atoms in the divalent organic group as R 2 in formula (1) is not particularly limited.
• the number of carbon atoms in the divalent organic group is, for example, preferably 1 or more and 20 or less, more preferably 1 or more and 12 or less, and even more preferably 1 or more and 8 or less.
• the divalent organic group as R 2 in formula (1) is preferably a divalent hydrocarbon group.
• the divalent hydrocarbon group may include a cyclic group.
• the cyclic group may be an aliphatic ring, an aromatic ring, or a condensed ring in which an aliphatic ring and an aromatic ring are condensed.
• the divalent hydrocarbon group as R 2 is preferably an alkylene group.
• Suitable examples of the alkylene group include a methylene group, an ethane-1,2-diyl group (ethylene group), an ethane-1,1-diyl group, a propane-1,3-diyl group, and a propane-1,2-diyl group. group, propane-1,1-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane-1,6-diyl group, heptane-1,7-diyl group, and octane- A 1,8-diyl group is mentioned.
• methylene group ethane-1,2-diyl group (ethylene group), propane-1,3-diyl group, butane-1,4-diyl group, and pentane-1,5-diyl group are preferable. .
• R 3 is a monovalent organic group that is bonded to the carbon atom to which R 3 is bonded through a C—C bond.
• the monovalent organic group may be a group containing a halogen atom, and a heteroatom such as O, S, and N.
• the number of carbon atoms in the monovalent organic group as R 3 in formula (1) is not particularly limited.
• the number of carbon atoms in the monovalent organic group is preferably 1 or more and 20 or less, more preferably 1 or more and 12 or less, and even more preferably 1 or more and 8 or less.
• the monovalent organic group as R 3 in formula (1) may be a chain aliphatic group, a cyclic group, or a group consisting of a chain aliphatic group and a cyclic group. There may be.
• the cyclic group may be an aliphatic ring, an aromatic ring, or a condensed ring in which an aliphatic ring and an aromatic ring are condensed.
• the monovalent organic group as R 3 in formula (1) include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert- Alkyl groups such as butyl group, n-pentyl group, n-hexyl group, n-heptyl group, and n-octyl group; methoxymethyl group, ethoxymethyl group, n-propyloxymethyl group, n-butyloxymethyl group, 2-methoxyethyl group, 2-ethoxyethyl group, 2-n-propyloxyethyl group, 2-n-butyloxyethyl group, 3-methoxypropyl group, 3-ethoxypropyl group, 3-n-propyloxypropyl group , 3-n-butyloxypropyl group, 4-methoxybutyl group, 4-ethoxybutyl group, 4-
• the divalent group represented by -R 2 -CHR 3 - in formula (1) include the following groups.
• * is the end of the bond bonding to the oxygen atom in the ester bond in formula (1).
• ** is the end of the bond that is bonded to the hydroxyl group in formula (1).
• the valent group comprises a cyclic group.
• Such a cyclic group may be an aromatic group, an alicyclic group, or a condensed cyclic group in which an aromatic ring and an aliphatic ring are condensed.
• Preferred specific examples of the compound represented by formula (1) include the following compounds.
• R 4 is a divalent organic group that is bonded to the oxygen atom in the ester bond through a C-O bond and bonded to the methylol group in formula (2) through a C-C bond.
• the divalent organic group may be a group containing a halogen atom, and a heteroatom such as O, S, and N.
• the number of carbon atoms in the divalent organic group as R 4 in formula (2) is not particularly limited.
• the number of carbon atoms in the divalent organic group is preferably 1 or more and 20 or less, more preferably 1 or more and 12 or less, and even more preferably 1 or more and 8 or less.
• the divalent organic group as R 4 in formula (2) may be a chain aliphatic group, a cyclic group, or a group consisting of a chain aliphatic group and a cyclic group. There may be.
• the cyclic group may be an aliphatic ring, an aromatic ring, or a condensed ring in which an aliphatic ring and an aromatic ring are condensed.
• Preferred specific examples of the divalent group represented by R 4 in formula (2) include the following groups.
• * is the end of the bond bonding to the oxygen atom in the ester bond in formula (2).
• ** is the terminal end of the bond that is bonded to the methylol group of formula (2).
• Preferred specific examples of the compound represented by formula (2) include the following compounds.
• Alcohol II is an alcohol that does not fall under Alcohol I.
• the structure of alcohol I is not particularly limited as long as the desired effect is not impaired. It is also preferable for the alcohol to have a radically polymerizable group, since photosensitivity can be imparted to the polyimide resin precursor and the composition for forming a resin film containing the polyimide resin precursor.
• the radically polymerizable group typically includes a group containing an ethylenically unsaturated double bond.
• an alkenyl group-containing group including an alkenyl group such as a vinyl group and an allyl group is preferable, and a (meth)acryloyl group-containing group is more preferable.
• alcohol II examples include alkane monools such as methanol, ethanol, n-propanol, isopropanol, n-butanol, n-pentanol, and n-hexanol; phenol, p-cresol, m-cresol, o-cresol, Phenols or naphthols such as ⁇ -naphthol and ⁇ -naphthol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, 1,3-propanediol monomethyl ether, 1,3 - Monoethers of glycols such as propanediol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, dipropylene glycol monomethyl ether, and dipropylene glycol monoethyl ether; alcohols having radically poly
• alcohols having radically polymerizable groups as alcohol II include mono(meth)acrylates of diols, N-hydroxyalkyl-substituted (meth)acrylamides, unsaturated ketones containing hydroxyl groups, alkenyl alcohols, and carbon atoms.
• examples include monoalkenyl ethers of diols having three or more alkenyl groups.
• these alcohols do not have a secondary hydroxyl group or a methylol group.
• Diols that give mono(meth)acrylates of diols include alkanediols (alkylene glycols) such as ethylene glycol, 1,2-propanediol, and 1,3-propanediol; diethylene glycol, dipropylene glycol, triethylene glycol and oligo- or polyalkylene glycols such as tripropylene glycol; and cycloalkanediols such as 1,4-cyclohexanediol, 1,3-cyclohexanediol, and 1,2-cyclohexanediol. Diols that provide mono(meth)acrylates of diols are not limited to these.
• the number of carbon atoms in the alkanediol is preferably 2 or more and 10 or less, more preferably 2 or more and 6 or less, and more preferably 2 or more and 4 or less.
• the number of carbon atoms in the oligo or polyalkylene glycol is preferably 4 or more and 20 or less, more preferably 4 or more and 10 or less.
• the number of carbon atoms in the cycloalkanediol is preferably 4 or more and 8 or less, more preferably 5 or more and 7 or less.
• the alkanediols and oligo- or polyalkylene glycols may be linear or branched.
• the number of carbon atoms in the N-hydroxyalkyl group of the N-hydroxyalkyl-substituted (meth)acrylamide is preferably 2 or more and 10 or less, more preferably 2 or more and 6 or less, and even more preferably 2 or more and 4 or less.
• the N-hydroxyalkyl group possessed by the N-hydroxyalkyl-substituted (meth)acrylamide may be linear or branched.
• the hydroxyl group-containing unsaturated ketone is preferably a compound in which a hydroxyalkyl group and an alkenyl group are bonded to a carbonyl group.
• the number of carbon atoms in the hydroxyalkyl group is preferably 2 or more and 10 or less, more preferably 2 or more and 6 or less, and even more preferably 2 or more and 4 or less.
• the hydroxyalkyl group may be linear or branched.
• a hydroxyalkyl group does not have a secondary hydroxyl group or a methylol group.
• the number of carbon atoms in the alkenyl group is preferably 2 or more and 10 or less, more preferably 2 or more and 6 or less, and even more preferably 2 or more and 4 or less.
• the alkenyl group may be linear or branched.
• the number of carbon atoms in the alkenyl alcohol is preferably 3 or more and 10 or less, more preferably 3 or more and 6 or less, and even more preferably 3 or 4.
• the alkenyl alcohol may be linear or branched. Alkenyl alcohols do not have secondary hydroxyl groups or methylol groups.
• the diols that give the monoalkenyl ether of the diols are the same as the diols that give the mono(meth)acrylate of the diols.
• the number of carbon atoms in the alkenyl group is 3 or more, preferably 3 or more and 10 or less, and more preferably 3 or more and 6 or less.
• the alkenyl group may be linear or branched.
• alcohol II having a radically polymerizable group examples include 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and 5-hydroxypentyl (meth)acrylate.
• 6-hydroxyhexyl (meth)acrylate, and mono(meth)acrylate of diols such as 2-(2-hydroxyethoxy)ethyl (meth)acrylate; N-(2-hydroxyethyl)(meth)acrylamide, N- Examples include N-hydroxyalkyl-substituted (meth)acrylamides such as (3-hydroxypropyl)(meth)acrylamide; hydroxyl group-containing ketones such as (hydroxymethyl)vinyl ketone and (2-hydroxyethyl)vinyl ketone.
• a dicarboxylic acid can be obtained by reacting the above-described tetracarboxylic dianhydride with an alcohol. Alcohol rules react with carboxylic acid anhydride groups to generate carboxy groups and ester groups.
• a dicarboxylic acid can be obtained by reacting the aforementioned tetracarboxylic dianhydride with an alcohol represented by R a21 -OH.
• R a21 is a residue obtained by removing the hydroxyl group from the above-mentioned alcohol.
• Such a dicarboxylic acid has two pairs of a carboxy group and a group represented by -CO-O-R a21 located on adjacent carbon atoms in the dicarboxylic acid.
• the above dicarboxylic acid has two pairs of a carboxy group and a group represented by -CO-O-R a21 , and the position of the carboxy group and the group represented by -CO-O-R a21 are Isomers differing in position may exist.
• one type of such isomers may be used alone, or two or more types may be used in combination.
• the specification and claims of the present application allow the polyimide resin precursor to contain multiple types of structural units derived from multiple isomers of dicarboxylic acids.
• dicarboxylic acid corresponding to pyromellitic dianhydride there are two isomers: a compound represented by the following formula (a4-a1) and a compound represented by the following formula (a4-a2). do.
• a compound represented by the following formula (a4-b1) and a compound represented by the following formula (a4 -b2) and a compound represented by the following formula (a4-b3) exist.
• R a21 is as described above.
• the dicarboxylic acids corresponding to the tetracarboxylic dianhydrides represented by the above formulas (a3-2) to (a3-4) include the following formulas (a4-2a) to (a4-2c), the formula ( Examples include compounds represented by formulas a4-3a) to (a4-3c) and formulas (a4-4a) to (a4-4c).
• formulas (a4-2a) to (a4-2c) formulas (a4-3a) to (a4-3c), and formulas (a4-4a) to (a4-4c)
• R a01 to R a05 are , are similar to those in formulas (a3-2) to (a3-4).
• formulas (a4-2a) to (a4-2c) formulas (a4-3a) to (a4-3c), and formulas (a4-4a) to (a4-4c)
• R a21 is the aforementioned That's right.
• the dicarboxylic acids corresponding to the tetracarboxylic dianhydrides represented by the above formulas (a3-5) to (a3-7) include the following formulas (a4-5a) to (a4-5c), and the formula ( Examples include compounds represented by formulas a4-6a) to (a4-6c), formula (a4-7a), and formula (a4-7b).
• formula (a4-5a) to formula (a4-5c) formula (a4-6a) to formula (a4-6c), formula (a4-7a), and formula (a4-7b)
• R a01 to R a03 , R a06 , m1, and m2 are the same as those in formulas (a3-5) to (a3-7).
• R a21 is the aforementioned That's right.
• the reaction between tetracarboxylic dianhydride and alcohol is usually carried out in an organic solvent.
• the organic solvent used for the reaction of tetracarboxylic dianhydride and alcohol is an organic solvent that can dissolve tetracarboxylic dianhydride and alcohol and does not react with tetracarboxylic dianhydride and alcohol. If so, there are no particular limitations. Organic solvents can be used alone or in combination of two or more.
• organic solvents used for the reaction of tetracarboxylic dianhydride and alcohols include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, N , N-dimethylacetamide, N,N-dimethylpropionamide, N,N-dimethylisobutyramide, N,N-diethylacetamide, N,N-dimethylformamide, N,N-diethylformamide, N,N-dimethylisobutyric acid amide , methoxy-N,N-dimethylpropionamide, butoxy-N,N-dimethylpropionamide, N-methylcaprolactam, N,N'-dimethylpropyleneurea, N,N,N',N'-tetramethylurea, and Nitrogen-containing polar solvents such as pyridine; dimethyl sulfoxide; sulfolane; lactones such as
• organic solvents are N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-diethylacetamide, N,N-dimethylformamide, N,N-diethylformamide, N-methylcaprolactam, and A nitrogen-containing polar solvent such as N,N,N',N'-tetramethylurea is preferred.
• the temperature at which the tetracarboxylic dianhydride and alcohol are reacted is not particularly limited as long as the reaction proceeds well.
• the reaction temperature between the tetracarboxylic dianhydride and the alcohol is preferably -5°C or higher and 120°C or lower, more preferably 0°C or higher and 80°C or lower, particularly preferably 0°C or higher and 50°C or lower.
• the time for reacting the tetracarboxylic dianhydride and the alcohol varies depending on the reaction temperature, but typically, it is preferably 30 minutes or more and 20 hours or less, more preferably 1 hour or more and 8 hours or less, and 2 hours. It is particularly preferable that the heating time be 6 hours or less.
• a small amount of polymerization inhibitor may be used for the purpose of preventing crosslinking between ethylenically unsaturated double bonds during the reaction between the tetracarboxylic dianhydride and the alcohol.
• the polymerization inhibitor include phenols such as hydroquinone, 4-methoxyphenol, tert-butylpyrocatechol, and bis-tert-butylhydroxytoluene, and phenothiazine.
• the amount of the polymerization inhibitor used is, for example, preferably 0.01 mol% or more and 5 mol% or less based on the number of moles of ethylenically unsaturated double bonds.
• reaction between tetracarboxylic dianhydride and alcohol is carried out in the presence of an organic base such as pyridine, triethylamine, diisopropylethylamine, 4-dimethylaminopyridine, or 1,4-azabicyclo[2,2,2]octane. It's okay.
• organic bases such as pyridine, triethylamine, diisopropylethylamine, 4-dimethylaminopyridine, or 1,4-azabicyclo[2,2,2]octane. It's okay.
• bases may be used alone or in combination of two or more.
• the amount of alcohol used is preferably 1.8 mol or more and 2.2 mol or less, more preferably 2 mol or more and 2.1 mol or less, per 1 mol of tetracarboxylic dianhydride.
• dicarboxylic acids In the production of dicarboxylic acids, depending on the production conditions, only one dicarboxylic anhydride group may react with an alcohol, resulting in the production of a monocarboxylic acid compound having a dicarboxylic anhydride group, or a tetracarboxylic dianhydride group. By reacting with water in the reaction system, a portion of the reaction system may generate tetracarboxylic acid compounds and tricarboxylic acid compounds. As long as the desired effect is not impaired, a dicarboxylic acid containing at least one selected from the above monocarboxylic acid compounds, tricarboxylic acid compounds, and tetracarboxylic acid compounds can be used in the production of the polyimide resin precursor. .
• the dicarboxylic acid contains at least one selected from the above monocarboxylic acid compounds, tricarboxylic acid compounds, and tetracarboxylic acid compounds as impurities, the above monocarboxylic acid compounds and tricarboxylic acid compounds as impurities in the dicarboxylic acid.
• the content of at least one selected from acid compounds and tetracarboxylic acid compounds is preferably 30% by mass or less, more preferably 10% by mass or less, and 5% by mass or less based on the mass of dicarboxylic acid including the mass of impurities. % or less is more preferable, and 1 mass % or less is particularly preferable.
• the method for producing a polyimide resin precursor includes polycondensing the diamine compound and dicarboxylic acid until the weight average molecular weight of the polyimide resin precursor increases to a desired level.
• a preferred method includes a method of condensing the diamine compound and dicarboxylic acid in the presence of a condensing agent. It is also preferable to use a condensation aid together with the condensation agent, if necessary.
• the condensing agent and condensing aid are not particularly limited as long as they are compounds conventionally used for condensing dicarboxylic acids and diamine compounds.
• Preferred condensing agents include dicyclohexylcarbodiimide, diisopropylcarbodiimide, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide, diisopropylcarbodiimide, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, 1-cyclohexyl -3-(2-morpholinoethyl)-carbodiimide methotoluenesulfonate, 1,3-bis(2,2-dimethyl-1,3-dioxolan-4-ylmethyl)carbodiimide, polymer-supported 1-benzyl-3 -cyclohexylcarbodiimide, and polymer-supported 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide.
• the amount of the condensing agent used is not particularly limited as long as a polyimide resin precursor having a desired molecular weight can be obtained.
• the amount of the condensing agent used is typically preferably 1 mol or more and 5 mols or less, more preferably 2 mols or more and 4 mols or less, and even more preferably 2 mols or more and 3 mols or less, per 1 mol of dicarboxylic acid.
• the ratio between the amount of dicarboxylic acid and the amount of diamine compound when producing a polyimide resin precursor is not particularly limited as long as a polyimide resin precursor having a desired molecular weight can be produced.
• the raw material ratio expressed by (number of moles of dicarboxylic acid)/(number of moles of diamine compound) is preferably 0.5/1 to 0.95/1, or more. Preferably, it is adjusted within the range of 0.55/1 to 0.80/1. The smaller the value of (number of moles of dicarboxylic acid)/(number of moles of diamine compound), the more difficult it is for the molecular chain of the polyimide resin precursor to extend, and the easier it is to obtain a low molecular weight polyimide resin precursor.
• the raw material ratio expressed by (number of moles of diamine compound)/(number of moles of dicarboxylic acid) is preferably from 0.5/1 to 0.95/1. Preferably, it is adjusted within the range of 0.55/1 to 0.80/1. The smaller the value of (number of moles of diamine compound)/(number of moles of dicarboxylic acid), the more difficult it is for the molecular chain of the polyimide resin precursor to extend, and the easier it is to obtain a low molecular weight polyimide resin precursor.
• a dicarboxylic acid and a diamine compound are mixed in an organic solvent in the presence of the above-mentioned condensing agent at, for example, -20°C or more and 150°C or less, preferably 0°C or more and 50°C or less, for 30 minutes.
• the reaction is allowed to occur for at least 24 hours, preferably for at least 1 hour and at most 4 hours.
• the solvent used in the polycondensation the above-mentioned solvents that can be used in the reaction between tetracarboxylic dianhydride and alcohol can be used.
• the amount of the solvent used is preferably 50 parts by mass or more and 10,000 parts by mass or less, more preferably 100 parts by mass or more and 2,000 parts by mass or less, based on the total of 100 parts by mass of the dicarboxylic acid and the diamine compound. It is preferably 150 parts by mass or more and 1,000 parts by mass or less.
• the amount of dicarboxylic acid and diamine compound to be used when producing a polyimide resin precursor is not particularly limited, but it is preferable to use 0.8 mol or more and 1.2 mol or less of diamine compound per 1 mol of dicarboxylic acid. It is more preferable to use 0.9 mol or more and 1.1 mol or less, and particularly preferably 0.95 mol or more and 1.05 mol or less.
• the polyimide resin precursor preferably has 2 to 50 carbon atoms, more preferably 3 to 40 carbon atoms.
• the divalent aliphatic hydrocarbon group is preferably included.
• the position of the divalent aliphatic hydrocarbon group in the molecular chain of the polyimide resin precursor is not particularly limited.
• Examples of monomers that provide a divalent aliphatic hydrocarbon group having 2 to 50 carbon atoms in the molecular chain include the above-mentioned dimer diamine compound (A-4) and the above-mentioned ⁇ , ⁇ -bis( Examples include 3,4-dicarboxyphenylcarbonyloxy)alkane dianhydride.
• the polyimide resin composition is made from a carboxylic acid derived from a tetracarboxylic dianhydride represented by the following formula (a1). It is preferable to include a structural unit derived from the following formula (a2) and/or a structural unit derived from a diamine compound represented by the following formula (a2).
• the tetracarboxylic dianhydride represented by formula (a1) and the diamine compound represented by formula (a2) are as described above.
• n is an integer of 1 or more.
• the weight average molecular weight of the polyimide resin precursor may be appropriately set according to its use.
• the weight average molecular weight of the polyimide resin precursor can be measured as a weight average molecular weight in terms of polystyrene by GPC (gel permeation chromatography).
• the weight average molecular weight of the polyimide resin precursor is, for example, 5,000 or more in terms of polystyrene, preferably 15,000 or more, and more preferably 250,000,000 or more, from the viewpoint of obtaining a resin film with good mechanical properties. preferable.
• the weight average molecular weight of the obtained polyimide resin precursor is, for example, 100,000 or less, preferably 80,000 or less, and more preferably 50,000 or less, in terms of solubility in organic solvents. preferable.
• This weight average molecular weight may be set to the above value by adjusting the blending amounts of the dicarboxylic acid and diamine compound described above, and reaction conditions such as the solvent and reaction temperature.
• polyimide For the purpose of improving the storage stability of photosensitive resin compositions containing polyimide resin precursors, further improving the mechanical properties of polyimide resin films, and improving the reproducibility of polymerization when producing polyimide resin precursors, polyimide
• the main chain end of the resin precursor may be capped with a terminal capping agent.
• the terminal capping agent include monoamines, acid anhydrides, monocarboxylic acids, monoacid halides, and monoactive ester compounds.
• the monoamine used for end-capping known compounds can be used.
• monoamines examples include aromatic monoamines such as aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 3-hydroxyaniline, 4-hydroxyaniline, 3-aminothiophenol, and 4-aminothiophenol.
• aromatic monoamines such as aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 3-hydroxyaniline, 4-hydroxyaniline, 3-aminothiophenol, and 4-aminothiophenol.
• aliphatic monoamines which may have a branched structure having 3 to 20 carbon atoms such as hexylamine and octylamine
• monoamines having an alicyclic structure such as cyclohexylamine, trimethoxyaminopropylsilane
• Examples include aminosilanes such as triethoxyaminopropylsilane.
• acid anhydrides are preferred.
• acid anhydride known acid anhydrides and derivatives thereof can be used.
• the introduction rate of the terminal capping agent in the polyimide resin precursor is preferably 40 mol% or less, and 20 mol% or less based on the number of moles of all monomers, from the viewpoint of excellent mechanical properties of the polyimide resin film formed.
• the content is more preferably 10 mol% or less.
• the polyimide resin precursor produced as described above is used in the production of polyimide resin in the form of a solution or suspension, or after being separated and recovered from the reaction solution by a well-known method.
• a polyimide resin is obtained by imidizing the aforementioned polyimide resin precursor.
• the polyimide resin exhibits a low dielectric loss tangent in a high frequency band and has excellent chemical resistance.
• the method of imidizing the polyimide resin precursor is not particularly limited. Imidization may be performed by heating or using an imidization agent.
• heating may be performed on a solution or suspension of the polyimide resin precursor, or may be performed on a solid polyimide resin precursor.
• the heating conditions for imidization are not particularly limited as long as the polyimide resin precursor does not decompose and imidization progresses satisfactorily.
• the heating temperature is preferably 80°C or more and 220°C or less, more preferably 100°C or more and 200°C or less, particularly preferably 120°C or more and 180°C or less. .
• the heating temperature is typically preferably 180°C or more and 400°C or less, more preferably 200°C or more and 350°C or less.
• the heating time depends on the heating temperature, typically, it is preferably 1 hour or more and 24 hours or less, and more preferably 2 hours or more and 12 hours or less.
• imidization is usually performed by adding the imidizing agent to a solution or suspension of the polyimide resin precursor.
• the organic solvent that can be used when imidizing with an imidizing agent for example, the same organic solvent as can be used for preparing the polyimide resin precursor can be used.
• the concentration of the polyimide resin precursor in the solution or suspension of the polyimide resin precursor is not particularly limited. Typically, the concentration of the polyimide resin precursor in the solution or suspension of the polyimide resin precursor is preferably 5% by mass or more and 50% by mass or less, more preferably 10% by mass or more and 30% by mass or less.
• the amount of imidizing agent used is not particularly limited.
• the amount of the imidizing agent used is selected depending on the type of imidizing agent so that the polyimide resin precursor is imidized to a desired degree.
• the reaction temperature when imidizing with an imidizing agent is not particularly limited.
• the reaction temperature is, for example, preferably 0°C or higher and 100°C or lower, more preferably 5°C or higher and 50°C or lower.
• the time for the imidization reaction when an imidization agent is used is not particularly limited.
• the imidization reaction is preferably carried out for 30 minutes or more and about 24 hours, more preferably 1 hour or more and 12 hours or less, and 2 hours or more and 6 hours or less, depending on the type of imidization agent. is even more preferable.
• Imidizing agents include acetic anhydride, propionic anhydride, benzoic anhydride, trifluoroacetic anhydride, acetyl chloride, tosyl chloride, mesyl chloride, ethyl chloroformate, triphenylphosphine and dibenzimidazolyl disulfide, dicyclohexylcarbodiimide, carbodiimidazole, Dehydrating agents such as 2-ethoxy-1-ethoxycarbonyl-1,2-dihydroquinoline and oxalic acid N,N'-disuccinimidyl ester, pyridine, picoline, 2,6-lutidine, collidine, triethylamine, N- Methylmorpholine, 4-N,N'-dimethylaminopyridine, isoquinoline, triethylamine, 1,4-diazabicyclo[2.2.2]octane, and 1,8-diazabicyclo[5.4.0
• the photosensitive resin composition includes a polymerizable resin (A), a photoradical polymerization initiator (C), and a solvent (S).
• the polymerizable resin (A) is the aforementioned polyimide resin precursor.
• a patterned polyimide resin film can be formed by the method described below. The resin film exhibits a low dielectric loss tangent in a high frequency band and has excellent chemical resistance.
• the photosensitive resin composition may contain a monomer compound (B) having a radically polymerizable group.
• the polymerizable resin (A) is the aforementioned polyimide resin precursor.
• ⁇ Monomer compound (B)> a monomer compound having an ethylenically unsaturated double bond as a radically polymerizable group is preferably used.
• Such monomer compound (B) may be a monofunctional monomer compound or a polyfunctional monomer compound, and a polyfunctional monomer compound is preferable.
• Examples of monofunctional monomer compounds include (meth)acrylamide, methylol (meth)acrylamide, methoxymethyl (meth)acrylamide, ethoxymethyl (meth)acrylamide, propoxymethyl (meth)acrylamide, butoxymethoxymethyl (meth)acrylamide, N - Methylol (meth)acrylamide, N-hydroxymethyl (meth)acrylamide, (meth)acrylic acid, fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, crotonic acid, 2 -Acrylamido-2-methylpropanesulfonic acid, tert-butylacrylamide sulfonic acid, methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, 2 -
• Polyfunctional monomer compounds include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, and propylene glycol.
• urethane (meth)acrylates described in Japanese Patent Publication No. 48-41708, Japanese Patent Publication No. 50-6034, and Japanese Patent Publication No. 51-37193; Polyester (meth)acrylates described in JP-A-43191 and Japanese Patent Publication No. 52-30490; Epoxy (meth)acrylates which are reaction products of epoxy resin and (meth)acrylic acid; JP-A-2008- Compounds described in paragraphs [0254] to [0257] of Publication No.
• polyfunctional (meth) obtained by reacting a polyfunctional carboxylic acid with a compound having an epoxy group such as glycidyl (meth)acrylate and an ethylenically unsaturated group; ) Acrylate; a compound having a fluorene ring and two or more groups having an ethylenically unsaturated bond, described in JP-A No. 2010-160418, JP-A No. 2010-129825, and Patent No. 4364216, etc. and cardo resin; unsaturated compounds described in Japanese Patent Publication No. 46-43946, Japanese Patent Publication No. 1-40337, and Japanese Patent Publication No. 1-40336; vinylphosphonic acid compounds described in Japanese Patent Publication No.
• polyfunctional monomer compounds having trifunctionality or more are preferred since they tend to increase the adhesion of the polyimide resin film to the substrate and the strength of the polyimide resin film.
• a polyfunctional monomer compound having four or more functionalities is more preferable, and a polyfunctional monomer compound having five or more functionalities is even more preferable.
• the content of the monomer compound (B) in the photosensitive resin composition is not particularly limited as long as it does not impede the purpose of the present invention.
• the content of the monomer compound (B) in the photosensitive resin composition is 0.1 parts by mass or more and 50 parts by mass when the mass of the photosensitive resin composition excluding the mass of the solvent (S) described below is 100 parts by mass. It is preferably 0.5 parts by mass or more and 40 parts by mass or less, particularly preferably 1 part by mass or more and 25 parts by mass or less.
• the radical photopolymerization initiator (C) is not particularly limited, and conventionally known photopolymerization initiators can be used.
• the photoradical polymerization initiator (C) includes 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxy)phenyl ]-2-hydroxy-2-methyl-1-propan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 2-hydroxy-1- ⁇ 4-[ 4-(2-hydroxy-2-methyl-propionyl)-benzyl]phenyl ⁇ -2-methyl-propan-1-one, 1-(4-dodecylphenyl)-2-hydroxy-2-methylpropan-1-one , 2,2-dimethoxy-1,2-diphenylethan-1-one, bis(4-dimethylaminophenyl)ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane-1 -one, 2-benzyl-2-dimethylamino-1-(4-morpholinopheny
• oxime ester compounds are preferred from the viewpoint of sensitivity of the photosensitive resin composition.
• a compound having a partial structure represented by the following formula (c1) is preferable.
• n1 is 0 or 1.
• R c2 is a monovalent organic group.
• R c3 is a hydrogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or an aryl group which may have a substituent. * is a bond.
• the content of the radical photopolymerization initiator (C) in the photosensitive resin composition is not particularly limited as long as the photosensitive resin composition has desired photolithographic properties.
• the content of the photoradical polymerization initiator (C) in the tree photosensitive resin composition is typically 100 parts by mass in total of the mass of the resin (A) and the mass of the monomer compound (B).
• the content is preferably 0.01 parts by mass or more and 20 parts by mass or less, more preferably 0.1 parts by mass or more and 15 parts by mass or less, and even more preferably 1 part by mass or more and 10 parts by mass or less.
• the photosensitive resin composition usually contains a solvent (S) for the purpose of adjusting coating properties.
• the type of solvent (S) is not particularly limited as long as it dissolves the resin (A) and other components well.
• the solvent (S) include N,N-dimethylformamide, N,N-dimethylacetamide, N,N-diethylformamide, and N-methyl-2 -pyrrolidone, N-ethyl-2-pyrrolidone, hexamethylphosphoramide, 1,3-dimethyl-2-imidazolidinone, N,N-dimethylisobutyric acid amide, 3-methoxy-N,N-dimethylpropionamide, 3 - Nitrogen-containing polar solvents such as butoxy-N,N-dimethylpropionamide, N,N-dimethylpropionamide, N,N-dimethylisobutyramide, N,N-dimethylpropylene urea; acetone, methyl ethyl ketone, methyl isobutyl ketone, 2 - Ketones such as heptanone, 3-heptanone, diisobuty
• Alcohols such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol dimethyl ether, and other glycol ethers ;
• Aromatic ethers such as anisole; Cyclic ethers such as dioxane and tetrahydrofuran; Cyclic esters such as ethylene carbonate and propylene carbonate;
• Aromatic solvents such as anisole, toluene, and xylene; Aliphatic hydrocarbons such as limonene sulfoxides such as dimethyl sulfoxide.
• the amount of the solvent (S) used is not particularly limited as long as a uniform liquid photosensitive resin composition can be prepared.
• the photosensitive resin composition may be in the form of a suspension or a solution, and is preferably a solution.
• the solvent (S) is used such that the solid content concentration of the photosensitive resin composition is preferably 15% by mass or more and 50% by mass or less, more preferably 20% by mass or more and 45% by mass or less. .
• the photosensitive resin composition may contain various additives other than the components described above, if necessary.
• Additives include colorants, dispersants, sensitizers, adhesion promoters, polymerization inhibitors, antioxidants, ultraviolet absorbers, anti-aggregation agents, antifoaming agents, surfactants, imidization promoters, and adhesion promoters.
• Examples of the improver include nitrogen-containing heterocyclic compounds and silane coupling agents.
• the photosensitive resin composition may contain various fillers or reinforcing materials as necessary.
• sensitizer known compounds can be used.
• the sensitizer include bis(dimethylamino)benzophenone, bis(diethylamino)benzophenone, diethylthioxanthone, N-phenyldiethanolamine, N-phenylglycine, 7-diethylamino-3-benzoylcoumarin, 7-diethylamino-4-methyl Coumarin, N-phenylmorpholine, and derivatives thereof.
• polymerization inhibitor known compounds can be used.
• the polymerization inhibitor include compounds having a phenolic hydroxyl group, nitroso compounds, N-oxide compounds, quinone compounds, N-oxyl compounds, and phenothiazine compounds.
• the polymerization inhibitors include Irganox1010, Irganox1035, Irganox1098, Irganox1135, Irganox245, Irganox259, Irganox3114, (all manufactured by BASF Japan), 2,6-di-tert-butyl- p-cresol, and 4-methoxyphenol is preferred, and Irganox 1010, 2,6-di-tert-butyl-p-cresol, and 4-methoxyphenol are more preferred.
• the amount of the polymerization inhibitor used is as follows: Based on the mass of the resin (A), preferably 0.005% by mass or more and 1% by mass or less, more preferably 0.01% by mass or more and 0.5% by mass or less, and 0.03% by mass or more and 0.3% by mass. The following are more preferred.
• the nitrogen-containing heterocyclic compound coordinates and stabilizes the metal surface, thereby improving the adhesion of the resin film formed using the photosensitive resin composition to the metal surface.
• known compounds can be used as the nitrogen-containing heterocyclic compound.
• the nitrogen-containing heterocyclic compound include imidazole, pyrazole, indazole, carbazole, triazole, pyrazoline, pyrazolidine, tetrazole, pyridine, piperidine, pyrimidine, pyrazine, triazine, cyanuric acid, isocyanuric acid, and derivatives thereof.
• nitrogen-containing heterocyclic compounds preferred from the viewpoint of coordination with metals include 1H-benzotriazole, 4-methyl-1H-methylbenzotriazole, 5-methyl-1H-methylbenzotriazole, and 4-carboxy- Examples include triazoles such as 1H-methylbenzotriazole and 5-carboxy-1H-methylbenzotriazole, and triazoles such as 1H-tetrazole, 5-methyl-1H-tetrazole, and 5-phenyl-1H-tetrazole.
• the amount of the nitrogen-containing heterocyclic compound to be used is determined. is preferably 0.01% by mass or more and 5% by mass or less, more preferably 0.05% by mass or more and 3% by mass or less, based on the mass of the resin (A).
• silane coupling agent By blending a silane coupling agent into a photosensitive resin composition, it is possible to improve the adhesion of a resin film formed using the photosensitive resin composition to a substrate or the like.
• the silane coupling agent known compounds can be used.
• the silane coupling agent include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, and 3-mercaptopropyltriethoxysilane.
• 3-glycidoxypropyltrimethoxysilane 3-glycidoxypropyltriethoxysilane, 2-(epoxycyclohexyl)ethyltrimethoxysilane, 2-(epoxycyclohexyl)triethoxysilane, tris(3-trimethoxysilylpropyl) ) isocyanurate, tris(3-triethoxysilylpropyl)isocyanurate, a reaction product of 3-aminopropyltrimethoxysilane and an acid anhydride, a reaction product of 3-aminopropyltriethoxysilane and an acid anhydride, etc. It will be done.
• Examples of acid anhydrides to be reacted with 3-aminopropyltrimethoxysilane or 3-aminopropyltriethoxysilane include succinic anhydride, maleic anhydride, nadic anhydride, 3-hydroxyphthalic anhydride, and pyromellitic dianhydride. anhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,2',3,3'-benzophenonetetracarboxylic dianhydride, and 4,4'-oxydiphthalic dianhydride etc.
• the amount of the silane coupling agent used is preferably 0.01% by mass or more and 10% by mass or less based on the mass of the resin (A).
• a surfactant By blending a surfactant into a photosensitive resin composition, the coatability of the photosensitive resin composition is improved, and the wettability of the photosensitive resin composition with a substrate is also improved.
• the surfactant known compounds can be used. Examples of the surfactant include fluorine surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and silicone surfactants.
• the amount of the surfactant used is preferably 0.001% by mass or more and 1% by mass or less based on the mass of the resin (A).
• Polymerizable resin (A) can be converted into polyimide resin by heating.
• the photosensitive resin composition may contain a cyclization accelerator.
• the cyclization accelerator promotes the production of a polyimide resin by cyclizing a polyamide resin containing a structural unit derived from a polyamic acid or a dicarboxylic acid compound that can be synthesized by a reaction between a tetracarboxylic dianhydride and an alcohol.
• the photosensitive resin composition contains a cyclization accelerator, the mechanical properties and weather resistance reliability of a resin film formed using the photosensitive resin composition while producing a polyimide resin through cyclization are improved.
• the cyclization accelerator known thermal base generators and thermal acid generators are used.
• the amount of each additive used is not particularly limited as long as it does not impede the purpose of the present invention.
• the amount of additives whose usage amount is not listed above may be adjusted as appropriate within the range of, for example, 0.001% by mass or more and 60% by mass or less based on the mass of the solid content of the photosensitive resin composition. , preferably from 0.01% by mass to 5% by mass.
• a photosensitive resin composition can be prepared by uniformly mixing the above-described essential components and, if necessary, arbitrary components in desired amounts.
• the mixing method is not particularly limited.
• a photosensitive dry film has a base film and a photosensitive layer formed on the surface of the base film.
• the photosensitive layer is made of the photosensitive resin composition described above.
• a film having light transmittance is preferable.
• polyethylene terephthalate (PET) film, polypropylene (PP) film, polyethylene (PE) film, etc. may be mentioned, but polyethylene terephthalate (PET) film is preferable because it has an excellent balance of light transmittance and breaking strength.
• a photosensitive dry film is manufactured by coating the above-described photosensitive resin composition on a base film to form a photosensitive layer.
• a photosensitive layer When forming a photosensitive layer on the base film, use an applicator, a bar coater, a wire bar coater, a roll coater, a curtain flow coater, etc. to form the photosensitive layer on the base film so that the film thickness after drying is preferably 0.5 ⁇ m.
• the photosensitive resin composition is coated to a thickness of 3 ⁇ m or more and 300 ⁇ m or less, more preferably 1 ⁇ m or more and 300 ⁇ m or less, particularly preferably 3 ⁇ m or more and 100 ⁇ m or less, and dried.
• the photosensitive dry film may further have a protective film on the photosensitive layer.
• this protective film include polyethylene terephthalate (PET) film, polypropylene (PP) film, and polyethylene (PE) film.
• ⁇ Resin film forming method a coating step of coating a photosensitive resin composition on a substrate to form a coating film;
• a resin film containing the aforementioned polyimide resin precursor can be formed by a method comprising a drying step of drying a coating film to obtain a resin film.
• the substrate is not particularly limited, and any conventionally known substrate can be used, such as a substrate for electronic components, a substrate on which a predetermined wiring pattern is formed, and the like.
• a substrate for electronic components such as a substrate for electronic components, a substrate on which a predetermined wiring pattern is formed, and the like.
• a silicon substrate, a glass substrate, etc. can also be used.
• a coating film having a desired thickness is formed by removing the solvent from the applied photosensitive resin composition.
• the thickness of the coating film is not particularly limited, but is preferably 0.5 ⁇ m or more, more preferably 0.5 ⁇ m or more and 300 ⁇ m or less, particularly preferably 1 ⁇ m or more and 150 ⁇ m or less, and most preferably 3 ⁇ m or more and 100 ⁇ m or less.
• a spin coating method As a method for applying the photosensitive resin composition onto the substrate, methods such as a spin coating method, a slit coating method, a roll coating method, a screen printing method, an applicator method, etc. can be adopted.
• the method of drying the photosensitive resin composition applied onto the substrate is not particularly limited. Preferably, drying is performed by heating.
• the heating conditions during drying vary depending on the type of each component in the photosensitive resin composition, blending ratio, coating film thickness, etc., but are usually 70°C or more and 200°C or less, preferably 80°C or more and 150°C or less, The time is about 2 minutes or more and 120 minutes or less.
• a resin film containing the aforementioned polyimide resin precursor is formed.
• ⁇ Method for forming patterned resin film a coating step of coating the aforementioned photosensitive resin composition on the substrate to form a coating film; an exposure step of positionally selectively irradiating the coating film with actinic rays or radiation; A patterned resin film is formed by a method including a developing step of developing the exposed coating film to obtain a patterned resin film.
• the patterned resin film contains the aforementioned polyimide resin precursor.
• the substrate and the method of applying the photosensitive resin composition are as described above for the resin film forming method.
• the photosensitive resin composition applied onto the substrate is usually dried to form a coating film.
• the method of drying the photosensitive resin composition applied onto the substrate is not particularly limited. Preferably, drying is performed by heating.
• the heating conditions during drying vary depending on the type of each component in the photosensitive resin composition, blending ratio, coating film thickness, etc., but are usually 70°C or more and 200°C or less, preferably 80°C or more and 150°C or less, The time is about 2 minutes or more and 120 minutes or less.
• the coating film formed as described above is exposed by irradiating active light or radiation in a position-selective manner.
• One selective exposure is usually performed by position-selectively irradiating actinic light or radiation, such as ultraviolet rays or visible light having a wavelength of 300 nm or more and 500 nm or less, through a mask with a predetermined pattern.
• a radiation source a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halide lamp, an argon gas laser, etc.
• radiation includes microwaves, infrared rays, visible light, ultraviolet rays, X-rays, ⁇ -rays, electron beams, proton beams, neutron beams, ion beams, and the like.
• the amount of radiation irradiation varies depending on the composition of the resin film-forming photosensitive resin, the thickness of the photosensitive layer, etc., but for example, in the case of using an ultra-high pressure mercury lamp, it is 100 mJ/cm 2 or more and 10000 mJ/cm 2 or less.
• the exposed coating film is developed according to a conventionally known method, and unnecessary portions are dissolved and removed, thereby forming a resin film patterned into a predetermined shape.
• a developer is used depending on the components contained in the photosensitive resin composition.
• the aforementioned polyimide resin precursor is a resin having an alkali-soluble group such as a carboxyl group
• an alkaline aqueous solution can be used as the developer.
• the above-mentioned solvent (S) can be used as the developer.
• alkaline developers include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, and methyldiethylamine.
• aqueous solution of an alkali such as 5-diazabicyclo[4,3,0]-5-nonane can be used.
• an aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant to the aqueous solution of the above-mentioned alkali can also be used as the developer.
• the development time varies depending on the composition of the photosensitive resin composition, the thickness of the coating film, etc., but is usually between 1 minute and 30 minutes.
• the developing method may be any of a piling method, a dipping method, a paddle method, a spray developing method, and the like.
• the cleaning solvent is not particularly limited.
• water, alcohol, or the like can be used as a cleaning solvent in the case of alkaline development.
• the solvent (S) can be used as long as solvent shock does not occur.
• the polyimide resin precursor contained in the resin film can be imidized by heating. Therefore, after development, the developed coating film may be baked, if necessary, to imidize the polyimide resin precursor in the resin film.
• the conditions for converting the polyimide resin precursor into polyimide resin by heating are as described above. Furthermore, baking is preferably performed in an atmosphere of an inert gas such as nitrogen or argon from the viewpoint of preventing oxidation of the resin film and obtaining a resin film with good mechanical properties.
• the patterned polyimide resin film formed as described above can be used, for example, as an insulating film for semiconductor devices, an interlayer insulating film for rewiring layers, an insulating film or a protective film in touch panel displays, organic electroluminescent display panels, etc. Suitably used. Since the photosensitive resin composition described above has good resolution, the patterned resin film formed as described above is particularly useful as an interlayer insulating film for a rewiring layer in a three-dimensional mounting device. , can be preferably used. Furthermore, the patterned resin film formed as described above can be suitably used as a photoresist, galvanic (electrolytic) resist, etching resist, solder top resist, etc. for electronics.
• the patterned resin film formed as described above can be used for manufacturing printing plates such as offset printing plates or screen printing plates, for forming etching masks when etching molded parts, and for electronic parts, especially microelectronic parts. It can also be used in the production of protective lacquers, dielectric layers, etc.
• Example 1 to 15 and Comparative Examples 1 to 3 In Examples and Comparative Examples, the following DA1 to DA4 were used as diamine compounds.
• Alc1 to Alc8 were used as alcohols to be reacted with tetracarboxylic dianhydride.
• Alc1 2-hydroxybutyl methacrylate (manufactured by Kyoeisha, light ester HOB (N))
• Alc2 Glycerin-1,3-dimethacrylate (manufactured by Kyoeisha, Light Ester G-10IP)
• Alc3 3-phenoxy-2-hydroxypropyl methacrylate (manufactured by Wako Pure Chemical Industries)
• Alc4 2-hydroxybutyl acrylate (manufactured by Kyoeisha, light acrylate HOB-A)
• Alc5 Glycerin-1,3-diacrylate (manufactured by Toagosei, Aronix M-920)
• Alc6 3-phenoxy-2-hydroxypropyl acrylate (manufactured by Tokyo Chemical Industry)
• Alc7 1,4-cyclohexaned
• the filtrate containing the polyimide resin precursor was dropped into a large amount of isopropyl alcohol aqueous solution.
• the polyimide resin precursor precipitated in the aqueous solution in isopropyl alcohol was collected by filtration. The collected precipitate was washed three times with isopropyl alcohol. The precipitates after washing were dried under reduced pressure to obtain polyimide resin precursors for each example and comparative example.
• the obtained polyimide resin was dissolved in ⁇ -butyrolactone to a concentration of 30% by mass.
• 5% by mass of a photoradical polymerization initiator (Irgacure OXE-02, manufactured by BASF Japan) based on the mass of the polyimide resin precursor and 0.05% by mass based on the mass of the polyimide resin precursor were added.
• % polymerization inhibitor (Irganox 1010, manufactured by BASF Japan), 0.02% by mass of surfactant (Polyflow No. 77, manufactured by Kyoeisha Chemical Co., Ltd.) based on the mass of the polyimide resin precursor, and the polyimide resin precursor.
• a silane coupling agent (N-(3-triethoxysilylpropyl)phthalic acid amide) was added in an amount of 3% by mass based on the body mass to obtain photosensitive resin compositions of each example and each comparative example. .
• Table 1 shows the imide group concentrations determined by the method described above for the polyimide resin precursors obtained in each Example and each Comparative Example. Further, a polyimide resin film was formed using the obtained photosensitive resin composition, and the dielectric loss tangent and chemical resistance of the obtained polyimide resin film were evaluated according to the following method. These evaluation results are shown in Table 1.
• the thin film of the photosensitive resin composition was baked at 90° C. for 240 seconds.
• the baked coating film was exposed to light using a high-pressure mercury lamp at a cumulative light intensity of 2000 mJ/cm 2 .
• the exposed film was heated in an inert oven under a nitrogen atmosphere at a rate of 5° C./min to 230° C., and the coated film was heated at the same temperature for 1 hour.
• the wafer When the temperature dropped to 100° C., the wafer was taken out and immersed in an aqueous solution of hydrofluoric acid with a concentration of 2% by mass for 5 to 30 minutes, and the resin film was peeled from the wafer to obtain a polyimide resin film.
• the thickness of the resin film after peeling was 10 ⁇ m.
• the dielectric dissipation tangent (tan ⁇ ) of the obtained film was calculated in the IEICE Technical Report of the Institute of Electronics, Information and Communication Engineers, vol. 118, no. 506, MW2018-158, pp. 13-18, March 2019.
• Study on millimeter-wave complex permittivity evaluation using cavity resonator method” Kermeti Takahagi (Utsunomiya University), Kazuaki Ebisawa (Tokyo Ohka Kogyo Co., Ltd.), Yoshinori Furugami (Utsunomiya University), Takashi Shimizu (Utsunomiya University)) Measured using the method described.
• Dielectric loss tangent is 0.07 or less.
• Dielectric loss tangent value is more than 0.07 and less than 0.01.
• Dielectric loss tangent value exceeds 0.01.
• the thin film of the photosensitive resin composition was baked at 90° C. for 240 seconds.
• the baked coating film was exposed to light using a high-pressure mercury lamp at a cumulative light intensity of 2000 mJ/cm 2 .
• the exposed film was heated in an inert oven under a nitrogen atmosphere at a rate of 5° C./min to 230° C., and the coated film was heated at the same temperature for 1 hour.
• the wafer was taken out.
• a test piece obtained by cutting this wafer into 5 cm square pieces was immersed in an aqueous sulfuric acid solution with a concentration of 30% by mass at 25° C. for 60 minutes. It was confirmed whether the appearance of the test piece after immersion had changed from the appearance of the test piece before immersion.
• the photolithographic properties of the photosensitive resin compositions of Examples were confirmed by the following method.
• the resulting photosensitive resin compositions of Examples 1 to 15 were applied onto silicon wafers on which a copper sputtered film was formed using a spin coater. Thereafter, the film made of the photosensitive resin composition was baked at 80° C. for 300 seconds to obtain a coating film with a thickness of 12 ⁇ m.
• the coating film was exposed to light at 2000 mJ/cm 2 and a focus of 0 ⁇ m using a ghi ray exposure machine (manufactured by Ultratech) through a negative mask capable of forming a via hole with an opening diameter of 50 ⁇ m.
• the exposed coating film was immersed in cyclopentanone for 120 seconds and developed to form a patterned resin film having via holes of 50 ⁇ m.
• the temperature of the obtained resin film was raised to 230°C at a rate of 5°C/min in an inert oven under a nitrogen atmosphere, and the coated film was heated at the same temperature for 1 hour. When the temperature dropped to 100° C., the wafer was taken out to obtain a patterned imidized resin film on the substrate.
• an alcohol having a combination of a secondary hydroxyl group and an ethylenically unsaturated double bond, or a combination of a methylol group and an ethylenically unsaturated double bond, and a tetracarboxylic dianhydride It can be seen that a polyimide resin film formed using a polyimide resin precursor obtained by condensing a dicarboxylic acid, which is a reaction product with a substance, with a diamine compound exhibits a low dielectric loss tangent and has excellent chemical resistance.
• a dicarboxylic acid which is a reaction product of 2-hydroxyethyl methacrylate (Alc8) having a combination of a primary hydroxyl group and an ethylenically unsaturated double bond and a tetracarboxylic dianhydride
• Alc8 2-hydroxyethyl methacrylate
• the polyimide resin film formed using the polyimide resin precursor obtained by condensing the above with a diamine compound is inferior in at least one of dielectric properties and chemical resistance.

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