Classifications

• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—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
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L101/00—Compositions of unspecified macromolecular compounds
  • C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
  • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
  • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
• • 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
• • 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 an anhydride thereof, a photopolymerization initiator, an organic solvent and the like is disclosed.
• the epoxy resin used as a raw material already contains a large amount of chlorine ion impurities, and it is very difficult to remove this after the epoxy acrylate modification.
• an insulating material containing a chlorine ion impurity has poor insulation reliability.
• the present invention has been made in view of the above-described problems of the prior art, 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 hydroxyl group-containing elastomer are contained.
• a photocurable thermosetting resin composition that can be developed with an alkaline aqueous solution is provided.
• the carboxyl group-containing resin preferably does not contain a hydroxyl group, and preferably has a photosensitive group.
• the hydroxyl group-containing elastomer is preferably a butadiene or isoprene derivative.
• the photocurable thermosetting resin composition of the present invention further contains a thermosetting component, and preferably for a solder resist containing a colorant.
• coating and drying the said photocurable thermosetting resin composition on a film is provided. Furthermore, according to the present invention, there is provided a cured product obtained by photocuring the photocurable thermosetting resin composition or dry film, preferably by photocuring in a pattern with a light source having a wavelength of 350 to 410 nm. . Furthermore, according to the present invention, the photocurable thermosetting resin composition or the dry film is photocured in a pattern by irradiation with active energy rays, preferably by direct drawing of ultraviolet rays, and then thermally cured. A printed wiring board having the resulting cured film is provided.
• the photocurable thermosetting resin composition of the present invention uses a carboxyl group-containing resin that does not use an epoxy resin as a starting material as a component that can be developed with an alkaline aqueous solution, the contained chlorine ion impurity is remarkably reduced. The electrical properties of the resulting cured coating are improved. Further, since it contains a hydroxyl group-containing elastomer in combination with this, not only the flexibility of the cured coating film is improved, but also it is very effective for stress relaxation when the coating film is overcured. Therefore, by using the photocurable thermosetting resin composition of the present invention, it is possible to form a cured film having PCT resistance, HAST resistance, electroless gold plating resistance, and thermal shock resistance important as a solder resist for semiconductor packages.
• the photocurable thermosetting resin composition of the present embodiment is characterized by containing a carboxyl group-containing resin not using an epoxy resin as a starting material, a photopolymerization initiator, and a hydroxyl group-containing elastomer.
• a carboxyl group-containing resin of this embodiment conventionally known various 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.
• a carboxyl group-containing photosensitive resin having a bond is preferable in terms of photocurability and development resistance.
• the unsaturated double bond of such a carboxyl group-containing resin is preferably derived from acrylic acid, methacrylic acid or derivatives thereof.
• carboxyl group-containing resin having no ethylenically unsaturated double bond is used, in order to make the composition photocurable, one or more ethylenically unsaturated groups per molecule as described later are used. It is necessary to use a compound having a group (photosensitive monomer) in combination.
• carboxyl group-containing resin for example, the following compounds (any of oligomers and polymers) are 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.
• a carboxyl group-containing photosensitive resin obtained by reacting a product with a polybasic acid anhydride such as maleic acid anhydride, tetrahydrophthalic acid anhydride, trimellitic acid anhydride, pyromellitic acid anhydride, or adipic acid anhydride.
• An unsaturated group-containing monocarboxylic acid is reacted with a reaction product obtained by reacting a compound having a plurality of phenolic hydroxyl groups in one molecule with a cyclic carbonate compound such as ethylene carbonate or propylene carbonate.
• a carboxyl group-containing photosensitive resin obtained by reacting a reaction product with a polybasic acid anhydride.
• Diisocyanate compounds such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates, aromatic diisocyanates, polycarbonate polyols, polyether polyols, polyester polyols, polyolefin polyols, acrylic polyols, bisphenol A systems
• 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 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 polyfunctional oxetane resin as described later is reacted with a dicarboxylic acid such as adipic acid, phthalic acid, hexahydrophthalic acid, etc., and the resulting primary hydroxyl group has phthalic anhydride, tetrahydrophthalic anhydride,
• a dicarboxylic acid such as adipic acid, phthalic acid, hexahydrophthalic acid, etc.
• One epoxy group in one molecule such as glycidyl (meth) acrylate and ⁇ -methylglycidyl (meth) acrylate is added to a carboxyl group-containing polyester resin to which a dibasic acid anhydride such as hexahydrophthalic anhydride is added.
• a carboxyl group-containing photosensitive resin obtained by adding a compound having one or more (meth) acryloyl groups.
• 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 embodiment has a feature that the halide content is very low because an epoxy resin is not used as a starting material.
• the chlorine ion impurity content of the carboxyl group-containing resin used in the present invention is 100 ppm or less, more preferably 50 ppm or less, and even more preferably 30 ppm or less.
• the carboxyl group-containing resin used in the present embodiment can easily obtain a resin not containing a 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 embodiment compared with the epoxy acrylate modified resin used for the general solder resist is demonstrated.
• Phenol novolac resin without chlorine can be easily obtained.
• urethane resin can also synthesize
• the 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 30 ppm or less synthesized from a raw material not using epihalohydrin, and more preferably synthesized so as not to theoretically contain a hydroxyl group.
• the carboxyl group-containing resins (1) to (5) shown as specific examples above can be particularly preferably used.
• a 3,4-epoxy is used with respect to the carboxyl group-containing resin (6) obtained by copolymerization with the unsaturated group-containing compound shown above.
• a carboxyl group-containing photosensitive resin obtained by reacting cyclohexylmethyl (meth) acrylate can be suitably used because it uses alicyclic epoxy and has few chloride ion impurities.
• the carboxyl group-containing resin (6) is reacted with glycidyl (meth) acrylate as a compound having a cyclic ether group and a (meth) acryloyl group in one molecule, or glycidyl (meth) as an unsaturated group-containing compound.
• glycidyl (meth) acrylate as a compound having a cyclic ether group and a (meth) acryloyl group in one molecule
• glycidyl (meth) as an unsaturated group-containing compound.
• an epoxy acrylate-modified raw material can 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 preferably in the range of 40 to 150 mgKOH / g.
• the acid value is less than 40 mgKOH / g, alkali development becomes difficult.
• the acid value exceeds 150 mgKOH / g, dissolution of the exposed portion by the developer proceeds, so that the line becomes thinner than necessary. It is difficult to draw a normal resist pattern due to dissolution and peeling with a developer without distinction between the unexposed area and the unexposed area. More preferably, it is in the range of 40 to 130 mgKOH / g.
• the weight average molecular weight of the carboxyl group-containing resin varies depending on the resin skeleton, but is preferably in the range of 2,000 to 150,000 in general.
• the weight average molecular weight is less than 2,000, tack-free performance may be inferior, the moisture resistance of the coated film after exposure may be poor, film thickness may be reduced during development, and resolution may be greatly inferior.
• the weight average molecular weight exceeds 150,000, developability may be remarkably deteriorated, and storage stability may be inferior. More preferably, it is in the range of 5,000 to 100,000.
• the blending amount of such a carboxyl group-containing resin is 20 to 60% by mass in the entire composition. When it is less than the above range, the coating film strength is lowered. On the other hand, when the amount is larger than the above range, the viscosity is increased or the coating property is decreased. More preferably, it is 30 to 50% by mass.
• an oxime ester photopolymerization initiator having an oxime ester group, an ⁇ -aminoacetophenone photopolymerization initiator, and an acylphosphine oxide photopolymerization initiator can be used. Of these, it is preferable to use at least one of them.
• oxime ester photopolymerization initiator examples 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. .
• a photopolymerization initiator having two oxime ester groups in the molecule can also be suitably used.
• Specific examples include oxime ester compounds having a carbazole structure represented by the following general formula (1).
• X is 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).
• Y and Z are each a hydrogen atom, an alkyl group having 1 to 17 carbon atoms, or a carbon atom having 1 carbon atom), substituted with an alkyl group having a C 1-8 alkyl group or a dialkylamino group.
• 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, 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 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 initiator examples 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 can be mentioned.
• Examples of commercially available products include Irgacure 907, Irgacure 369, and Irgacure 379 manufactured by Ciba Japan.
• 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 Japan.
• 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 the blending amount is less than 0.01 parts by mass, the photocurability on copper is similarly insufficient, the coating film is peeled off, and the coating properties such as chemical resistance are lowered. On the other hand, if it exceeds 15 parts by mass, a sufficient effect of reducing the outgas cannot be obtained, and 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 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
• a dialkylamino group-containing coumarin compound ethyl 4-dimethylaminobenzoate (Kayacure EPA manufactured by Nippon Kayaku Co., Ltd.), ethyl 2-dimethylaminobenzoate (Quantacure® DMB manufactured by International Bio-Synthetics), 4-dimethylamino Ethyl benzoate (n-butoxy) (Quantacure® BEA, manufactured by International Bio-Synthetics), p-dimethylaminobenzoic acid isoamyl ethyl ester (Kayacure DMBI, manufactured by Nippon Kayaku Co., Ltd.), 2-ethylhexyl 4-dimethylaminobenzoate ( Examples include Esolol® 507 manufactured by Van Dyk.
• thioxanthone compounds and tertiary amine compounds are preferred.
• a thioxanthone compound it is possible to improve deep curability.
• 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. If the blending amount 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 obtain 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.
• the blending amount of such a tertiary amine compound is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin.
• the blending amount is less than 0.1 parts by mass, a sufficient sensitizing effect tends not to be obtained.
• the amount exceeds 20 parts by mass, light absorption on the surface of the coating film by the tertiary amine compound becomes violent, and the deep curability tends to decrease. More preferably, it is 0.1 to 10 parts by mass.
• 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 carboxyl group-containing resin. When the total amount 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 improve the photoreactivity of the surface, change the resist line shape and opening to vertical, tapered, reverse taper, and processing accuracy of line width and opening diameter Can be improved.
• the hydroxyl group-containing elastomer used in the photocurable thermosetting resin composition of the present embodiment not only improves the flexibility of the resulting cured coating film, but is also very effective for stress relaxation during solder resist overcuring. In other words, it was revealed that it is excellent in PCT resistance.
• Such a hydroxyl group-containing elastomer can be used without particular limitation as long as it is a compound having a hydroxyl group at the side chain or terminal, for example, a hydroxyl group-containing acrylic elastomer, a hydroxyl group-containing polyester elastomer, a hydroxyl group-containing polyester urethane type
• a hydroxyl group-containing acrylic elastomer a hydroxyl group-containing polyester elastomer
• a hydroxyl group-containing polyester urethane type examples include elastomers, hydroxyl group-containing urethane elastomers, cellulose derivative elastomer resins, and polylactic acid elastomers.
• Particularly preferable examples include polybutadiene elastomers, polyisoprene elastomers and derivatives thereof.
• hydroxyl group-containing elastomer examples include hydroxyl group-terminated liquid polybutadiene (Poly bd, manufactured by Idemitsu Kosan Co., Ltd.), hydroxyl group-terminated liquid isoprene (Poly ip, manufactured by Idemitsu Kosan Co., Ltd.), and hydroxyl group-terminated polyolefin-based polyol (Epol, Idemitsu Kosan Co., Ltd.).
• Product hydroxyl-terminated liquid polybutadiene water additive (Polytail H, manufactured by Mitsubishi Chemical Corporation), and the like.
• the blending amount of such a hydroxyl group-containing elastomer is preferably 5 to 60 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin.
• the blending amount is less than 5 parts by mass, the effect of the hydroxyl group-containing elastomer is not confirmed.
• it exceeds 60 parts by mass the tackiness of the coating film may be deteriorated and the development may be poor. More preferably, it is 10 to 50 parts by mass.
• thermosetting component can be added to the photocurable thermosetting resin composition of the present embodiment in order to impart heat resistance.
• thermosetting components used in this embodiment include blocked isocyanate compounds, amino resins, maleimide compounds, benzoxazine resins, carbodiimide resins, cyclocarbonate compounds, polyfunctional epoxy compounds, polyfunctional oxetane compounds, episulfide resins, melamine derivatives, and the like. These known thermosetting resins can be used.
• a preferable thermosetting component is a thermosetting component having a plurality of cyclic ether groups and / or cyclic thioether groups (hereinafter abbreviated as cyclic (thio) ether groups) in one molecule.
• cyclic (thio) ether groups There are many commercially available thermosetting components having a cyclic (thio) ether group, and various properties can be imparted depending on the structure.
• the hydroxyl group of the above-mentioned hydroxyl group-containing elastomer is made strong by reacting with a hydroxyl group produced by a reaction between a carboxyl group and a cyclic (thio) ether group (for example, an epoxy group), or by reacting the hydroxyl groups with each other.
• a hydroxyl group produced by a reaction between a carboxyl group and a cyclic (thio) ether group (for example, an epoxy group), or by reacting the hydroxyl groups with each other.
• thermosetting component having a plurality of cyclic (thio) ether groups in one molecule is either one or two of three, four or five-membered cyclic ether groups or cyclic thioether groups in one molecule.
• a compound having at least a plurality of epoxy groups in one molecule that is, a polyfunctional epoxy compound, a compound having at least a plurality of oxetanyl groups in a molecule, that is, a polyfunctional oxetane compound, Examples thereof include a compound having a plurality of thioether groups in the molecule, that is, a polyfunctional episulfide resin.
• Examples of the polyfunctional epoxy compound include jER828, jER834, jER1001, jER1004 manufactured by Japan Epoxy Resin, Epicron 840, Epicron 850, Epicron 1050, Epicron 2055 manufactured by DIC, Epototo YD-011, YD manufactured by Toto Kasei Co., Ltd. -013, YD-127, YD-128, D.C. E. R. 317, D.E. E. R. 331, D.D. E. R. 661, D.D. E. R. 664, Ciba Japan's Araldide 6071, Araldide 6084, Araldide GY250, Araldide GY260, Sumitomo Chemical Co., Ltd.
• A. E. R. Novolak type epoxy resins such as ECN-235 and ECN-299 (both trade names); Epicron 830 manufactured by DIC, jER807 manufactured by Japan Epoxy Resin, Epototo YDF-170, YDF-175 manufactured by Toto Kasei -2004, bisphenol F type epoxy resin such as Araldide XPY306 manufactured by Ciba Japan Co., Ltd.
• glycidylamine type epoxy resin glycidylamine type epoxy resin
• Hydantoin-type epoxy resins such as Arapide CY-350 (trade name) manufactured by Japan
• alicyclic epoxy such as Celoxide 2021 manufactured by Daicel Chemical Industries, Araldide CY175 and CY179 manufactured by Ciba Japan Resin
• YL-933 manufactured by Japan Epoxy Resin Co., Ltd. E. N. , EPPN-501, EPPN-502, etc. (all trade names) trihydroxyphenylmethane type epoxy resin
• Japan Epoxy Resin YL-6056, YX-4000, YL-6121 all trade names
• Xylenol type or biphenol type epoxy resins or mixtures thereof bisphenol S type epoxy resins such as EBPS-200 manufactured by Nippon Kayaku Co., Ltd., EPX-30 manufactured by Asahi Denka Kogyo Co., Ltd., EXA-1514 manufactured by DIC Co., Ltd.
• Bisphenol A novolak type epoxy resin such as jER157S (trade name) manufactured by Japan Epoxy Resin; Tetraphenylol such as jERYL-931 manufactured by Japan Epoxy Resin, Araldide 163 manufactured by Ciba Japan Co., Ltd.
• Ethane type epoxy resin manufactured by Ciba Japan Heterocyclic epoxy resins such as Rudide PT810, TEPIC manufactured by Nissan Chemical Industries (all trade names); Diglycidyl phthalate resins such as Bremer DGT manufactured by Nippon Oil &Fats; Tetraglycidyl such as ZX-1063 manufactured by Tohto Kasei Xylenoylethane resin; ESN-190, ESN-360 manufactured by Nippon Steel Chemical Co., Ltd.
• Naphtalene group-containing epoxy resins such as HP-4032, EXA-4750, EXA-4700 manufactured by DIC; HP- manufactured by DIC Epoxy resins having a dicyclopentadiene skeleton such as 7200 and HP-7200H; glycidyl methacrylate copolymer epoxy resins such as CP-50S and CP-50M manufactured by NOF Corporation; and a copolymer epoxy of cyclohexylmaleimide and glycidyl methacrylate Resin; Epoxy-modified polybutadiene rubber Derivatives (e.g., manufactured by Daicel Chemical Industries, PB-3600, etc.), CTBN modified epoxy resin (e.g., Tohto Kasei Co.
• CTBN modified epoxy resin e.g., Tohto Kasei Co.
• YR-102, YR-450, etc. and others as mentioned, is not limited thereto.
• These epoxy resins can be used alone or in combination of two or more.
• novolak-type epoxy resins, modified novolak-type epoxy resins, heterocyclic epoxy resins, bixylenol-type epoxy resins or mixtures thereof are particularly preferable.
• Polyfunctional oxetane compounds 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) In addition to 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 novolac resin, poly (P-hydroxystyrene), card
• polyfunctional episulfide resin examples include YL7000 (bisphenol A type episulfide resin) manufactured by Japan Epoxy Resin Co., Ltd. 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 one molecule is in the range of 0.6 to 2.5 equivalents relative to 1 equivalent of carboxyl group of the carboxyl group-containing resin. Is preferred. When the blending amount is less than 0.6 equivalent, a carboxyl group remains in the solder resist film, and heat resistance, alkali resistance, electrical insulation, and the like are deteriorated. On the other hand, when the amount exceeds 2.5 equivalents, the low molecular weight cyclic (thio) ether group remains in the dried coating film, thereby reducing the strength of the coating film. More preferably, it is in the range of 0.8 to 2.0 equivalents.
• thermosetting components examples include melamine derivatives and benzoguanamine derivatives.
• examples include methylol melamine compounds, methylol benzoguanamine compounds, methylol glycoluril compounds, and methylol urea compounds.
• the alkoxymethylated melamine compound, alkoxymethylated benzoguanamine compound, alkoxymethylated glycoluril compound and alkoxymethylated urea compound are the methylol groups 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 components can be used alone or in combination of two or more.
• the photocurable thermosetting resin composition of the present embodiment 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.
• the compound having can be added.
• Such a compound having an isocyanate group or blocked isocyanate group in one molecule is a compound having a plurality of isocyanate groups in one molecule, that is, a polyisocyanate compound, or a compound having a plurality of blocked isocyanate groups in one molecule. That is, a blocked isocyanate compound etc. are mentioned.
• polyisocyanate compound for example, aromatic polyisocyanate, aliphatic polyisocyanate or alicyclic polyisocyanate is used.
• aromatic polyisocyanate include 4,4′-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, naphthalene-1,5-diisocyanate, o-xylylene diisocyanate, m- Examples include xylylene diisocyanate and 2,4-tolylene dimer.
• aliphatic polyisocyanate examples include tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, trimethylhexamethylene diisocyanate, 4,4-methylenebis (cyclohexyl isocyanate), and isophorone diisocyanate.
• alicyclic polyisocyanate examples include bicycloheptane triisocyanate.
• adduct bodies, burette bodies, and isocyanurate bodies of the isocyanate compounds listed above may be mentioned.
• the blocked isocyanate group contained in the blocked isocyanate compound is a group in which the isocyanate group is protected by reaction with a blocking agent and temporarily deactivated. When heated to a predetermined temperature, the blocking agent is dissociated to produce isocyanate groups.
• the blocked isocyanate compound an addition reaction product of an isocyanate compound and an isocyanate blocking agent is used.
• the isocyanate compound that can react with the blocking agent include isocyanurate type, biuret type, and adduct type.
• an isocyanate compound for example, aromatic polyisocyanate, aliphatic polyisocyanate, or alicyclic polyisocyanate is used.
• aromatic polyisocyanate, aliphatic polyisocyanate, and alicyclic polyisocyanate include the compounds exemplified above.
• isocyanate blocking agent examples include phenolic blocking agents such as phenol, cresol, xylenol, chlorophenol and ethylphenol; lactam blocking agents such as ⁇ -caprolactam, ⁇ -valerolactam, ⁇ -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, acetoaldoxime, acetoxime, methylethyl ketoxime, diacetyl monooxime, cyclohexane oxime; butyl mercaptan, hexyl mercaptan, t-butyl mercaptan, thiophenol, Mercaptan block agents such as methylthiophenol and
• 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 preferably 1 to 100 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin. When the blending amount is less than 1 part by mass, sufficient toughness of the coating film cannot be obtained, while when it exceeds 100 parts by mass, the storage stability is lowered. More preferably, it is 2 to 70 parts by mass.
• a urethanization catalyst can be added to the photocurable thermosetting resin composition of the present embodiment in order to accelerate the curing reaction between a hydroxyl group or a carboxyl group and an isocyanate group.
• the urethanization catalyst it is possible to use one or more urethanization catalysts selected from the group consisting of tin-based catalysts, metal chlorides, metal acetylacetonate salts, metal sulfates, amine compounds, and / or amine salts. preferable.
• tin-based catalyst examples include organic tin compounds such as stannous octoate and dibutyltin dilaurate, and inorganic tin compounds.
• 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. Can be 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 ′, N ′′, N ′′ -pentamethyldiethylenetriamine, N-methylmorpholine, N-ethylmorpholine, N, N-dimethylethanolamine, dimorpholinodiethyl ether, N-methylimidazole, dimethylaminopyridine, triazine, N′- (2-hydroxyethyl) -N, N, N′-trimethyl-bis (2-aminoethyl) ether, N, N-dimethylhexanolamine, N, N-dimethylaminoethoxyethanol, N, N, N′-trimethyl -N '-(2-hydroxyethyl) ethylenediamine, N- (2-hydroxyethyl) ) -N
• Examples of the amine salt include DBU (1,8-diaza-bicyclo [5,4,0] undecene-7) organic acid salt.
• the amount of these urethanization catalysts to be blended is a normal quantitative ratio, for example, preferably 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts per 100 parts by weight of carboxyl group-containing resin. 0 parts by mass.
• thermosetting component having a plurality of cyclic (thio) ether groups in one molecule
• thermosetting catalysts include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole.
• Imidazole derivatives such as 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole; dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N -Amine compounds such as dimethylbenzylamine and 4-methyl-N, N-dimethylbenzylamine; hydrazine compounds such as adipic acid dihydrazide and sebacic acid dihydrazide; and phosphorus compounds such as triphenylphosphine.
• Examples of commercially available products include 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (both trade names of imidazole compounds) manufactured by Shikoku Kasei Kogyo Co., Ltd. and U-CAT (registered by San Apro). Trademarks) 3503N, U-CAT3502T (all are trade names of blocked isocyanate compounds of dimethylamine), DBU, DBN, U-CATSA102, U-CAT5002 (all are bicyclic amidine compounds and salts thereof), and the like.
• 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.
• thermosetting catalysts is sufficient in a normal quantitative ratio, for example, for 100 parts by mass of a thermosetting component having a carboxyl group-containing resin or a plurality of cyclic (thio) ether groups in one molecule.
• the amount is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 15.0 parts by mass.
• the photocurable resin composition of the present embodiment can contain a colorant.
• a colorant known colorants such as red, blue, green and yellow can be used, and any of pigments, dyes and pigments may be used. However, it is preferable not to contain a halogen from the viewpoint of reducing the environmental burden and affecting the human body.
• 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.
• Monoazo lakes Pigment Red 48: 1, 48: 2, 48: 3, 48: 4, 49: 1, 49: 2, 50: 1, 52: 1, 52: 2, 53: 1, 53: 2, 57 : 1, 58: 4, 63: 1, 63: 2, 64: 1,68.
• Benzimidazolone series Pigment Red 171, 175, 176, 185, 208.
• Perylene series Solvent Red 135, 179, Pigment Red 123, 149, 166, 178, 179, 190, 194, 224.
• Diketopyrrolopyrrole type Pigment Red 254, 255, 264, 270, 272.
• Condensed azo series Pigment Red 144, 166, 214, 220, 221, 242.
• Anthraquinone series Pigment Red 168, 177, 216, Solvent Red 52, 149, 150, 207.
• Quinacridone series Pigment Red 122, 202, 206, 207, 209.
• Blue colorant include phthalocyanine-based and anthraquinone-based compounds, and pigment-based compounds include those classified as Pigments, specifically, the following: Pigment Blue: 15 : 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 60. Solvent Blue 35, 63, 67, 68, 70, 83, 87, 94, 97, 122, 136 etc. can be used as the dye system. In addition to the above, a metal-substituted or unsubstituted phthalocyanine compound can also be used.
• the green colorant includes phthalocyanine, anthraquinone, and perylene, and specifically, Pigment Green 7, 36, Solvent Green 3, 5, 20, 28, and the like can be used.
• a metal-substituted or unsubstituted phthalocyanine compound can also be used.
• Yellow colorant examples include monoazo, disazo, condensed azo, benzimidazolone, isoindolinone, anthraquinone, and the like.
• Anthraquinone series Solvent Yellow 163, Pigment Yellow 24, 108, 147, 193, 199, 202.
• Isoindolinone series Pigment Yellow 110, 109, 139, 179, 185.
• Condensed azo type Pigment Yellow 93, 94, 95, 128, 155, 166, 180.
• Benzimidazolone series Pigment Yellow 120, 151, 154, 156, 175, 181.
• Monoazo Pigment Yellow 1, 2, 3, 4, 5, 6, 9, 10, 12, 61, 62, 62: 1, 65, 73, 74, 75, 97, 100, 104, 105, 111, 116 , 167, 168, 169, 182, 183.
• the blending amount of these colorants is not particularly limited, but is preferably 10 parts by mass or less, particularly preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin.
• the compound having a plurality of ethylenically unsaturated groups in one molecule used in the photocurable thermosetting resin composition of the present embodiment is photocured by irradiation with active energy rays to convert the carboxyl group-containing resin into an alkali. It helps insolubilize or insolubilize in an aqueous solution.
• known polyester (meth) acrylate, polyether (meth) acrylate, urethane (meth) acrylate, carbonate (meth) acrylate, epoxy (meth) acrylate, and the like can be used.
• Hydroxyalkyl acrylates such as hydroxyethyl acrylate and 2-hydroxypropyl acrylate; diacrylates of glycols such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol and propylene glycol; N, N-dimethylacrylamide, N-methylolacrylamide, Acrylamides such as N, N-dimethylaminopropyl acrylamide; N, N-dimethylaminoethyl acrylate, N, N-dimethylaminopropyl acrylate Aminoalkyl acrylates such as relates; polyhydric alcohols such as hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, tris-hydroxyethyl isocyanurate or their ethylene oxide adducts, propylene oxide adducts, or ⁇ -caprolactone Polyvalent acrylates such as adducts; poly
• 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 one molecule is preferably 5 to 100 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin.
• 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.
• it exceeds 100 mass parts the solubility with respect to alkaline aqueous solution falls, and a coating film becomes weak.
• a ratio of 1 to 70 parts by mass is more preferable.
• a filler can be blended as necessary in order to increase the physical strength of the coating film.
• known inorganic or organic fillers can be used, but barium sulfate, spherical silica, and talc are particularly preferably used.
• metal hydroxides such as titanium oxide, metal oxides, and aluminum hydroxide can be used as extender pigment fillers.
• the blending amount of these fillers is preferably 200 parts by mass or less with respect to 100 parts by mass of the carboxyl group-containing resin. When the compounding amount exceeds 200 parts by mass, the viscosity of the composition increases, printability is reduced, and the cured product becomes brittle. More preferred is 0.1 to 150 parts by mass, and particularly preferred is 1 to 100 parts by mass.
• the photocurable thermosetting resin composition of the present embodiment 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.
• the photocurable thermosetting resin composition of the present embodiment can further use other elastomers for the purpose of imparting flexibility and improving the brittleness of the cured product.
• a polyester elastomer, a polyurethane elastomer, a polyester urethane elastomer, a polyamide elastomer, a polyesteramide elastomer, an acrylic elastomer, or an olefin elastomer can be used.
• resins in which a part or all of epoxy groups of epoxy resins having various skeletons are modified with carboxylic acid-modified butadiene-acrylonitrile rubber at both ends can be used.
• epoxy-containing polybutadiene elastomers, acrylic-containing polybutadiene elastomers, and the like can also be used. These elastomers can be used alone or as a mixture of two or more.
• the photocurable thermosetting resin composition of the present embodiment uses an organic solvent for the synthesis of a carboxyl group-containing resin and the adjustment of the composition, or for the adjustment of the viscosity for application to a substrate or a carrier film. can do.
• organic solvents examples include ketones, aromatic hydrocarbons, glycol ethers, glycol ether acetates, esters, alcohols, aliphatic hydrocarbons, petroleum solvents, and the like. More specifically, ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene; cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl Glycol ethers such as ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether; ethyl acetate, butyl acetate, dipropylene glycol methyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether a
• the photocurable thermosetting resin composition of the present embodiment is used.
• Antioxidants can be added.
• the radical scavenger may be commercially available, for example, ADK STAB AO-30, ADK STAB AO-330, ADK STAB AO-20, ADK STAB LA-77, ADK STAB LA-57, ADK STAB LA-67, ADK STAB LA-67, ADK STAB LA-68, ADK STAB LA-87 (Asahi Denka Co., Ltd., trade name), IRGANOX 1010, IRGANOX 1035, IRGANOX 1076, IRGANOX 1135, TINUVIN 111FDL, TINUVIN 123, TINUVIN 144, TINUVIN 152, TINUVIN 292, TINUVIN Japan brand name, product name) and the like.
• 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.
• the peroxide decomposing agent may be a commercially available one, for example, ADK STAB TPP (trade name, manufactured by Asahi Denka Co., Ltd.), Mark AO-412S (trade name, manufactured by Adeka Argus Chemical Co., Ltd.), Sumilyzer TPS (Sumitomo Chemical). Company name, product name) and the like. These antioxidants can be used alone or in combination of two or more.
• the photocurable thermosetting resin composition of the present embodiment has the above-described oxidation in order to take a countermeasure against stabilization against ultraviolet rays.
• an ultraviolet absorber can be used.
• ultraviolet absorber examples include benzophenone derivatives, benzoate derivatives, benzotriazole derivatives, triazine derivatives, benzothiazole derivatives, cinnamate derivatives, anthranilate derivatives, dibenzoylmethane derivatives, and the like.
• benzophenone derivatives include 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2,2′-dihydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, and the like. Is mentioned.
• 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.
• triazine derivative examples 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 (manufactured by Ciba Japan, trade name) and the like.
• ultraviolet absorbers can be used singly or in combination of two or more, and stabilization of a molded product obtained from the photocurable thermosetting resin composition of the present embodiment by using in combination with the above antioxidant. Can be planned.
• the photocurable thermosetting resin composition of the present embodiment uses known N phenylglycines, phenoxyacetic acids, thiophenoxyacetic acids, mercaptothiazole, etc. as chain transfer agents in order to improve sensitivity. Can do.
• chain transfer agents include, for example, chain transfer agents having a carboxyl group such as mercaptosuccinic acid, mercaptoacetic acid, mercaptopropionic acid, methionine, cysteine, thiosalicylic acid and derivatives thereof; mercaptoethanol, mercaptopropanol, mercaptobutanol, Chain transfer agents having a hydroxyl group such as mercaptopropanediol, mercaptobutanediol, hydroxybenzenethiol and derivatives thereof; 1-butanethiol, butyl-3-mercaptopropionate, methyl-3-mercaptopropionate, 2,2- (Ethylenedioxy) diethanethiol, ethanethiol, 4-methylbenzenethiol, dodecyl mercaptan, propanethiol, butanethiol, pentanethiol, 1-octanethiol, cyclo
• Polyfunctional mercaptan compounds can be used and are not particularly limited.
• Aliphatic thiols such as xylylene dimercaptan, 4,4′-dimercaptodiphenyl sulfide, and aromatic thiols such as 1,4-benzenedithiol; ethylene glycol bis (mercaptoacetate), polyethylene glycol bis (mercaptoacetate), Propylene glycol bis (mercaptoacetate), glycerin tris (mercaptoacetate), trimethylol ethane tris (mercaptoacetate), trimethylolpropane tris (mercaptoacetate), pentaerythri Poly (mercaptoacetate) s of polyhydric alcohols such as tetrakis (mercaptoacetate) and dipent
• Examples of these commercially available products include BMPA, MPM, EHMP, NOMP, MBMP, STMP, TMMP, PEMP, DPMP, and TEMPIC (above, manufactured by Sakai Chemical Industry Co., Ltd.), Karenz MT-PE1, Karenz MT-BD1, and Karenz- NR1 (manufactured by Showa Denko KK) and the like can be mentioned.
• heterocyclic compound having a mercapto group that acts as a chain transfer agent for example, mercapto-4-butyrolactone (also known as 2-mercapto-4-butanolide), 2-mercapto-4-methyl-4-butyrolactone, 2-mercapto- 4-ethyl-4-butyrolactone, 2-mercapto-4-butyrothiolactone, 2-mercapto-4-butyrolactam, N-methoxy-2-mercapto-4-butyrolactam, N-ethoxy-2-mercapto-4-butyrolactam N-methyl-2-mercapto-4-butyrolactam, N-ethyl-2-mercapto-4-butyrolactam, N- (2-methoxy) ethyl-2-mercapto-4-butyrolactam, N- (2-ethoxy) ethyl -2-Mercapto-4-butyrolactam, 2-mercapto-5-va Lolactone, 2-mercapto-5-val
• mercaptobenzothiazole, 3-mercapto-4-methyl-4H is a heterocyclic compound having a mercapto group that is a chain transfer agent that does not impair the developability of the photocurable thermosetting resin composition of the present embodiment.
• Preferred are -1,2,4-triazole, 5-methyl-1,3,4-thiadiazole-2-thiol, and 1-phenyl-5-mercapto-1H-tetrazole. These chain transfer agents can be used alone or in combination of two or more.
• an adhesion promoter can be used in order to improve the adhesion between layers or the adhesion between the photosensitive resin layer and the substrate.
• Specific examples include, for example, benzimidazole, benzoxazole, benzothiazole, 2-mercaptobenzoimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole (trade name: Axel M manufactured by Kawaguchi Chemical Industry Co., Ltd.), 3- Morpholinomethyl-1-phenyl-triazole-2-thione, 5-amino-3-morpholinomethyl-thiazole-2-thione, 2-mercapto-5-methylthio-thiadiazole, triazole, tetrazole, benzotriazole, carboxybenzotriazole, amino Examples include group-containing benzotriazoles and silane coupling agents.
• the photocurable thermosetting resin composition of the present embodiment can further contain a thixotropic agent such as finely divided silica, organic bentonite, montmorillonite, hydrotalcite, etc., if necessary.
• a thixotropic agent such as finely divided silica, organic bentonite, montmorillonite, hydrotalcite, etc.
• Organic bentonite and hydrotalcite are preferred as the thixotropic agent over time, and hydrotalcite is particularly excellent in electrical characteristics.
• Known additives such as copper damage preventing agents such as triazine and triazine thiol can be blended.
• the thermal polymerization inhibitor can be used to prevent thermal polymerization or temporal polymerization of the polymerizable compound contained in the photocurable thermosetting resin composition of the present embodiment.
• thermal polymerization inhibitors 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, Examples include picric acid, 4-toluidine, methylene blue, copper and organic chelating agent reactant, methyl salicylate, nitroso compound, chelate of nitroso compound and Al, and
• the photocurable thermosetting resin composition of the present embodiment is adjusted to a viscosity suitable for the coating method using, for example, the above organic solvent, and on the substrate, a dip coating method, a flow coating method, a roll coating method, a bar coater method
• a tack-free coating film can be formed by applying the organic solvent contained in the composition at a temperature of about 60 to 100 ° C. by volatile drying (preliminary drying).
• the contact pattern (or non-contact pattern) is selectively exposed with an active energy ray through a photomask on which a pattern is formed, or directly exposed with a pattern using a laser direct exposure machine.
• a resist pattern is formed by development with a 3 to 3% sodium carbonate aqueous solution.
• thermosetting component for example, by heating to a temperature of about 140 to 180 ° C. and thermosetting, the carboxyl group of the carboxyl group-containing resin in the composition and one molecule
• a thermosetting component having a plurality of cyclic (thio) ether groups reacts to form a cured coating film having excellent characteristics such as heat resistance, chemical resistance, moisture absorption resistance, adhesion, and electrical characteristics. it can.
• heat treatment thermosetting may be performed depending on the purpose and application.
• the base material examples include printed circuit boards and flexible printed circuit boards that are pre-formed with a circuit, paper-phenol resin, paper-epoxy resin, glass cloth-epoxy resin, glass-polyimide, glass cloth / non-woven cloth-epoxy resin. , Glass cloth / paper-epoxy resin, synthetic fiber-epoxy resin, copper-clad laminates of all grades (FR-4 etc.) using polyimide, polyethylene, PPO, cyanate ester, etc., polyimide film, PET A film, a glass substrate, a ceramic substrate, a wafer plate, or the like can be used.
• Volatile drying performed after applying the photocurable thermosetting resin composition of the present embodiment is a hot air circulation drying oven, an IR oven, a hot plate, a convection oven, or the like (having a heat source of an air heating method using steam). And a method in which the hot air in the dryer is brought into countercurrent contact and a method in which the hot air is blown onto the support from the nozzle).
• Exposure irradiation of active energy rays
• Exposure is performed on the coating film thus obtained.
• the exposed portion (the portion irradiated by the active energy ray) is cured.
• a direct drawing apparatus for example, a laser direct imaging apparatus that directly draws an image with a laser using CAD data from a computer
• an exposure apparatus equipped with a metal halide lamp and an (ultra) high pressure mercury lamp.
• either a gas laser or a solid laser may be used as long as laser light having a maximum wavelength in the range of 350 to 410 nm is used.
• the exposure amount varies depending on the film thickness and the like, but can be generally 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. .
• dipping method As the developing method, dipping method, shower method, spray method, brush method, etc. can be used, and as the developer, potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia
• An alkaline aqueous solution such as amines can be used.
• the photo-curable thermosetting resin composition of the present embodiment has a solder resist layer formed by applying and drying a solder resist on a film of polyethylene terephthalate or the like in advance, in addition to the method of directly applying to a substrate in a liquid state. It can also be used in the form of a dry film. The case where the photocurable thermosetting resin composition of this embodiment is used as a dry film is shown below.
• the dry film has a structure in which a carrier film, a solder resist layer, and a peelable cover film used as necessary are laminated in this order.
• the solder resist layer is a layer obtained by applying and drying an alkali-developable photocurable thermosetting resin composition on a carrier film or a cover film. After forming a solder resist layer on the carrier film, a cover film is laminated thereon, or a solder resist layer is formed on the cover film, and this laminate is laminated on the carrier film to obtain a dry film.
• the carrier film a thermoplastic film such as a polyester film having a thickness of 2 to 150 ⁇ m is used.
• the photocurable thermosetting resin composition of the present embodiment is uniformly applied to a carrier film or a cover film with a thickness of 10 to 150 ⁇ m using a blade coater, lip coater, comma coater, film coater, etc., and dried. Formed.
• a 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.
• a cured coating film can be formed by exposing, developing, and heat-curing the formed solder resist layer in the same manner as described above.
• the carrier film may be peeled off either before exposure or after exposure.
• 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.
• varnish A-1 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.
• varnish A-1 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.
• varnish A-1 this is referred to as varnish A-1.
• varnish A-3 363.9 g of 3,4-epoxycyclohexylmethyl acrylate (manufactured by Daicel Chemical Industries, Ltd., trade name: Cyclomer A200) and 3.6 g of dimethylbenzylamine as a ring-opening catalyst were added to the obtained carboxyl group-containing copolymer resin. Then, 1.80 g of hydroquinone monomethyl ether was added as a polymerization inhibitor, 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.
• varnish R-2 a resin solution of a carboxyl group-containing photosensitive resin having a value of 40 mgKOH / g and a nonvolatile content of 65% was obtained.
• varnish R-2 this is referred to as varnish R-2.
• varnish R-3 786 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 % Resin solution was obtained.
• 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 various components and proportions (parts by mass) shown in Table 1, premixed with a stirrer, kneaded with a three-roll mill, and photocurable heat A curable 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.
• thermosetting resin compositions of Examples and Comparative Examples shown in Table 2 were applied on the entire surface of a patterned copper foil substrate by screen printing, dried at 80 ° C., and every 10 minutes from 20 minutes to 80 minutes. The substrate was taken out and allowed to cool to room temperature. This substrate was developed with a 1% aqueous sodium carbonate solution at 30 ° C. for 60 seconds under the condition of a spray pressure of 0.2 MPa, and the maximum allowable drying time in which no residue remained was defined as the maximum development life.
• Electroless gold plating resistance Using 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 tape peeling is used to check for resist layer peeling and plating penetration. After the evaluation, the presence or absence of peeling of the resist layer was evaluated by tape peeling. The judgment criteria are as follows. ⁇ : Slight penetration was confirmed after plating, but there was no peeling after tape peeling. ⁇ : Slight penetration was confirmed 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 (HEST SYSTEM TPC-412MD manufactured by Espec Corp.), and the state of the coating film was evaluated. did.
• the judgment criteria are as follows. ⁇ : No swelling, peeling, discoloration, or dissolution ⁇ : Some swelling, peeling, discoloration, or dissolution ⁇ : Many swelling, peeling, discoloration, or dissolution
• Examples 14 to 21, Comparative Examples 7 to 9 Each composition of Examples 3, 5, 6, 8, 9, 10, 11, 13 and Comparative Examples 4, 5, 6 prepared at the blending ratios shown in Table 2 was diluted with methyl ethyl ketone and applied onto a PET film. And it dried at 80 degreeC for 30 minutes, and formed the photosensitive resin composition layer of thickness 20 micrometers. Further, a cover film was laminated thereon to produce a dry film, which were designated as Examples 14 to 21 and Comparative Examples 7 to 9, respectively.
• ⁇ 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 examples. Exposed. After the exposure, the carrier film was peeled off, and a 1% 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 150 ° 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, thermal shock resistance, HAST characteristics (electrical characteristics) required for the solder resist for semiconductor packages. It was recognized that it was useful as a photocurable thermosetting resin composition having

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