WO2011001484A1 - 光硬化性熱硬化性樹脂組成物 - Google Patents

光硬化性熱硬化性樹脂組成物 Download PDF

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Publication number
WO2011001484A1
WO2011001484A1 PCT/JP2009/006734 JP2009006734W WO2011001484A1 WO 2011001484 A1 WO2011001484 A1 WO 2011001484A1 JP 2009006734 W JP2009006734 W JP 2009006734W WO 2011001484 A1 WO2011001484 A1 WO 2011001484A1
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Prior art keywords
group
resin
resin composition
compound
film
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PCT/JP2009/006734
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English (en)
French (fr)
Japanese (ja)
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伊藤信人
有馬聖夫
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太陽インキ製造株式会社
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Publication of WO2011001484A1 publication Critical patent/WO2011001484A1/ja

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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
    • 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
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/40—Treatment after imagewise removal, e.g. baking
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/22—Secondary treatment of printed circuits
    • H05K3/28—Applying non-metallic protective coatings
    • H05K3/285—Permanent coating compositions
    • H05K3/287—Photosensitive compositions

Definitions

  • the present invention is a photocurable thermosetting resin composition that can be developed with an aqueous alkali solution, in particular, a solder resist composition that is photocured by ultraviolet exposure or laser exposure, its dry film and cured product, and these.
  • the present invention relates to a printed wiring board having a cured film.
  • the current alkali development type photo solder resist still has problems in terms of durability. That is, the alkali resistance, water resistance, heat resistance and the like are inferior to those of conventional thermosetting type and solvent developing type.
  • the alkali-developable photo solder resist is mainly composed of a hydrophilic group in order to enable alkali development, and it is easy for chemicals, water, water vapor, etc. to permeate, resulting in reduced chemical resistance and resist film. This is thought to reduce the adhesion between copper and copper.
  • the alkali resistance as chemical resistance is weak, especially in semiconductor packages such as BGA (Ball Grid Array) and CSP (Chip Scale Package), especially PCT resistance (pressure cooker test resistance) that should be called moisture heat resistance.
  • Patent Document 1 discloses a photosensitive resin obtained by adding an acid anhydride to a reaction product of a novolak type epoxy compound and an unsaturated monobasic acid, a photopolymerization initiator, and a diluent. And a solder resist composition comprising an epoxy compound has been reported. Japanese Patent Laid-Open No.
  • Patent Document 2 adds (meth) acrylic acid to an epoxy resin obtained by reacting a reaction product of salicylaldehyde with a monohydric phenol with epichlorohydrin. Furthermore, a solder resist composition comprising a photosensitive resin obtained by reacting a polybasic carboxylic acid or its anhydride, a photopolymerization initiator, an organic solvent, and the like is disclosed.
  • the carboxyl group-containing resin used in the conventional solder resist composition has poor electrical characteristics.
  • the present invention has been made in view of the problems of the prior art as described above, and its main purpose is to have PCT resistance, HAST resistance, electroless gold plating resistance, and thermal shock resistance, which are important as solder resists for semiconductor packages. It is providing the photocurable thermosetting resin composition which can form a cured film. Furthermore, the object of the present invention is to provide a dry film and a cured product excellent in various properties as described above obtained by using such a photocurable thermosetting resin composition, and a solder resist using the dry film and the cured product. An object of the present invention is to provide a printed wiring board on which a cured film such as the above is formed.
  • a carboxyl group-containing resin (excluding a carboxyl group-containing resin starting from an epoxy resin), a photopolymerization initiator, and a functional group-containing elastomer are contained.
  • a photocurable thermosetting resin composition that can be developed with an aqueous alkali solution is provided.
  • the carboxyl group-containing resin preferably does not contain a hydroxyl group, and preferably has a photosensitive group.
  • the functional group-containing elastomer is preferably a butadiene derivative.
  • the photocurable thermosetting resin composition of the present invention further contains a thermosetting component, and preferably for a solder resist containing a colorant.
  • a cured product obtained by photocuring a film or dry film, preferably by photocuring in a pattern with a light source having a wavelength of 350 nm to 410 nm is provided.
  • the print or dry film is a print having a cured film obtained by photocuring the active energy ray, preferably by photocuring into a pattern by direct drawing of ultraviolet rays, and then thermally curing.
  • a wiring board is also provided.
  • the photocurable thermosetting resin composition of the present invention is characterized in that it contains a carboxyl group-containing resin, a photopolymerization initiator, and a functional group-containing elastomer that do not use an epoxy resin as a starting material.
  • the carboxyl group-containing resin various conventionally known carboxyl group-containing resins can be used as long as the carboxyl group-containing resin does not use an epoxy resin as a starting material. Among them, a carboxyl having an ethylenically unsaturated double bond in the molecule.
  • a group-containing photosensitive resin is preferable in terms of photocurability and development resistance.
  • the unsaturated double bond is preferably derived from acrylic acid, methacrylic acid or derivatives thereof.
  • carboxyl group-containing resin that can be used in the present invention
  • compounds listed below may be preferable.
  • a plurality of phenols in one molecule such as bisphenol A, bisphenol F, bisphenol S, novolac type phenol resin, poly-p-hydroxystyrene, condensate of naphthol and aldehydes, condensate of dihydroxynaphthalene and aldehydes, etc.
  • Reaction product obtained by reacting a compound having a reactive hydroxyl group with an alkylene oxide such as ethylene oxide or propylene oxide and an unsaturated group-containing monocarboxylic acid such as (meth) acrylic acid
  • Carboxyl group-containing photosensitive resin obtained by reacting polybasic acid anhydrides such as maleic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, adipic acid and the like.
  • Diisocyanate compounds such as aliphatic diisocyanate, branched aliphatic diisocyanate, alicyclic diisocyanate, aromatic diisocyanate, polycarbonate polyol, polyether polyol, polyester polyol, polyolefin polyol, acrylic polyol, bisphenol A type A terminal carboxyl group-containing urethane resin obtained by reacting an acid anhydride with a terminal of a urethane resin by a polyaddition reaction of a diol compound such as an alkylene oxide adduct diol, a compound having a phenolic hydroxyl group and an alcoholic hydroxyl group.
  • a diol compound such as an alkylene oxide adduct diol, a compound having a phenolic hydroxyl group and an alcoholic hydroxyl group.
  • a carboxyl group-containing urethane resin obtained by adding a compound having two isocyanate groups and one or more (meth) acryloyl groups, and then terminally (meth) acrylating.
  • a carboxyl group-containing resin obtained by copolymerization of an unsaturated carboxylic acid such as (meth) acrylic acid and an unsaturated group-containing compound such as styrene, ⁇ -methylstyrene, lower alkyl (meth) acrylate, and isobutylene.
  • a carboxyl group-containing photosensitive resin obtained by adding a compound having a cyclic ether group and a (meth) acryloyl group in one molecule to the carboxyl group-containing resins (1) to (7).
  • (meth) acrylate is a term that collectively refers to acrylate, methacrylate, and mixtures thereof, and the same applies to other similar expressions.
  • the carboxyl group-containing resin used in the present invention does not use an epoxy resin as a starting material, it has a feature that the halide content is very low.
  • the chloride ion content of the carboxyl group-containing resin used in the present invention is 0 to 100 ppm, more preferably 0 to 50 ppm, and still more preferably 0 to 30 ppm.
  • the carboxyl group-containing resin used in the present invention can easily obtain a resin containing no hydroxyl group.
  • the presence of a hydroxyl group has excellent characteristics such as improved adhesion by hydrogen bonding, but it is known to significantly reduce moisture resistance.
  • the outstanding point of the carboxyl group-containing resin of this invention compared with the epoxy acrylate modified resin currently used for the general solder resist is demonstrated.
  • a phenol novolak resin free from chlorine can be easily obtained.
  • Resin that has no hydroxyl group in the range of double bond equivalent 300-550, acid value 40-120 mgKOH / g by partial acrylation of phenol resin modified with alkyl oxide and introduction of acid anhydride It is possible to obtain
  • the acid value becomes very large with a double bond equivalent of 400 to 500.
  • Even after exposure, a coating film having development resistance cannot be obtained.
  • the acid value is high, the water resistance is inferior, and the insulation reliability and PCT resistance are significantly reduced. That is, it is very difficult to completely eliminate the hydroxyl group from an epoxy acrylate resin derived from a similar phenol novolac type epoxy resin.
  • urethane resin can also synthesize
  • a preferred resin is an isocyanate compound not using phosgene as a starting material and a carboxyl group-containing resin having a chlorine ion impurity amount of 0 to 30 ppm synthesized from a raw material not using epihalohydrin, and more preferably so as not to theoretically contain a hydroxyl group. It is a synthesized resin. From such a viewpoint, the carboxyl group-containing resins (1) to (5) shown as specific examples above can be particularly preferably used.
  • 3,4-epoxy is used as a compound having a cyclic ether group and a (meth) acryloyl group in one molecule.
  • a carboxyl group-containing photosensitive resin obtained by reacting cyclohexylmethyl methacrylate can also be suitably used because it uses alicyclic epoxy and has few chlorine ion impurities.
  • the carboxyl group-containing resin (6) is obtained by reacting glycidyl methacrylate as a compound having a cyclic ether group and a (meth) acryloyl group in one molecule, or copolymerizing glycidyl methacrylate as an unsaturated group-containing compound.
  • glycidyl methacrylate as a compound having a cyclic ether group and a (meth) acryloyl group in one molecule
  • an epoxy acrylate modified raw material can also be used as a diol compound in the synthesis of a urethane resin.
  • chlorine ion impurities enter, it can be used from the viewpoint that the amount of chlorine ion impurities can be controlled.
  • the acid value of the carboxyl group-containing resin is desirably in the range of 40 to 150 mgKOH / g, more preferably in the range of 40 to 130 mgKOH / g.
  • the acid value of the carboxyl group-containing resin is less than 40 mgKOH / g, alkali development becomes difficult.
  • it exceeds 150 mgKOH / g dissolution of the exposed area by the developing solution proceeds, so that the line becomes thinner than necessary.
  • the exposed portion and the unexposed portion are not distinguished from each other by dissolution and peeling with a developer, which makes it difficult to draw a normal resist pattern.
  • the blending amount of such a carboxyl group-containing resin is 20 to 60% by mass, preferably 30 to 50% by mass in the total composition.
  • the amount is less than the above range, the coating strength is lowered, which is not preferable.
  • the amount is larger than the above range, the viscosity becomes high and the coating property and the like deteriorate, which is not preferable.
  • the photopolymerization initiator one or more light selected from the group consisting of an oxime ester photopolymerization initiator having an oxime ester group, an ⁇ -aminoacetophenone photopolymerization initiator, and an acylphosphine oxide photopolymerization initiator.
  • a polymerization initiator can be used.
  • the oxime ester-based photopolymerization initiator include CGI-325, Irgacure OXE01, Irgacure OXE02 manufactured by Ciba Specialty Chemicals, N-1919 manufactured by Adeka, Adeka Arcles NCI-831, and the like as commercially available products. It is done.
  • a photopolymerization initiator having two oxime ester groups in the molecule can also be suitably used.
  • oxime ester compounds having a carbazole structure represented by the following general formula. wherein X represents a hydrogen atom, an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a phenyl group, a phenyl group (an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms) Group, an amino group, an alkylamino group having an alkyl group having 1 to 8 carbon atoms or a dialkylamino group), a naphthyl group (an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms),
  • Y and Z are each a hydrogen atom, an alkyl group having 1 to 17 carbon atoms, or a carbon number 1), and substituted with an alkylamin
  • Anthryl group, pyridyl group, benzofuryl group, benzothienyl group, Ar represents alkylene having 1 to 10 carbon atoms, vinylene, phenylene, biphenylene, pyridylene, naphthylene, thiophene, anthrylene, thienylene , Furylene, 2,5-pyrrole-diyl, 4,4
  • n is represented by an integer of 0 or 1.
  • X and Y are each a methyl group or an ethyl group
  • Z is methyl or phenyl
  • n is 0, and Ar is preferably phenylene, naphthylene, thiophene or thienylene.
  • the blending amount of such oxime ester photopolymerization initiator is preferably 0.01 to 5 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin.
  • the blending amount of such oxime ester photopolymerization initiator is preferably 0.01 to 5 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin.
  • it is less than 0.01 parts by mass, the photocurability on copper is insufficient, the coating film is peeled off, and the coating properties such as chemical resistance are deteriorated.
  • it exceeds 5 parts by mass light absorption on the surface of the solder resist coating film becomes violent, and the deep curability tends to decrease. More preferably, it is 0.5 to 3 parts by mass.
  • ⁇ -aminoacetophenone photopolymerization initiators include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone, N , N-dimethylaminoacetophenone and the like.
  • Examples of commercially available products include Irgacure 907, Irgacure 369, and Irgacure 379 manufactured by Ciba Specialty Chemicals.
  • acylphosphine oxide photopolymerization initiators include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, and bis (2,6-dimethoxy). And benzoyl) -2,4,4-trimethyl-pentylphosphine oxide.
  • examples of commercially available products include Lucilin TPO manufactured by BASF and Irgacure 819 manufactured by Ciba Specialty Chemicals.
  • the blending amount of these ⁇ -aminoacetophenone photopolymerization initiator and acylphosphine oxide photopolymerization initiator is preferably 0.01 to 15 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin. If it is less than 0.01 parts by mass, the photo-curability on copper is similarly insufficient, the coating film peels off, and the coating properties such as chemical resistance deteriorate. On the other hand, when the amount exceeds 15 parts by mass, the effect of reducing the outgas cannot be obtained, the light absorption on the surface of the solder resist coating film becomes intense, and the deep curability tends to be lowered. More preferably, it is 0.5 to 10 parts by mass.
  • a photopolymerization initiator a photoinitiator assistant, and a sensitizer that can be suitably used for the photocurable resin composition of the present embodiment
  • a benzoin compound an acetophenone compound, an anthraquinone compound, a thioxanthone compound, a ketal compound
  • examples include benzophenone compounds, tertiary amine compounds, and xanthone compounds.
  • benzoin compound examples include benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether.
  • acetophenone compound examples include acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, and the like.
  • anthraquinone compound examples include 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, 1-chloroanthraquinone and the like.
  • thioxanthone compound examples include 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone, and the like.
  • ketal compound examples include acetophenone dimethyl ketal and benzyl dimethyl ketal.
  • benzophenone compound examples include benzophenone, 4-benzoyldiphenyl sulfide, 4-benzoyl-4′-methyldiphenyl sulfide, 4-benzoyl-4′-ethyldiphenyl sulfide, and 4-benzoyl-4′-propyldiphenyl. And sulfides.
  • the tertiary amine compound include an ethanolamine compound and a compound having a dialkylaminobenzene structure, such as 4,4′-dimethylaminobenzophenone (Nisso Cure MABP manufactured by Nippon Soda Co., Ltd.), Dialkylaminobenzophenones such as 4'-diethylaminobenzophenone (EAB manufactured by Hodogaya Chemical Co.), 7- (diethylamino) -4-methyl-2H-1-benzopyran-2-one (7- (diethylamino) -4-methylcoumarin), etc.
  • 4,4′-dimethylaminobenzophenone Non-dimethylaminobenzophenone
  • Dialkylaminobenzophenones such as 4'-diethylaminobenzophenone (EAB manufactured by Hodogaya Chemical Co.), 7- (diethylamino) -4-methyl-2H-1-benzopyran-2-one (7- (die
  • Dialkylamino group-containing coumarin compounds ethyl 4-dimethylaminobenzoate (Kayacure EPA manufactured by Nippon Kayaku Co., Ltd.), ethyl 2-dimethylaminobenzoate (Quantacure® DMB manufactured by International Bio-Synthetics), 4-dimethyl Minobenzoic acid (n-butoxy) ethyl (Quantacure® BEA manufactured by International Bio-Synthetics), p-dimethylaminobenzoic acid isoamyl ethyl ester (Kayacure DMBI manufactured by Nippon Kayaku Co., Ltd.), 2-dimethylhexyl 4-dimethylaminobenzoic acid (Esolol® 507 manufactured by Van Dyk), 4,4′-diethylaminobenzophenone (EAB manufactured by Hodogaya Chemical Co., Ltd.), and the like.
  • Kayacure EPA manufactured by
  • thioxanthone compounds and tertiary amine compounds are preferred.
  • the inclusion of a thioxanthone compound is preferable from the viewpoint of deep curability.
  • thioxanthone compounds such as 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, and 2,4-diisopropylthioxanthone are preferably included.
  • the compounding amount of such a thioxanthone compound is preferably 20 parts by mass or less with respect to 100 parts by mass of the carboxyl group-containing resin.
  • the blending amount of the thioxanthone compound exceeds 20 parts by mass, the thick film curability is lowered and the cost of the product is increased. More preferably, it is 10 parts by mass or less.
  • a compound having a dialkylaminobenzene structure is preferable, and among them, a dialkylaminobenzophenone compound, a dialkylamino group-containing coumarin compound having a maximum absorption wavelength of 350 to 450 nm, and ketocoumarins are particularly preferable.
  • dialkylaminobenzophenone compound 4,4′-diethylaminobenzophenone is preferable because of its low toxicity.
  • the dialkylamino group-containing coumarin compound has a maximum absorption wavelength of 350 to 410 nm in the ultraviolet region, so it is less colored and uses a colored pigment as well as a colorless and transparent photosensitive composition, and reflects the color of the colored pigment itself. It becomes possible to provide a solder resist film.
  • 7- (diethylamino) -4-methyl-2H-1-benzopyran-2-one is preferred because it exhibits an excellent sensitizing effect on laser light having a wavelength of 400 to 410 nm.
  • photopolymerization initiators can be used alone or as a mixture of two or more.
  • the total amount of such photopolymerization initiator, photoinitiator assistant, and sensitizer is preferably 35 parts by mass or less with respect to 100 parts by mass of the carboxylic acid-containing resin. When it exceeds 35 parts by mass, the deep curability tends to decrease due to light absorption.
  • these photopolymerization initiators, photoinitiator assistants, and sensitizers absorb a specific wavelength, the sensitivity may be lowered in some cases, and may function as an ultraviolet absorber. However, they are not used only for the purpose of improving the sensitivity of the composition. Absorbs light of a specific wavelength as necessary to enhance the photoreactivity of the surface, and changes the resist line shape and opening to vertical, tapered, and inversely tapered, and processing accuracy of line width and opening diameter Can be improved.
  • any compound having a functional group in the skeleton can be used without particular limitation.
  • a (meth) acryloyl group, an acid anhydride group, a carboxyl group, an epoxy can be used as the functional group.
  • a compound having a group can be suitably used.
  • a butadiene derivative is suitable for imparting the above characteristics.
  • Examples of functional group-containing elastomers are shown.
  • Examples of the acid anhydride group that may be used include Ricon130MA8, Ricon130MA13, Ricon130MA20, Ricon131MA5, Ricon131MA10, Ricon131MA17, Ricon131MA20, Ricon184MA6, Ricon156MA17 (and above, trade names manufactured by Sartomer).
  • Examples of those having a (meth) acryl group include CN301, CN307 (trade name, manufactured by Sartomer), BAC-45 (trade name, manufactured by Osaka Organic Chemical Industry Co., Ltd.), and the like.
  • those having a carboxyl group may be a carboxyl group-modified butadiene-acrylonitrile copolymer or the like at both ends.
  • the blending amount of such a functional group-containing elastomer is suitably 5 parts by mass or more and 60 parts by mass or less, more preferably 10 parts by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the carboxyl group-containing resin. It is. If the amount is less than 5 parts by mass, the effect of the functional group-containing elastomer is not confirmed. On the other hand, if the amount exceeds 60 parts by mass, the tackiness of the coating film may be deteriorated or the development may be poor.
  • thermosetting component having a plurality of cyclic (thio) ether groups in the molecule includes either one of a three-, four- or five-membered cyclic ether group or a cyclic thioether group or two kinds of groups in the molecule.
  • a compound having at least a plurality of epoxy groups in the molecule that is, a polyfunctional epoxy compound, a compound having at least a plurality of oxetanyl groups in the molecule, that is, a polyfunctional oxetane compound, Examples thereof include compounds having a plurality of thioether groups, that is, episulfide resins.
  • Examples of the polyfunctional epoxy compound include jER828, jER834, jER1001, and jER1004 manufactured by Japan Epoxy Resin, Epicron 840, Epicron 850, Epicron 1050, Epicron 2055, and Epoto manufactured by Tohto Kasei Co., Ltd. YD-011, YD-013, YD-127, YD-128, D.C. E. R. 317, D.E. E. R. 331, D.D. E. R. 661, D.D. E. R.
  • Bisphenol A type epoxy resin such as 664 (all trade names); jERYL903 manufactured by Japan Epoxy Resin Co., Epicron 152, Epicron 165 manufactured by Dainippon Ink and Chemicals, Epototo YDB-400, YDB-500 manufactured by Tohto Kasei Co., Ltd. D. Chemicals manufactured by Dow Chemical Company.
  • E. R. 542 Araldide 8011 manufactured by Ciba Specialty Chemicals, Sumi-epoxy ESB-400, ESB-700 manufactured by Sumitomo Chemical Co., Ltd., and A.D. E. R. 711, A.I. E. R.
  • E. R. Novolak type epoxy resins such as ECN-235, ECN-299, etc. (both trade names); Epicron 830 manufactured by Dainippon Ink & Chemicals, jER807 manufactured by Japan Epoxy Resin, Epototo YDF-170 manufactured by Toto Kasei Co., YDF- 175, YDF-2004, Araldide XPY306 manufactured by Ciba Specialty Chemicals (both trade names), bisphenol F type epoxy resins; Epototo ST-2004, ST-2007, ST-3000 (trade names, manufactured by Tohto Kasei) Hydrogenated bisphenol A type epoxy resin such as JER604 manufactured by Japan Epoxy Resin Co., Ltd., Epotot YH-434 manufactured by Toto Kasei Co., Ltd., Araldide MY720 manufactured by Ciba Specialty Chemicals Co., Ltd., Sumi-epoxy ELM manufactured by Sumitomo Chemical Co., Ltd.
  • Xylenol type or biphenol type epoxy resins or mixtures thereof bisphenol S type such as EBPS-200 manufactured by Nippon Kayaku Co., Ltd., EPX-30 manufactured by Asahi Denka Kogyo Co., Ltd., EXA-1514 manufactured by Dainippon Ink & Chemicals, Inc.
  • Epoxy resin bisphenol A novolak type epoxy resin such as jER157S (trade name) manufactured by Japan Epoxy Resin; jERYL-931 manufactured by Japan Epoxy Resin, Araldide 163 manufactured by Ciba Specialty Chemicals (all trade names) Tetraphenylolethane type epoxy Fatty; heterocyclic epoxy resins such as Araldide PT810 manufactured by Ciba Specialty Chemicals, TEPIC manufactured by Nissan Chemical Industries, Ltd. (all trade names); diglycidyl phthalate resin such as Bremer DGT manufactured by Nippon Oil &Fats; Toto Kasei Co., Ltd.
  • Tetraglycidylxylenoylethane resins such as ZX-1063 manufactured by Nippon Steel Chemical Co .; naphthalene groups such as ESN-190 and ESN-360 manufactured by Nippon Steel Chemical Co., Ltd., HP-4032 manufactured by Dainippon Ink and Chemicals, EXA-4750, and EXA-4700 Containing epoxy resin: Epoxy resin having a dicyclopentadiene skeleton such as HP-7200, HP-7200H, etc. manufactured by Dainippon Ink & Chemicals, Inc.
  • EXA-4816, EXA-4822, EXA-4850 series flexible tough epoxy resin Glycidylme such as CP-50S, CP-50M Acrylate copolymer based epoxy resins; and copolymer epoxy resins of cyclohexylmaleimide and glycidyl methacrylate, and the like, but not limited thereto. These epoxy resins can be used alone or in combination of two or more.
  • polyfunctional oxetane compound examples include bis [(3-methyl-3-oxetanylmethoxy) methyl] ether, bis [(3-ethyl-3-oxetanylmethoxy) methyl] ether, 1,4-bis [(3-methyl -3-Oxetanylmethoxy) methyl] benzene, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, (3-methyl-3-oxetanyl) methyl acrylate, (3-ethyl-3-oxetanyl)
  • polyfunctional oxetanes such as methyl acrylate, (3-methyl-3-oxetanyl) methyl methacrylate, (3-ethyl-3-oxetanyl) methyl methacrylate and oligomers or copolymers thereof, oxetane alcohol and novolak resin, Poly (p-hydroxystyrene
  • Examples of the episulfide resin having a plurality of cyclic thioether groups in the molecule include YL7000 (bisphenol A type episulfide resin) manufactured by Japan Epoxy Resin, YSLV-120TE manufactured by Tohto Kasei Co., Ltd., and the like. Moreover, episulfide resin etc. which replaced the oxygen atom of the epoxy group of the novolak-type epoxy resin with the sulfur atom using the same synthesis method can be used.
  • the amount of the thermosetting component having a plurality of cyclic (thio) ether groups in the molecule is preferably 0.6 to 2.5 equivalents, more preferably 1 equivalent to 1 equivalent of the carboxyl group of the carboxyl group-containing resin. Is in the range of 0.8 to 2.0 equivalents.
  • the compounding amount of thermosetting components having multiple cyclic (thio) ether groups in the molecule is less than 0.6, carboxyl groups remain in the solder resist film, resulting in decreased heat resistance, alkali resistance, electrical insulation, etc. Therefore, it is not preferable.
  • the amount exceeds 2.5 equivalents the low molecular weight cyclic (thio) ether group remains in the dry coating film, which is not preferable because the strength of the coating film decreases.
  • thermosetting components examples include amino resins such as melamine derivatives and benzoguanamine derivatives.
  • examples include methylol melamine compounds, methylol benzoguanamine compounds, methylol glycoluril compounds, and methylol urea compounds.
  • the alkoxymethylated melamine compound, the alkoxymethylated benzoguanamine compound, the alkoxymethylated glycoluril compound and the alkoxymethylated urea compound have the methylol group of the respective methylolmelamine compound, methylolbenzoguanamine compound, methylolglycoluril compound and methylolurea compound. Obtained by conversion to an alkoxymethyl group.
  • the type of the alkoxymethyl group is not particularly limited and can be, for example, a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, a butoxymethyl group, or the like.
  • a melamine derivative having a formalin concentration which is friendly to the human body and the environment is preferably 0.2% or less.
  • thermosetting component can be used individually or in combination of 2 or more types.
  • the photocurable thermosetting resin composition of the present invention has a plurality of isocyanate groups or blocked isocyanate groups in one molecule in order to improve the curability of the composition and the toughness of the resulting cured film.
  • Compounds can be added.
  • Such a compound having a plurality of isocyanate groups or blocked isocyanate groups in one molecule is a compound having a plurality of isocyanate groups in one molecule, that is, a polyisocyanate compound, or a plurality of blocked isocyanate groups in one molecule.
  • the compound which has, ie, a blocked isocyanate compound, etc. are mentioned.
  • isocyanate blocking agent for example, phenol blocking agents such as phenol, cresol, xylenol, chlorophenol and ethylphenol; lactam blocking agents such as ⁇ -caprolactam, ⁇ -palerolactam, ⁇ -butyrolactam and ⁇ -propiolactam; Active methylene blocking agents such as ethyl acetoacetate and acetylacetone; methanol, ethanol, propanol, butanol, amyl alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, benzyl Ether, methyl glycolate, butyl glycolate, diacetone alcohol, lactic acid Alcohol-based blocking agents such as chill and ethyl lactate; oxime-based blocking agents such as formaldehyde oxime, acetaldoxime, acetoxi
  • the blocked isocyanate compound may be commercially available, for example, Sumidur BL-3175, BL-4165, BL-1100, BL-1265, Death Module TPLS-2957, TPLS-2062, TPLS-2078, TPLS-2117.
  • the compounds having a plurality of isocyanate groups or blocked isocyanate groups in one molecule can be used singly or in combination of two or more.
  • the compounding amount of the compound having a plurality of isocyanate groups or blocked isocyanate groups in one molecule is 1 to 100 parts by mass, more preferably 2 to 70 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin. The proportion of parts is appropriate. When the amount is less than 1 part by mass, sufficient toughness of the coating film cannot be obtained, which is not preferable. On the other hand, when it exceeds 100 parts by mass, the storage stability is lowered, which is not preferable.
  • the metal chloride is a metal chloride made of Cr, Mn, Co, Ni, Fe, Cu, or Al, and examples thereof include cobalt chloride, ferrous nickel chloride, and ferric chloride.
  • the metal acetylacetonate salt is a metal acetylacetonate salt made of Cr, Mn, Co, Ni, Fe, Cu or Al, for example, cobalt acetylacetonate, nickel acetylacetonate, iron acetylacetonate, etc. Is mentioned.
  • the metal sulfate is a metal sulfate composed of Cr, Mn, Co, Ni, Fe, Cu, or Al, and examples thereof include copper sulfate.
  • Examples of the amine compound include conventionally known triethylenediamine, N, N, N ′, N′-tetramethyl-1,6-hexanediamine, bis (2-dimethylaminoethyl) ether, N, N, N ′.
  • thermosetting catalyst for epoxy resins or oxetane compounds or a catalyst that promotes the reaction of epoxy groups and / or oxetanyl groups with carboxyl groups, either alone or in combination of two or more. Can be used.
  • Red colorant examples include monoazo, diazo, azo lake, benzimidazolone, perylene, diketopyrrolopyrrole, condensed azo, anthraquinone, and quinacridone.
  • -Indexes (CI; issued by The Society of Dyers and Colorists) are listed.
  • Monoazo Pigment Red 1, 2, 3, 4, 5, 6, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 112, 114, 146, 147, 151 , 170, 184, 187, 188, 193, 210, 245, 253, 258, 266, 267, 268, 269.
  • Disazo Pigment Red 37, 38, 41.
  • a colorant such as purple, orange, brown, or black may be added for the purpose of adjusting the color tone.
  • the blending ratio of the colorant as described above is not particularly limited, but is preferably 0 to 10 parts by weight, particularly preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of the carboxyl group-containing resin. It is enough.
  • an epoxy acrylate resin obtained by reacting acrylic acid with a polyfunctional epoxy resin such as a cresol novolac type epoxy resin, and further, a hydroxy acrylate such as pentaerythritol triacrylate and a diisocyanate such as isophorone diisocyanate on the hydroxyl group of the epoxy acrylate resin.
  • a polyfunctional epoxy resin such as a cresol novolac type epoxy resin
  • a hydroxy acrylate such as pentaerythritol triacrylate
  • a diisocyanate such as isophorone diisocyanate
  • the compounding amount of the compound having a plurality of ethylenically unsaturated groups in the molecule is 5 to 100 parts by mass, more preferably 1 to 70 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin. It is. When the blending amount is less than 5 parts by mass, photocurability is lowered, and pattern formation becomes difficult by alkali development after irradiation with active energy rays, which is not preferable. On the other hand, when the amount exceeds 100 parts by mass, the solubility in an alkaline aqueous solution is lowered, and the coating film becomes brittle.
  • the photo-curable thermosetting resin composition of the present invention can be blended with a filler as necessary in order to increase the physical strength of the coating film.
  • a filler known and commonly used inorganic or organic fillers can be used.
  • barium sulfate, spherical silica and talc are preferably used.
  • metal hydroxides such as titanium oxide, metal oxides, and aluminum hydroxide can be used as extender pigment fillers.
  • the amount of these fillers is preferably 200 parts by mass or less, more preferably 0.1 to 150 parts by mass, and particularly preferably 1 to 100 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin. When the blending amount of the filler exceeds 200 parts by mass, the viscosity of the composition becomes high, the printability is lowered, and the cured product becomes brittle.
  • the photocurable thermosetting resin composition of the present invention can use a binder polymer for the purpose of improving dryness to touch and improving handling properties.
  • a binder polymer for the purpose of improving dryness to touch and improving handling properties.
  • polyester polymers, polyurethane polymers, polyester urethane polymers, polyamide polymers, polyester amide polymers, acrylic polymers, cellulose polymers, polylactic acid polymers, phenoxy polymers, and the like can be used.
  • These binder polymers can be used alone or as a mixture of two or more.
  • antioxidant that acts as a peroxide decomposer
  • phosphorus compounds such as triphenyl phosphite, pentaerythritol tetralauryl thiopropionate, dilauryl thiodipropionate, distearyl 3,3 ′.
  • -Sulfur compounds such as thiodipropionate.
  • benzoate derivatives include 2-ethylhexyl salicylate, phenyl salicylate, pt-butylphenyl salicylate, 2,4-di-t-butylphenyl-3,5-di-t. -Butyl-4-hydroxybenzoate and hexadecyl-3,5-di-t-butyl-4-hydroxybenzoate.
  • benzotriazole derivative examples include 2- (2′-hydroxy-5′-t-butylphenyl) benzotriazole, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2 -(2'-hydroxy-3'-t-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'-di-t-butylphenyl) -5 -Chlorobenzotriazole, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-t-amylphenyl) benzotriazole and the like.
  • the triazine derivative include hydroxyphenyl triazine, bisethylhexyloxyphenol methoxyphenyl triazine, and the like.
  • Ultraviolet absorbers may be commercially available, for example, TINUVIN PS, TINUVIN 99-2, TINUVIN 109, TINUVIN 384-2, TINUVIN 900, TINUVIN 928, TINUVIN 1130, TINUVIN 400, TINUVIN 405, TINUVIN 460, TINUVIN 479 (above, manufactured by Ciba Specialty Chemicals, Inc., trade name).
  • Said ultraviolet absorber can be used individually by 1 type or in combination of 2 or more types, The molded product obtained from the photocurable thermosetting resin composition of this invention by using together with the said antioxidant. Can be stabilized.
  • Polyfunctional mercaptan compounds can be used and are not particularly limited.
  • hexane-1,6-dithiol, decane-1,10-dithiol, dimercaptodiethyl ether, dimercaptodiethylsulfide Aliphatic thiols such as xylylene dimercaptan, 4,4′-dimercaptodiphenyl sulfide, aromatic thiols such as 1,4-benzenedithiol; ethylene glycol bis (mercaptoacetate), polyethylene glycol bis (mercaptoacetate), Propylene glycol bis (mercaptoacetate), glycerin tris (mercaptoacetate), trimethylolethane tris (mercaptoacetate), trimethylolpropane tris (mercaptoacetate), pentaerythrito Poly (mercaptoacetate) polyhydric alcohols such as rutetrakis (mercaptoacetate) and dipentaerythri
  • heterocyclic compound having a mercapto group acting as a chain transfer agent examples include mercapto-4-butyrolactone (also known as 2-mercapto-4-butanolide), 2-mercapto-4-methyl-4-butyrolactone, 2-mercapto.
  • heterocyclic compound having a mercapto group that is a chain transfer agent that does not impair the developability of the photocurable thermosetting resin composition mercaptobenzothiazole, 3-mercapto-4-methyl-4H-1,2, 1,4-triazole, 5-methyl-1,3,4-thiadiazole-2-thiol, 1-phenyl-5-mercapto-1H-tetrazole are preferred.
  • chain transfer agents can be used alone or in combination of two or more.
  • the thermal polymerization inhibitor can be used to prevent thermal polymerization or temporal polymerization of the polymerizable compound.
  • the thermal polymerization inhibitor include 4-methoxyphenol, hydroquinone, alkyl or aryl-substituted hydroquinone, t-butylcatechol, pyrogallol, 2-hydroxybenzophenone, 4-methoxy-2-hydroxybenzophenone, cuprous chloride, phenothiazine, Chloranil, naphthylamine, ⁇ -naphthol, 2,6-di-tert-butyl-4-cresol, 2,2′-methylenebis (4-methyl-6-tert-butylphenol), pyridine, nitrobenzene, dinitrobenzene, picric acid, 4-Toluidine, methylene blue, copper and organic chelating agent reactant, methyl salicylate, and phenothiazine, nitroso compound, chelate of nitroso compound and Al, and the like.
  • thermosetting even when it does not contain a thermosetting component, by performing heat treatment, the ethylenically unsaturated bond of the photocurable component remaining in an unreacted state at the time of exposure undergoes thermal radical polymerization, and the coating film characteristics are improved. Therefore, heat treatment (thermosetting) may be performed depending on the purpose and application.
  • Volatile drying performed after applying the photocurable thermosetting resin composition of the present invention is performed using a hot air circulation drying furnace, an IR furnace, a hot plate, a convection oven, or the like (equipped with an air heating heat source using steam). And a method in which hot air in the dryer is brought into countercurrent contact and a method in which the hot air in the dryer is blown onto the support from the nozzle).
  • the exposure amount varies depending on the film thickness and the like, but can generally be in the range of 5 to 200 mJ / cm 2 , preferably 5 to 100 mJ / cm 2 , more preferably 5 to 50 mJ / cm 2 .
  • the direct drawing apparatus for example, those manufactured by Nippon Orbotech, Pentax, etc. can be used, and any apparatus may be used as long as it oscillates laser light having a maximum wavelength of 350 to 410 nm. .
  • the developing method can be a dipping method, a shower method, a spray method, a brush method or the like, and as a developer, potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, Alkaline aqueous solutions such as ammonia and amines can be used.
  • the photo-curable thermosetting resin composition of the present invention is not a liquid and directly applied to a substrate, but also a dry resist layer formed by applying and drying a solder resist on a film of polyethylene terephthalate or the like in advance. It can also be used in the form of a film.
  • the case where the photocurable thermosetting resin composition of this invention is used as a dry film is shown below.
  • the carrier film a thermoplastic film such as a polyester film having a thickness of 2 to 150 ⁇ m is used.
  • the alkali-developable photo-curable thermosetting resin composition is uniformly applied to a carrier film or cover film with a thickness of 10 to 150 ⁇ m using a blade coater, lip coater, comma coater, film coater, etc., and dried. Formed.
  • the cover film a polyethylene film, a polypropylene film, or the like can be used, but a cover film having a smaller adhesive force than the solder resist layer is preferable.
  • a protective film permanent protective film
  • peel off the cover film layer the solder resist layer and the substrate on which the circuit is formed, and bond them together using a laminator, etc.
  • a solder resist layer is formed on the formed substrate. If the formed solder resist layer is exposed, developed, and heat cured in the same manner as described above, a cured coating film can be formed.
  • the carrier film may be peeled off either before exposure or after exposure.
  • Synthesis example 1 A novolac-type cresol resin (manufactured by Showa Polymer Co., Ltd., trade name “Shonol CRG951”, OH equivalent: 119.4) 119. 4 g, 1.19 g of potassium hydroxide and 119.4 g of toluene were charged, the inside of the system was replaced with nitrogen while stirring, and the temperature was raised by heating. Next, 63.8 g of propylene oxide was gradually dropped and reacted at 125 to 132 ° C. and 0 to 4.8 kg / cm 2 for 16 hours. Thereafter, the reaction solution was cooled to room temperature, and 1.56 g of 89% phosphoric acid was added to and mixed with the reaction solution to neutralize potassium hydroxide.
  • the nonvolatile content was 62.1% and the hydroxyl value was 182.2 g / eq.
  • a novolak-type cresol resin propylene oxide reaction solution was obtained. This was an average of 1.08 moles of alkylene oxide added per equivalent of phenolic hydroxyl group.
  • 293.0 g of the resulting novolak-type cresol resin alkylene oxide reaction solution, 43.2 g of acrylic acid, 11.53 g of methanesulfonic acid, 0.18 g of methylhydroquinone and 252.9 g of toluene were mixed with a stirrer, thermometer and air.
  • a reactor equipped with a blowing tube was charged, air was blown at a rate of 10 ml / min, and the reaction was carried out at 110 ° C. for 12 hours while stirring.
  • As the water produced by the reaction 12.6 g of water was distilled as an azeotrope with toluene. Thereafter, the mixture was cooled to room temperature, and the resulting reaction solution was neutralized with 35.35 g of a 15% aqueous sodium hydroxide solution and then washed with water. Thereafter, toluene was distilled off while substituting 118.1 g of diethylene glycol monoethyl ether acetate with an evaporator to obtain a novolak acrylate resin solution.
  • varnish A-1 332.5 g of the obtained novolac acrylate resin solution and 1.22 g of triphenylphosphine were charged into a reactor equipped with a stirrer, a thermometer and an air blowing tube, and air was blown at a rate of 10 ml / min. While stirring, 60.8 g of tetrahydrophthalic anhydride was gradually added and reacted at 95 to 101 ° C. for 6 hours. A resin solution of a carboxyl group-containing photosensitive resin having a solid acid value of 88 mgKOH / g and a nonvolatile content of 71% was obtained. Hereinafter, this is referred to as varnish A-1.
  • Synthesis example 2 In a 5 liter separable flask equipped with a thermometer, a stirrer and a reflux condenser, 1,245 g of polycaprolactone diol (PLACCEL 208, molecular weight 830, manufactured by Daicel Chemical Industries, Ltd.) as a polymer polyol, a dihydroxyl compound having a carboxyl group Dimethylolpropionic acid 201 g as polyisocyanate, 777 g of isophorone diisocyanate as polyisocyanate, 119 g of 2-hydroxyethyl acrylate as hydroxyl group-containing (meth) acrylate, p-methoxyphenol and di-t-butyl-hydroxytoluene each of 0 .5 g was added.
  • polycaprolactone diol PLACCEL 208, molecular weight 830, manufactured by Daicel Chemical Industries, Ltd.
  • Synthesis Example 3 In a 2 liter separable flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel and nitrogen introducing tube, 900 g of diethylene glycol dimethyl ether as a solvent and t-butylperoxy 2-ethylhexanoate as a polymerization initiator (Japan) 21.4 g of oil and fat Co., Ltd., trade name: Perbutyl O) was added and heated to 90 ° C.
  • varnish A-3 363.9 g of 3,4-epoxycyclohexylmethyl acrylate (manufactured by Daicel Chemical Industries, Ltd., trade name: Cyclomer A200) and dimethylbenzylamine 3 as a ring-opening catalyst were added to the obtained carboxyl group-containing copolymer resin. .6 g, 1.80 g of hydroquinone monomethyl ether as a polymerization inhibitor was added, and the mixture was heated to 100 ° C. and stirred to carry out an epoxy ring-opening addition reaction. After 16 hours, a resin solution having a solid content acid value of 108.9 mgKOH / g, a weight average molecular weight of 25,000, and a solid content of 54% was obtained. Hereinafter, this is referred to as varnish A-3.
  • Comparative synthesis example 1 Orthocresol novolac type epoxy resin (manufactured by Dainippon Ink & Chemicals, EPICLON N-695, softening point 95 ° C., epoxy equivalent 214, average functional group number 7.6) 1070 g (number of glycidyl groups) (diethylene glycol monoethyl ether acetate 600 g) Total number of aromatic rings): 5.0 mol), 360 g of acrylic acid (5.0 mol), and 1.5 g of hydroquinone were charged, and the mixture was heated and stirred at 100 ° C. to uniformly dissolve. Next, 4.3 g of triphenylphosphine was charged, heated to 110 ° C.
  • varnish R-1 a resin solution having a solid content of 65% was obtained.
  • varnish R-1 this is referred to as varnish R-1.
  • Comparative synthesis example 2 Cresol novolac type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., EOCN-104S, softening point 92 ° C., epoxy equivalent 220) 2200 parts, dimethylolpropionic acid 134 parts, acrylic acid 648.5 parts, methylhydroquinone 4.6 parts Then, 1131 parts of carbitol acetate and 484.9 parts of solvent naphtha were charged, heated to 90 ° C. and stirred to dissolve the reaction mixture.
  • Cresol novolac type epoxy resin manufactured by Nippon Kayaku Co., Ltd., EOCN-104S, softening point 92 ° C., epoxy equivalent 220
  • reaction solution was cooled to 60 ° C., charged with 13.8 parts of triphenylphosphine, heated to 100 ° C., and allowed to react for about 32 hours to obtain a reaction product having an acid value of 0.5 mg KOH / g.
  • 364.7 parts of tetrahydrophthalic anhydride, 137.5 parts of carbitol acetate, and 58.8 parts of solvent naphtha were added to this, heated to 95 ° C., reacted for about 6 hours, cooled, and solid acid value
  • a resin solution of a carboxyl group-containing photosensitive resin having 40 mg KOH / g and a nonvolatile content of 65% was obtained.
  • varnish R-2 this is referred to as varnish R-2.
  • the reaction was carried out at 70 ° C. for 1 hour. After completion of the reaction, washing was performed twice with 200 parts of water. After the oil / water separation, methyl isobutyl ketone was recovered by distillation from the oil layer to obtain 370 parts of an epoxy resin (a-1) having an epoxy equivalent of 290 and a softening point of 62 ° C. 2900 parts (10 equivalents) of the obtained epoxy resin (a-1), 720 parts (10 equivalents) of acrylic acid, 2.8 parts of methylhydroquinone and 1950 parts of carbitol acetate were charged, heated to 90 ° C., stirred and reacted. The mixture was dissolved.
  • reaction solution was cooled to 60 ° C., charged with 16.7 parts of triphenylphosphine, heated to 100 ° C., and reacted for about 32 hours to obtain a reaction product having an acid value of 1.0 mgKOH / g.
  • 786 parts (7.86 mol) of succinic anhydride and 423 parts of carbitol acetate were added to this, heated to 95 ° C., reacted for about 6 hours, solid content acid value 100 mg KOH / g, solid content 65% A resin solution was obtained.
  • varnish R-3 this is referred to as varnish R-3.
  • Examples 1 and 2 and Comparative Examples 1 to 3 Using the resin solutions obtained in each of the above synthesis examples, blended in the proportions (parts by mass) shown in Table 1 together with various components shown in Table 1 below, premixed with a stirrer, and then kneaded with a three-roll mill. A photocurable thermosetting resin composition was prepared. The obtained photocurable thermosetting resin composition was quantified in halide content (total of chloride and bromide) by using a flask combustion treatment ion chromatography method based on the JPCA standard. The results are also shown in Table 1.
  • Examples 3 to 14 and Comparative Examples 4 to 6 Using the resin solution of the above synthesis example, blended in the proportions (parts by mass) shown in Table 2 together with various components shown in Table 2 below, premixed with a stirrer, kneaded with a three-roll mill, and used for solder resist A photosensitive resin composition was prepared. Here, it was 15 micrometers or less when the dispersion degree of the obtained photosensitive resin composition was evaluated by the particle size measurement by the grindometer by Eriksen.
  • ⁇ Optimum exposure amount> A circuit pattern substrate having a copper thickness of 18 ⁇ m was subjected to a copper surface roughening treatment (MEC etch bond CZ-8100 manufactured by MEC Co., Ltd.), washed with water, dried, and then subjected to photocurable thermosetting resin compositions of the above examples and comparative examples.
  • the product was applied to the entire surface by a screen printing method, and dried for 60 minutes in an 80 ° C. hot air circulation drying oven. After drying, it is exposed through a step tablet (Kodak No. 2) using an exposure apparatus equipped with a high-pressure mercury lamp, and remains when development (30 ° C., 0.2 MPa, 1 wt% sodium carbonate aqueous solution) is performed in 90 seconds.
  • the step tablet pattern is 7 steps, the optimum exposure was set.
  • ⁇ Maximum development life> The compositions of Examples and Comparative Examples were applied on the entire surface of a patterned copper foil substrate by screen printing, dried at 80 ° C., taken out every 20 minutes from 20 to 80 minutes, and allowed to cool to room temperature. .
  • This substrate was developed with a 1 wt% sodium carbonate aqueous solution at 30 ° C. under a spray pressure of 0.2 MPa for 90 seconds, and the maximum allowable drying time in which no residue remained was defined as the maximum development life.
  • ⁇ Electroless gold plating resistance> Using a commercially available electroless nickel plating bath and electroless gold plating bath, plating is performed under the conditions of nickel 5 ⁇ m and gold 0.05 ⁇ m, and the presence or absence of peeling of the resist layer or plating penetration is evaluated by tape peeling. Then, the presence or absence of peeling of the resist layer was evaluated by tape peeling. The judgment criteria are as follows. A: No soaking or peeling is observed. ⁇ : Slight penetration was confirmed after plating, but there was no peeling after tape peeling. ⁇ : Slight penetration was observed after plating, and peeling was also observed after tape peeling. X: There is peeling after plating.
  • ⁇ PCT resistance> The evaluation substrate on which the solder resist cured coating film was formed was treated for 168 hours under the conditions of 121 ° C., saturation, and 0.2 MPa using a PCT apparatus (HAST SYSTEM TPC-412MD manufactured by ESPEC Corporation), and the state of the coating film Evaluated.
  • the judgment criteria are as follows. ⁇ : No swelling, peeling, discoloration, or dissolution ⁇ : Some swelling, peeling, discoloration, or dissolution ⁇ : Many swelling, peeling, discoloration, or dissolution
  • Example 4 had a viscosity increase rate of 172% when allowed to stand at room temperature for 5 days, while Comparative Example 6 had a viscosity increase rate of 208%. Further, the separation of the elastomer component was confirmed to be more remarkable in Comparative Example 6 than in Example 4. This is considered to be due to the polarity of the used resin and the elastomer, and the resin used in the examples is considered to show a result of better compatibility with the elastomer.
  • ⁇ Dry film evaluation> The cover film is peeled off from the dry film obtained as described above, the film is thermally laminated on the patterned copper foil substrate, and then, under the same conditions as the substrate used for the coating film property evaluation of the above example. Exposed. After the exposure, the carrier film was peeled off, and a 1 wt% sodium carbonate aqueous solution at 30 ° C. was developed for 90 seconds under a spray pressure of 0.2 MPa to obtain a resist pattern. This substrate was irradiated with ultraviolet rays under a condition of an integrated exposure amount of 1000 mJ / cm 2 in a UV conveyor furnace, and then cured by heating at 160 ° C. for 60 minutes. About the test substrate which has the obtained cured film, the evaluation test of each characteristic was done with the test method and evaluation method which were mentioned above. The results are shown in Table 4.
  • the photo-curable thermosetting resin composition of the present invention has the PCT resistance, the thermal shock resistance, the HAST characteristics (electrical characteristics) required for the solder resist for semiconductor packages. ) was found to be useful as a photocurable thermosetting resin composition.

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