WO2007032326A1 - Composition de résine photosensible et objet durci obtenu à partir de cette composition - Google Patents

Composition de résine photosensible et objet durci obtenu à partir de cette composition Download PDF

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Publication number
WO2007032326A1
WO2007032326A1 PCT/JP2006/318017 JP2006318017W WO2007032326A1 WO 2007032326 A1 WO2007032326 A1 WO 2007032326A1 JP 2006318017 W JP2006318017 W JP 2006318017W WO 2007032326 A1 WO2007032326 A1 WO 2007032326A1
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Prior art keywords
compound
reaction
resin composition
epoxy
photosensitive
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PCT/JP2006/318017
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English (en)
Japanese (ja)
Inventor
Ryutaro Tanaka
Toru Kurihashi
Yasumasa Akatsuka
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Nippon Kayaku Kabushiki Kaisha
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Priority to JP2007535470A priority Critical patent/JPWO2007032326A1/ja
Publication of WO2007032326A1 publication Critical patent/WO2007032326A1/fr

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    • 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
    • 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
    • C08G59/20—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 epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • C08G59/24—Di-epoxy compounds carbocyclic
    • C08G59/245—Di-epoxy compounds carbocyclic aromatic
    • 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
    • C08G59/20—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 epoxy compounds used
    • C08G59/32—Epoxy compounds containing three or more epoxy groups
    • C08G59/38—Epoxy compounds containing three or more epoxy groups together with di-epoxy compounds
    • 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
    • C08L63/10—Epoxy resins modified by unsaturated compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • 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
    • 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

Definitions

  • the present invention uses a 4,4'-integrated bisphenol F-type epoxy resin having good molecular symmetry as a curing agent, a photosensitive alkaline aqueous solution-soluble resin, a reactive crosslinking agent, and a photopolymerization initiator.
  • This invention relates to a photosensitive resin composition containing selenium and its cured product. More specifically, it is useful as a solder resist for printed wiring boards, an interlayer insulation material for multilayer printed wiring boards, a solder resist for flexible printed wiring boards, a dry film resist, a Maki resist, a photosensitive optical waveguide, and the like.
  • the present invention relates to a liquid or dry film type resin composition that gives a cured product having excellent properties, heat stability, electrical insulation, adhesion, chemical resistance, and resistance to scratching, and the cured product.
  • a photosensitive resin composition using a photosensitive epoxy carboxylate compound is excellent in balance of various characteristics such as environmentally friendly thermal and mechanical properties and adhesion to a substrate. ing. For this reason, it is used in the fields of coatings and coatings, and recently, it has been used in a wide range of industrial fields such as electrical and electronic parts manufacturing and printed wiring board manufacturing. The range is expanding. On the other hand, with the expansion of this field of use, photosensitive resin compositions using photosensitive epoxy carboxylate compounds are required to have higher performance in terms of characteristics such as heat resistance and adhesion. Speak.
  • Patent Document 1 describes a solder mask composition containing a photosensitive resin in which an acid anhydrous is added to a reaction product of a novolac-type epoxy resin and an unsaturated monobasic acid. The cured product of the composition was not sufficient in heat resistance, adhesion, and scratch resistance.
  • Patent Document 2 describes a photopolymerizable resin composition containing urethane-modified bull ester resin, and the cured product of this composition has flexibility, heat resistance, adhesion, Not enough performance.
  • Patent Document 3 describes a resin composition in which a hardly soluble fine particulate epoxy resin is used as a curing agent and a part thereof can be replaced with a soluble resin such as a bisphenol F type epoxy resin. ing. Patent Document 4 exemplifies bisphenol F type epoxy resin as a soluble epoxy resin.
  • Patent Document 1 Japanese Patent Application Laid-Open No. 61-243869
  • Patent Document 2 JP-A-9-52925
  • Patent Document 3 Japanese Patent Publication No. 7-17737
  • Patent Document 4 Japanese Unexamined Patent Publication No. 2000-109541
  • Patent Document 5 JP-A-8-73563
  • Patent Document 6 WO2006Z00 4
  • An object of the present invention is to provide an active energy line for printing fine images in response to high performance requirements for solder masks that can be used for the above-described high-performance printed wiring boards and the like. It has excellent photosensitivity to patterns, and pattern formation by development with alkaline aqueous solution is easy.
  • a resin composition that is easy and excellent in flexibility, adhesion, solder heat resistance, electroless gold plating resistance, etc. of cured products obtained by heat curing in a post-curing (post-cure) process. It is to provide a cured product.
  • the curing agent (D) is represented by the formula (1) [0014]
  • n the number of repetitions.
  • a photosensitive resin composition that is a bisphenol F-type epoxy resin that is integrated with 4, 4 ′ represented by: [0015] 2) n of the curing agent (D) is a positive number from 1 to 7, and its melting point Above is a crystal of 80-150 ° C 1
  • a photosensitive alkaline aqueous solution-soluble resin (A) comprising an epoxy compound ( a ) having two or more epoxy groups in the molecule and a monocarboxylic acid having an ethylenically unsaturated group in the molecule
  • Composition
  • Photosensitive alkaline aqueous solution soluble resin (A) is an epoxy compound (d) having two epoxy groups in the molecule and a monocarboxylic acid compound having an ethylenically unsaturated group in the molecule.
  • Epoxy carboxylate compound obtained by reaction of compound (b), diisocyanate compound (e), carboxylic acid compound (f) having two hydroxyl groups in the molecule, and optional components 1) or 2 above, which is a reaction product of a dioli compound (g) having no carboxyl group or a reaction product of the reaction product with an optional polybasic acid anhydride (c).
  • the photosensitive resin composition of the present invention containing F type epoxy resin as a curing agent (D) is excellent in tackiness and photosensitivity, can be patterned by development with an alkaline aqueous solution, and is cured by active energy rays.
  • the cured product obtained by thermal curing as a post-curing process is flexible, solvent-resistant, acid-resistant, thermal stability, flexibility, adhesion, solder heat resistance, electroless gold plating resistance, etc.
  • it is suitable for a photosensitive resin composition for printed wiring boards and a photosensitive resin composition for dry films.
  • the photosensitive resin composition of the present invention comprises a photosensitive alkaline aqueous solution-soluble resin (A), a reactive crosslinking agent (B), a photopolymerization initiator (C), and the above formula (1) [wherein n represents the number of repetitions.
  • the hardener (D) which is a 4,4′-form bisphenol F type epoxy resin represented by the formula:
  • the photosensitive aqueous alkali-soluble soluble resin has an active group that is cured by active energy rays or the like and is developable with an aqueous alkaline solution.
  • the photosensitive alkaline aqueous solution-soluble resin (A) contained in the photosensitive resin composition includes, for example, an epoxy compound (a) having two or more epoxy groups in the molecule and the molecule Examples thereof include a reaction product of an epoxy strength lpoxylate compound obtained by the reaction of a monocarboxylic acid compound (b) having an ethylenically unsaturated group and a polybasic acid anhydride (c).
  • the epoxy compound (a) shown in the present invention is not particularly limited as long as it has two or more epoxy groups in one molecule.
  • a plurality of ethylenically unsaturated groups can be introduced into one molecule when reacted with the monocarboxylic acid compound (b).
  • the epoxy equivalent is 900
  • the number of epoxy groups in one molecule is preferably 2 or more and 50 or less.
  • the number is 3 to 20. If it is this range, the curability fall by the reduction
  • Examples of the epoxy compound (a) include phenol novolac type epoxy resin, taresole novolac type epoxy resin, trishydroxyphenylmethane type epoxy resin, dicyclopentadiene phenol type epoxy resin.
  • Bisphenol type epoxy resin bisphenol-A type epoxy resin, bisphenol-F type epoxy resin, etc.
  • biphenol type epoxy resin bisphenol-A novolac type epoxy resin, naphthalene skeleton-containing epoxy resin, alicyclic And epoxy epoxy resin and heterocyclic epoxy resin.
  • phenol novolac type epoxy resins examples include Epiclon N-770 (Dainippon Ink Chemical Co., Ltd.), DE N438 (Dow Chemical Co., Ltd.), Epicoat 154 (Oilized Shell Epoxy), EPPN-201 , RE-306 (all manufactured by Nihon Shakuyaku) and the like.
  • cresol novolac type epoxy resin examples include Epiclone N-695 (Dainippon Ink Chemical Co., Ltd.), EOCN-102S, EOCN-103S, EOCN-104S (all manufactured by Nippon Kayaku), UVR- 6650 (made by Union Carbide), ESCN-195 (made by Sumitomo Chemical), etc. are mentioned.
  • Trishydroxyphenol methane type epoxy resin includes, for example, EPPN-503, EP PN-502H, EPPN-501H (all manufactured by Nippon Kayaku), TACTIX-742 (manufactured by Dow Chemical Company), Epicoat E1032H60 (Oilized Shell Epoxy) and the like.
  • Examples of the dicyclopentadiene phenol type epoxy resin include epiclone EXA.
  • Examples of the bisphenol type epoxy resin include Epicoat 828, Epicoat 1001 (Oilized Shell Epoxy), UVR-6410 (Union Carbide), DE R-331 (Dow Chemical), RE — 31 OS (manufactured by Nippon Kayaku Co., Ltd.), YD— 8125 (manufactured by Toto Kasei), etc.
  • polyfunctional bisphenol A type epoxy resin such as NER—1202, NER—1322, NER—1504 (manufactured by Nippon Kayaku Co., Ltd.), NE R— 7403
  • polyfunctional bisphenol F type epoxy resin such as NER-7604 (manufactured by Nippon Kayaku).
  • biphenol type epoxy resin examples include biphenol type epoxy resin such as NC-3000 and NC-3000H (both manufactured by Nippon Kayaku Co., Ltd.), YX-4000 (manufactured by Yuka Shell Epoxy), etc. And bixylenol type epoxy resin, YL-6121 (made by oil-based shell epoxy), and the like.
  • Examples of the bisphenol A A novolak type epoxy resin include Epiclon N-880 (Dainippon Ink Chemical Co., Ltd.), Epicoat E157S75 (Oilized Shell Epoxy), and the like.
  • Examples of the naphthalene skeleton-containing epoxy resin include NC-7000 (manufactured by Nippon Kayaku), E
  • Examples of the alicyclic epoxy resin include EHPE-3150 (manufactured by Daicel Chemical Industries).
  • heterocyclic epoxy resin examples include TEPIC (manufactured by Nissan Chemical Industries).
  • epoxy compound (a) phenol novolac type epoxy resin, talesol novolac type epoxy resin, polyfunctional bisphenol type epoxy resin, and biphenol type epoxy resin are preferably used. These can provide a photosensitive resin composition having excellent properties such as heat resistance, mechanical strength, and chemical resistance, especially when a permanent resist material such as a solder resist is taken into consideration.
  • Examples of the monocarboxylic acid compound (b) having an ethylenically unsaturated group in the molecule include acrylic acids, crotonic acid, OC cyanocinnamic acid, cinnamic acid, and saturated or unsaturated dibasic acid. Examples include a reaction product of an acid and an unsaturated group-containing monoglycidyl compound.
  • Acrylic acids include, for example, (meth) acrylic acid, j8-styrylacrylic acid, j8-furfurylacrylic acid, (meth) acrylic acid and ratatones (eg, ⁇ -force prolatatone) , Half-esters, saturated or unsaturated dibasic acid and monoglycidyl, which are equimolar reactants of a saturated or unsaturated dibasic acid anhydride and a (meth) atalylate derivative having one hydroxyl group per molecule (Meth) acrylic acid in terms of sensitivity when it is used as a photosensitive resin composition.
  • ratatones eg, ⁇ -force prolatatone
  • a reaction product of (meth) acrylic acid and ⁇ -force prolatatone or cinnamic acid is particularly preferred.
  • the polybasic acid anhydride (c) is a compound having one or more acid anhydride structures in the molecule, such as succinic anhydride, phthalic anhydride, pyromellitic anhydride, maleic anhydride.
  • the photosensitive aqueous alkali-soluble resin (A) contained in the photosensitive resin composition of the present invention is an epoxy compound (a) having two or more epoxy groups in the molecule as described above. ) And a monocarboxylic acid compound (b) having an ethylenically unsaturated group in the molecule (hereinafter referred to as the first reaction), an epoxycarboxylate compound having an alcoholic hydroxyl group. And a polybasic acid anhydride (c) (hereinafter referred to as a second reaction).
  • the first reaction is solvent-free! / Is a solvent having no alcoholic hydroxyl group, for example, ketones such as acetone, ethylmethyl ketone, cyclohexanone, benzene, toluene, xylene , Aromatic hydrocarbons such as tetramethylbenzene, ethylene glycol dimethyl ether, ethylene glycol jetyl ether, dipropylene glycolinoresimethinoate , Glycol ethers such as dipropylene glycol jetyl ether, triethylene glycol glycol diethyl ether, triethylene glycol jetyl ether, ethyl acetate, butyl acetate, methyl solvate sorb acetate, cetyl solvate acetate, butyl celsonol levacetate , Carbitol acetate, propylene glycol monomono methinoate acetate, dialkyl glutarate (eg, dimethyl glutarate), dialky
  • the charge ratio of the raw material in the first reaction is as follows: the monocarboxylic acid compound (b) having an ethylenically unsaturated group in the molecule with respect to 1 equivalent of the epoxy group of the epoxy compound (a).
  • a range in which the carboxyl group is from 0.8 to 1.2 equivalents is preferred. Within this range, the epoxy group remaining as unreacted or the monocarboxylic acid (b) remaining as an excess is also small, so that the storage stability of the resin (A) over time, thermal stability, Improves stability during manufacturing.
  • the first reaction it is preferable to use a catalyst to promote the reaction.
  • the amount used is about 0.1 to 10% by weight with respect to the reaction product. .
  • Examples of the catalyst include triethylamine, benzyldimethylamine, sodium salt triethylamine, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, and triphenyl.
  • Examples include ruphosphine, triphenylstibine, chromium octoate, and zirconium octoate.
  • the reaction temperature is 60 to 150 ° C, and the reaction time is preferably 5 to 60 hours.
  • a thermal polymerization inhibitor that may be used in the first reaction is preferably hydroquinone monomethyl ether, 2-methylhydroquinone, hydroquinone, diphenylpicrylhydrazine. , Diphenylamine, 2, 6 di-tert-butyl p-talesol and the like.
  • the first reaction has an end point when the acid value of the sample is 1 mg'KOHZg or less, preferably 0.5 mg'KOHZg or less, with appropriate sampling.
  • the solid content acid value is the amount (mg) of potassium hydroxide and potassium salt necessary to neutralize the acidity of the carboxylic acid in the resin lg. This is the amount (mg) of potassium hydroxide required to neutralize the solution lg containing fat, and is measured by the usual neutralization titration method according to JIS K0070. If the concentration of the resin in the solution is known, the solid content acid value can be calculated from the acid value of the solution.
  • the second reaction is an esterification reaction in which the polybasic acid anhydride (c) is added to the reaction solution and reacted after completion of the first reaction. Even if the second reaction is performed after the product of the first reaction is separated, the second reaction may be continued without separating the product of the first reaction.
  • a solvent used for the second reaction, a solvent similar to the solvent that can be used for the first reaction can be used.
  • the second reaction can be carried out without a catalyst
  • a basic catalyst is used to accelerate the reaction.
  • pyridine triethylamine, benzyldimethylamine, triethylamine hydroxide, dimethylaminopyridine, etc.
  • the amount used is relative to the reactants. Up to 10% by weight.
  • the reaction temperature is 40 to 120 ° C, and the reaction time is preferably 5 to 60 hours.
  • the acid value of the reaction product is within the range of plus or minus 10% of the acid value set according to the intended use while appropriately sampling.
  • the point is the end point.
  • the photosensitive aqueous alkali-soluble resin (A) contained in the photosensitive resin composition of the present invention includes an epoxy compound (d) having two epoxy groups in the molecule and a molecule.
  • a reaction product of a carboxylic acid compound (f) having one hydroxyl group, a diol compound (g) having no carboxyl group as an optional component, and a polybasic acid anhydride (c) as an optional component can also be used.
  • the epoxy compound (d) shown in the present invention is a compound having two epoxy groups in one molecule. If it has more than two epoxy groups, react with the monocarboxylic acid compound (b) and then react with the diisocyanate compound (e). Cause gelling to act as a polyol with more than hydroxyl groups.
  • the epoxy compound (d) a compound having an epoxy equivalent of 100 to 900 gZ equivalent is desirable. When the epoxy equivalent is greater than or equal to the loogZ equivalent, it is possible to prevent a decrease in film formability due to a decrease in the molecular weight of the resulting photosensitive alkaline aqueous solution soluble resin (A). In addition, the toughness of the coating is improved.
  • the epoxy equivalent is 900 gZ equivalent or less
  • the introduction ratio of the monocarboxylic acid compound (b) having an ethylenically unsaturated group into the photosensitive alkaline aqueous solution-soluble resin (A) is increased and the photosensitivity is increased. Can be increased.
  • epoxy compound (d) examples include phenolic glycidyl ether compounds such as hydride quinone diglycidyl ether, catechol diglycidyl ether, resorcinol diglycidyl ether, bisphenol-A type epoxy resin, bisphenol-F.
  • phenolic glycidyl ether compounds such as hydride quinone diglycidyl ether, catechol diglycidyl ether, resorcinol diglycidyl ether, bisphenol-A type epoxy resin, bisphenol-F.
  • Type epoxy resin bisphenol I S type epoxy resin, 2, 2 bis (4 hydroxyphenol)-1, 1, 1, 3, 3, 3 bisphenol such as epoxidized hexafluoropropane
  • Type epoxy resin hydrogenated bisphenol A type epoxy resin, hydrogenated bisphenol one loop F type epoxy resin, hydrogenated bisphenol- S type epoxy resin, hydrogenated 2, 2-bis (4 hydroxyphenol) 1, 1, 1, 3, 3, 3 Hydrogenated bisphenol type epoxy compounds such as epoxides of hexaphanoleopropane and brominated bisphenol Enol-A type epoxy resin, brominated bisphenol- Halogenated bisphenol type epoxy compound such as F type epoxy resin, cycloaliphatic diglycidyl ether compound such as cyclohexanedimethanol diglycidyl ether compound, 1, 6 hexane Aliphatic diglycidyl ether compounds such as diol diglycidyl ether, 1,4 butanediol diglycidyl ether, diethylene glycol diglycidyl ether
  • epoxy compounds are also commercially available, for example, Epicoat 828, Epicote 1001, Epicote 1002, Epicote 1003, Epicote 1004 (all made by Japan Epoxy Resin), Epomic R-140, Epomic R-301, Epomic R-304 (all manufactured by Mitsui Chemicals), DER-331, DER-332, DER-324 (all manufactured by Dow Chemical Co.), Epiclon 840, Epiclon 850 (all manufactured by Dainippon Ink), UVR — 6410 (manufactured by Union Power-Bidede), RE—310S (manufactured by Nippon Kayaku), YD—8125 (manufactured by Tohto Kasei), etc.
  • Epicoat 828 Epicote 1001, Epicote 1002, Epicote 1003, Epicote 1004 (all made by Japan Epoxy Resin), Epomic R-140, Epomic R-301, Epomic R-304 (all manufactured by Mitsui Chemicals), DER-331,
  • Nord—A type epoxy resin UVR—6490 (Union Carbide), YDF—2001, YDF—2004, YDF—8170 (all manufactured by Tohto Kasei), Epiclon 830, Epiclon 835 (all manufactured by Dainippon Ink) ) Bisphenols such as F-type epoxy resin, HBPA-D GE (manufactured by Maruzen Petrochemicals), Rikaresin HBE-100 (manufactured by Shin Nippon Chemical Co., Ltd.), etc.
  • Brominated bisphenols such as DER—514 and DER—542 (both manufactured by Dow Chemical Co.) — A-type epoxy resin, Celoxide 2021 (manufactured by Daicel), Guatemala Resin DME—100 (manufactured by Nippon Shinritsu), EX-216 (manufactured by Nagase Kasei) and other alicyclic epoxy resins, ED-503 (manufactured by Asahi Denki Co., Ltd.), Guatemala Resin W-100 (manufactured by Nippon Steel
  • Aliphatic diglycidyl ether compounds such as EX-212, EX—214, EX—850 (all manufactured by Nagase Kasei), and polysulfide type diglycidyl ether compounds such as FLEP—50, FLEP—60 (all manufactured by Toray Rethiocol),
  • Examples include biphenol type epoxy compounds such as YX-4000 (Japan Epoxy Resin).
  • the mononuclear content is preferably bisphenol A type epoxy resin.
  • the diisocyanate compound (e) used in the production of the photosensitive aqueous alkali-soluble resin (A) contained in the photosensitive resin composition of the present invention includes two compounds in the molecule.
  • the compound is not particularly limited as long as it is a compound having an isocyanate group, and a plurality of diisocyanate compounds may be mixed and used.
  • diisocyanate compound (e) examples include phenol-diisocyanate, tolylene diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, diphenyl.
  • the carboxylic acid compound (f) having two hydroxyl groups in the molecule used in the production of the photosensitive alkaline aqueous solution-soluble resin (A) contained in the photosensitive resin composition of the present invention is not particularly limited as long as it is a compound having a total of two alcoholic hydroxyl groups or phenolic hydroxyl groups in the molecule and a carboxyl group at the same time, and is a carboxylic acid salt having two alcoholic hydroxyl groups excellent in alkaline aqueous solution developability.
  • the compound is particularly preferred, for example, compounds such as dimethyl oral propionic acid and dimethylol butanoic acid.
  • a diol compound (g) having no carboxyl group may be used for the production of the photosensitive alkaline aqueous solution-soluble resin (A) contained in the photosensitive resin composition of the present invention! / ⁇ .
  • the diol compound (g) is an aliphatic or alicyclic compound in which two hydroxyl groups are bonded to two different carbon atoms, and has no carboxyl group. If it is, it will not be specifically limited. These are used as optional components according to the purpose, and are used according to the required properties of the materials used.
  • aliphatic hydrocarbons such as ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, heptanediol, octanediol, nonanediol, decanediol, cyclopentanediol, cyclohexanediol, Cyclohexane dimethanol, tricyclodecane dimethanol, adamantane dimethanol and other alicyclic hydrocarbon-based diols, polyethylene glycol, polypropylene glycol, polybutylene glycol and other polyalkylene glycols, poly force prolataton diol, etc.
  • aliphatic hydrocarbons such as ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, heptanediol, octane
  • Polyester-based diols such as polyhexanediol carbonate, polycyclohexane dimethanol power-polycarbonate diols such as bonates, spiroglycol, dioxane Heterocyclic diols such as alcohol, hydroxyl groups-modified polybutadiene polymers at both ends, hydroxyl groups-modified polybutadiene monoacrylonitrile copolymers at both ends, hydroxyl groups-modified styrene-taratonitrile copolymers, hydroxyl groups-modified polyethylene at both ends, Examples thereof include terminal hydroxyl group-modified copolymers such as terminal hydroxyl group-modified polypropylene.
  • alicyclic hydrocarbon diols polyalkylene glycols, polyester diols and heterocyclic diols are preferred. These are generally industrially available, are relatively inexpensive, and are excellent.
  • a photosensitive resin composition having improved developability and flexibility can be provided.
  • the photosensitive alkaline aqueous solution-soluble resin (A) contained in the photosensitive resin composition of the present invention is, as described above, an epoxy compound (d) having two epoxy groups in the molecule. And an epoxy carboxylate compound having an alcoholic hydroxyl group obtained by the reaction of a monocarboxylic acid compound (b) having an ethylenically unsaturated group in the molecule (hereinafter referred to as the third reaction). And a diisocyanate compound (e) and a carboxylic acid compound (f) having two hydroxyl groups in the molecule, separately prepared by urethane reaction (hereinafter referred to as fourth reaction).
  • the fourth reaction may be carried out by adding a diol compound (g) having no carboxyl group as an optional component.
  • an optional component, polybasic acid anhydride (c), may be added and reacted.
  • the third reaction is a solvent-free or alcoholic hydroxyl group-free solvent such as ketones such as acetone, ethylmethylketone, cyclohexanone, benzene, toluene, xylene, tetramethylbenzene, etc.
  • ketones such as acetone, ethylmethylketone, cyclohexanone, benzene, toluene, xylene, tetramethylbenzene, etc.
  • Aromatic hydrocarbons ethylene glycol dimethyl ether, ethylene glycol jetyl ether, dipropylene glycol dimethyl ether, dipropylene glycol dimethyl ether, triethylene glycol dimethyl ether, triethylene glycol dimethyl ether, and other glycol ethers, ethyl acetate, acetic acid Butyl, methyl solvate acetate, cetyl sorb acetate, butyl cellosolve acetate, carbitol acetate, propylene glycol monomethyl ether acetate, dialkyl glutarate (E.g., dimethyl glutarate), dialkyl succinate (e.g., dimethyl succinate), esters such as dialkyl adipate (e.g., dimethyl adipate), cyclic esters such as ⁇ -butyrolatatone, petroleum ether, Petroleum solvents such as petroleum naphtha, hydrogenated petroleum naphtha, and solvent naphtha, and the reactive cross-linking agent ( ⁇
  • the charge ratio of the raw material in the third reaction is as follows.
  • a range in which the carboxyl group is from 0.8 to 1.2 equivalents is preferred. Within this range, the epoxy group remaining as unreacted or the monocarboxylic acid (b) remaining as an excess is also small, so that the storage stability of the resin (A) over time, thermal stability, Stability during production Etc. are improved.
  • the third reaction it is preferable to use a catalyst to promote the reaction.
  • the amount used is about 0.1 to 10% by weight with respect to the reaction product. .
  • Examples of the catalyst include triethylamine, benzyldimethylamine, sodium salt triethylamine, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, and triphenyl.
  • Examples include ruphosphine, triphenylstibine, chromium octoate, and zirconium octoate.
  • the reaction temperature is 60 to 150 ° C, and the reaction time is preferably 5 to 60 hours.
  • thermal polymerization inhibitor that may be used in the third reaction is preferably used as the thermal polymerization inhibitor, for example, hydroquinone monomethyl ether, 2-methylhydroquinone, hydrated quinone, diphenol Examples include rupicrylhydrazine, diphenylamine, and 2,6-di-tert-butyl-p-talesole.
  • the third reaction samples the sample with an acid value (based on JIS K5601-2-1: 1999) of lmg ⁇ KOH / g or less, preferably 0.
  • the end point will be the time when it falls below 5mg'KOHZg.
  • the fourth reaction After completion of the third reaction, the fourth reaction has a carboxylic acid compound (f) having two hydroxyl groups in the molecule and a carboxyl group as an optional component in the reaction solution. It is a urethanization reaction in which the diol compound (g) is added to form a dispersion or solution, and the diisocyanate compound (e) is gradually added and reacted.
  • the fourth reaction may be performed after the product of the third reaction is separated, or the fourth reaction may be performed subsequently without separating the product of the third reaction.
  • the fourth reaction can be carried out without a catalyst, but a basic catalyst can be used to promote the reaction, and the catalyst is the same as the catalyst used in the second reaction described above.
  • the amount used may be 10% by weight or less based on the reaction product.
  • the reaction temperature is 40 to 120 ° C, and the reaction time is preferably 5 to 60 hours.
  • the above-mentioned solvent or thermal polymerization inhibitor may be used.
  • the urethane reaction process which is the fourth reaction, performs an infrared absorption scan while appropriately sampling.
  • Moshiku ⁇ Contact IS K1556 those measured by a titration method indicated in 1968 or the like can be applied.
  • the latter method is more preferable.
  • the end point is preferably a point that falls within the range of the content power of the isocyanate group calculated from the actual charging ratio plus or minus 2%.
  • polybasic acid anhydride (c) When the polybasic acid anhydride (c) is reacted as an optional component, it may be reacted in the same manner as the second reaction after the fourth reaction.
  • the amount of the carboxylic acid compound (f) having two hydroxyl groups in the molecule and the polybasic acid anhydride (c) as an optional component is the amount of the photosensitive alkaline aqueous solution soluble resin (A). It is preferable to add a calculated amount that gives a solid acid value of 0 to 150 mg'KOHZg. If the solid content acid value is 50 mg'KOH / g or more, good solubility in an alkaline aqueous solution is exhibited, and if the solid content acid value is 150 mg'KOH / g or less, during patterning during development, It is possible to prevent the patterning badness caused by overdissolution.
  • the amount of the diisocyanate compound (e) charged is (the number of moles of the epoxycarboxylate compound formed in the third reaction + the carboxyl oxidation having two hydroxyl groups in the molecule).
  • the ratio of the number of moles of compound (f) + the number of moles of diol compound (g) as an optional component) / (number of moles of diisocyanate compound (e)) is preferably in the range of 1-5. ,. If this ratio is 1 or more, the isocyanate group remaining after the completion of the reaction does not remain, so that it is possible to prevent poor storage stability due to crosslinking of the isocyanate group. On the other hand, when this ratio is 5 or less, the molecular weight increases, so that the poor tackiness prevents the sensitivity from being lowered.
  • the content ratio of the photosensitive alkaline aqueous solution-soluble resin (A) in the photosensitive resin composition of the present invention is usually when the solid content of the photosensitive resin composition is 100% by weight. It is 15 to 70% by weight, preferably 20 to 60% by weight.
  • the photosensitive aqueous alkali-soluble soluble resin (A) of the present invention thus obtained can be made solid by removing it with an appropriate method when a solvent is used.
  • the reactive crosslinking agent (B) contained in the active energy ray-curable resin composition of the present invention is the same as the alkali aqueous solution-soluble resin (A) of the present invention, which cures the photosensitive resin composition.
  • A alkali aqueous solution-soluble resin
  • it is a generic term for those that show reactivity and form a crosslinked structure. These are used to give physical properties before and after curing according to the purpose of use.
  • reactive crosslinking agent (B) examples include radical reaction type attalylates, cation reaction type other epoxy compounds, vinyl compounds that are sensitive to both, and the like. Examples include so-called reactive oligomers. Among these, it is preferable to select a radical reaction type crosslinking agent because the alkaline water solution soluble resin (A) of the present invention has an acidic group. This is because the crosslinking reaction proceeds with the cation derived from (A).
  • radical reaction type acrylates examples include monofunctional (meth) acrylates, polyfunctional (meth) acrylates, other epoxy acrylates, polyester acrylates, uretan acrylates, and the like. .
  • Monofunctional (meth) acrylates include alkyl (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate and lauryl (meth) acrylate.
  • alkyl (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate and lauryl (meth) acrylate.
  • Cycloaliphatic (meth) acrylates such as aromatic (meth) acrylates, isobornyl (meth) acrylates, cyclohexyl (meth) acrylates, and heterocycles such as tetrahydrofurfuryl (meth) acrylates Contains (meth) attalylates.
  • polyfunctional (meth) acrylates examples include butanediol di (meth) acrylate, hexane diol di (meth) acrylate, neopentyl glycol di (meth) acrylate, nonanediol all (meth) acrylate Alkylene diols (meth) acrylates, glycol di (meth) acrylate, diethylene di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, etc.
  • Cycloaliphatics such as aromatic (meth) acrylate, hydrogenated bisphenol ethylene oxide (meth) acrylate, etc., bisphenol ethylene oxide di (meth) acrylate, bisphenol di (meth) acrylate, etc. (Meta) atarylates, Squirrel (meth) ⁇ methacryloyl Ruo key heterocycle containing such Chez chill iso Xia isocyanurate (meth) Atari rates acids, adipic Other epoxy acrylates such as epoxy di (meth) acrylate, dipentaerythritol poly (meth) acrylate, trimethylolpropane tri (meth) acrylate, triethylol propane tri (meth) acrylate, etc.
  • Ethylene oxide adducts such as dipentaerythritol poly (meth) acrylate, trimethylol propane tri (meth) acrylate, triethylene propane tri (meth) acrylate, or propylene oxide adduct (meth) ate Poly (meth) atalylate, a reaction product of dipentaerythritol and ⁇ -force prolataton Lumpur force Purorataton modified (meth) Atari rate such like.
  • Examples of the bull compounds that can be used include bull ethers, styrenes, and other bull compounds.
  • the bull ethers include ethyl vinyl ether, propyl vinylenoatenole, hydroxyethinorevininoatenole, and ethylene glyconoresininoatele.
  • Examples of styrenes include styrene, methyl styrene, ethyl styrene and the like.
  • Other bully compounds include triallyl isocyanurate, trimethallyl isocyanurate, and the like.
  • the addition ratio of these reactive crosslinking agents ( ⁇ ) is usually 2 to 40 wt%, preferably 5 to 30 wt%, when the solid content of the photosensitive resin composition is 100 wt%. .
  • the photopolymerization initiator (C) used in the present invention is preferably a radical photoinitiator.
  • benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ethere, benzoin propyl ether, benzoin isobutyl ether; Cetophenone, 1,1-dichloroacetophenone, 2-hydroxy-2-methyl-phenylpropane 1-one, methoxyacetophenone, 1-hydroxyl hexylphenol ketone, 2-methyl-1-phenyl [4- (methylthio) phenol ]
  • Acetophenones such as 2 morpholinopropane 1-one; anthraquinones such as 2-ethylanthraquinone, 2-t-butinoleanthraquinone, 2-cloanthraquinone, 2-aminoleanthraquinone; 2, 4 Jetylthioxanthone, 2-Isopropylthio Thi
  • the addition ratio of the photopolymerization initiator (C) is usually 1 to 30% by weight, preferably 2 to 25% by weight, when the solid content of the photosensitive resin composition is 100% by weight.
  • photopolymerization started Agent (C) can be used alone or as a mixture of two or more thereof, and further, tertiary amines such as triethanolamine and methyldiethanolamine, ethyl ester of N, N-dimethylaminobenzoate, isoamyl N, N-dimethylaminobenzoate. May be used in combination with reaction accelerators such as benzoic acid derivatives such as esters! The addition amount of these reaction accelerators is preferably 100% by weight or less based on the photopolymerization initiator (C).
  • the curing agent (D) contained in the photosensitive resin composition of the present invention is the above formula (1) [wherein n represents the number of repetitions. ] This is a 4,4'-integrated bisphenol F-type epoxy resin with good molecular symmetry.
  • the curing agent (D) forms a cured coating film having stronger chemical resistance and the like by post-curing which reacts by heating with the carboxyl group remaining in the resin film after photocuring.
  • the 4,4'-integrated bisphenol F-type epoxy resin having good molecular symmetry represented by the formula (1) has liquid crystallinity.
  • the melting point of the curing agent (D) is usually 70 to 150 ° C, preferably 80 to 150 ° C.
  • the epoxy equivalent is usually 250 to 2000 gZ equivalent, preferably 300 to lOOOOgZ equivalent.
  • the epoxy resin used as the curing agent (D) represented by the above formula (1) contained in the photosensitive resin composition of the present invention includes, for example, the following formula (2):
  • the phenolic compound represented by The compound is a crystal having a melting point of around 163 ° C., and is commercially available, for example, under the trade name p, p′-BPF (Honshu Chemical; purity> 99%).
  • the phenolic compound is reacted with epino and rhohydrin in the presence of an alkali metal hydroxide to obtain a low molecular weight epoxy resin. Further, this compound and the phenolic compound represented by the formula (2) are used. And by precipitating crystals from the resulting reaction mixture, an epoxy resin as a curing agent (D) contained in the photosensitive resin composition can be obtained.
  • epichlorohydrin or epipibromhydrin can be used, and the amount used is 1 mol of phenolic hydroxyl group of the phenolic compound represented by the formula (2).
  • the amount is usually 2 to 15 mol, preferably 3 to 12 mol.
  • Examples of the alkali metal hydroxide include sodium hydroxide, potassium hydroxide, and the like, which can be used in a solid form or an aqueous solution thereof. When using an aqueous solution, it is added to the reaction system continuously.
  • a method in which water, epino and lohydrin are distilled off under reduced pressure or normal pressure, followed by liquid separation to remove water and epino and lohydrin being continuously returned to the reaction system can be preferably used.
  • the amount of alkali metal hydroxide used in the above reaction is usually 0.9 to 1.2 monolayers with respect to 1 monoreoxy group of hydroxyl groups of the phenolic compound represented by formula (2). , Preferably 0.95: L 15 mol.
  • reaction temperature is usually 20 to 110 ° C, preferably 25 to 100 ° C.
  • Reaction time is usually 0.5
  • an aprotic polar solvent such as dimethyl sulfoxide or dimethyl sulfone
  • an alcohol such as methanol, ethanol, propanol or butanol, or to promote the reaction smoothly.
  • the amount used is usually 3 to 3 with respect to the amount of epino and rhohydrin.
  • the amount used is usually 10 to 150% by weight, preferably 15 to 120% by weight, based on the amount of epihalohydrin.
  • salts such as tetramethylammonium chloride, tetramethylammonium bromide, trimethylbenzylammonium chloride, etc.
  • a quaternary ammonium salt as a catalyst and react for 30 to 110 hours) for 0.5 to 8 hours to a halohydrin ether compound obtained by adding a solid or aqueous solution of an alkali metal hydroxide.
  • the reaction may be carried out at 20-100 ° C for 1-10 hours, followed by denomination and Logeny hydrogen (ring closure).
  • the obtained epoxy resin is dissolved in toluene, methylisobutyl ketone, etc.
  • An epoxy resin having less hydrolyzable halogen can be obtained by providing an aqueous solution of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide to ensure ring closure.
  • the amount of alkali metal hydroxide used is usually 0.01 to 0.3 monolayer, preferably 0.05 to 0.2 monolayer, with respect to 1 mol of hydroxyl group of the phenolic compound. .
  • reaction time is usually 0.5 to 2 hours.
  • the produced salt is removed by filtration or washing with water, and the solvent is removed under reduced pressure by heating to obtain a low molecular weight epoxy resin.
  • the epoxy equivalent of the epoxy resin is usually about 160 to 200 gZ equivalent.
  • the epoxy equivalent has the same meaning as commonly used, and means the mass of an epoxy compound containing 1 lg equivalent of an epoxy group, and is expressed in units of gZ equivalent, usually
  • the content ratio of the above polymers can be increased.
  • the charge ratio of the epoxy resin to the compound represented by the formula (2) is generally 0.05 to 0.95 for the phenolic hydroxyl group of the compound of the formula (2) to 1 mol of the epoxy group of the epoxy resin.
  • a ratio of mol, preferably 0.1 to 0.9 mol is preferred.
  • a catalyst is preferred to promote the reaction.
  • the catalyst include quaternary phosphonium salts such as benzyl chloride phosphor bromide, butyl triphenyl phosphor bromide, bromide tilt triphosphor phosphate, and iodinated tilt triphosphor phosphorous. And triphenylphosphine, sodium tetramethyl ammonium, sodium hydroxide, potassium hydroxide and the like.
  • the amount of the catalyst used is usually 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight, based on 1 mol of epoxy groups of the epoxy resin.
  • the quaternary phosphonium salt is preferable because it gives a linear epoxy resin, and the salt is water-soluble and can be easily removed by washing with water after the reaction. .
  • solvent examples include clopentanone, cyclohexanone, methyl isobutyl ketone, methyl ethyl ketone, acetonitrile, toluene, N-methylpyrrolidone, dimethyl sulfoxide, and N, N-dimethylformamide.
  • the amount used is usually about 5 to 150% by weight, preferably about 10 to about LOO% by weight, based on the total weight of the epoxy resin and the phenolic compound represented by the formula (2).
  • the reaction temperature is usually 60 to 180 ° C, preferably 70 to 160 ° C.
  • the progress of the reaction can be monitored by GPC (gel permeation chromatography) or the like, and is continued until the phenolic compound represented by the formula (2) is not detected.
  • the reaction time is usually 0.5 to 15 hours, preferably 1 to 10 hours.
  • reaction solution is cooled as it is to crystallize the desired epoxy resin, and filtered, but the desired solvent for the epoxy resin (the solubility of the epoxy resin is less
  • the method of cooling by adding a low solvent is preferred.
  • this reaction is carried out in a poor solvent for the desired epoxy resin, and after cooling, a good solvent such as N, N-dimethylformamide, dimethyl sulfoxide (a solvent having a high solubility for the desired epoxy resin) is used.
  • a good solvent such as N, N-dimethylformamide, dimethyl sulfoxide (a solvent having a high solubility for the desired epoxy resin) is used.
  • the epoxy resin represented by the above formula (1) which is obtained by dissolving the crystals obtained by addition and then adding a poor solvent thereto, is preferred because the temperature range showing its liquid crystallinity is wider. That's right.
  • Examples of the poor solvent include methyl isobutyl ketone, methyl ethyl ketone, acetone, toluene, methanol, ethanol, water and the like.
  • the amount of the poor solvent used is usually about 50 to 400% by weight, preferably about 100 to 300% by weight, based on the total weight of the epoxy resin and the compound represented by the formula (2).
  • the epoxy resin is represented by the above formula (1), n represents the number of repetitions, and the average value is usually a positive number of 0 to 7, preferably 1 to 7, and a positive number of 3 to 5 Particularly preferred.
  • the content ratio of compounds with different n can be determined by HPLC using a GPC column, and the average value of n can also be determined.
  • the epoxy resin represented by the above formula (1) is measured by DSC (differential thermal analyzer), many endothermic peaks are observed at two or more locations. Force that peaks may overlap This indicates that the epoxy resin has liquid crystallinity.
  • DSC differential thermal analyzer
  • the existence state in the system is considered to be able to achieve both excellent thermal stability and developability.
  • the epoxy resin is usually liquid at normal temperature or has a melting point of 40 ° C or lower. The temperature range that is crystalline and exhibits liquid crystallinity is very narrow.
  • various additives such as talc, barium sulfate, calcium carbonate, magnesium carbonate, barium titanate, aluminum hydroxide, aluminum oxide are optionally added to the photosensitive resin composition of the present invention.
  • Fillers such as silica and clay, thixotropic agents such as aerosil, colorants such as phthalocyanine blue, phthalocyanine green and titanium oxide, silicone and fluorine leveling agents and antifoaming agents, hydroquinone and hydroquinone monomethyl ether
  • a polymerization inhibitor such as can be added for the purpose of enhancing various performances of the composition.
  • the photosensitive resin composition of the present invention contains the photosensitive aqueous alkali-soluble resin (A), a reactive crosslinking agent (B), a photopolymerization initiator (C), and a curing agent (D). To do.
  • the photosensitive alkaline aqueous solution-soluble resin (A) of the present invention is usually soluble in an alkaline aqueous solution, but is also soluble in the solvent used in the production described above, and is used for solder resists, plating resists, and the like. In this case, development with these solvents is also possible.
  • the curing agent (D) may be mixed in advance in the resin composition, but it may be a printed wiring board. It can also be mixed before use. That is, the above-mentioned photosensitive alkaline aqueous solution-soluble resin (A) is mixed into a two-pack type of a main agent solution mainly composed of component (A) and a curing agent solution mainly composed of curing agent (D), and these are mixed in use. Method and such use is preferred.
  • the photosensitive resin composition of the present invention can also be used as a dry film resist having a structural strength in which the resin composition is sandwiched between a support film and a protective film.
  • the above-mentioned photosensitive aqueous alkali-soluble soluble resin (A), reactive crosslinking agent (B), photopolymerization initiator (C), curing agent (D) A photosensitive resin composition containing a filler, an additive, and the like is used as a photosensitive layer, and the photosensitive layer is sandwiched between a support layer and a protective layer to form a dry film.
  • the protective layer is peeled off, the substrate is laminated, exposed to light, the support layer is peeled off and developed.
  • the dry film is specifically prepared as follows, but is not limited thereto.
  • the alkaline water-soluble resin solution (A), the reactive crosslinking agent (B), the photopolymerization initiator (C), A curing agent (D), a thermosetting catalyst, and a concentration adjusting solvent are added, and the mixture is kneaded with a bead mill and uniformly dispersed to obtain a resist resin composition.
  • a hot air drying furnace having a temperature sufficient to volatilize the solvent used, for example, a temperature of 70 ° C, is uniformly applied to a support film such as a polyethylene terephthalate film by a roll coating method. Pass through to form a 30 m thick resin layer, and apply a protective film such as polyethylene film on this resin layer to obtain a dry film.
  • a heated roll on a printed circuit board such as a polyimide blind substrate (copper circuit thickness: 12 m, polyimide film thickness: 25 m) to remove the protective film. Affix to the entire surface of the substrate.
  • the pasting process is preferably performed in a vacuum.
  • Ultraviolet light is irradiated through a mask on which a circuit pattern is drawn using an ultraviolet exposure device.
  • Spray development is performed with an alkaline aqueous solution such as a 1% aqueous sodium carbonate solution to remove the non-ultraviolet-irradiated portion of the resin, washed with water and dried, and the printed circuit board is heated and cured with a hot air dryer to obtain a cured film.
  • the photosensitive resin composition (liquid or film-like) of the present invention includes an insulating material between electronic component layers, an optical waveguide connecting optical components, a solder resist for printed circuit boards, and a resist material such as a coverlay. In addition, it can be used as a color filter, printing ink, sealant, paint, coating agent, adhesive and the like.
  • a cured product obtained by curing the photosensitive resin composition of the present invention by irradiation with active energy rays such as ultraviolet rays is also included in the present invention.
  • Curing by irradiation with active energy rays such as ultraviolet rays can be performed by a conventional method.
  • an ultraviolet generator such as a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a xenon lamp, or an ultraviolet light emitting laser (such as an excimer laser).
  • the cured product of the photosensitive resin composition of the present invention is, for example, a resist film, an interlayer insulating material for a buildup method, an optical waveguide such as a printed board, an optoelectronic board, or an optical board as an optical waveguide. Used for optical substrates.
  • Specific examples of articles having these base materials include computers, home appliances, and portable devices. These base materials and articles are also included in the present invention.
  • the thickness of the cured product layer is about 0.5 to 160 m, preferably 1 to about LOO / zm.
  • a liquid resin composition is used to print a printed wiring board on a screen printing method, spray method, roll coating method, electrostatic coating method.
  • the photosensitive resin composition of the present invention is applied at a film thickness of 5 to 160 ⁇ m by a method such as curtain coating, and is usually dried at a temperature of 50 to 110 ° C., preferably 60 to 100 ° C.
  • a coating film is formed by baking.
  • the coating film is directly or indirectly irradiated with active energy rays such as ultraviolet rays with an intensity of about 10 to 2000 mjZcm 2 through a photomask having an exposure pattern such as a negative film.
  • active energy rays such as ultraviolet rays with an intensity of about 10 to 2000 mjZcm 2
  • development is performed by spraying, rocking immersion, brushing, scraping, or the like.
  • it is further irradiated with ultraviolet rays and then heat-treated at a temperature of usually 100 to 200 ° C, preferably 140 to 180 ° C, so that it has excellent gold plating resistance, heat resistance and solvent resistance. It is possible to obtain a printed wiring board having a permanent protective film excellent in various properties such as property, acid resistance, adhesion, and flexibility.
  • alkaline aqueous solution used for development examples include inorganic alkaline aqueous solutions such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium phosphate, and potassium phosphate.
  • Organic alkali aqueous solutions such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, monoethanolamine, diethanolamine and triethanolamine Can be used.
  • an organic solvent can also be used.
  • GPC was measured according to the following conditions.
  • the coating film after (photosensitivity) drying, exposure by irradiation with ultraviolet light at an accumulated light intensity 500MiZcm 2 is brought into close contact 21 step tablet (manufactured by Kodak). Next, develop with a 1% sodium carbonate solution for 60 seconds at a spray pressure of 2. OkgZcm 2 , and check the number of coating layers remaining without development.
  • Test substrate is acidic degreasing solution at 30 ° C (Nippon McDermitt, Metex L
  • test substrate was immersed in an acid ammonium aqueous solution at room temperature for 3 minutes and then washed with water. Further, the test substrate was immersed in a 10 vol% sulfuric acid aqueous solution at room temperature for 1 minute and then washed with water.
  • This substrate is immersed in a 30 ° C catalyst solution (Meltex, 10vol% aqueous solution of Metal Plate Actuator 350) for 7 minutes, washed with water, and 85 ° C nickel plating solution (Meltex, Melplate) After being immersed in Ni-865M 20vol% aqueous solution, pH 4.6) for 20 minutes and nickel plating, it was immersed in 10vol% sulfuric acid aqueous solution for 1 minute at room temperature and washed with water. Next, immerse the test substrate in a gold plating solution at 95 ° C (Meltex, UP15vol% of the inlet port and 3vol% potassium cyanide, pH 6) for 10 minutes, perform electroless gold plating, and then wash with water. Further, it was immersed in warm water at 60 ° C for 3 minutes, washed with water and dried. Cellotape (registered trademark) was adhered to the obtained electroless gold plating evaluation substrate, and the state when peeled was observed.
  • the photosensitive resin composition of the present invention using the photosensitive alkaline aqueous solution-soluble resin and the curing agent represented by the formula (1) has no tackiness and high sensitivity.
  • the cured film is excellent in solder heat resistance, chemical resistance, gold plating resistance, etc.
  • the resin composition according to the present invention has an excellent developability with no residue, 4-4, low bisphenol F content, and a comparative example using bisphenol F type resin as a curing agent. It is clear that the resin composition is inferior in developability due to the formation of residues.

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Abstract

La présente invention concerne une composition de résine photosensible présentant une excellente photosensibilité et d'excellentes caractéristiques de flexion, d'adhérence, de résistance au crayon, de résistance aux solvants, de résistance à l’acide, de résistance à la chaleur, de résistance à la dorure, etc. Une telle composition de résine photosensible comprend une résine photosensible (A) soluble dans une solution alcaline aqueuse, un agent de réticulation réactif (B), un initiateur de photopolymérisation (C), et un durcisseur (D), le durcisseur (D) étant une résine époxy au bisphénol F à liant 4-4' représentée par la formule (1) : [n indiquant le nombre de répétitions].
PCT/JP2006/318017 2005-09-15 2006-09-12 Composition de résine photosensible et objet durci obtenu à partir de cette composition WO2007032326A1 (fr)

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JP2007128059A (ja) * 2005-10-04 2007-05-24 Hitachi Chem Co Ltd 感光性樹脂組成物及び感光性フィルム
EP2145880A1 (fr) * 2007-05-09 2010-01-20 Adeka Corporation Nouveau composé époxy, composition de résine pouvant être développée par un composé alcalin, et composition de résine photosensible pouvant être développée par un composé alcalin
WO2015190476A1 (fr) * 2014-06-13 2015-12-17 日本化薬株式会社 Composition de résine photosensible, stratifié de résine photosensible, produit durci de composition de résine photosensible, et produit durci de stratifié de résine photosensible (11)
WO2018117214A1 (fr) * 2016-12-21 2018-06-28 三菱ケミカル株式会社 Composition de résine pouvant durcir et film, article moulé, pré-impregné et plastique renforcé par des fibres utilisant ladite composition de résine pouvant durcir

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TW201235776A (en) * 2011-02-17 2012-09-01 Brave C & H Supply Co Ltd Production method of printing screen plate with protective layer
JP6275620B2 (ja) * 2014-10-17 2018-02-07 日本化薬株式会社 感光性樹脂組成物及びその硬化物
WO2016208187A1 (fr) * 2015-06-24 2016-12-29 互応化学工業株式会社 Composition de réserve de soudure, revêtement, carte de câblage imprimée revêtue, procédé de fabrication de revêtement, et procédé de fabrication de carte de câblage imprimée revêtue
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