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WO2010047271A1 - Résine de polyamide et sa composition - Google Patents

Résine de polyamide et sa composition Download PDF

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Publication number
WO2010047271A1
WO2010047271A1 PCT/JP2009/067867 JP2009067867W WO2010047271A1 WO 2010047271 A1 WO2010047271 A1 WO 2010047271A1 JP 2009067867 W JP2009067867 W JP 2009067867W WO 2010047271 A1 WO2010047271 A1 WO 2010047271A1
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WO
WIPO (PCT)
Prior art keywords
polyimide resin
hydroxyl group
phenolic hydroxyl
dianhydride
film
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2009/067867
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English (en)
Japanese (ja)
Inventor
竜太朗 田中
健二 関根
誠 内田
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nippon Kayaku Co Ltd
Original Assignee
Nippon Kayaku Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nippon Kayaku Co Ltd filed Critical Nippon Kayaku Co Ltd
Priority to CN2009801417673A priority Critical patent/CN102186904A/zh
Priority to JP2010534783A priority patent/JP5649118B2/ja
Publication of WO2010047271A1 publication Critical patent/WO2010047271A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/62—Alcohols or phenols
    • 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
    • C08G73/1046—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
    • C08G73/1046—Polyimides containing oxygen in the form of ether bonds in the main chain
    • C08G73/105—Polyimides containing oxygen in the form of ether bonds in the main chain with oxygen only in the diamino moiety
    • 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
    • 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
    • C08G73/1075—Partially aromatic polyimides
    • 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
    • C08G73/1075—Partially aromatic polyimides
    • C08G73/1078—Partially aromatic polyimides wholly aromatic in the diamino moiety
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—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
    • G03F7/022—Quinonediazides
    • G03F7/023—Macromolecular quinonediazides; Macromolecular additives, e.g. binders
    • 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
    • G03F7/022—Quinonediazides
    • G03F7/023—Macromolecular quinonediazides; Macromolecular additives, e.g. binders
    • G03F7/0233—Macromolecular quinonediazides; Macromolecular additives, e.g. binders characterised by the polymeric binders or the macromolecular additives other than the macromolecular quinonediazides
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/40—Treatment after imagewise removal, e.g. baking

Definitions

  • the present invention relates to a phenolic hydroxyl group-containing polyimide resin and a composition thereof.
  • Epoxy resins are cured with various curing agents, and generally become cured products with excellent mechanical properties, water resistance, chemical resistance, heat resistance, electrical properties, etc., and adhesives, paints, laminates, molding materials It is used in a wide range of fields such as casting materials.
  • the most commonly used epoxy resin includes bisphenol A type epoxy resin.
  • bisphenol A type epoxy resin As other flame retardants, compounds obtained by reacting tetrabromobisphenol A with bisphenol A type epoxy resins are generally known.
  • acid anhydrides and amine compounds are known as curing agents for epoxy resins, but phenol novolac is often used in the electrical / electronic field from the viewpoint of reliability such as heat resistance.
  • aromatic polyamides having phenolic hydroxyl groups have been used as curing agents for the purpose of improving heat resistance and flexibility (Patent Document 1).
  • Polyimide resin on the other hand, has excellent heat resistance, flame retardancy, flexibility, mechanical properties, electrical properties, and chemical resistance, and is used in electrical and electronic parts, semiconductors, communication equipment and its circuit parts, and peripheral equipment. Widely used. However, since polyimide resin is hardly soluble in an organic solvent, it is necessary to apply polyamic acid as a precursor to a substrate, and then to heat and dehydrate. At that time, curling and water generation due to curing shrinkage have been problems. In recent years, a solvent-soluble polyimide resin has been developed, and a polyimide resin composition that can be patterned is prepared by mixing a photosensitive agent with the polyimide resin and used as a coating application, an alignment film, and an insulating film (Patent Document 2).
  • An object of the present invention is to provide a resin composition satisfying various properties such as flame retardancy, heat resistance, mechanical properties, and flexibility, and a cured product thereof, which can cope with the high functionality of various electronic devices today. There is to do.
  • the present inventors have completed the present invention as a result of intensive studies. That is, the present invention
  • a phenolic hydroxyl group-containing polyimide resin obtained by polycondensation reaction of an aminophenol compound (a), a tetrabasic acid dianhydride (b) and a diamino compound (c) as an optional component, the aminophenol compound (A) is the formula (1)
  • thermosetting polyimide resin composition containing the phenolic hydroxyl group-containing polyimide resin (A) and the epoxy resin (B) according to any one of (1) to (5) above, (7) The phenolic hydroxyl group-containing polyimide resin (A) described in any one of (1) to (5) above, a diazo positive photosensitive agent (C), and an epoxy resin (B) as an optional component.
  • Positive photosensitive polyimide resin composition (8)
  • the phenolic hydroxyl group-containing polyimide resin of the present invention has high solvent solubility, and when the polyimide resin is combined with an epoxy resin to form a thermosetting composition, the cured product has excellent heat resistance and flame retardancy, and Sufficient flexibility.
  • the photosensitive resin composition in which the polyimide resin is combined with a photosensitive agent is excellent in developability and resolution, and the cured product has adhesion, solvent resistance, acid resistance, heat resistance, PCT resistance, Excellent impact resistance, excellent flame resistance without halogen, phosphorus, antimony and other flame retardants, low warpage when coated and cured on a film-like substrate, and sufficient flexibility
  • the polyimide resin composition of the present invention containing the polyimide resin of the present invention and the cured product thereof are a solder mask for thin package substrates, a coverlay for flexible printed wiring boards, an interlayer insulating film for multilayer printed wiring boards, a semiconductor passivation film, etc. Useful for a wide range of applications.
  • the phenolic hydroxyl group-containing polyimide resin (A) of the present invention is obtained by reacting a specific aminophenol compound (a), a tetrabasic acid dianhydride (b), and a diamino compound (c) as an optional component.
  • Tetrabasic dianhydride (b) used in the reaction represents the number of acid anhydrides in one molecule and the number of moles of tetrabasic dianhydride (b) as X and x, respectively, and the amino group in one molecule of aminophenol compound (a) And the number of moles of the aminophenol compound (a) are Y and y, respectively, and the number of moles of the diamino compound (c) is z, if Xx> Yy + 2z, the end is an acid anhydride, and if Xx ⁇ Yy + 2z The terminal is an amine.
  • the value of Xx / (Yy + 2z) is preferably in the range of 0.5 to 2, and more preferably in the range of 0.7 to 1.5. More preferably, the value is 0.8 or more and less than 1, and most preferably 0.9 or more and less than 1.
  • both ends of the resulting polyimide resin (A) are amino groups. .
  • the molecular weight is small and unreacted raw materials remain, and various properties such as heat resistance and flexibility after curing cannot be obtained.
  • the aminophenol compound (a) has a phenolic hydroxyl group equivalent of the phenolic hydroxyl group-containing polyimide resin (A) obtained by the reaction of 200 to 5,000 g / eq.
  • the phenolic hydroxyl group-containing polyimide resin (A) of the present invention is synthesized by a simple dehydration condensation reaction between an acid anhydride structure and an amino group. Therefore, the aminophenol compound (a), tetrabasic acid dianhydride (a) necessary for synthesizing a phenolic hydroxyl group-containing polyimide resin (A) having an intended terminal structure (an acid anhydride group or amino group) and a hydroxyl group equivalent ( The charged amounts of b) and diamino compound (c) are easily calculated from the molecular weights of (a) to (c), the number of acid anhydride structures in one molecule, the number of amino groups, and the number of phenolic hydroxyl groups. be able to.
  • an aminophenol compound having two amino groups and two phenolic hydroxyl groups in one molecule used as a raw material for the phenolic hydroxyl group-containing polyimide resin (A) in Example 2 of the present invention (aHPB (1,3-bis (4-amino-3-hydroxyphenoxy) benzene, molecular weight 324.33) which is a), ODPA (3,3 ′, 4,4) which is tetrabasic acid dianhydride (b) '-Diphenyl ether tetracarboxylic dianhydride, molecular weight 310.22), and diamino compound (c) APB-N (1,3-bis- (3-aminophenoxy) benzene, molecular weight 292.33) If the terminal of the phenolic hydroxyl group-containing polyimide resin (A) is to be amine, AHPB and APB-N total 1 per 1 mol of ODPA.
  • the phenolic hydroxyl group equivalent of the phenolic hydroxyl group-containing polyimide resin (A) is 200 to 5,000 g / eq.
  • AHPB is approximately 0.06 mol or more (less than 1 mol)
  • ABPS and APB with respect to 1 mol of ODPA.
  • ABPS When using a total of 1.5 mol of -N, ABPS is generally 0.07 mol or more (less than 1.5 mol), and when using a total of 2 mol of ABPS and APB-N per mol of ODPA, ABPS is used. What is necessary is just to use about 0.09 mol or more (less than 2.0 mol).
  • the aminophenol compound (a) used for producing the phenolic hydroxyl group-containing polyimide resin (A) is represented by the following formula (1):
  • aminophenol compound represented by the formula (AHPB (1,3-bis (4-amino-3-hydroxyphenoxy) benzene)). Can also be used together.
  • the aminophenol compound that can be used in combination is not particularly limited as long as it is a compound having at least two amino groups and at least one phenolic hydroxyl group in one molecule.
  • aminophenol compounds that can be used in combination include 3,3′-diamino-4,4′-dihydroxydiphenyl sulfone, 3,3′-diamino-4,4′-dihydroxydiphenyl ether, and 3,3′-diamino- 4,4'-dihydroxybiphenyl, 3,3'-dihydroxy-4,4'-diaminobiphenyl, 2,2-bis (3-amino-4-hydroxyphenyl) propane, 1,3-hexafluoro-2,2 -Bis (3-amino-4-hydroxyphenyl) propane, 9,9'-bis (3-amino-4-hydroxyphenyl) fluorene, and the like, but are not limited thereto.
  • the content of the aminophenol compound represented by the formula (1) in the aminophenol compound (a) is preferably at least 3 mol%, more preferably at least 10 mol%, still more preferably 50%, based on the total amount of the aminophenol compound. More than mol%, most preferably 100 mol%. If the content of the aminophenol compound represented by the formula (1) is extremely reduced, various properties may be hardly expressed.
  • the tetrabasic acid dianhydride (b) used for producing the phenolic hydroxyl group-containing polyimide resin (A) is not particularly limited as long as it has at least two acid anhydride structures in one molecule. Can do.
  • Specific examples of the tetrabasic acid dianhydride (b) include pyromellitic anhydride, ethylene glycol-bis (anhydrotrimellitate), glycerin-bis (anhydrotrimellitate) monoacetate, 1,2,3 , 4, -butanetetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 3 , 3 ′, 4,4′-biphenyltetracarboxylic dianhydride, hydrogenated product of 3,3 ′, 4,4′-biphenyltetracar
  • 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenone is preferred in view of solvent solubility, adhesion to a substrate, and photosensitivity.
  • These tetrabasic acid dianhydrides (b) may be used alone or in combination of two or more.
  • diamino compound (c) used as an optional component for producing the phenolic hydroxyl group-containing polyimide resin (A) include m-phenylenediamine, p-phenylenediamine, m-tolylenediamine, 4,4′- Diaminodiphenyl ether, 3,3'-dimethyl-4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl thioether, 3,3'-dimethyl-4,4'-diaminodiphenyl thioether 3,3′-diethoxy-4,4′-diaminodiphenyl thioether, 3,3′-diaminodiphenyl thioether, 4,4′-diaminobenzophenone, 3,3′-dimethyl-4,4′-diaminobenzophenone, 3, , 3'-Diaminodiphen
  • 3,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl ether, and 1,3-bis- (3-aminophenoxy) exhibit excellent effects in adhesion to substrates, developability, and flexibility.
  • Benzene, silicone diamine and 1- (4-aminophenyl) -1,3,3-trimethyl-1H-indene-5-amine are preferred, 1,3-bis- (3-aminophenoxy) benzene and 1- (4 -Aminophenyl) -1,3,3-trimethyl-1H-indene-5-amine is more preferred, and 1,3-bis- (3-aminophenoxy) benzene is particularly preferred.
  • These diamino compounds (c) may be used alone or in combination of two or more.
  • the phenolic hydroxyl group-containing polyimide resin (A) of the present invention includes an aminophenol compound (a) containing the aminophenol compound represented by the formula (1) and the aminophenol compound that can be used in combination, and the preferred tetrabasic acid diacid.
  • an anhydride (b) the aminophenol compound (a) containing the aminophenol compound shown by Formula (1) and the aminophenol compound which can be used together, said preferable tetrabasic acid dianhydride What is obtained by the combination of a product (b) and the said preferable diamino compound (c) is more preferable,
  • the aminophenol compound (a) which consists only of an aminophenol compound shown by Formula (1), and the said preferable tetrabasic acid dianhydride What is obtained by the combination of (b) is still more preferable, Formula (1)
  • Aminophenol compound consisting of aminophenol compound represented (a), the preferred tetracarboxylic acid dianhydride (b) and those obtained by the combination of the preferred diamino compound (c) is particularly preferred.
  • the preferred phenolic hydroxyl group-containing polyimide resin (A) of the present invention includes an aminophenol compound represented by the formula (1) as the aminophenol compound (a) and the aminophenol compound that can be used in combination.
  • an aminophenol compound represented by the formula (1) and an aminophenol compound that can be used in combination as the aminophenol compound (a) are used.
  • anhydride (b) 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 3,3 ′, 4 , 4'-biphenyltetracarboxylic dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 3,3', 4,4'-diphenyl ether tetracarboxylic dianhydride Or 1,2,4,5-cyclohexanetetracarboxylic dianhydride, preferably 1,2,4,5-cyclohexanetetracarboxylic dianhydride or 3,3 ′, 4 '-Diphen
  • phenolic hydroxyl group-containing polyimide resin (A) of the present invention only the aminophenol compound represented by the formula (1) is used as the aminophenol compound (a), and as the tetrabasic acid dianhydride (b), 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic Acid dianhydride, hydrogenated 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride, or 1,2,4 , 5-cyclohexanetetracarboxylic dianhydride, preferably 1,2,4,5-cyclohexanetetracarboxylic dianhydride or 3,3 ′, 4,4′
  • the aminophenol compound represented by the formula (1) is used as the aminophenol compound (a), and as the tetrabasic acid dianhydride (b), 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic Acid dianhydride, hydrogenated 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride, or 1,2,4 , 5-cyclohexanetetracarboxylic dianhydride, preferably 1,2,4,5-cyclohexanetetracarboxylic dianhydride or 3,3 ′, 4,4′-
  • the phenolic hydroxyl group-containing polyimide resin (A) of the present invention comprises an aminophenol compound (a), a tetrabasic acid dianhydride (b) and a basic catalyst or a catalyst produced by an equilibrium reaction between a lactone and a base. If necessary, it can be obtained by polycondensation reaction of the diamino compound (c). At this time, using toluene, xylene or the like as a dehydrating agent is more effective because the reaction proceeds.
  • the aromatic polyimide copolymer can be easily produced.
  • the ratio of the tetrabasic dianhydride (b) and the diamine component (aminophenol compound (a) and diamine compound (c) as an optional component) is preferably in the above-described range.
  • the phenolic hydroxyl group-containing polyimide resin of the present invention any of those synthesized as described above can be used, but preferably both of the diamine components obtained in a small excess (excess of about 0.1 to 5 mol%).
  • a polyimide resin having a terminal amino group is preferred.
  • the use ratio (molar ratio) of both the aminophenol compound (a) and the diamino compound (c) is preferably a diamino compound relative to 1 mol of the aminophenol compound (a).
  • (C) is 0.1 to 10 mol, more preferably 0.1 to 6.0 mol, still more preferably 0.5 to 3.0 mol, and particularly preferably about 1.0 to 2.0 mol. When used in such a proportion, the proportion of each component in the polyimide resin is determined according to the proportion of these compounds used.
  • the lactone used as the catalyst is preferably ⁇ -valerolactone, and the base used as the catalyst is preferably pyridine or N-methylmorpholine.
  • Solvents used in the synthesis of the phenolic hydroxyl group-containing polyimide resin (A) include methyl ethyl ketone, methyl propyl ketone, methyl isopropyl ketone, methyl butyl ketone, methyl isobutyl ketone, methyl n-hexyl ketone, diethyl ketone, diisopropyl ketone, diisobutyl ketone.
  • solvents may be used alone or in combination of two or more.
  • a solvent that dissolves the phenolic hydroxyl group-containing polyimide resin (A) produced by the reaction is preferable, and a ketone solvent such as ⁇ -butyrolactone, more preferably a cyclic ketone having a 4- to 5-membered ring. preferable.
  • a diamine component (aminophenol compound (a) and, if necessary, a diamino compound) in a solvent according to any one of the above, wherein a basic catalyst or a mixed catalyst of a lactone and a base is mixed under an inert atmosphere such as nitrogen.
  • C) tetrabasic acid dianhydride
  • a dehydrating agent for removing water generated by the reaction and then water generated when an imide ring is formed under heating and stirring.
  • a phenolic hydroxyl group-containing polyimide resin (A) solution is obtained by sufficiently performing the reaction while distilling off.
  • the dehydrating agent at this time examples include toluene and xylene.
  • the reaction temperature is usually preferably 120 to 230 ° C.
  • the reaction time is greatly affected by the degree of polymerization of the target polyimide and the reaction temperature. Usually, under conditions set according to the degree of polymerization of the target polyimide (for example, the ratio of use of tetrabasic acid dianhydride (b) and diamine component and reaction temperature, etc.), the viscosity increases as the reaction proceeds.
  • the reaction is preferably continued until equilibrium is reached and the maximum molecular weight is obtained, and is usually about several minutes to 20 hours.
  • a contained polyimide resin (A) can also be obtained.
  • the number average molecular weight of the phenolic hydroxyl group-containing polyimide resin (A) of the present invention obtained as described above is preferably about 5,000 to 50,000, more preferably about 10,000 to 40,000, and the weight average molecular weight is preferably about 30,000 to 300,000. More preferably, it is about 30,000 to 200,000, and the hydroxyl group equivalent of the solid content is 100 to 3000 g / eq.
  • the number average molecular weight and the weight average molecular weight are values converted to polystyrene by gel permeation chromatography (the same applies hereinafter).
  • the polyimide resin composition of the present invention includes a thermosetting polyimide resin composition containing the phenolic hydroxyl group-containing polyimide resin (A) and epoxy resin (B) of the present invention as essential components, and the phenolic hydroxyl group-containing polyimide of the present invention.
  • a positive photosensitive polyimide resin composition having a resin (A) and a diazo positive photosensitive agent (C) as essential components and an epoxy resin (B) as optional components.
  • polyimide resin composition these are collectively referred to as “polyimide resin composition”.
  • the epoxy resin (B) which is an essential component of the thermosetting polyimide resin composition, is not particularly limited as long as it has an average of two or more epoxy groups in one molecule, but it has aspects such as mechanical strength and flame retardancy.
  • epoxy resins having an aromatic ring such as a benzene ring, a biphenyl ring and a naphthalene ring.
  • epoxy resin (B) examples include novolak type epoxy resins, xylylene skeleton-containing epoxy resins, biphenyl skeleton-containing epoxy resins, naphthalene skeleton-containing epoxy resins, tricyclodecane skeleton-containing epoxy resins, bisphenol A type epoxy resins, bisphenol F.
  • the addition amount of the epoxy resin (B) is such that the epoxy group in the epoxy resin (B) is 0 with respect to the total of the phenolic hydroxyl group and the terminal acid anhydride group or terminal amino group of the phenolic hydroxyl group-containing polyimide resin (A).
  • the amount of the phenolic hydroxyl group and the acid anhydride group or amino group in the phenolic hydroxyl group-containing polyimide resin (A) is the aminophenol compound (a) used when synthesizing the phenolic hydroxyl group-containing polyimide resin (A). It can be calculated from the number of moles of tetrabasic acid dianhydride (b) and diamino compound (c), the number of acid anhydride structures in one molecule, the number of amino groups and the number of phenolic hydroxyl groups.
  • the epoxy resin (B) is added for the purpose of reacting with the phenolic hydroxyl group and the terminal acid anhydride group or terminal amino group in the phenolic hydroxyl group-containing polyimide resin (A).
  • the crosslink density of the polyimide resin of the present invention is increased, and resistance to polar solvents is improved. , Adhesion to the substrate and heat resistance are improved.
  • the reaction temperature at that time is preferably 150 to 250 ° C.
  • thermosetting catalyst can be added to the thermosetting polyimide resin composition of the present invention for the purpose of promoting the thermosetting reaction between the phenol hydroxyl group-containing polyimide resin (A) and the epoxy resin (B).
  • thermosetting catalysts 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole Imidazoles such as 2-amine, 2- (dimethylaminomethyl) phenol, tertiary amines such as 1,8-diaza-bicyclo (5,4,0) undecene-7, phosphines such as triphenylphosphine and octyl Examples thereof include metal compounds such as tin oxide, and preferred are imidazoles.
  • thermosetting catalyst is 0 to 10% by weight, preferably 0.1 to 10% by weight, more preferably 0.2 to 5% by weight, still more preferably, with respect to the addition amount of the epoxy resin (B). Is 0.2 to 3% by weight.
  • the diazo positive photosensitive agent (C) which is an essential component of the positive photosensitive polyimide resin composition, has a diazido group such as an ester of a diazoquinonesulfonic acid compound (quinonediazidesulfonic acid compound).
  • the photosensitizer is not particularly limited as long as it is a photosensitizer that can generate acid with light and can be used for positive development.
  • an ester of a sulfonic acid-substituted diazide quinone compound and a hydroxy compound preferably an ester of a diazoquinone sulfonic acid compound and a hydroxy compound (preferably a phenol compound) can be mentioned.
  • ester examples include diazobenzoquinonesulfonyl ester and diazonaphthoquinonesulfonyl ester, and diazonaphthoquinonesulfonyl ester is more preferable.
  • ester of diazoquinone sulfonic acid examples include 1,2-benzoquinone diazide-4-sulfonic acid ester, 1,2-naphthoquinone-2-diazide-5-sulfonic acid ester, 1,2-naphthoquinone-2-diazide-4- Examples thereof include sulfonic acid esters, 1,2-naphthoquinone-2-diazide-5-sulfonic acid ester-orthocresol ester, and 1,2-naphthoquinone-2-diazide-5-sulfonic acid ester-paracresol ester.
  • the esterification component (hydroxy compound) for the ester is preferably a phenol compound, such as 2,4-dihydroxybenzophenone, 2,3,4-trihydroxybenzophenone, 2,3,4,4′-tetrahydroxy.
  • the addition amount of the diazo positive photosensitive agent (C) is usually 5 to 30% by weight, preferably 10 to 20% by weight, based on the phenolic hydroxyl group-containing polyimide resin (A).
  • the positive photosensitive polyimide resin composition of the present invention may contain an epoxy resin (B) in order to improve the alkali resistance and solvent resistance after patterning. Thereafter, a curing treatment (post-curing) by heating can also be performed.
  • the epoxy resin that can be used include epoxy resins that can be used in the thermosetting polyimide resin composition, including preferred ones, and the amount used is the same as that in the thermosetting polyimide resin composition. At that time, the same kind and amount of thermosetting catalyst as can be used for the thermosetting polyimide resin composition may be used in combination.
  • the polyimide resin composition of the present invention includes talc, barium sulfate, calcium carbonate, magnesium carbonate, barium titanate, a filler such as aluminum hydroxide, aluminum oxide, silica, clay, a thixotropic agent such as aerosil, a phthalocyanine.
  • Coloring agents such as blue, phthalocyanine green and titanium oxide, silicone, fluorine leveling agents and antifoaming agents can be added. These are used in an amount of 0 to 50% by weight in the polyimide resin composition (solid content) of the present invention.
  • the polyimide resin composition of the present invention can also be used as a dry film resist having a structure in which a resin composition is sandwiched between a support film and a protective film.
  • the liquid or film-like polyimide resin composition of the present invention is useful as a resist material such as an insulating material between electronic components, an optical waveguide connecting optical components, a solder resist for printed circuit boards, a coverlay, etc. It can also be used as a semiconductor passivation film, buffer coat film, color filter, printing ink, alignment film, sealant, paint, coating agent, adhesive and the like.
  • the cured product of the polyimide resin composition of the present invention is used for electrical and electronic parts such as resist films and interlayer insulation materials for buildup methods. Specific examples of these applications include computers, home appliances, and portable devices.
  • the thickness of the cured product layer is about 1 to 160 ⁇ m, preferably about 5 to 100 ⁇ m.
  • cured material layer of the polyimide resin composition of this invention can be obtained as follows, for example. That is, when using a liquid resin composition, the film thickness after drying is 1 to 160 ⁇ m on the substrate by methods such as screen printing, spraying, roll coating, electrostatic coating, curtain coating, applicator, bar coater, etc.
  • a coating film can be formed by applying the composition of the present invention and drying the coating film at a temperature of usually 50 to 150 ° C., preferably 70 to 130 ° C. Thereafter, in the case of a thermosetting polyimide resin composition, heat treatment is performed at 140 to 250 ° C., preferably 150 to 220 ° C.
  • a positive photosensitive polyimide resin composition it is applied to the coating film through a photomask on which an exposure pattern is formed.
  • the active energy ray is usually irradiated at an intensity of 10 to 2,000 mJ / cm 2 , and development is performed by using, for example, spraying, rocking immersion, brushing, scrubbing, etc.
  • Heat treatment is usually performed at a temperature of 100 to 250 ° C., preferably 140 to 220 ° C., so that it has excellent flame retardancy and satisfies various properties such as heat resistance, solvent resistance, acid resistance, adhesion, and flexibility.
  • a substrate having a cured film of the polyimide resin composition is obtained.
  • Examples of the active energy rays include ultraviolet rays, visible rays, infrared rays, electron beams, radiations, etc. In consideration of the intended use, ultraviolet rays or electron beams are most preferable.
  • alkaline aqueous solution used for development examples include potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium phosphate, potassium phosphate, and other inorganic alkaline solutions and tetramethylammonium.
  • Organic alkaline aqueous solutions such as hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, monoethanolamine, diethanolamine, and triethanolamine can be used.
  • Example 1 A 500 mL flask equipped with a stirrer, a reflux tube, a moisture trap and a thermometer was purged with nitrogen gas, and then 106.80 g of ⁇ -butyrolactone as a solvent, 0.72 g of ⁇ -valerolactone as a catalyst, and pyridine 1 .13 g, 23.62 g of AHPB (1,3-bis (4-amino-3-hydroxyphenoxy) benzene, manufactured by Nippon Pure Chemicals Co., Ltd., molecular weight 324.33) as the aminophenol compound (a), dibasic acid dibasic acid 22.15 g of ODPA (3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride, manufactured by Manac Co., Ltd., molecular weight 310.22) as anhydride (b) was charged with 23.90 g of toluene as a dehydrating agent, Stirring while removing water produced by the reaction at
  • the obtained polyimide resin had a hydroxyl group equivalent (solid content) of 290.9 g / eq.
  • the number average molecular weight in terms of styrene was 35,500, and the weight average molecular weight was 161,500.
  • Example 2 A 500 mL flask equipped with a stirrer, reflux tube, moisture trap and thermometer was purged with nitrogen gas, and then 127.66 g of ⁇ -butyrolactone as a solvent, 1.71 g of pyridine as a catalyst, and AHPB ( 16.684 g of 1,3-bis (4-amino-3-hydroxyphenoxy) benzene, manufactured by Nippon Pure Chemicals Co., Ltd., molecular weight 324.33), ODPA (3,3 ′) as tetrabasic acid dianhydride (b) , 4,4′-diphenyl ether tetracarboxylic dianhydride, manufactured by Manac Co., Ltd., 33.57 g of molecular weight 310.22), APB-N (1,3-bis (3-aminophenoxy) benzene as diamino compound (c) , Made by Mitsui Chemicals, Inc., molecular weight 292.33) 18.49g, tol
  • polyimide resin had a hydroxyl equivalent (solid content) of 630.3 g / eq.
  • the number average molecular weight in terms of styrene was 14,800, and the weight average molecular weight was 57,400.
  • Example 3 A 500 mL flask equipped with a stirrer, a reflux tube, a moisture trap and a thermometer was purged with nitrogen gas. Then, 133.31 g of N-methylpyrrolidone as a solvent, 1.42 g of pyridine as a catalyst, an aminophenol compound ( a) as AHPB (1,3-bis (4-amino-3-hydroxyphenoxy) benzene, manufactured by Nippon Pure Chemicals Co., Ltd., molecular weight 324.33), PMDA as tetrabasic acid dianhydride (b) 31.70 g of HS (1,2,4,5-cyclohexanetetracarboxylic dianhydride, manufactured by Iwatani Gas Co., Ltd., molecular weight 224.17), TMDA (1- (4-aminophenyl) as the diamino compound (c) ) -1,3,3-trimethyl-1H-indene-5-amine, manufactured by Nippon Pure Chemicals Co.
  • the obtained polyimide resin had a hydroxyl equivalent (solid content) of 1500 g / eq.
  • the number average molecular weight in terms of styrene was 26,500, and the weight average molecular weight was 107,400.
  • the resin solution was obtained (the solution to R-1) containing 33.6% by weight polyimide resin having a phenolic hydroxyl group.
  • the obtained polyimide resin had a hydroxyl equivalent (solid content) of 630.3 g / eq.
  • the number average molecular weight in terms of styrene was 10,100, and the weight average molecular weight was 40,300.
  • Comparative Examples 2-3 Table 1 shows the resin solution (R-1) obtained in Comparative Example 1 as a comparative polyimide resin, DTEP-350 as a diazo positive photosensitive agent, NC-3000 as an epoxy resin, and 2PHZ as a curing accelerator.
  • a comparative thermosetting polyimide resin composition Comparative Example 2
  • a comparative positive photosensitive polyimide resin composition Comparative Example 3
  • thermosetting polyimide resin composition Glass transition temperature, flexibility and flame retardancy of cured product of thermosetting polyimide resin composition
  • the film thickness upon drying of the thermosetting polyimide resin composition (Example 5, Comparative Example 2) It apply
  • the glass transition temperature, flexibility, and flame retardancy of the obtained cured resin film were evaluated by the methods described below, and the results are shown in Table 2.
  • test method and evaluation method for the above (I) are as follows.
  • TMA7 Three Mechanical Analyzer
  • Test methods and evaluation methods for the above (II) to (IV) are as follows.
  • ⁇ Absorbent cotton does not stick.
  • ⁇ ⁇ Absorbent cotton lint sticks to the membrane.
  • (V) Solvent resistance The cured resin film on the printed board was immersed in N-methylpyrrolidone for 30 minutes at room temperature. After taking out and confirming that there was no abnormality in the appearance, a peeling test with a cellophane tape was performed, and the solvent resistance was evaluated according to the following criteria. ⁇ ⁇ No abnormality on the surface, no swelling or peeling. ⁇ : The surface is rough, but there is no swelling or peeling. X ⁇ There are swelling and peeling.
  • PCT resistance The cured resin film on the printed board was immersed in 121 ° C., 2 atm hot water for 96 hours. After taking out and confirming that there was no abnormality in the appearance, a peeling test using a cellophane tape was performed, and the PCT resistance was evaluated according to the following criteria. (PCT: Pressure Cooker Test) ⁇ ⁇ No abnormality on the surface, no swelling or peeling. X ⁇ There are swelling and peeling.
  • the phenolic hydroxyl group-containing polyimide resin of the present invention is easy to synthesize, and the thermosetting polyimide resin composition and the positive photosensitive polyimide resin composition using the same are heat resistant and It is clear that it is excellent in flexibility, easy to pattern, and has adhesion to the substrate and flame retardancy.
  • the phenolic hydroxyl group-containing polyimide resin of the present invention has high solvent solubility, and when the polyimide resin is combined with an epoxy resin to form a thermosetting composition, the cured product has excellent heat resistance and flame retardancy, and Sufficient flexibility.
  • the photosensitive resin composition in which the polyimide resin is combined with a photosensitive agent is excellent in developability and resolution, and the cured product has adhesion, solvent resistance, acid resistance, heat resistance, PCT resistance, Excellent impact resistance, excellent flame resistance without halogen, phosphorus, antimony and other flame retardants, low warpage when coated and cured on a film-like substrate, and sufficient flexibility
  • the polyimide resin composition of the present invention containing the polyimide resin of the present invention and the cured product thereof are a solder mask for thin package substrates, a coverlay for flexible printed wiring boards, an interlayer insulating film for multilayer printed wiring boards, a semiconductor passivation film, etc. Useful for a wide range of applications.

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Abstract

L'invention concerne une composition de résine qui fournit diverses caractéristiques, telles qu'un caractère ignifuge, une résistance à la chaleur, des caractéristiques mécaniques et une flexibilité, et son produit durci. La composition de résine est une résine de polyamide contenant un groupe hydroxyle phénolique, obtenue par une réaction de polycondensation d'un composé d'aminophénol (a), d'un dianhydride d'acide tétrabasique (b) et d'un composé de diamine (c) en tant qu'ingrédient arbitraire. Le composé d'aminophénol (a) contient, en tant qu'ingrédient essentiel, une résine de polyamide contenant un groupe hydroxyle phénolique (A), qui contient un composé d'aminophénol représenté par la formule (1).
PCT/JP2009/067867 2008-10-20 2009-10-15 Résine de polyamide et sa composition Ceased WO2010047271A1 (fr)

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WO2014045434A1 (fr) * 2012-09-24 2014-03-27 東レ株式会社 Composition de résine photosensible positive
WO2015170432A1 (fr) * 2014-05-09 2015-11-12 日立化成株式会社 Composition d'agent adhésif photosensible de type positif, motif d'agent adhésif, tranche de semi-conducteur avec couche d'agent adhésif, dispositif à semi-conducteur et son procédé de production
KR20220072786A (ko) 2020-11-25 2022-06-02 아지노모토 가부시키가이샤 포지티브형 감광성 수지 조성물
JP2023001636A (ja) * 2021-06-21 2023-01-06 株式会社ピーアイ技術研究所 感光性ポリイミド樹脂組成物
US12247104B2 (en) 2019-03-15 2025-03-11 Nippon Kayaku Kabushiki Kaisha Polyamic acid resin, polyimide resin, and resin composition including these
WO2025148605A1 (fr) * 2024-01-10 2025-07-17 上海八亿时空先进材料有限公司 Résine soluble dans les alcalis et son utilisation
KR20250134035A (ko) 2024-03-01 2025-09-09 아지노모토 가부시키가이샤 감광성 수지 조성물

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CN118027405B (zh) * 2023-03-07 2025-02-11 江汉大学 一种光引发产酸固化型聚酰亚胺及其制备方法和光引发产酸固化型光刻胶

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WO2012002134A1 (fr) * 2010-07-02 2012-01-05 東レ株式会社 Composition de résine photosensible, pellicule de composition de résine photosensible, et dispositif semi-conducteur utilisant la composition de résine photosensible ou la pellicule de composition de résine photosensible
JP2012208360A (ja) * 2011-03-30 2012-10-25 Toray Ind Inc ポジ型感光性樹脂組成物
JPWO2014045434A1 (ja) * 2012-09-24 2016-08-18 東レ株式会社 ポジ型感光性樹脂組成物
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WO2015170432A1 (fr) * 2014-05-09 2015-11-12 日立化成株式会社 Composition d'agent adhésif photosensible de type positif, motif d'agent adhésif, tranche de semi-conducteur avec couche d'agent adhésif, dispositif à semi-conducteur et son procédé de production
US12247104B2 (en) 2019-03-15 2025-03-11 Nippon Kayaku Kabushiki Kaisha Polyamic acid resin, polyimide resin, and resin composition including these
KR20220072786A (ko) 2020-11-25 2022-06-02 아지노모토 가부시키가이샤 포지티브형 감광성 수지 조성물
JP2023001636A (ja) * 2021-06-21 2023-01-06 株式会社ピーアイ技術研究所 感光性ポリイミド樹脂組成物
JP7633666B2 (ja) 2021-06-21 2025-02-20 株式会社ピーアイ技術研究所 感光性ポリイミド樹脂組成物
WO2025148605A1 (fr) * 2024-01-10 2025-07-17 上海八亿时空先进材料有限公司 Résine soluble dans les alcalis et son utilisation
KR20250134035A (ko) 2024-03-01 2025-09-09 아지노모토 가부시키가이샤 감광성 수지 조성물

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CN102186904A (zh) 2011-09-14

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