Classifications

• • 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
• • 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
• • 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
• • 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
  • C08G73/14—Polyamide-imides
• • 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
  • C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
  • C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
  • C08G81/024—Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L87/00—Compositions of unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
  • C08L87/005—Block or graft polymers not provided for in groups C08L1/00 - C08L85/04
• • 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
  • 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
  • G03F7/16—Coating processes; Apparatus therefor
  • G03F7/168—Finishing the coated layer, e.g. drying, baking, soaking
• • 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 block copolymer containing a block derived from a polyimide macromonomer and / or a block derived from a polyamide macromonomer, a polyimide resin obtained by imidizing the block copolymer, and the block copolymer described above. and a method for producing a resin film using the resin film-forming composition.
• Polyimide resins and polyamide resins have properties such as excellent heat resistance, mechanical strength, insulation, and low dielectric constant. It is widely used as an insulating and protective material in parts.
• a specific structural unit having a structural unit derived from 4,4'-bis(4-aminophenoxy)biphenyl is proposed 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 a side chain, and a specific radical generation
• Patent Document 2 A photosensitive resin composition containing a photopolymerization initiator having an oxime structure indicating the amount thereof (see Patent Document 2) has been proposed.
• the present invention has been made in view of the above problems, a block copolymer having a low dielectric loss tangent and excellent mechanical properties such as elongation and strength, and a polyimide obtained by imidating the block copolymer
• An object of the present invention is to provide a resin, a resin film-forming composition capable of forming a resin film containing the block copolymer, and a method for producing a resin film using the resin film-forming composition.
• the present inventors have found that a macromonomer that is a polyamide macromonomer and/or a polyimide macromonomer, a tetracarboxylic dianhydride, and/or a dicarboxylic acid that is a reaction product of a tetracarboxylic dianhydride and an alcohol , A block derived from a polyamide macromonomer, and / or a block derived from a polyimide macromonomer, copolymerized with a diamine compound, a block derived from a polyamide macromonomer, and / or a block derived from a polyimide macromonomer.
• the inventors have found that the above problems can be solved by using a block copolymer having a weight average molecular weight of 1,500 or more and 30,000 or less, and have completed the present invention. More specifically, the present invention provides the following.
• a first aspect of the present invention is a macromonomer that is a polyamide macromonomer and/or a polyimide macromonomer;
• a tetracarboxylic dianhydride and/or a dicarboxylic acid that is a reaction product of a tetracarboxylic dianhydride and an alcohol
• a polyamide macromonomer is a macromonomer obtained by polymerizing a dicarboxylic acid, which is a reaction product of a tetracarboxylic dianhydride and an alcohol, and a diamine compound
• the polyimide macromonomer is a polyamic acid macromonomer obtained by polymerizing a tetracarboxylic dianhydride and a diamine compound, or a
• a second aspect of the present invention is a polyimide resin obtained by imidizing the block copolymer according to the first aspect.
• a third aspect of the present invention is including a resin (A) and a solvent (S),
• the resin (A) is a resin film-forming composition containing the block copolymer according to the first aspect and/or the polyimide resin according to the second aspect.
• a fourth aspect of the present invention is a coating step of coating the resin film-forming composition according to the third aspect on a substrate to form a coating film; and a drying step of drying the coating film to obtain a resin film.
• a fifth aspect of the present invention is a coating step of coating the resin film-forming composition according to the third aspect on a substrate to form a coating film; an exposure step of position-selectively irradiating the coating film with actinic rays or radiation for exposure; a developing step of developing the coated film after exposure to obtain a patterned resin film
• the macromonomer is a polyamide macromonomer
• a polyamide macromonomer is a polymer of a dicarboxylic acid, which is a reaction product of a tetracarboxylic dianhydride and an alcohol having a radically polymerizable group, and a diamine compound
• a method for forming a patterned resin film wherein the resin film-forming composition contains a photoradical polymerization initiator (C).
• a block copolymer having a low dielectric loss tangent and excellent mechanical properties such as elongation and strength, a polyimide resin obtained by imidizing the block copolymer, and the block copolymer A resin film-forming composition capable of forming a resin film and a method for producing a resin film using the resin film-forming composition can be provided.
• the block copolymer is a macromonomer that is a polyamide macromonomer and/or a polyimide macromonomer; A tetracarboxylic dianhydride and/or a dicarboxylic acid that is a reaction product of a tetracarboxylic dianhydride and an alcohol, It is a copolymer with a diamine compound.
• block copolymers include blocks derived from polyamide macromonomers derived from polyamide macromonomers and/or blocks derived from polyimide macromonomers derived from polyimide macromonomers.
• a polyamide macromonomer is a macromonomer obtained by polymerizing a dicarboxylic acid, which is a reaction product of a tetracarboxylic dianhydride and an alcohol, and a diamine compound.
• the polyimide macromonomer is a polyamic acid macromonomer obtained by polymerizing a tetracarboxylic dianhydride and a diamine compound, or a macromonomer obtained by imidizing the above polyamide macromonomer.
• the weight average molecular weight of the polyamide macromonomer and the polyimide macromonomer is 1,500 or more and 30,000 or less, preferably 1,500 or more and 25,000 or less, and more preferably 2,500 or more and 25,000 or less.
• the weight average molecular weights of the polyamide macromonomer and the polyimide macromonomer can be measured as polystyrene-equivalent weight average molecular weights by GPC (gel permeation chromatography).
• the above block copolymer has a low dielectric loss tangent and excellent mechanical properties such as elongation and strength.
• the polyamide macromonomer is a macromonomer obtained by polymerizing a dicarboxylic acid, which is a reaction product of tetracarboxylic dianhydride and an alcohol, and a diamine compound.
• the polyimide macromonomer is a polyamic acid macromonomer obtained by polymerizing a tetracarboxylic dianhydride and a diamine compound, or a macromonomer obtained by imidizing the above polyamide macromonomer.
• the weight average molecular weight of the polyamide macromonomer and the polyimide macromonomer is 1500 or more and 30000 or less.
• the weight average molecular weights of the polyamide macromonomer and the polyimide macromonomer can be adjusted by adjusting the conditions for polymerizing the monomer compounds when producing the polyamide macromonomer and the polyimide macromonomer. For example, if the polymerization reaction time is short, the weight average molecular weight tends to be low. The longer the polymerization reaction time, the higher the weight average molecular weight.
• the weight average molecular weight of the polyamide macromonomer and the polyimide macromonomer can be adjusted.
• the raw material ratio represented by (number of moles of dicarboxylic acid or tetracarboxylic dianhydride)/(number of moles of diamine compound) is preferably 0.5/1 to 0.5. It should be adjusted within the range of 95/1, more preferably 0.55/1 to 0.80/1.
• the raw material ratio represented by (number of moles of diamine compound) / (number of moles of dicarboxylic acid or tetracarboxylic dianhydride) is preferably It should be adjusted within the range of 0.5/1 to 0.95/1, more preferably 0.55/1 to 0.80/1.
• a polyamide macromonomer and/or a polyimide macromonomer are polymerized with a monomer selected from tetracarboxylic dianhydrides, dicarboxylic acids, and diamine compounds, which will be described later. Therefore, polyamide macromonomers and polyimide macromonomers must have terminal groups that can react with dicarboxylic anhydride groups, carboxy groups, or amino groups.
• Polyimide macromonomers and polyamide macromonomers are generally linear macromonomers having reactive terminal groups at both ends.
• both terminals may be amino group terminals, both may be dicarboxylic anhydride group terminals, and both dicarboxylic anhydride groups may be ring-opened by reaction with water. It may be dicarboxylic acid terminated. Further, one end may be an amino group end and the other end may be a dicarboxylic anhydride group end, and one end may be an amino group end and the other end is a dicarboxylic anhydride group that reacts with water. It may be a dicarboxylic acid terminal ring-opened.
• the content ratio of the structural unit derived from the polyamide macromonomer and the structural unit derived from the polyimide macromonomer is preferably 1% by mass or more and 70% by mass or less, and 5% by mass or more and 50% by mass or less. is particularly preferred.
• the polyamide macromonomer and the polyimide macromonomer are described below.
• a polyamide macromonomer is a macromonomer obtained by polymerizing a dicarboxylic acid, which is a reaction product of a tetracarboxylic dianhydride and an alcohol, and a diamine compound.
• Polyamide macromonomers provide blocks derived from polyamide macromonomers in block copolymers.
• a polyamide macromonomer is a macromonomer obtained by polymerizing one or more dicarboxylic acids, which are reaction products of tetracarboxylic dianhydride and alcohols, and one or more diamine compounds.
• one type of polyamide macromonomer may be used, or two or more types of polyamide macromonomers may be used.
• the diamine compound, the dicarboxylic acid that is the reaction product of the tetracarboxylic dianhydride and the alcohol, and the diamine compound are described below.
• a diamine compound As the diamine compound, any diamine compound that has been conventionally used in the production of polyimide resins, polyamic acids, and polyamide resins can be used without particular limitation.
• a diamine compound is represented by the following formula (A2). H 2 NA 1 -NH 2 (A2)
• A1 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.
• 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 the number of carbon atoms.
• One to six fluorinated alkoxy groups, carboxy groups, or hydroxy groups are preferred.
• the substituent is a fluorinated alkyl group or fluorinated alkoxy group, it is preferably a perfluoroalkyl group or perfluoroalkoxy group.
• the lower limit of the number of carbon atoms in the organic group as A1 is preferably 2, more preferably 6.
• the upper limit is preferably 50, more preferably 30.
• a 1 may be an aliphatic group, but 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 one aromatic group itself, and two or more aromatic groups are aliphatic hydrocarbon groups and halogenated aliphatic group hydrocarbon group, or a group bonded via a bond containing a heteroatom such as an oxygen atom, a sulfur atom, or a nitrogen atom.
• the aromatic ring in A1 that bonds 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 heterocyclic ring.
• a 1 is an organic group containing an aromatic ring
• the organic group is a group represented by the following formulas (21) to (24) from the viewpoint of improving the electrical properties and mechanical properties of the resin film to be formed. is preferably at least one of
• 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 one selected from the group consisting of alkyl groups.
• Q 1 is a 9,9'-fluorenylidene group, or formulas: -C 6 H 4 -, -C 6 H 4 -C 6 H 4 -, -OC 6 H 4 -C 6H4 -O-, -O- C6H4 - CO- C6H4 - O- , -O- C6H4 - C( CH3 ) 2- C6H4 - 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- , -CH2- , -O - C6H4 - SO2- C6H4 -O-, -C( CH3 ) 2 - C6H4 - C( CH3 ) 2- , —O—C 10 H 6
• —C 6 H 4 — in the examples of Q 1 is a phenylene group, preferably an m-phenylene group and a p-phenylene group, more preferably a p-phenylene group.
• -C 10 H 6 - is a naphthalene diyl group, naphthalene-1,2-diyl group, naphthalene-1,4-diyl group, naphthalene-2,3-diyl group, naphthalene-2,6-diyl and naphthalene-2,7-diyl groups are preferred, and naphthalene-1,4-diyl groups and naphthalene-2,6-diyl groups are more preferred.
• 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 to be formed. Atoms or trifluoromethyl groups are particularly preferred.
• Q 1 in formula (24) is -C 6 H 4 -C 6 H 4 -, -OC 6 H 4 -C 6 H 4 from the viewpoint of the electrical and mechanical properties of the resin film to be formed.
• Q 1 in formula (24) includes -O-C 6 H 4 -C 6 H 4 -O- and -O-C 6 H 4 -.
• C(CH 3 ) 2 -C 6 H 4 -O- is more preferred, represented by -O-C 6 H 4 -C 6 H 4 -O- and -C 6 H 4 - are both p-phenylene groups groups are particularly preferred.
• aromatic diamine compounds shown below can be preferably 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 chain-like aliphatic group and/or a silicon atom-containing group optionally having an aromatic ring can be employed.
• a silicon atom-containing group typically the groups shown below can be used.
• Specific examples of compounds having amino groups at both ends and having a silicon atom-containing group include amino-modified methylphenyl silicone at both ends (for example, Shin-Etsu Chemical Co., Ltd., X-22-1660B-3 (number average molecular weight: 4 , about 400) and X-22-9409 (number average molecular weight about 1,300)), amino-modified dimethyl silicone at both ends (for example, Shin-Etsu Chemical Co., Ltd., X-22-161A (number average molecular weight about 1,600), X-22-161B (number average molecular weight about 3,000) and KF8012 (number average molecular weight about 4,400); BY16-835U manufactured by Dow Corning Toray (number average molecular weight about 900); and Silaplane FM3311 manufactured by JNC (number average molecular weight of about 1000)) and the like.
• amino-modified methylphenyl silicone at both ends for example, Shin-Etsu Chemical Co.
• 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 an ethyleneoxy group, a propyleneoxy group (--C( CH.sub.3 )-- CH.sub.2 --O--, --CH.sub.2-- C( CH.sub.3 )--O--, or --CH.sub.2CH.sub.2CH 2 -O-).
• a diamine having an oxyalkylene group may contain a combination of two or more oxyalkylene groups. When the diamine having an oxyalkylene group contains two or more oxyalkylene groups, the two or more oxyalkylene groups may be included in the diamine blockwise or randomly.
• the diamines having oxyalkylene groups are preferably free of cyclic groups and more preferably free of aromatic groups.
• 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 (manufactured by HUNTSUMAN).
• the diamine compound is a diamine compound (A-1) represented by the following formula (A1), a formula described later (A2)
• the diamine compound (A-1) is a compound represented by the following formula (A1).
• X is an organic group having 1 to 100 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 of 0 or more and 10 or less.
• ma2 is an integer of 0 or more and 7 or less.
• ma3 is an integer of 1 or more and 10 or less.
• Ar is a phenyl group optionally substituted with R a2 or a naphthyl group optionally substituted with R a2 .
• Ar is preferably a phenyl group or a naphthyl group. That is, ma2 is preferably 0 in formula (A1).
• 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 heteroatoms such as O, N, S, P, B, Si, and halogen atoms.
• 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 for 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 and n-hexyl.
• 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 chain alkyl groups such as group, 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, cyclohexy
• Alkyl group Hydroxy chain alkyl group such as hydroxymethyl group, 2-hydroxyethyl group, 3-hydroxy-n-propyl group, and 4-hydroxy-n-butyl group; 2-hydroxycyclohexyl group, 3-hydroxycyclohexyl group , and hydroxycycloalkyl groups such as 4-hydroxycyclohexyl group; methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butyloxy group, isobutyloxy group, sec-butyloxy group, tert-butyloxy group, n- pentyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, 2-ethylhexyloxy group, n-nonyloxy group, n-decyloxy group, n-undecyloxy group, n-tridecyloxy chain such as group, n-tetradecy
• ma3 is an integer of 1 or more and 10 or less.
• the value of ma3 is not particularly limited as long as it is 1 or more and 10 or less, and is appropriately selected according to the structure of X.
• the value of ma3 is preferably 1 or more and 4 or less, more preferably 1 or 2.
• X is an organic group having 1 to 100 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 heteroatoms such as O, N, S, P, B, Si, and halogen atoms.
• 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 chain or cyclic, and may be a combination of a chain aliphatic group and a cyclic aliphatic group. good too.
• a 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 having 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 more preferable.
• the organic group as X is a group containing an aromatic group
• the group composed of X, Ar, R a1 and R a2 in formula (A1) is represented by the following formulas (11) to (15) ) and groups represented by.
• 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 of 0 or more and 3 or less.
• ma15 is an integer of 0 or more and 5 or less.
• the sum of ma14 and ma15 is 0 or more and 8 or less.
• ma16 is an integer of 0 or more and 3 or less.
• ma17 is an integer of 0 or more and 5 or less.
• the sum of ma16 and ma17 is 1 or more and 8 or less.
• ma1 is preferably 0, ma2 is preferably 0, and ma3 is preferably 1 or 2.
• ma1 is preferably 0, ma2 is preferably 0, and ma3 is preferably 1 or 2.
• ma2 is preferably 0, ma4 and ma5 are each preferably 0, ma6 and ma7 are each preferably 0, 1, or 2, and the sum of ma6 and ma7 is 1 or more and 4 or less. is preferred.
• ma2 is preferably 0, ma8, ma9, and ma10 are each preferably 0, ma11, ma12, and ma13 are each preferably 0, 1, or 2, and ma11, ma12, and ma13 The sum is 1 or more, preferably 6 or less.
• ma2 is preferably 0, ma14 and ma15 are each preferably 0, ma16 and ma17 are each preferably 0, 1, or 2, and the sum of ma16 and ma17 is 1 or more and 4 or less. is preferred.
• 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, or may contain a ring structure.
• aliphatic hydrocarbon group as the linking group examples include methylene group, ethane-1,2-diyl group (ethylene group), ethane-1,1-diyl group, propane-1,3-diyl group, propane -1,2-diyl group, propane-1,1-diyl group, propane-2,2-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane-1,6- diyl group, heptane-1,7-diyl group, octane-1,8-diyl group, nonane-1,9-diyl group, decane-1,10-diyl group, undecane-1,11-diyl group, dodecane- 1,12-diyl group, tridecane-1,13-diyl group, tetradecane-1,14-diyl group, pentadecane-1
• linking group examples 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 alkynylene 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, alkyleneamino group having 1 to 6 carbon atoms, alkenyleneamino group having 2 to 6 carbon atoms, alkynyleneamino 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) is represented by the following formula (A1-1). It is preferably a compound represented by
• R a1 , R a2 , Ar, ma1, ma2, and ma3 are the same as those in formula (A1).
• Y a1 is an organic compound having 1 to 20 carbon atoms. or a single bond
• Y a2 is an organic group having 1 to 20 carbon atoms
• na1 is 0 or 1
• na2 is 0 or 1.
• na1 is 1, Ya1 is , not a single bond.
• the organic group as Y a1 may contain heteroatoms such as O, N, S, P, B, Si, and halogen atoms.
• the organic group for Y a1 is preferably a hydrocarbon group.
• the hydrocarbon group for 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 for Y a1 is preferably an aromatic hydrocarbon group, more preferably a phenylene group and a naphthalenediyl group.
• aromatic hydrocarbon groups for Y a1 include p-phenylene group, m-phenylene group, o-phenylene group, naphthalene-1,4-diyl group, naphthalene-1,2-diyl group and naphthalene.
• naphthalene-2,6- Diyl groups naphthalene-2,7-diyl groups, and naphthalene-2,3-diyl groups are included.
• 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) is easily packed well, and excellent mechanical properties, thermal properties, electrical properties, etc. It is considered that block copolymers are easily obtained.
• ma1 is preferably 0, ma2 is preferably 0, and 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) is a diamine compound that has a partial structure represented by the following formula (A2) and does not correspond to the diamine compound (A-1).
• R a3 and R a4 are each independently 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 group having 1 to 4 carbon atoms as R a3 and R a4 includes methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec- butyl and tert-butyl groups.
• a methyl group and an ethyl group are preferred, and a methyl group is more preferred.
• the alkoxy group having 1 to 4 carbon atoms as R a3 and R a4 includes a methoxy group, an ethoxy group, an n-propyloxy group, an isopropyloxy group, an n-butyloxy group and an isobutyloxy group. , sec-butyloxy, and tert-butyloxy groups. Among these alkoxy groups, a methoxy group and an ethoxy group are preferred, and a methoxy group is more preferred.
• the halogen atoms as R a3 and R a4 include fluorine, chlorine, bromine and iodine atoms. Among these halogen atoms, a chlorine atom and a bromine atom are preferred.
• ma4 and ma5 are each independently integers of 0 or more and 4 or less. Since the diamine compound (A-2) is easily available, ma4 and ma5 are respectively. An integer of 0 or more and 2 or less is preferable, and 0 is more preferable.
• 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 optionally substituted with one or more groups.
• 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. mentioned.
• alkyl groups a methyl group and an ethyl group are preferred, and a methyl group is more preferred.
• alkoxy groups having 1 to 4 carbon atoms as substituents include methoxy, ethoxy, n-propyloxy, isopropyloxy, n-butyloxy, isobutyloxy, sec-butyloxy, and tert- A butyloxy group is mentioned.
• a methoxy group and an ethoxy group are preferred, and a methoxy group is more preferred.
• a halogen atom as a substituent includes a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among these halogen atoms, a chlorine atom and a bromine atom are preferred.
• the number of carbon atoms in the aromatic hydrocarbon group for 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.
• the number of carbon atoms in the aromatic hydrocarbon group does not include the number of carbon atoms in the substituent.
• the aromatic hydrocarbon group as X 1 and X 2 includes phenylene groups such as o-phenylene group, m-phenylene group and p-phenylene group, naphthalene-1,4-diyl group, naphthalene-1,3 -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.
• phenylene groups such as o-phenylene group, m-phenylene group and p-phenylene group, naphthalene-1,4-diyl group, naphthalene-1,3 -diyl group, naphthalene-2,6-diyl group and n
• X 1 and X 2 are preferably p-phenylene group, m-phenylene group, naphthalene-1,4-diyl group and biphenyl-4,4'-diyl group, and p-phenylene group and biphenyl-4 ,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) is a diamine compound that has a partial structure represented by the following formula (A3) and does not correspond to the diamine compound (A-1) and the diamine compound (A-2).
• R a5 and R a6 are each independently 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 are each independently 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 combine with each other to form a ring.
• the alkyl group having 1 to 4 carbon atoms as R a5 and R a6 includes methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec- butyl and tert-butyl groups.
• a methyl group and an ethyl group are preferred, and a methyl group is more preferred.
• the alkoxy group having 1 to 4 carbon atoms as R a5 and R a6 includes a methoxy group, an ethoxy group, an n-propyloxy group, an isopropyloxy group, an n-butyloxy group and an isobutyloxy group. , sec-butyloxy, and tert-butyloxy groups. Among these alkoxy groups, a methoxy group and an ethoxy group are preferred, and a methoxy group is more preferred.
• halogen atoms for R a5 and R a6 include fluorine, chlorine, bromine and iodine atoms. Among these halogen atoms, a chlorine atom and a bromine atom are preferred.
• ma6 and ma7 are each independently integers of 0 or more and 4 or less. Since the diamine compound (A-3) is easily available, each of ma6 and ma7 is preferably an integer of 0 or more and 2 or less, more preferably 0.
• the alkyl group having 1 to 4 carbon atoms as R a7 and R a8 includes methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec- butyl and tert-butyl groups.
• the halogenated alkyl group having 1 to 4 carbon atoms as R a7 and R a8 includes chloromethyl group, dichloromethyl group, trichloromethyl group, bromomethyl group, dibromomethyl group, tribromomethyl fluoromethyl, difluoromethyl, trifluoromethyl, 1,1-difluoroethyl, and 1,1,2,2,2-pentafluoroethyl groups.
• R a7 and R a8 in the formula (A3) hydrogen is used because the block copolymer has good solubility in organic solvents and the diamine compound (A-3) is easily available.
• R a7 and R a8 are bonded to each other to form a cycloalkylidene group having 5 to 8 carbon atoms, such as a cyclopentylidene group, a cyclohexylidene group, a cycloheptylidene group, and a cyclooctylidene group. It is also preferable to
• Preferred specific examples of the partial structure represented by formula (A3) include the following structures.
• 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 optionally substituted with one or more groups.
• 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. mentioned.
• alkyl groups a methyl group and an ethyl group are preferred, and a methyl group is more preferred.
• alkoxy groups having 1 to 4 carbon atoms as substituents include methoxy, ethoxy, n-propyloxy, isopropyloxy, n-butyloxy, isobutyloxy, sec-butyloxy, and tert- A butyloxy group is mentioned.
• a methoxy group and an ethoxy group are preferred, and a methoxy group is more preferred.
• a halogen atom as a substituent includes a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among these halogen atoms, a chlorine atom and a bromine atom are preferred.
• the number of carbon atoms in the aromatic hydrocarbon group for 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.
• the number of carbon atoms in the aromatic hydrocarbon group does not include the number of carbon atoms in the substituent.
• the aromatic hydrocarbon group for X 3 and X 4 includes phenylene groups such as o-phenylene group, m-phenylene group and p-phenylene group, naphthalene-1,4-diyl group, naphthalene-1,3- diyl, naphthalene-2,6-diyl and naphthalene-2,7-diyl, biphenyl-4,4'-diyl, biphenyl-3,4'-diyl and biphenyl-
• a biphenyldiyl group such as a 3,3'-diyl group is preferred.
• X 3 and X 4 are preferably p-phenylene group, m-phenylene group, naphthalene-1,4-diyl group and biphenyl-4,4′-diyl group, and p-phenylene group and biphenyl-4, 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.
• a dimer diamine compound (A-4) is also preferred as the diamine compound, since it is easy to obtain a block copolymer having a low dielectric constant and a low dielectric loss tangent in a high frequency band.
• the dimer diamine compound (A-4) is a diamine compound in which the two terminal carboxy groups of dimer acid are substituted with aminomethyl groups or amino groups.
• a dimer acid is a known dibasic acid obtained by an intermolecular polymerization reaction of unsaturated fatty acids. Industrial manufacturing processes for producing dimer acids are 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 with 36 carbon atoms obtained by dimerizing unsaturated fatty acids with 18 carbon atoms such as oleic acid, linoleic acid and linolenic acid.
• the industrially obtained dimer acid is a monomeric acid having 18 carbon atoms, a trimer acid having 54 carbon atoms, and other polymerized fatty acids having 20 to 54 carbon atoms, depending on the degree of purification.
• 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 represents a carbon-carbon single bond or a carbon-carbon double bond.
• the compound represented by the following formula (32) is preferable as the diamine compound represented by the formula (31), since a cured product having excellent elongation can be formed. (32)
• a tetracarboxylic dianhydride represented by the following formula (34) is obtained by reacting a diamine compound represented by the 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 polyamide macromonomers, polyimide macromonomers, and block copolymers.
• i, j, k, and l are each integers of 0 or greater.
• i+j is an integer of 6 or more and 17 or less, and k+l is 8 or more and 19 or less.
• the wavy line represents a carbon-carbon single bond or a carbon-carbon double bond.
• the molar ratio 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.
• the dicarboxylic acid used for producing the polyamide macromonomer is a reaction product of tetracarboxylic dianhydride and alcohols.
• the dicarboxylic acid used in the production of the polyamide macromonomer is a dicarboxylic acid that is a reaction product of a tetracarboxylic dianhydride and an alcohol. do. Tetracarboxylic dianhydrides and alcohols are described below.
• the tetracarboxylic dianhydride is not particularly limited as long as the desired effects are not impaired.
• a tetracarboxylic dianhydride conventionally used for the production of polyamic acid and polyimide resin can be used.
• Tetracarboxylic dianhydrides include compounds represented by the following formula (A3).
• A2 is a tetravalent organic group having 6 to 50 carbon atoms.
• a 2 is a tetravalent organic group having 6 to 50 carbon atoms, and the acid anhydride group represented by two -CO-O-CO- in formula (A3) In addition, 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 the number of carbon atoms. Fluorinated alkoxy groups of 1 to 6 are preferred.
• the compound represented by formula (a1-1) may contain a carboxy group and a carboxylic acid ester group in addition to the acid anhydride group.
• the substituent is a fluorinated alkyl group or fluorinated alkoxy group, it is preferably a perfluoroalkyl group or perfluoroalkoxy group.
• the number of carbon atoms constituting A2 is more preferably 8 or more, still more preferably 12 or more. In addition, the number of carbon atoms constituting A2 is more preferably 40 or less, even more preferably 30 or less.
• A2 may be an aliphatic group, an aromatic group, or a group combining these structures.
• A2 may contain a halogen atom, an oxygen atom, a nitrogen atom and a sulfur atom in addition to the carbon atom and the hydrogen atom.
• A2 contains an oxygen atom, a nitrogen atom, or a sulfur atom
• a 1 may be included in A 1 as a group selected from N—, —COO—, —O—, —CO—, —SO—, —SO 2 —, —S—, and —S—S—;
• the tetracarboxylic dianhydride represented by the formula (A3) is an aliphatic tetracarboxylic dianhydride having two dicarboxylic anhydride groups that bind to an aliphatic group, but also binds to an aromatic group. It may be an aromatic tetracarboxylic dianhydride having at least one dicarboxylic anhydride group.
• 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 having no alicyclic structure include 1,2,3,4-tetracarboxylic dianhydrides (eg, Rikacid BT-100, manufactured by Shin Nippon Rika Co., Ltd.). mentioned.
• Aliphatic tetracarboxylic dianhydrides having an alicyclic structure include cyclobutanetetracarboxylic dianhydride, cyclopentane-1,2,3,4-tetracarboxylic dianhydride, cyclohexane-1,2,4 ,5-tetracarboxylic dianhydride, norbornane-2-spiro- ⁇ -cyclopentanone- ⁇ '-spiro-2′′-norbornane-5,5′′,6,6′′-tetracarboxylic dianhydride (for example , Enehyde (registered trademark) CpODA, manufactured by Eneos), 2,2-bis(2,3-dicarboxyphenoxy)hexafluoropropane dianhydride [5,5'-(1,4-phenylene)bisnorbornane]- 2,2′,3,3′-tetracarboxylic dianhydride (e.g., Enehyde (registered trademark
• aromatic tetracarboxylic dianhydride having two dicarboxylic anhydride groups bonded to the aromatic group represented by the formula (A3) 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 easily formed into a cured product with excellent electrical properties.
• 4,4′-bis(3,4-dicarboxyphenylcarbonyloxy)biphenyl dianhydride, 4,4′-bis(3,4-dicarboxyphenyloxy)biphenyl dianhydride, 2,6-bis (3,4-Dicarboxyphenylcarbonyloxy)naphthalene dianhydride and ⁇ , ⁇ -bis(3,4-dicarboxyphenylcarbonyloxy)alkane dianhydride are preferred.
• the number of carbon atoms in the linear alkylene group in ⁇ , ⁇ -bis(3,4-dicarboxyphenylcarbonyloxy)alkane dianhydride is preferably 1 or more and 20 or less, more preferably 2 or more and 12 or less.
• ⁇ , ⁇ -bis(3,4-dicarboxyphenylcarbonyloxy)alkane dianhydride examples include 1,2-bis(3,4-dicarboxyphenylcarbonyloxy)ethane dianhydride (eg , Rikashid TMEG100, manufactured by Shin Nippon Rika Co., Ltd.), and 1,10-bis(3,4-dicarboxyphenylcarbonyloxy)decane dianhydride (eg, 10BTA, manufactured by Kurogane Kasei Co., Ltd.).
• the aromatic tetracarboxylic dianhydride is also preferably biphenyltetracarboxylic dianhydride.
• Biphenyltetracarboxylic dianhydrides 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, compounds represented by the following general formulas (a3-2) to (a3-4).
• R a01 , R a02 and R a03 are each an optionally halogen-substituted aliphatic group, an oxygen atom, a sulfur atom, one or more It is either an aromatic group via a divalent element, or a divalent group composed of 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).
• Compounds 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 dianhydride, and 1,4-bis(3,4-dicarboxyphenoxy)benzene dianhydride.
• R a04 and R a05 are either an aliphatic group optionally substituted with halogen, an aromatic group via one or more divalent elements, or halogen. , or a monovalent substituent constituted by a combination thereof.
• R a04 and R a05 may be the same or different.
• Difluoropyromellitic dianhydride, dichloropyromellitic dianhydride, and the like can also be used as the compound represented by formula (a3-4).
• the block copolymer also preferably has radically polymerizable group-containing groups on its molecular chain. Therefore, the tetravalent organic group A 2 in formula (A3) may be a group represented by formulas (a3-5) to (a3-7) below.
• R a01 , R a02 , and R a03 in formulas (a3-5) to (a3-7) are , R a01 , R a02 , and R a03 .
• R a06 in formulas (a3-5), (a3-6) and (a3-7) is a radically polymerizable group-containing group. The radically polymerizable group-containing group will be described later.
• dicarboxylic acids are reaction products of tetracarboxylic dianhydrides and alcohols.
• the structure of alcohols is not particularly limited as long as the desired effect is not impaired. It is also preferable that the alcohol has a radically polymerizable group because it can impart photosensitivity to the block copolymer and the resin film-forming composition containing the block copolymer.
• Radically polymerizable groups typically include groups containing ethylenically unsaturated double bonds. As the ethylenically unsaturated double bond-containing group, alkenyl group-containing groups including alkenyl groups such as vinyl groups and allyl groups are preferred, and (meth)acryloyl group-containing groups are more preferred.
• Alcohols that give dicarboxylic acid compounds by reacting with tetracarboxylic dianhydrides include alkane monools such as methanol, ethanol, n-propanol, isopropanol, n-butanol, n-pentanol, and n-hexanol; Phenols or naphthols such as phenol, p-cresol, m-cresol, o-cresol, ⁇ -naphthol, and ⁇ -naphthol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl Monoethers of glycols such as ethers, 1,3-propanediol monomethyl ether, 1,3-propanediol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, dipropylene glyco
• alcohols having a radically polymerizable group include mono(meth)acrylates of diols, N-hydroxyalkyl-substituted (meth)acrylamides, hydroxyl group-containing unsaturated ketones, alkenyl alcohols, and alkenyl groups having 3 or more carbon atoms. and monoalkenyl ethers of diols having
• 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.
• Alkanediols and oligo- or polyalkylene glycols can 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.
• a hydroxyalkyl group may be straight or branched.
• 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.
• Alkenyl groups may be straight 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 still more preferably 3 or 4.
• Alkenyl alcohols may be linear or branched.
• the diols that give the monoalkenyl ethers of the diols are the same as the diols that give the mono(meth)acrylates of the diols.
• the alkenyl group has 3 or more carbon atoms, preferably 3 or more and 10 or less, and more preferably 3 or more and 6 or less.
• Alkenyl groups may be straight or branched.
• alcohols having a radically polymerizable group include 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 2-hydroxy-3-methoxypropyl.
• hydroxyl group-containing ketones such as (2-hydroxyethyl) vinyl ketone; 5-octen-1-ol, 3-octen-1-ol, 3-nonen-1-ol, 6-nonen-1-ol, 9-decen-1-ol, 4-decen-1-ol, 10- alkenyl alcohols such as undecen-1-ol, 11-dodecen-1-ol, elaide linoleyl alcohol, oleyl alcohol, linoleyl alcohol, linolenyl alcohol, and erucyl alcohol; ethylene glycol monoallyl ether, 2-allyl oxypropan-1-ol, 1-allyloxypropan-2-ol, 1,3-propanediol monoallyl ether, 1,4-butanediol monoallyl ether, 1,5-pentanediol monoallyl ether, and 1 and monoalkenyl ethers of diols having an alkenyl
• a polymerizable dicarboxylic acid can be obtained by reacting the tetracarboxylic dianhydride described above with an alcohol. Alcohols react with carboxylic anhydride groups to form 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 a hydroxyl group from an alcohol.
• Such a dicarboxylic acid has two pairs of a carboxy group and a group represented by —CO—OR a21 located on adjacent carbon atoms in the dicarboxylic acid.
• Positional isomers may exist.
• one kind of such isomers may be used alone, or two or more kinds thereof may be used in combination.
• blocks derived from polyamide macromonomers and blocks derived from polyimide macromonomers contain multiple types of structural units derived from multiple isomers of dicarboxylic acids. shall be allowed.
• a dicarboxylic acid corresponding to pyromellitic dianhydride has, as isomers, a compound represented by the following formula (a4-a1) and a compound represented by the following formula (a4-a2). do.
• the isomers are 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).
• R a21 is as described above.
• 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), formula ( a4-3a) to formula (a4-3c), and compounds represented by 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 , and 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 Street In formulas (a4-2a) to (a4-2c), formulas (a4-3a) to (a4-3c), and formula
• 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), formula ( a4-6a) to formula (a4-6c), formula (a4-7a), and compounds represented by formula (a4-7b).
• formulas (a4-5a) to (a4-5c) formulas (a4-6a) to (a4-6c), formulas (a4-7a), and formulas (a4-7b)
• R a01 to R a03 , R a06 , m1 and m2 are the same as those in formulas (a3-5) to (a3-7).
• formulas (a4-5a) to (a4-5c) formulas (a4-6a) to (a4-6c), formulas (a4-7a), and formulas (a4-7b)
• R a21 Street In formulas (a4-5a) to (a4-5c), formulas (a4-6a) to (a4-6c),
• the reaction between tetracarboxylic dianhydride and alcohols is usually carried out in an organic solvent.
• the organic solvent used for the reaction between the tetracarboxylic dianhydride and the alcohol is an organic solvent that can dissolve the tetracarboxylic dianhydride and the alcohol and does not react with the tetracarboxylic dianhydride and the alcohol. is not particularly limited.
• An organic solvent can be used individually or in mixture of 2 or more types.
• organic solvents used in the reaction between tetracarboxylic dianhydrides 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-dimethylisobutyamide , 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; Esters such as ethyl,
• N-methyl-2-pyrrolidone N,N-dimethylacetamide, N,N-diethylacetamide, N,N-dimethylformamide, N,N-diethylformamide, N-methylcaprolactam
• Nitrogen-containing polar solvents such as N,N,N',N'-tetramethylurea are preferred.
• the temperature at which the tetracarboxylic dianhydride and the 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, and 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 is typically preferably 30 minutes or more and 20 hours or less, more preferably 1 hour or more and 8 hours or less, and 2 hours. More than 6 hours or less is particularly preferable.
• a small amount of a polymerization inhibitor may be used for the purpose of preventing cross-linking between the ethylenically unsaturated double bonds during the reaction between the tetracarboxylic dianhydride and the alcohol.
• Polymerization inhibitors include phenols such as hydroquinone, 4-methoxyphenol, tert-butylpyrocatechol, and bis-tert-butylhydroxytoluene, and phenothiazine.
• the amount of the polymerization inhibitor used is preferably 0.01 mol % or more and 5 mol % or less with respect to the number of moles of ethylenically unsaturated double bonds.
• the reaction between tetracarboxylic dianhydride and alcohols is carried out in the presence of an organic base such as pyridine, triethylamine, diisopropylethylamine, 4-dimethylaminopyridine, 1,4-azabicyclo[2,2,2]octane.
• organic base such as pyridine, triethylamine, diisopropylethylamine, 4-dimethylaminopyridine, 1,4-azabicyclo[2,2,2]octane.
• 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, relative to 1 mol of the tetracarboxylic dianhydride.
• dicarboxylic acids depending on the production conditions, only one of the dicarboxylic anhydride groups reacts with alcohols to produce a monocarboxylic acid compound having a dicarboxylic anhydride group, or to form a tetracarboxylic dianhydride. A part of reacts with moisture in the reaction system to produce a tetracarboxylic acid compound or a tricarboxylic acid compound.
• a dicarboxylic acid containing at least one selected from the above monocarboxylic acid compounds, tricarboxylic acid compounds, and tetracarboxylic acid compounds is added to a polyamide macromonomer, a polyimide macromonomer, and a block comonomer. It can be used for the production of polymers.
• the polymerizable 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 as impurities in the dicarboxylic acid.
• the content of at least one selected from , tricarboxylic acid compounds, and tetracarboxylic acid compounds is preferably 30% by mass or less, more preferably 10% by mass or less, relative to the mass of the dicarboxylic acid containing the mass of impurities, 5% by mass or less is more preferable, and 1% by mass or less is particularly preferable.
• the method for producing a polyamide macromonomer includes the above-described diamine compound and dicarboxylic acid, and the above-described diamine compound and dicarboxylic acid are polymerized until the weight average molecular weight of the polyamide macromonomer increases within the above-described predetermined range.
• the method is not particularly limited as long as it can be condensed.
• a preferred method includes a method of condensing the aforementioned 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 condensation aid are not particularly limited as long as they are compounds conventionally used for condensing a dicarboxylic acid and a diamine compound.
• 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 condensing agent to be used is not particularly limited as long as a polyamide macromonomer having a desired molecular weight can be obtained.
• the amount of the condensing agent to be used is typically preferably 1 mol or more and 5 mol or less, more preferably 2 mol or more and 4 mol or less, and even more preferably 2 mol or more and 3 mol or less, relative to 1 mol of the dicarboxylic acid.
• the ratio between the amount of dicarboxylic acid and the amount of diamine compound when producing the polyamide macromonomer is not particularly limited as long as the polyamide macromonomer having the desired molecular weight can be produced.
• the raw material ratio represented by (number of moles of dicarboxylic acid or tetracarboxylic dianhydride) / (number of moles of diamine compound) is preferably 0.5/1 to 0 0.95/1, more preferably 0.55/1 to 0.80/1.
• the raw material ratio represented by (number of moles of diamine compound) / (number of moles of dicarboxylic acid or tetracarboxylic dianhydride) is preferably should be adjusted within the range of 0.5/1 to 0.95/1, more preferably 0.55/1 to 0.80/1.
• a dicarboxylic acid and a diamine compound are mixed in the presence of the condensing agent in an organic solvent at, for example, ⁇ 20° C. or higher and 150° C. or lower, preferably 0° C. or higher and 50° C. or lower, for 30 minutes.
• the reaction is carried out for 24 hours or less, preferably 1 hour or more and 4 hours or less.
• the solvent used for the polycondensation the above-described solvent that can be used in the reaction between the tetracarboxylic dianhydride and the alcohol can be used.
• the amount of the solvent used is preferably 50 parts by mass or more and 10000 parts by mass or less, more preferably 100 parts by mass or more and 2000 parts by mass or less, with respect to the total of 100 parts by mass of the dicarboxylic acid and the diamine compound. Part or more and 1000 parts by mass or less is more preferable.
• the amount of dicarboxylic acid and diamine compound used when producing a polyamide macromonomer is not particularly limited.
• the amount of the diamine compound is preferably 0.8 mol or more and 1.2 mol or less, more preferably 0.9 mol or more and 1.1 mol or less, particularly preferably 0.8 mol or more and 1.1 mol or less, relative to 1 mol of dicarboxylic acid. It is 95 mol or more and 1.05 mol or less.
• the polyamide macromonomer produced as described above is used in the production of a block copolymer after being in the form of a solution or suspension, or after being separated and recovered from the reaction liquid by a well-known method.
• the polyimide macromonomer is a polyamic acid macromonomer obtained by polymerizing a tetracarboxylic dianhydride and a diamine compound, or a macromonomer obtained by imidizing the above polyamide macromonomer. For example, when the above macromonomer is heated, the imidization proceeds with elimination of the alcohol.
• a polyamic acid macromonomer can be synthesized by a well-known method using a tetracarboxylic dianhydride and a diamine compound.
• a tetracarboxylic dianhydride the tetracarboxylic dianhydride described as the raw material of the dicarboxylic acid for the polyamide macromonomer can be preferably used.
• the diamine compound the diamine compounds described for the polyamide macromonomer can be preferably used.
• the amounts of the tetracarboxylic dianhydride and the diamine compound used when synthesizing the polyamic acid macromonomer are not particularly limited.
• the amount of the diamine compound is preferably 0.8 mol or more and 1.2 mol or less, more preferably 0.9 mol or more and 1.1 mol or less, relative to 1 mol of the tetracarboxylic dianhydride. It is preferably 0.95 mol or more and 1.05 mol or less.
• the reaction between the tetracarboxylic dianhydride and the diamine compound is usually carried out in an organic solvent.
• the organic solvent used for the reaction of the tetracarboxylic dianhydride and the diamine compound is an organic solvent that can dissolve the tetracarboxylic dianhydride and the diamine compound and that does not react with the tetracarboxylic dianhydride and the diamine compound. is not particularly limited.
• An organic solvent can be used individually or in mixture of 2 or more types.
• organic solvents used in the reaction between the tetracarboxylic dianhydride and the diamine compound 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-dimethylisobutyamide , 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
• N-methyl-2-pyrrolidone N,N-dimethylacetamide, N,N-diethylacetamide, N,N-dimethylformamide, N, Nitrogen-containing polar solvents such as N-diethylformamide, N-methylcaprolactam, and N,N,N',N'-tetramethylurea are preferred.
• the temperature at which the tetracarboxylic dianhydride and the diamine compound are reacted is not particularly limited as long as the reaction proceeds well.
• the reaction temperature between the tetracarboxylic dianhydride and the diamine compound is preferably ⁇ 5° C. or higher and 120° C. or lower, more preferably 0° C. or higher and 80° C. or lower, and particularly preferably 0° C. or higher and 50° C. or lower.
• the time for reacting the tetracarboxylic dianhydride and the diamine compound varies depending on the reaction temperature, but is typically preferably 30 minutes or more and 20 hours or less, more preferably 1 hour or more and 12 hours or less, and 4 hours. More than 10 hours or less is particularly preferable.
• ring closure may occur in part of the polyamic acid macromonomer, and imidization may proceed partially.
• a resin with an imidization rate of 50% or less is defined as a polyamic acid macromonomer, and a resin with an imidization rate of more than 50% is defined as a polyimide macromonomer.
• a polymerization inhibitor when the tetracarboxylic dianhydride and/or diamine compound has a radical polymerizable group-containing group containing an ethylenically unsaturated double bond, the purpose of preventing cross-linking between the ethylenically unsaturated double bonds during the reaction.
• Polymerization inhibitors include phenols such as hydroquinone, 4-methoxyphenol, tert-butylpyrocatechol, and bis-tert-butylhydroxytoluene, and phenothiazine.
• the amount of the polymerization inhibitor used is preferably 0.01 mol % or more and 5 mol % or less with respect to the number of moles of ethylenically unsaturated double bonds.
• a solution containing a polyamic acid macromonomer is obtained by the method described above.
• the resulting polyamic acid macromonomer is ring-closed and imidized to produce a polyimide macromonomer.
• the imidization method is not particularly limited. The imidization may be performed by heating or may be performed using an imidizing agent.
• the heating may be performed on the polyamic acid macromonomer solution or suspension, or may be performed on the solid polyamic acid macromonomer.
• the polyamic acid macromonomer solution is heated for imidization, it is preferable to heat while removing water produced as a by-product during imidization.
• the heating conditions for imidization are not particularly limited as long as the polyamic acid macromonomer or polyimide macromonomer does not decompose and imidization proceeds satisfactorily.
• the heating temperature is typically preferably 80° C. or higher and 220° C. or lower, more preferably 100° C. or higher and 200° C. or lower, and particularly preferably 120° C.
• the heating temperature is typically preferably 180° C. or higher and 400° C. or lower, more preferably 200° C. or higher and 350° C. or lower.
• the heating time depends on the heating temperature, it is typically preferably from 1 hour to 24 hours, more preferably from 2 hours to 12 hours.
• the imidization is usually carried out by adding the imidizing agent to a solution or suspension of the polyamic acid macromonomer.
• an organic solvent that can be used for imidization with an imidizing agent for example, the same organic solvent that can be used for preparing the polyamic acid macromonomer can be used.
• the concentration of the polyamic acid macromonomer in the solution or suspension of the polyamic acid macromonomer is not particularly limited.
• the concentration of the polyamic acid macromonomer in the solution or suspension of the polyamic acid macromonomer 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 the imidizing agent used is not particularly limited. The amount of the imidizing agent used is selected according to the type of imidizing agent so that the polyamic acid macromonomer is imidized to the desired degree.
• the reaction temperature for imidization 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 imidization reaction time when using an imidizing agent is not particularly limited.
• the imidization reaction is preferably carried out for, for example, 30 minutes to 24 hours, more preferably 1 hour to 12 hours, and 2 hours to 6 hours, depending on the type of imidizing agent. is more preferred.
• 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 block copolymer is a macromonomer that is a polyamide macromonomer and/or a polyimide macromonomer, a tetracarboxylic dianhydride, and/or a dicarboxylic acid that is a reaction product of a tetracarboxylic dianhydride and an alcohol. , and a diamine compound.
• the polyamide macromonomer and polyimide macromonomer are as described above.
• the dicarboxylic acid that is the reaction product of the tetracarboxylic dianhydride and the alcohol the dicarboxylic acid described above as a raw material for the polyamide macromonomer can be suitably used.
• the tetracarboxylic dianhydride the tetracarboxylic dianhydride described above as a raw material of dicarboxylic acid for the polyamide macromonomer can be suitably used.
• the content ratio of the structural unit derived from the polyamide macromonomer and the structural unit derived from the polyimide macromonomer in the block copolymer is as described above.
• the amount of the tetracarboxylic dianhydride and/or the auxiliary carboxylic acid and the amount of the diamine compound used when synthesizing the block copolymer are not particularly limited as long as the desired effect is not impaired.
• the amount of the diamine compound used is preferably 0.8 mol or more and 1.2 mol or less, relative to a total of 1 mol of the tetracarboxylic dianhydride and/or the above-mentioned dicarboxylic acid, and more More preferably, it is used in an amount of 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 block copolymer can be produced by the same method as the method for producing the polyamide macromonomer described above.
• the condensing agent of the type and amount described above.
• a dicarboxylic acid and a diamine compound are combined in an organic solvent in the presence of the condensing agent, for example, at -20°C or higher and 150°C or lower, preferably 0°C or higher and 50°C or lower, for 30 minutes.
• a block copolymer can be obtained by reacting for 24 hours or less, preferably 1 hour or more and 4 hours or less.
• the block copolymer can be produced by the same method as the above-described method for producing polyamic acid.
• the reaction temperature of the tetracarboxylic dianhydride, the diamine compound, the polyamide macromonomer and / or the polyimide macromonomer is preferably -5 ° C. or higher and 120 ° C. or lower, more preferably 0 ° C. or higher and 80 ° C. or lower.
• the temperature is preferably 0° C. or higher and 50° C. or lower, particularly preferably.
• the time for reacting the tetracarboxylic dianhydride, the diamine compound, the polyamide macromonomer and/or the polyimide macromonomer varies depending on the reaction temperature, but is typically preferably 30 minutes or more and 20 hours or less. 8 hours or less is more preferable, and 2 hours or more and 6 hours or less is particularly preferable.
• the block copolymer preferably has 2 to 50 carbon atoms, more preferably 3 to 40 carbon atoms, from the viewpoint that it is easy to obtain a block copolymer that exhibits excellent dielectric properties in a high frequency band. It preferably contains an aliphatic hydrocarbon group.
• the position of the divalent aliphatic hydrocarbon group in the molecular chain of the block copolymer is not particularly limited. Examples of the monomer that provides a divalent aliphatic hydrocarbon group having 2 to 50 carbon atoms in the molecular chain include the aforementioned dimer diamine compound (A-4) and the aforementioned ⁇ , ⁇ -bis( 3,4-dicarboxyphenylcarbonyloxy)alkane dianhydrides.
• the weight average molecular weight of the block copolymer may be appropriately set according to its use.
• the weight average molecular weight of the block copolymer can be measured as a polystyrene equivalent weight average molecular weight by GPC (gel permeation chromatography).
• the weight average molecular weight of the block copolymer is, for example, 5000 or more, preferably 15000 or more, more preferably 250000000 or more in terms of polystyrene, from the viewpoint of obtaining a resin film having good mechanical properties.
• the weight-average molecular weight of the obtained block copolymer is, for example, 100,000 or less, preferably 80,000 or less, more preferably 50,000 or less in terms of polystyrene, from the viewpoint of solubility in organic solvents.
• the weight-average molecular weight may be the above value by adjusting the compounding amount of the tetracarboxylic dianhydride and/or the dicarboxylic acid and the diamine compound described above, and the reaction conditions such as the solvent and the reaction temperature.
• Terminal blockers include monoamines, acid anhydrides, monocarboxylic acids, monoacid halides, monoactive ester compounds, and the like. A known compound can be used as the monoamine used for terminal blocking.
• monoamines examples include aromatic monoamines such as aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 3-hydroxyaniline, 4-hydroxyaniline, 3-aminothiophenol, and 4-aminothiophenol. and aliphatic monoamines having 3 to 20 carbon atoms which may have a branched structure such as hexylamine and octylamine, monoamines having an alicyclic structure such as cyclohexylamine, trimethoxyaminopropylsilane, and Aminosilanes such as triethoxyaminopropylsilane can be mentioned.
• aromatic monoamines such as aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 3-hydroxyaniline, 4-hydroxyaniline, 3-aminothiophenol, and 4-aminothiophenol.
• acid anhydrides monoacid halides, and monoactive ester compounds used as terminal blocking agents
• acid anhydrides are preferred.
• known acid anhydrides and derivatives thereof can be used.
• the introduction rate of the terminal blocking agent in the block copolymer is such that the mechanical properties of the resin film formed using the block copolymer or the composition for forming a resin film containing the polyimide resin derived from the block copolymer are From the standpoint of superiority, it is preferably 40 mol % or less, more preferably 20 mol % or less, and even more preferably 10 mol % or less, relative to the number of moles of all monomers.
• the block copolymer produced as described above is used for various purposes as it is or after being converted into a polyimide resin.
• a polyimide resin is obtained by imidating the block copolymer described above.
• the polyimide resin contains a block derived from the polyimide macromonomer described above in its molecular chain. Therefore, the polyimide resin exhibits a low dielectric loss tangent in a high frequency band and is excellent in mechanical properties such as elongation and strength.
• the imidization of the block copolymer can be carried out by the same method as described above for the imidization of the polyamic acid macromonomer and the polyamide macromonomer.
• the resin film-forming composition contains a resin (A) and a solvent (S).
• the resin (A) contains the aforementioned block copolymer and/or the aforementioned polyimide resin.
• a resin film containing the above-described block copolymer and/or the above-described polyimide resin can be formed by forming a resin film using such a resin film-forming composition according to the method described below.
• the resin film exhibits a low dielectric loss tangent in a high frequency band and is excellent in mechanical properties such as elongation and strength.
• the block copolymer may have radically polymerizable groups as described above.
• the resin film-forming composition preferably contains a radical photopolymerization initiator (C).
• the composition for resin film formation may contain the monomer compound (B) which has a radically polymerizable group.
• Resin (A) contains a block copolymer and/or a polyimide resin.
• the block copolymer and polyimide resin are as described above.
• a monomer compound having an ethylenically unsaturated double bond as a radically polymerizable group is preferably used as the monomer compound (B).
• Such a monomer compound (B) may be a monofunctional monomer compound or a polyfunctional monomer compound, preferably a polyfunctional monomer compound.
• 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-butylacrylamidosulfonic acid, methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, 2 -hydroxyethyl (
• 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, propylene glycol.
• trifunctional or higher polyfunctional monomer compounds are preferred because they tend to increase the adhesion of the cured product to the substrate and the strength of the cured product.
• a polyfunctional monomer compound having a functionality of 4 or more is more preferable, and a polyfunctional monomer compound having a functionality of 5 or more is more preferable.
• the content of the monomer compound (B) in the resin film-forming composition is not particularly limited as long as the object of the present invention is not impaired.
• the content of the monomer compound (B) in the resin film-forming composition is 0.1 parts by mass when the mass of the resin film-forming composition excluding the mass of the solvent (S) described later is 100 parts by mass. 50 parts by mass or less is preferable, 0.5 parts by mass or more and 40 parts by mass or less is more preferable, and 1 part by mass or more and 25 parts by mass or less is particularly preferable.
• the resin (A) has a radically polymerizable group on its molecular chain, or the resin film-forming composition contains a monomer compound (B) having a radically polymerizable group
• the resin film-forming composition is exposed to light. It preferably contains a radical polymerization initiator (C).
• the radical photopolymerization initiator (C) is not particularly limited, and conventionally known photopolymerization initiators can be used.
• photoradical polymerization initiators (C) include 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-morpholinophenyl
• oxime ester compounds are preferred from the viewpoint of the sensitivity of the resin film-forming composition.
• oxime ester compound a compound having a partial structure represented by the following formula (c1) is preferable.
• the following aliphatic hydrocarbon groups or optionally substituted aryl groups * are bonds.
• the content of the photoradical polymerization initiator (C) in the resin film-forming composition is not particularly limited as long as the resin film-forming composition has desired photolithography properties.
• the content of the radical photopolymerization initiator (C) in the resin film-forming composition is typically 0.01 to 20 parts by mass is preferable, 0.1 to 15 parts by mass is more preferable, and 1 to 10 parts by mass is even more preferable.
• the resin film-forming composition usually contains a solvent (S) for the purpose of adjusting coatability.
• the type of solvent (S) is not particularly limited as long as the resin (A) and other components are well dissolved.
• An organic solvent is usually used as the solvent (S).
• the solvent (S) include N,N-dimethylformamide, N,N-dimethylacetamide, N,N-diethylformamide, N-methyl-2 -pyrrolidone, N-ethyl-2-pyrrolidone, hexamethylphosphoramide, 1,3-dimethyl-2-imidazolidinone, N,N-dimethylisobutyamide, 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, diisobutyl ketone
• 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; hydrocarbons; and sulfoxides such as dimethylsulfoxide.
• the amount of the solvent (S) used is not particularly limited as long as a uniform liquid resin film-forming composition can be prepared.
• the resin film-forming composition may be a suspension or a solution, preferably a solution.
• the solvent (S) is used so that the solid content concentration of the resin film-forming 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. be done.
• the resin film-forming composition may, if necessary, contain various additives other than the components described above.
• Additives include colorants, dispersants, sensitizers, adhesion promoters, polymerization inhibitors, antioxidants, UV absorbers, anti-coagulants, antifoaming agents, surfactants, imidization accelerators, adhesion Nitrogen-containing heterocyclic compounds as improvers, silane coupling agents, and the like can be mentioned.
• the photosensitive resin composition may contain various fillers or reinforcing materials as necessary.
• Sensitizers include, for example, 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 inhibitors include compounds having a phenolic hydroxyl group, nitroso compounds, N-oxide compounds, quinone compounds, N-oxyl compounds, and phenothiazine compounds.
• the polymerization inhibitors include Irganox 1010, Irganox 1035, Irganox 1098, Irganox 1135, Irganox 245, Irganox 259, Irganox 3114 (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 is 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, relative to the mass of the resin (A). % by mass or less is more preferable.
• the nitrogen-containing heterocyclic compound coordinates with and stabilizes the metal surface, thereby improving the adhesion of the resin film formed using the resin film-forming composition to the metal surface.
• a known compound can be used as the nitrogen-containing heterocyclic compound.
• Nitrogen-containing intercompounds include, for example, imidazole, pyrazole, indazole, carbazole, triazole, pyrazoline, pyrazolidine, tetrazole, pyridine, piperidine, pyrimidine, pyrazine, triazine, cyanuric acid, isocyanuric acid, and derivatives thereof.
• preferred nitrogen-containing hetero-compounds from the viewpoint of coordination with metals include 1H-benzotriazole, 4-methyl-1H-methylbenzotriazole, 5-methyl-1H-methylbenzotriazole, 4-carboxy- 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 composition for forming a resin film contains a photoradical polymerization initiator (C)
• the composition for forming a resin film has excellent developability, and the resin film formed using the composition for forming a resin film can be applied to a substrate or the like.
• the amount of the nitrogen-containing heterocyclic compound used is preferably 0.01% by mass or more and 5% by mass or less, and 0.05% by mass. More than 3 mass % or less is more preferable.
• silane coupling agents include, for example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane.
• Acid anhydrides to be reacted with 3-aminopropyltrimethoxysilane or 3-aminopropyltriethoxysilane include succinic anhydride, maleic anhydride, nadic anhydride, 3-hydroxyphthalic anhydride, pyromellitic acid di 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 with respect to the mass of the resin (A).
• surfactant By adding a surfactant to the resin film-forming composition, the applicability of the resin film-forming composition is improved, and the wettability of the resin film-forming composition with the substrate is improved.
• a known compound can be used as the surfactant.
• surfactants include fluorine surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and silicone surfactants.
• the amount of surfactant used is preferably 0.001% by mass or more and 1% by mass or less with respect to the mass of the resin (A).
• the resin film-forming composition may contain a cyclization accelerator.
• the cyclization accelerator promotes the formation of a polyimide resin by cyclization of a polyamide resin containing structural units derived from polyamic acids or dicarboxylic acid compounds that can be synthesized by reacting tetracarboxylic dianhydrides with alcohols.
• the resin film-forming composition contains a cyclization accelerator, the mechanical properties and weather resistance reliability of the resin film formed using the resin film-forming composition while generating a polyimide resin through cyclization are improved.
• the cyclization accelerator a known thermal base generator or thermal acid generator is used.
• the amount of various additives used is not particularly limited as long as it does not impair the purpose of the present invention.
• the amount of the additives not described above may be adjusted appropriately 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 resin film-forming composition.
• a photosensitive resin composition can be prepared by uniformly mixing the above-described essential components and, if necessary, optional components in desired amounts.
• a mixing method is not particularly limited.
• the photosensitive dry film has a base film and a photosensitive layer formed on the surface of the base film, wherein the photosensitive layer contains the photoradical polymerization initiator (C). It consists of a composition.
• the base film one having light transmittance is preferable.
• Specific examples thereof include polyethylene terephthalate (PET) film, polypropylene (PP) film, polyethylene (PE) film, etc., but polyethylene terephthalate (PET) film is preferred in that it has an excellent balance between light transmittance and breaking strength.
• a photosensitive dry film is produced by applying the aforementioned composition for forming a resin film on a base film to form a photosensitive layer.
• an applicator, bar coater, wire bar coater, roll coater, curtain flow coater, etc. are used to form a film having a thickness of preferably 0.5 ⁇ m after drying on the base film.
• the resin film-forming composition is applied to a thickness of 300 ⁇ m or more, 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.
• the protective film include polyethylene terephthalate (PET) film, polypropylene (PP) film, polyethylene (PE) film, and the like.
• a resin film can be formed by a method comprising a drying step of drying the coating film to obtain a resin film.
• the substrate is not particularly limited, and conventionally known substrates can be used.
• substrates for electronic components and substrates on which a predetermined wiring pattern is formed can be exemplified.
• a silicon substrate, a glass substrate, or the like can also be used as the substrate.
• 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.
• methods such as spin coating, slit coating, roll coating, screen printing, and applicator methods can be employed.
• the method for drying the resin film-forming composition applied on the substrate is not particularly limited. Preferably, drying is performed by heating.
• the heating conditions for drying vary depending on the type and mixing ratio of each component in the resin film-forming composition, the coating film thickness, etc., but are usually 70° C. or higher and 200° C. or lower, preferably 80° C. or higher and 150° C. or lower. , about 2 minutes or more and 120 minutes or less.
• a resin film containing the block copolymer or the polyimide resin derived from the block copolymer is formed.
• a block copolymer containing a block derived from a polyamide macromonomer which is a polymer of a tetracarboxylic dianhydride, a dicarboxylic acid which is a reaction product of an alcohol having a radically polymerizable group, and a diamine compound A resin film-forming composition containing a polymer and a photoradical polymerization initiator (C) is preferably used.
• the substrate and the method of applying the resin film-forming composition are as described above for the resin film-forming method.
• the resin film-forming composition coated on the substrate is usually dried to form a coating film.
• the method for drying the resin film-forming composition applied on the substrate is not particularly limited. Preferably, drying is performed by heating.
• the heating conditions for drying vary depending on the type and mixing ratio of each component in the resin film-forming composition, the coating film thickness, etc., but are usually 70° C. or higher and 200° C. or lower, preferably 80° C. or higher and 150° C. or lower. , about 2 minutes or more and 120 minutes or less.
• the coating film formed as described above is subjected to position-selective irradiation with actinic rays or radiation for exposure.
• One selective exposure is usually performed by positionally irradiating actinic rays or radiation, for example, ultraviolet rays or visible rays with a wavelength of 300 nm or more and 500 nm or less through a mask of a predetermined pattern.
• Low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, argon gas lasers, and the like can be used as radiation sources.
• Radiation includes microwaves, infrared rays, visible rays, ultraviolet rays, X-rays, ⁇ -rays, electron beams, proton beams, neutron beams, ion beams, and the like.
• the dose of radiation varies depending on the composition of the resin film-forming composition, the film thickness of the photosensitive layer, etc., it is 100 mJ/cm 2 or more and 10000 mJ/cm 2 or less when using an ultra-high pressure mercury lamp, for example.
• the exposed coating film is developed according to a conventionally known method, and unnecessary portions are dissolved and removed to form a resin film patterned into a predetermined shape.
• a developer suitable for the components contained in the resin film-forming composition is used.
• the block copolymer is a resin having an alkali-soluble group such as a carboxyl group
• an alkaline aqueous solution can be used as the developer.
• the composition for forming a resin film contains a combination of a resin having a radically polymerizable group and a radical photopolymerization initiator (C)
• the aforementioned solvent (S) can be used as the developer.
• Alkaline developers include, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, and methyldiethylamine.
• aqueous solutions of alkalis such as 5-diazabicyclo[4,3,0]-5-nonane can be used.
• an aqueous solution prepared 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 alkalis can be used as a developer.
• the development time varies depending on the composition of the resin film-forming composition, the film thickness of the coating film, etc., but it is usually between 1 minute and 30 minutes.
• the developing method may be any of a liquid-filling method, a dipping method, a puddle method, a spray developing method, and the like.
• the cleaning solvent is not particularly limited. As an example, water, alcohols, etc. can be used as a washing solvent in the case of alkali development. When the solvent (S) is used for development, the solvent (S) can be used as long as solvent shock does not occur.
• the block copolymer contained in the resin film can be imidized
• the block copolymer in the resin film is imidized by baking the developed coating film after development, if necessary.
• the conditions for converting the block copolymer into the polyimide resin by heating are as described above.
• the patterned resin film formed as described above is suitable as, for example, an insulating film of a semiconductor device, an interlayer insulating film for a rewiring layer, an insulating film or a protective film in a touch panel display, an organic electroluminescence display panel, or the like.
• 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.
• the patterned resin film formed as described above can be suitably used as a photoresist for electronics, a galvanic (electrolytic) resist, an etching resist, a solder top resist, and the like.
• the patterned resin film formed as described above can be used for the manufacture of printing plates such as offset printing plates or screen printing plates, the formation of etching masks when etching molded parts, electronic parts, especially microelectronic parts. It can also be used for the production of protective lacquers and dielectric layers in .
• DA6 is a compound represented by the above formula (32).
• Example 1 (Production of polyimide macromonomer) 26.63 g (0.133 mol) of DA1 was dissolved in 63.2 g of NMP (N-methyl-2-pyrrolidone). Then, 52.22 g (0.10 mol) of 10BTA (1,10-bis(3,4-dicarboxyphenylcarbonyloxy)decane dianhydride) was added to the resulting solution. The resulting solution was stirred for 2 hours while being heated to 40° C. to obtain a polyamic acid macromonomer solution.
• NMP N-methyl-2-pyrrolidone
• the polyamic acid macromonomer was removed by refluxing toluene to azeotropically remove water produced as a by-product of the ring closure reaction using a Dean-Stark apparatus. The solution was stirred at 180° C. for 4 hours. After that, toluene was distilled off to obtain a solution of a polyimide macromonomer having an amino group terminal. The obtained polyimide macromonomer was analyzed by gel permeation chromatography and found to have a weight average molecular weight of 15,000.
• the filtrate after removing the precipitate by filtration was added dropwise to an isopropyl alcohol aqueous solution to precipitate the resin.
• the resulting resin was washed with isopropyl alcohol three times to obtain a polyamide resin copolymerized with the polyimide macromonomer.
• the obtained polyamide resin was a block copolymer in which a polyimide macromonomer was copolymerized.
• a resin film was formed according to the following method, and the formed resin film was subjected to dielectric loss tangent evaluation and elongation evaluation.
• the block copolymer in the resin film contains blocks derived from the polyimide macromonomer.
• ⁇ Dielectric loss tangent evaluation> After applying the resin film-forming composition onto a silicon wafer with a spin coater, a thin film of the resin film-forming composition was baked at 90° C. for 240 seconds. The baked coating film was exposed with an integrated light quantity of 2000 mJ/cm 2 using a high-pressure mercury lamp. The exposed film was heated to 230° C. at a rate of 5° C./min in an inert oven under a nitrogen atmosphere, and the coating film was heated at the same temperature for 1 hour.
• the wafer When the temperature dropped to 100° C., the wafer was taken out, immersed in a 2 wt % hydrofluoric acid aqueous solution for 5 to 30 minutes, and the resin film was peeled off from the wafer, whereby the block copolymer was imidized by ring closure. A resin film made of polyimide resin was obtained. The film thickness of the resin film after peeling was 10 ⁇ m.
• the dielectric loss tangent (tan ⁇ ) of the obtained film was calculated in IEICE Technical Report vol. 118, no. 506, MW2018-158, pp. 13-18, March 2019, Investigation on Millimeter Wave Complex Permittivity Evaluation by Cavity Resonator Method” (Kohei Takahagi (Utsunomiya University), Kazuaki Ebisawa (Tokyo Ohka Kogyo Co., Ltd.), Yoshinori Furukami (Utsunomiya University), Takashi Shimizu (Utsunomiya University)) It was measured by the method described.
• Dielectric loss tangent value is less than 0.012.
• x Dielectric loss tangent value is 0.012 or more.
• ⁇ Tensile test (elongation)> A strip-shaped test piece having a width of 1 cm and a length of 5 cm was cut out from the film obtained in the same manner as the evaluation of the dielectric loss tangent. Using the obtained test piece and a tensile tester (EZ-test, manufactured by Shimadzu Corporation), a tensile test was performed under conditions of a chuck distance of 2 cm and a tensile speed of 1 mm/min to measure the tensile elongation. Tensile elongation was obtained according to the following formula.
• Tensile elongation (%) (distance between chucks at break (cm) / 2 (cm) - 1) x 100 Regarding the tensile elongation, 30% or more was determined as ⁇ , and less than 30% was determined as x.
• ⁇ Tensile test (strength)> A strip-shaped test piece having a width of 1 cm and a length of 5 cm was cut out from the film obtained in the same manner as the evaluation of the dielectric loss tangent. Using the obtained test piece and a tensile tester (EZ-test, manufactured by Shimadzu Corporation), a tensile test was performed under conditions of a chuck distance of 2 cm and a tensile speed of 1 mm/min to measure the maximum stress. When the maximum stress during the test was 100 MPa or more, the strength was evaluated as ⁇ , and when the maximum stress was less than 100 MPa as x.
• Example 2 Changing the amount of DA1 used to make the polyimide macromonomer to 30.83 g (0.154 mol) and changing the amount of DA1 used to make the block copolymer to 69.31 g (0.346 mol) A resin film-forming composition was obtained in the same manner as in Example 1 except for this.
• the polystyrene equivalent weight average molecular weight measured by gel permeation chromatography of the polyimide macromonomer used in the production of the block copolymer was 7,000.
• the polystyrene equivalent weight average molecular weight of the block copolymer measured by gel permeation chromatography was 40,000.
• Dielectric loss tangent evaluation and elongation evaluation were performed in the same manner as in Example 1 using the obtained resin film-forming composition.
• the block copolymer in the resin film was imidized by baking.
• the dielectric loss tangent evaluation, the elongation evaluation, and the strength evaluation were both good.
• Example 3 Changing the amount of DA1 used in the production of the polyimide macromonomer to 33.38 g (0.167 mol) and changing the amount of DA1 used in the production of the block copolymer to 66.74 g (0.333 mol) A resin film-forming composition was obtained in the same manner as in Example 1 except for the above.
• the polystyrene equivalent weight average molecular weight measured by gel permeation chromatography of the polyimide macromonomer used in the production of the block copolymer was 3,000.
• the polystyrene equivalent weight average molecular weight of the block copolymer measured by gel permeation chromatography was 40,000.
• Dielectric loss tangent evaluation and elongation evaluation were performed in the same manner as in Example 1 using the obtained resin film-forming composition.
• the block copolymer in the resin film was imidized by baking.
• the dielectric loss tangent evaluation, the elongation evaluation, and the strength evaluation were both good.
• Example 4 26.63 g (0.133 mol) of DA1 used to make the polyimide macromonomer was replaced with 0.133 mol of DA2 and 73.42 g (0.37 mol) used to make the block copolymer.
• a resin film-forming composition was obtained in the same manner as in Example 1, except that DA1 was changed to 0.37 mol of DA2.
• the polystyrene equivalent weight average molecular weight measured by gel permeation chromatography of the polyimide macromonomer used in the production of the block copolymer was 15,000.
• the polystyrene equivalent weight average molecular weight of the block copolymer measured by gel permeation chromatography was 40,000.
• Dielectric loss tangent evaluation and elongation evaluation were performed in the same manner as in Example 1 using the obtained resin film-forming composition.
• the block copolymer in the resin film was imidized by baking.
• the dielectric loss tangent evaluation, the elongation evaluation, and the strength evaluation were both good.
• Example 5 124.1 g (0.4 mol) of 4,4'-oxydiphthalic anhydride used in the production of the block copolymer was added to 0.4 mol of 3,3',4,4'-biphenyltetracarboxylic dianhydride.
• a resin film-forming composition was obtained in the same manner as in Example 1, except that the composition was changed to a substance.
• the polystyrene equivalent weight average molecular weight measured by gel permeation chromatography of the polyimide macromonomer used in the production of the block copolymer was 15,000.
• the polystyrene equivalent weight average molecular weight of the block copolymer measured by gel permeation chromatography was 40,000.
• Dielectric loss tangent evaluation and elongation evaluation were performed in the same manner as in Example 1 using the obtained resin film-forming composition.
• the block copolymer in the resin film was imidized by baking.
• the dielectric loss tangent evaluation, the elongation evaluation, and the strength evaluation were both good.
• Example 6 26.63 g (0.133 mol) of DA1 used in the production of the polyimide macromonomer was changed to 0.133 mol of DA2, and 4,4'-oxydiphthalic anhydride used in the production of the block copolymer. 124.1 g (0.4 mol) was converted to 0.4 mol of 3,3',4,4'-biphenyltetracarboxylic dianhydride, and 73.42 g used in the production of the block copolymer. A resin film-forming composition was obtained in the same manner as in Example 1, except that (0.37 mol) of DA1 was changed to 0.37 mol of DA2.
• the polystyrene equivalent weight average molecular weight measured by gel permeation chromatography of the polyimide macromonomer used in the production of the block copolymer was 15,000.
• the polystyrene equivalent weight average molecular weight of the block copolymer measured by gel permeation chromatography was 40,000.
• Dielectric loss tangent evaluation and elongation evaluation were performed in the same manner as in Example 1 using the obtained resin film-forming composition.
• the block copolymer in the resin film was imidized by baking. As a result of the evaluation, the dielectric loss tangent evaluation, the elongation evaluation, and the strength evaluation were both good.
• Example 7 124.1 g (0.4 mol) of 4,4'-oxydiphthalic anhydride used in the production of the block copolymer was added to 0.4 mol of 2,2-bis[4-(3,4-dicarboxyphenyl).
• a resin film-forming composition was obtained in the same manner as in Example 1, except that oxy)phenyl]propane dianhydride was used.
• the polystyrene equivalent weight average molecular weight measured by gel permeation chromatography of the polyimide macromonomer used in the production of the block copolymer was 15,000.
• the polystyrene equivalent weight average molecular weight of the block copolymer measured by gel permeation chromatography was 40,000.
• Dielectric loss tangent evaluation and elongation evaluation were performed in the same manner as in Example 1 using the obtained resin film-forming composition.
• the block copolymer in the resin film was imidized by baking.
• the dielectric loss tangent evaluation, the elongation evaluation, and the strength evaluation were both good.
• Example 8 26.63 g (0.133 mol) of DA1 used in making the polyimide macromonomer was replaced with 0.133 mol of DA3 and 73.42 g (0.37 mol) used in making the block copolymer.
• a resin film-forming composition was obtained in the same manner as in Example 1, except that DA1 of was changed to 0.37 mol of DA3.
• the polystyrene equivalent weight average molecular weight measured by gel permeation chromatography of the polyimide macromonomer used in the production of the block copolymer was 15,000.
• the polystyrene equivalent weight average molecular weight of the block copolymer measured by gel permeation chromatography was 40,000.
• Dielectric loss tangent evaluation and elongation evaluation were performed in the same manner as in Example 1 using the obtained resin film-forming composition.
• the block copolymer in the resin film was imidized by baking.
• the dielectric loss tangent evaluation, the elongation evaluation, and the strength evaluation were both good.
• Example 9 26.63 g (0.133 mol) of DA1 used in making the polyimide macromonomer was replaced with 0.133 mol of DA4, and 73.42 g (0.37 mol) used in making the block copolymer.
• a resin film-forming composition was obtained in the same manner as in Example 1, except that DA1 of 0.37 mol was changed to DA5 of 0.37 mol.
• the polystyrene equivalent weight average molecular weight measured by gel permeation chromatography of the polyimide macromonomer used in the production of the block copolymer was 15,000.
• the polystyrene equivalent weight average molecular weight of the block copolymer measured by gel permeation chromatography was 40,000.
• Dielectric loss tangent evaluation and elongation evaluation were performed in the same manner as in Example 1 using the obtained resin film-forming composition.
• the block copolymer in the resin film was imidized by baking.
• the dielectric loss tangent evaluation, the elongation evaluation, and the strength evaluation were both good.
• Example 10 26.63 g (0.133 mol) of DA1 used in the production of the polyimide macromonomer was changed to 0.133 mol of DA4, and 52.22 g (0.10 mol) of the polyimide macromonomer was produced. 73.42 g ( A resin film-forming composition was obtained in the same manner as in Example 1, except that 0.37 mol of DA1 was changed to 0.37 mol of DA5. The polystyrene equivalent weight average molecular weight measured by gel permeation chromatography of the polyimide macromonomer used in the production of the block copolymer was 15,000.
• the polystyrene equivalent weight average molecular weight of the block copolymer measured by gel permeation chromatography was 40,000.
• Dielectric loss tangent evaluation and elongation evaluation were performed in the same manner as in Example 1 using the obtained resin film-forming composition.
• the block copolymer in the resin film was imidized by baking. As a result of the evaluation, the dielectric loss tangent evaluation, the elongation evaluation, and the strength evaluation were both good.
• the resulting reaction solution was added dropwise to an isopropyl alcohol aqueous solution to precipitate a brown polyamide resin powder. After collecting the precipitated powder by filtration, it was washed with isopropyl alcohol three times. The washed powder was dried under reduced pressure to obtain di-2-methacryloyloxyethyl ester of 4,4′-oxydiphthalic acid, di-2-methacryloyloxyethyl ester of tetracarboxylic acid derived from 10BTA, and the above DA1. to obtain a polyamide resin which is a polycondensate of The resulting polyamide resin has a 2-(methacryloyloxy)ethoxycarbonyl group as a radically polymerizable group.
• the polystyrene-equivalent weight average molecular weight of the resulting polyamide resin measured by gel permeation chromatography was 40,000.
• Dielectric loss tangent evaluation and elongation evaluation were performed in the same manner as in Example 1 using the obtained resin film-forming composition. As a result of the evaluation, the dielectric loss tangent evaluation was ⁇ , the elongation evaluation was x, and the strength evaluation was x.
• the polystyrene-equivalent weight average molecular weight of the resulting polyamide resin measured by gel permeation chromatography was 45,000.
• Dielectric loss tangent evaluation and elongation evaluation were performed in the same manner as in Example 1 using the obtained resin film-forming composition. As a result of the evaluation, the dielectric loss tangent evaluation was ⁇ , the elongation evaluation was x, and the strength evaluation was x.
• Dielectric loss tangent evaluation and elongation evaluation were performed in the same manner as in Example 1 using the obtained resin film-forming composition.
• the dielectric loss tangent evaluation was x
• the elongation evaluation was ⁇
• the strength evaluation was ⁇ .
• Example 11 (Production of Polyamide Macromonomer) 52.22 g (0.10 mol) of 10BTA was dispersed in 100 g of N-methyl-2-pyrrolidone (NMP). To the resulting solution were added 26.03 g (0.20 mol) of 2-hydroxyethyl methacrylate (HEMA), 15.82 g (0.20 mol) of pyridine, and 2.443 g (0.02 mol) of dimethylaminopyridine. was added, and the solution was stirred at room temperature for 16 hours to obtain di-2-methacryloyloxyethyl ester of tetracarboxylic acid derived from 10BTA.
• NMP N-methyl-2-pyrrolidone
• a dicarboxylic acid solution containing 0.1 mol of the resulting diester was cooled to 0°C. Then a solution of 42.30 g (0.21 mol) dicyclohexylcarbodiimide and 42 g NMP, 43.33 g (0.21 mol) 1-hydroxybenzotriazole monohydrate and 26.63 g (0.133 mol) DA1 and a diamine solution consisting of 60 g of NMP were added dropwise into the dicarboxylic acid solution. After completion of dropping, the resulting reaction solution was stirred at room temperature for 2 hours to carry out condensation reaction. After the condensation reaction, a precipitate was filtered to obtain a solution of a polyamide macromonomer having an amino group terminal. The polystyrene-equivalent weight average molecular weight of the resulting polyamide macromonomer measured by gel permeation chromatography was 8,000.
• the filtrate after removing the precipitate by filtration was added dropwise to an isopropyl alcohol aqueous solution to precipitate the resin.
• the resulting resin was washed with isopropyl alcohol three times to obtain a polyamide resin copolymerized with the above polyamide macromonomer.
• As a result of analyzing the obtained polyamide resin by gel permeation chromatography it was found to have a weight average molecular weight of 40,000.
• the obtained chart was unimodal, and it was confirmed that the polyamide macromonomer was copolymerized in the obtained polyamide resin.
• a resin film-forming composition was obtained in the same manner as in Example 1 using the obtained block copolymer containing blocks derived from the polyamide macromonomer. Using the obtained resin film-forming composition, a resin film was formed, and the formed resin film was subjected to dielectric loss tangent evaluation, elongation evaluation, and strength evaluation in the same manner as in Example 1. . As a result of the evaluation, the dielectric loss tangent evaluation, the elongation evaluation, and the strength evaluation were both good.
• Example 12 52.22 g (0.10 mol) of 10BTA used in the production of the polyamide macromonomer was changed to 0.10 mol of 4,4'-oxydiphthalic anhydride, and 26.63 g (0.10 mol) used in the production of the polyamide macromonomer.
• a resin film-forming composition was obtained in the same manner as in Example 11, except that DA1 (133 mol) was changed to DA6 (0.133 mol).
• the resulting polyamide resin copolymerized with the polyamide macromonomer was analyzed by gel permeation chromatography and found to have a weight average molecular weight of 40,000.
• Dielectric loss tangent evaluation, elongation evaluation, and strength evaluation were performed in the same manner as in Example 1 using the obtained resin film-forming composition. As a result of the evaluation, the dielectric loss tangent evaluation, the elongation evaluation, and the strength evaluation were both good.
• Example 13 26.63 g (0.133 mol) of DA1 used in the production of the polyamide macromonomer was changed to 0.133 mol of DA2, and 73.42 g (0.37 mol) of DA1 used in the production of the block copolymer.
• a resin film-forming composition was obtained in the same manner as in Example 11, except that DA2 was changed to 0.37 mol.
• the polystyrene equivalent weight average molecular weight measured by gel permeation chromatography of the polyamide macromonomer used for producing the block copolymer was 8,000.
• the resulting polyamide resin copolymerized with the polyamide macromonomer was analyzed by gel permeation chromatography and found to have a weight average molecular weight of 40,000.
• Dielectric loss tangent evaluation, elongation evaluation, and strength evaluation were performed in the same manner as in Example 1 using the obtained resin film-forming composition.
• the block copolymer in the resin film contained blocks derived from polyamide macromonomers.
• the dielectric loss tangent evaluation, the elongation evaluation, and the strength evaluation were both good.
• Example 14 52.22 g (0.10 mol) of 10BTA used in the production of the polyamide macromonomer was changed to 0.10 mol of 4,4'-oxydiphthalic anhydride, and 26.63 g (0.10 mol) used in the production of the polyamide macromonomer. 133 mol) of DA1 was changed to 0.133 mol of DA6, and 73.42 g (0.37 mol) of DA1 used in the production of the block copolymer was changed to 0.37 mol of DA2. , in the same manner as in Example 11 to obtain a resin film-forming composition.
• the polystyrene equivalent weight average molecular weight measured by gel permeation chromatography of the polyamide macromonomer used for producing the block copolymer was 8,000.
• the resulting polyamide resin copolymerized with the polyamide macromonomer was analyzed by gel permeation chromatography and found to have a weight average molecular weight of 40,000.
• Dielectric loss tangent evaluation, elongation evaluation, and strength evaluation were performed in the same manner as in Example 1 using the obtained resin film-forming composition.
• the block copolymer in the resin film contained blocks derived from polyamide macromonomers. As a result of the evaluation, the dielectric loss tangent evaluation, the elongation evaluation, and the strength evaluation were both good.
• Example 15 124.1 g (0.4 mol) of 4,4'-oxydiphthalic anhydride used in producing the block copolymer was added to 0.4 mol of 3,3',4,4'-biphenyltetracarboxylic dianhydride.
• a resin film-forming composition was obtained in the same manner as in Example 11, except for changing to The polystyrene equivalent weight average molecular weight measured by gel permeation chromatography of the polyamide macromonomer used for producing the block copolymer was 8,000. The resulting polyamide resin copolymerized with the polyamide macromonomer was analyzed by gel permeation chromatography and found to have a weight average molecular weight of 40,000.
• Dielectric loss tangent evaluation, elongation evaluation, and strength evaluation were performed in the same manner as in Example 1 using the obtained resin film-forming composition.
• the block copolymer in the resin film contained blocks derived from polyamide macromonomers.
• the dielectric loss tangent evaluation, the elongation evaluation, and the strength evaluation were both good.
• Example 16 26.63 g (0.133 mol) of DA1 used in the preparation of the polyamide macromonomer was changed to 0.133 mol of DA6, and 4,4'-oxydiphthalic anhydride used in the preparation of the block copolymer 124.
• 1 g (0.4 mol) was changed to 0.4 mol of 3,3',4,4'-biphenyltetracarboxylic dianhydride.
• a composition was obtained.
• the resulting polyamide resin copolymerized with the polyamide macromonomer was analyzed by gel permeation chromatography and found to have a weight average molecular weight of 40,000.
• Dielectric loss tangent evaluation, elongation evaluation, and strength evaluation were performed in the same manner as in Example 1 using the obtained resin film-forming composition.
• the block copolymer in the resin film contained blocks derived from polyamide macromonomers. As a result of the evaluation, the dielectric loss tangent evaluation, the elongation evaluation, and the strength evaluation were both good.
• Example 17 26.63 g (0.133 mol) of DA1 used in the preparation of the polyamide macromonomer was changed to 0.133 mol of DA3, and 124.4,4'-oxydiphthalic anhydride used in the preparation of the block copolymer. 1 g (0.4 mol) was changed to 0.4 mol of 3,3′,4,4′-biphenyltetracarboxylic dianhydride, and 73.42 g (0.4 mol) used in the production of the block copolymer. A resin film-forming composition was obtained in the same manner as in Example 11, except that DA1 (37 mol) was changed to DA3 (0.37 mol).
• the polystyrene equivalent weight average molecular weight measured by gel permeation chromatography of the polyamide macromonomer used for producing the block copolymer was 8,000.
• the resulting polyamide resin copolymerized with the polyamide macromonomer was analyzed by gel permeation chromatography and found to have a weight average molecular weight of 40,000.
• Dielectric loss tangent evaluation, elongation evaluation, and strength evaluation were performed in the same manner as in Example 1 using the obtained resin film-forming composition.
• the block copolymer in the resin film contained blocks derived from polyamide macromonomers. As a result of the evaluation, the dielectric loss tangent evaluation, the elongation evaluation, and the strength evaluation were both good.
• Example 18 52.22 g (0.10 mol) of 10BTA used in the production of the polyamide macromonomer was changed to 0.10 mol of 4,4'-oxydiphthalic anhydride, and 26.63 g (0.10 mol) used in the production of the polyamide macromonomer. 133 mol) of DA1 was changed to 0.133 mol of DA6, and 124.1 g (0.4 mol) of 4,4'-oxydiphthalic anhydride used in the production of the block copolymer was replaced with 0.4 mol.
• Dielectric loss tangent evaluation, elongation evaluation, and strength evaluation were performed in the same manner as in Example 1 using the obtained resin film-forming composition.
• the block copolymer in the resin film contained blocks derived from polyamide macromonomers.
• the dielectric loss tangent evaluation, the elongation evaluation, and the strength evaluation were both good.
• Example 19 26.63 g (0.133 mol) of DA1 used in the preparation of the polyamide macromonomer was changed to 0.133 mol of DA5, and 4,4'-oxydiphthalic anhydride used in the preparation of the block copolymer 124. 1 g (0.4 mol) was changed to 0.4 mol of 3,3′,4,4′-biphenyltetracarboxylic dianhydride, and 73.42 g (0.4 mol) used in the production of the block copolymer. A resin film-forming composition was obtained in the same manner as in Example 11, except that DA1 (37 mol) was changed to DA3 (0.37 mol).
• the polystyrene equivalent weight average molecular weight measured by gel permeation chromatography of the polyamide macromonomer used for producing the block copolymer was 8,000.
• the resulting polyamide resin copolymerized with the polyamide macromonomer was analyzed by gel permeation chromatography and found to have a weight average molecular weight of 40,000.
• Dielectric loss tangent evaluation, elongation evaluation, and strength evaluation were performed in the same manner as in Example 1 using the obtained resin film-forming composition.
• the block copolymer in the resin film contained blocks derived from polyamide macromonomers. As a result of the evaluation, the dielectric loss tangent evaluation, the elongation evaluation, and the strength evaluation were both good.
• Example 20 Converting 52.22 g (0.10 mol) of 10BTA used in the production of polyamide macromonomer to 0.10 mol of 2,2-bis[4-(3,4-dicarboxyphenyloxy)phenyl]propane dianhydride And, 26.63 g (0.133 mol) of DA1 used in the production of the polyamide macromonomer was changed to 0.133 mol of DA5, and the 4,4'-oxydiphthalic anhydride used in the production of the block copolymer.
• a resin film-forming composition was obtained in the same manner as in Example 11, except that 0.37 mol of DA1 was changed to 0.37 mol of DA3.
• the polystyrene equivalent weight average molecular weight measured by gel permeation chromatography of the polyamide macromonomer used for producing the block copolymer was 8,000.
• the resulting polyamide resin copolymerized with the polyamide macromonomer was analyzed by gel permeation chromatography and found to have a weight average molecular weight of 40,000.
• Dielectric loss tangent evaluation, elongation evaluation, and strength evaluation were performed in the same manner as in Example 1 using the obtained resin film-forming composition.
• the block copolymer in the resin film contained blocks derived from polyamide macromonomers.
• the dielectric loss tangent evaluation, the elongation evaluation, and the strength evaluation were both good.
• Example 21 52.22 g (0.10 mol) of 10BTA used in the production of the polyamide macromonomer was changed to 0.10 mol of 4,4'-oxydiphthalic anhydride, and 26.63 g (0.10 mol) used in the production of the polyamide macromonomer. 133 mol) of DA1 was changed to 0.133 mol of DA6, and 124.1 g (0.4 mol) of 4,4'-oxydiphthalic anhydride used in the production of the block copolymer was replaced with 0.4 mol.
• Dielectric loss tangent evaluation, elongation evaluation, and strength evaluation were performed in the same manner as in Example 1 using the obtained resin film-forming composition.
• the block copolymer in the resin film contained blocks derived from polyamide macromonomers.
• the dielectric loss tangent evaluation, the elongation evaluation, and the strength evaluation were both good.
• Example 22 26.63 g (0.133 mol) of DA1 used in the preparation of the polyamide macromonomer was changed to 0.133 mol of DA6, and 4,4'-oxydiphthalic anhydride used in the preparation of the block copolymer 124. 1 g (0.4 mol) was changed to 0.4 mol of 3,3′,4,4′-biphenyltetracarboxylic dianhydride, and 73.42 g (0.4 mol) used in the production of the block copolymer.
• a resin film-forming composition was obtained in the same manner as in Example 11, except that DA1 (37 mol) was changed to DA4 (0.37 mol).
• the polystyrene equivalent weight average molecular weight measured by gel permeation chromatography of the polyamide macromonomer used for producing the block copolymer was 8,000.
• the resulting polyamide resin copolymerized with the polyamide macromonomer was analyzed by gel permeation chromatography and found to have a weight average molecular weight of 40,000.
• Dielectric loss tangent evaluation, elongation evaluation, and strength evaluation were performed in the same manner as in Example 1 using the obtained resin film-forming composition.
• the block copolymer in the resin film contained blocks derived from polyamide macromonomers. As a result of the evaluation, the dielectric loss tangent evaluation, the elongation evaluation, and the strength evaluation were both good.
• Example 23 26.63 g (0.133 mol) of DA1 used in the preparation of the polyamide macromonomer was changed to 0.133 mol of DA5, and 4,4'-oxydiphthalic anhydride used in the preparation of the block copolymer 124. 1 g (0.4 mol) was changed to 0.4 mol of 3,3′,4,4′-biphenyltetracarboxylic dianhydride, and 73.42 g (0.4 mol) used in the production of the block copolymer.
• a resin film-forming composition was obtained in the same manner as in Example 11, except that DA1 (37 mol) was changed to DA4 (0.37 mol).
• the polystyrene equivalent weight average molecular weight measured by gel permeation chromatography of the polyamide macromonomer used for producing the block copolymer was 8,000.
• the resulting polyamide resin copolymerized with the polyamide macromonomer was analyzed by gel permeation chromatography and found to have a weight average molecular weight of 40,000.
• Dielectric loss tangent evaluation, elongation evaluation, and strength evaluation were performed in the same manner as in Example 1 using the obtained resin film-forming composition.
• the block copolymer in the resin film contained blocks derived from polyamide macromonomers. As a result of the evaluation, the dielectric loss tangent evaluation, the elongation evaluation, and the strength evaluation were both good.
• Example 24 Converting 52.22 g (0.10 mol) of 10BTA used in the production of polyamide macromonomer to 0.10 mol of 2,2-bis[4-(3,4-dicarboxyphenyloxy)phenyl]propane dianhydride And, 73.42 g (0.37 mol) of DA1 used during polyamide macromonomer production was changed to 0.37 mol of DA5, and 4,4'-oxydiphthalic anhydride used during block copolymer production.
• a resin film-forming composition was obtained in the same manner as in Example 11, except that 0.37 mol of DA1 was changed to 0.37 mol of DA4.
• the polystyrene equivalent weight average molecular weight measured by gel permeation chromatography of the polyamide macromonomer used for producing the block copolymer was 8,000.
• the resulting polyamide resin copolymerized with the polyamide macromonomer was analyzed by gel permeation chromatography and found to have a weight average molecular weight of 40,000.
• Dielectric loss tangent evaluation, elongation evaluation, and strength evaluation were performed in the same manner as in Example 1 using the obtained resin film-forming composition.
• the block copolymer in the resin film contained blocks derived from polyamide macromonomers.
• the dielectric loss tangent evaluation, the elongation evaluation, and the strength evaluation were both good.
• Example 25 Changing the amount of DA1 used in the production of the polyamide macromonomer from 0.133 mol to 0.118 mol, and changing the amount of DA1 used in the production of the block copolymer from 0.37 mol to 0.382 mol.
• a resin film-forming composition was obtained in the same manner as in Example 11 except for the above.
• the polystyrene equivalent weight average molecular weight measured by gel permeation chromatography of the polyamide macromonomer used in the production of the block copolymer was 25,000.
• the resulting polyamide resin copolymerized with the polyamide macromonomer was analyzed by gel permeation chromatography and found to have a weight average molecular weight of 40,000.
• Dielectric loss tangent evaluation, elongation evaluation, and strength evaluation were performed in the same manner as in Example 1 using the obtained resin film-forming composition.
• the block copolymer in the resin film contained blocks derived from polyamide macromonomers.
• the dielectric loss tangent evaluation, the elongation evaluation, and the strength evaluation were both good.
• Example 26 Changing the amount of DA1 used in the production of the polyamide macromonomer from 0.133 mol to 0.167 mol, and changing the amount of DA1 used in the production of the block copolymer from 0.37 mol to 0.333 mol.
• a resin film-forming composition was obtained in the same manner as in Example 11 except for the above.
• the polystyrene equivalent weight average molecular weight measured by gel permeation chromatography of the polyamide macromonomer used in the production of the block copolymer was 3,000.
• the resulting polyamide resin copolymerized with the polyamide macromonomer was analyzed by gel permeation chromatography and found to have a weight average molecular weight of 40,000.
• Dielectric loss tangent evaluation, elongation evaluation, and strength evaluation were performed in the same manner as in Example 1 using the obtained resin film-forming composition.
• the block copolymer in the resin film contained blocks derived from polyamide macromonomers.
• the dielectric loss tangent evaluation, the elongation evaluation, and the strength evaluation were both good.
• Example 27 (Production of Polyamide Macromonomer) 52.22 g (0.10 mol) of 10BTA was dispersed in 100 g of N-methyl-2-pyrrolidone (NMP). To the resulting solution were added 26.03 g (0.20 mol) of 2-hydroxyethyl methacrylate (HEMA), 15.82 g (0.20 mol) of pyridine, and 2.443 g (0.02 mol) of dimethylaminopyridine. was added, and the solution was stirred at room temperature for 16 hours to obtain di-2-methacryloyloxyethyl ester of tetracarboxylic acid derived from 10BTA.
• NMP N-methyl-2-pyrrolidone
• a dicarboxylic acid solution containing 0.1 mol of the resulting diester was cooled to 0°C. Then a solution of 42.30 g (0.21 mol) dicyclohexylcarbodiimide and 42 g NMP, 43.33 g (0.21 mol) 1-hydroxybenzotriazole monohydrate and 15.02 g (0.075 mol) DA1 and a diamine solution consisting of 60 g of NMP were added dropwise into the dicarboxylic acid solution. After completion of dropping, the resulting reaction solution was stirred at room temperature for 2 hours to carry out condensation reaction. After the condensation reaction, a precipitate was filtered to obtain a solution of a polyamide macromonomer having a terminal carboxyl group. The polystyrene-equivalent weight average molecular weight of the resulting polyamide macromonomer measured by gel permeation chromatography was 8,000.
• the filtrate after removing the precipitate by filtration was added dropwise to an isopropyl alcohol aqueous solution to precipitate the resin.
• the resulting resin was washed with isopropyl alcohol three times to obtain a polyamide resin copolymerized with the above polyamide macromonomer.
• the resulting polyamide resin copolymerized with a polyamide macromonomer having a carboxy group end was analyzed by gel permeation chromatography to find a weight average molecular weight of 40,000.
• the obtained chart was unimodal, confirming that the polyamide macromonomer was copolymerized.
• a resin film-forming composition was obtained in the same manner as in Example 1 using the obtained block copolymer containing blocks derived from the polyamide macromonomer. Using the obtained resin film-forming composition, a resin film was formed, and the formed resin film was subjected to dielectric loss tangent evaluation, elongation evaluation, and strength evaluation in the same manner as in Example 1. . As a result of the evaluation, the dielectric loss tangent evaluation, the elongation evaluation, and the strength evaluation were both good.
• Example 28 15.02 g (0.075 mol) of DA1 used during polyamide macromonomer production was changed to 0.075 mol of DA3, and 4,4'-oxydiphthalic anhydride 85 used during block copolymer production. .31 g (0.275 mol) was converted to 0.275 mol of 3,3',4,4'-biphenyltetracarboxylic dianhydride, and 60.07 g ( A resin film-forming composition was obtained in the same manner as in Example 27, except that 0.30 mol of DA1 was changed to 0.30 mol of DA3.
• the polystyrene equivalent weight average molecular weight measured by gel permeation chromatography of the polyamide macromonomer used for producing the block copolymer was 8,000.
• the resulting polyamide resin copolymerized with the polyamide macromonomer was analyzed by gel permeation chromatography and found to have a weight average molecular weight of 40,000.
• Dielectric loss tangent evaluation, elongation evaluation, and strength evaluation were performed in the same manner as in Example 1 using the obtained resin film-forming composition.
• the block copolymer in the resin film contained blocks derived from polyamide macromonomers. As a result of the evaluation, the dielectric loss tangent evaluation, the elongation evaluation, and the strength evaluation were both good.
• Example 29 15.02 g (0.075 mol) of DA1 used during polyamide macromonomer production was changed to 0.075 mol of DA5, and 4,4'-oxydiphthalic anhydride 85 used during block copolymer production. .31 g (0.275 mol) was converted to 0.275 mol of 3,3',4,4'-biphenyltetracarboxylic dianhydride, and 60.07 g ( A resin film-forming composition was obtained in the same manner as in Example 27, except that 0.30 mol of DA1 was changed to 0.30 mol of DA4.
• the polystyrene equivalent weight average molecular weight measured by gel permeation chromatography of the polyamide macromonomer used for producing the block copolymer was 8,000.
• the resulting polyamide resin copolymerized with the polyamide macromonomer was analyzed by gel permeation chromatography and found to have a weight average molecular weight of 40,000.
• Dielectric loss tangent evaluation, elongation evaluation, and strength evaluation were performed in the same manner as in Example 1 using the obtained resin film-forming composition.
• the block copolymer in the resin film contained blocks derived from polyamide macromonomers. As a result of the evaluation, the dielectric loss tangent evaluation, the elongation evaluation, and the strength evaluation were both good.
• the obtained resin film-forming compositions of Examples 1 to 29 were applied by a spin coater onto a silicon wafer having a copper sputtered film formed thereon. After that, the film made of the resin film-forming composition was baked at 80° C. for 300 seconds to obtain a coating film having a thickness of 12 ⁇ m.
• the coating film was exposed at 2000 mJ/cm 2 at 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 obtained resin film was heated to 230° C. at a rate of 5° C./min in an inert oven under a nitrogen atmosphere, and the coating 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.

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