Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
  • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
  • C08F290/14—Polymers provided for in subclass C08G
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/14—Polycondensates modified by chemical after-treatment
• • 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
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
  • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
  • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
  • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
  • H01B3/44—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins

Definitions

• the present invention relates to a (meth) acrylate resin having an acid group having excellent alkali developability, excellent elongation in a cured product and adhesion to a substrate, a curable resin composition containing the same, and the curability.
• the present invention relates to a cured product made of a resin composition, an insulating material, and a resist member.
• an acid group-containing epoxy acrylate resin obtained by reacting an epoxy resin with acrylic acid and then reacting with an acid anhydride has been widely used as a resin material for a solder resist for a printed wiring substrate.
• the required performance for the resin material for solder resist is that it cures with a small exposure amount, it has excellent alkali developability, and it has excellent heat resistance, strength, flexibility, elongation, dielectric properties, substrate adhesion, etc. in the cured product.
• Various things can be mentioned.
• the problem to be solved by the present invention is a (meth) acrylate resin having an acid group having excellent alkali developability, excellent elongation in a cured product, and adhesion to a substrate, and a curable resin containing the same.
• the present invention provides a composition, a cured product made of the curable resin composition, an insulating material, and a resist member.
• an epoxy resin (A), an unsaturated monobasic acid (B), a compound (C) having a hydroxyl group and a carboxyl group, and a polybasic acid anhydride (D) are essential reaction raw materials.
• the present invention relates to a (meth) acrylate resin having an acid group, which comprises the same, a curable resin composition containing the same, a cured product made of the curable resin composition, an insulating material, and a resist member.
• the (meth) acrylate resin having an acid group of the present invention has excellent alkali developability, excellent elongation in a cured product and adhesion to a substrate, and is therefore suitable for use as an insulating material and a resist member. Can be done.
• the (meth) acrylate resin having an acid group of the present invention includes an epoxy resin (A), an unsaturated monobasic acid (B), a compound (C) having a hydroxyl group and a carboxyl group, and a polybasic acid anhydride (D). It is characterized by using and as an essential reaction raw material.
• (meth) acrylate means acrylate and / or methacrylate.
• (meth) acryloyl means acryloyl and / or methacryloyl.
• (meth) acrylic means acrylic and / or methacrylic.
• the specific structure of the epoxy resin (A) is not particularly limited as long as it has a plurality of epoxy groups in the resin and can react with the unsaturated monobasic acid (B).
• the epoxy resin (A) include bisphenol type epoxy resin, phenylene ether type epoxy resin, naphthylene ether type epoxy resin, biphenyl type epoxy resin, triphenylmethane type epoxy resin, phenol novolac type epoxy resin, and cresol novolac type.
• Epoxy resin bisphenol novolak type epoxy resin, naphthol novolak type epoxy resin, naphthol-phenol co-shrink novolak type epoxy resin, naphthol-cresol co-shrink novolak type epoxy resin, phenol aralkyl type epoxy resin, naphthol aralkyl type epoxy resin, dicyclopentadiene -Phenol addition reaction type epoxy resin, biphenyl aralkyl type epoxy resin, fluorene type epoxy resin, xanthene type epoxy resin, dihydroxybenzene type epoxy resin, trihydroxybenzene type epoxy resin, oxazolidone type epoxy resin and the like can be mentioned.
• These epoxy resins (A) can be used alone or in combination of two or more.
• a novolak type epoxy resin is preferable because a (meth) acrylate resin having an acid group having excellent alkali developability and excellent elongation and substrate adhesion in a cured product can be obtained.
• Cresol novolac type epoxy resin is more preferable.
• bisphenol type epoxy resin examples include bisphenol A type epoxy resin, bisphenol AP type epoxy resin, bisphenol B type epoxy resin, bisphenol BP type epoxy resin, bisphenol E type epoxy resin, bisphenol F type epoxy resin, and bisphenol S type epoxy. Examples include resin.
• Examples of the hydrogenated bisphenol type epoxy resin include hydrogenated bisphenol A type epoxy resin, hydrogenated bisphenol B type epoxy resin, hydrogenated bisphenol E type epoxy resin, hydrogenated bisphenol F type epoxy resin, and hydrogenated bisphenol S type epoxy. Examples include resin.
• biphenol type epoxy resin examples include 4,4'-biphenol type epoxy resin, 2,2'-biphenol type epoxy resin, tetramethyl-4,4'-biphenol type epoxy resin, and tetramethyl-2,2'.
• -Biphenol type epoxy resin and the like can be mentioned.
• hydrogenated biphenol type epoxy resin examples include hydrogenated 4,4'-biphenol type epoxy resin, hydrogenated 2,2'-biphenol type epoxy resin, and hydrogenated tetramethyl-4,4'-biphenol type epoxy resin. , Hydrogenated tetramethyl-2,2'-biphenol type epoxy resin and the like.
• the epoxy resin (A) preferably has a softening point of 80 ° C. or higher, more preferably 80 ° C. or higher and 100 ° C. or lower, and particularly preferably 85 ° C. or higher and 100 ° C. or lower.
• the softening point is a value measured by a method based on JIS K7234 (1986).
• the unsaturated monobasic acid (B) refers to a compound having an acid group and a polymerizable unsaturated bond in one molecule.
• the "polymerizable unsaturated bond” means an unsaturated bond capable of radical polymerization.
• Examples of the acid group include a carboxyl group, a sulfonic acid group, and a phosphoric acid group.
• Examples of the unsaturated monobasic acid (B) include acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, ⁇ -cyanocinnamic acid, ⁇ -styrylacrylic acid, ⁇ -fulfurylacrylic acid and the like. Further, an esterified product of the unsaturated monobasic acid, an acid halide, an acid anhydride and the like can also be used. Further, a compound represented by the following structural formula (1) can also be used.
• X represents an alkylene chain having 1 to 10 carbon atoms, a polyoxyalkylene chain, a (poly) ester chain, an aromatic hydrocarbon chain, or a (poly) carbonate chain, and is a halogen atom in the structure. Or an alkoxy group or the like.
• Y is a hydrogen atom or a methyl group.
• polyoxyalkylene chain examples include a polyoxyethylene chain and a polyoxypropylene chain.
• Examples of the (poly) ester chain include a (poly) ester chain represented by the following structural formula (X-1).
• R 1 is an alkylene group having 1 to 10 carbon atoms, and n is an integer of 1 to 5.
• aromatic hydrocarbon chain examples include a phenylene chain, a naphthylene chain, a biphenylene chain, a phenylnaphthylene chain, and a binaphthylene chain.
• a hydrocarbon chain having an aromatic ring such as a benzene ring, a naphthalene ring, an anthracene ring, or a phenanthrene ring can also be used.
• Examples of the (poly) carbonate chain include a (poly) carbonate chain represented by the following structural formula (X-2).
• R 2 is an alkylene group having 1 to 10 carbon atoms, and n is an integer of 1 to 5.
• the molecular weight of the compound represented by the structural formula (1) is preferably in the range of 100 to 500, more preferably in the range of 150 to 400.
• These unsaturated monobasic acids (B) can be used alone or in combination of two or more.
• the compound (C) having a hydroxyl group and a carboxyl group may have at least two hydroxyl groups and at least one carboxyl group.
• Examples of the compound (C) having a hydroxyl group and a carboxyl group include dimethylol propionic acid and dimethylol butanoic acid.
• the compound (C) having a hydroxyl group and a carboxyl group can be used alone or in combination of two or more.
• dimethylol propionic acid is preferable because a (meth) acrylate resin having an acid group having excellent alkali developability and excellent elongation and substrate adhesion in a cured product can be obtained. ..
• the amount of the compound (C) having a hydroxyl group and a carboxyl group a (meth) acrylate resin having an acid group having excellent alkali developability and excellent elongation and substrate adhesion in a cured product can be obtained. Therefore, the range of 0.2 to 0.4 mol is preferable, and the range of 0.25 to 0.35 is more preferable with respect to 1 mol of the epoxy group contained in the epoxy resin (A).
• the ratio of the epoxy resin (A), the unsaturated monobasic acid (B) and the compound (C) has excellent alkali developability, and excellent elongation and substrate adhesion in the cured product. Since a (meth) acrylate resin having an acid group having an acid group can be obtained, the carboxyl group of the unsaturated monobasic acid (B) and the compound (with respect to 1 mol of the epoxy group of the epoxy resin (A) can be obtained.
• the total number of moles of the carboxyl group contained in C) is preferably in the range of 0.95 to 1.05.
• polybasic acid anhydride (D) examples include aliphatic polybasic acid anhydrides, alicyclic polybasic acid anhydrides, aromatic polybasic acid anhydrides and the like.
• Examples of the aliphatic polybasic acid anhydride include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelli acid, suberic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, citraconic acid and itacone. Examples thereof include acid, glutaconic acid, and acid anhydrides of 1,2,3,4-butanetetracarboxylic acid.
• the aliphatic hydrocarbon group may be either a linear type or a branched type, and may have an unsaturated bond in the structure.
• an alicyclic polybasic acid anhydride having an acid anhydride group bonded to an alicyclic structure is used as an alicyclic polybasic acid anhydride, and an aromatic ring in other structural parts is used. It does not matter whether it is present or not.
• the alicyclic polybasic acid anhydride include tetrahydrophthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, cyclohexanetricarboxylic acid, cyclohexanetetracarboxylic acid, and bicyclo [2.2.1] heptane-2.
• aromatic polybasic acid anhydride examples include phthalic acid, trimellitic acid, pyromellitic acid, naphthalenedicarboxylic acid, naphthalenetricarboxylic acid, naphthalenetetracarboxylic acid, biphenyldicarboxylic acid, biphenyltricarboxylic acid and biphenyltetracarboxylic acid.
• aromatic polybasic acid anhydride examples include phthalic acid, trimellitic acid, pyromellitic acid, naphthalenedicarboxylic acid, naphthalenetricarboxylic acid, naphthalenetetracarboxylic acid, biphenyldicarboxylic acid, biphenyltricarboxylic acid and biphenyltetracarboxylic acid.
• examples thereof include acid anhydrides of benzophenone tetracarboxylic acid.
• polybasic acid anhydrides (D) can be used alone or in combination of two or more.
• tetrahydrophthalic anhydride and cyclohexane can be obtained because a (meth) acrylate resin having an acid group having excellent alkali developability and excellent elongation and substrate adhesion in a cured product can be obtained.
• -1,2-Dicarboxylic acid anhydride and succinic anhydride are preferable.
• the amount of the polybasic acid anhydride (D) used is such that a (meth) acrylate resin having an acid group having excellent alkali developability and excellent elongation and substrate adhesion in a cured product can be obtained. Therefore, the range of 0.35 to 1 mol is preferable, and the range of 0.45 to 0.95 mol is more preferable with respect to 1 mol of the epoxy resin (A).
• the method for producing the (meth) acrylate resin having an acid group of the present invention is not particularly limited, and any method may be used for producing the (meth) acrylate resin.
• the epoxy resin (A), the unsaturated monobasic acid (B), and the compound (C) having a hydroxyl group and a carboxyl group are first subjected to the presence of a basic catalyst.
• a method of reacting in a temperature range of 80 to 140 ° C., then adding a polybasic acid anhydride (D) and reacting in a temperature range of 80 to 140 ° C. is preferable.
• the reaction between the epoxy resin (A), the unsaturated monobasic acid (B), the compound (C) having a hydroxyl group and a carboxyl group, and the polybasic acid anhydride (D) is necessary. Alternatively, it can be carried out in an organic solvent.
• organic solvent examples include ketone solvents such as methyl ethyl ketone, acetone, dimethylformamide and methyl isobutyl ketone; cyclic ether solvents such as tetrahydrofuran and dioxolan; ester solvents such as methyl acetate, ethyl acetate and butyl acetate; toluene, xylene and solvent.
• ketone solvents such as methyl ethyl ketone, acetone, dimethylformamide and methyl isobutyl ketone
• cyclic ether solvents such as tetrahydrofuran and dioxolan
• ester solvents such as methyl acetate, ethyl acetate and butyl acetate
• toluene, xylene and solvent examples of the organic solvent.
• Aromatic solvents such as naphtha; alicyclic solvents such as cyclohexane and methylcyclohexane; alcohol solvents such as carbitol, cellosolve, methanol, isopropanol, butanol and propylene glycol monomethyl ether; alkylene glycol monoalkyl ethers and dialkylene glycol monoalkyl ethers.
• Glycol ether solvent such as dialkylene glycol monoalkyl ether acetate; methoxypropanol, cyclohexanone, methyl cellosolve, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate and the like.
• These organic solvents may be used alone or in combination of two or more. Further, the amount of the organic solvent used is preferably in the range of about 0.1 to 5 times the total mass of the reaction raw materials because the reaction efficiency is good.
• Examples of the basic catalyst include N-methylmorpholin, pyridine, 1,8-diazabicyclo [5.4.0] undecene-7 (DBU), 1,5-diazabicyclo [4.3.0] nonen-. 5 (DBN), 1,4-diazabicyclo [2.2.2] octane (DABCO), tri-n-butylamine or dimethylbenzylamine, butylamine, octylamine, monoethanolamine, diethanolamine, triethanolamine, imidazole, 1 -Methylimidazole, 2,4-dimethylimidazole, 1,4-diethylimidazole, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3- (N-phenyl) aminopropyltrimethoxysilane, 3-( Amine compounds such as 2-aminoethyl) aminopropyltrimethoxysilane, 3- (2-aminoethyl)
• Class ammonium salts phosphines such as trimethylphosphine, tributylphosphine, triphenylphosphine; tetramethylphosphonium chloride, tetraethylphosphonium chloride, tetrapropylphosphonium chloride, tetrabutylphosphonium chloride, tetrabutylphosphonium bromide, trimethyl (2-hydroxylpropyl) phosphonium Phosphonium salts such as chloride, triphenylphosphonium chloride, benzylphosphonium chloride; dibutyltin dilaurate, octyltin trilaurate, octyltin diacetate, dioctyltin diacetate, dioctyltin dineodecanoate, dibutyltin diacetate, tin octylate, Organic tin compounds such as 1,1,3,3-tetrabutyl-1
• the amount of the basic catalyst used is such that a (meth) acrylate resin having an acid group having excellent alkali developability and excellent elongation and substrate adhesion in a cured product can be obtained. 0.01 with respect to a total of 100 parts by mass of the epoxy resin (A), the unsaturated monobasic acid (B), the compound (C) having a hydroxyl group and a carboxyl group, and the polybasic acid anhydride (D).
• the range of about 1.0 part by mass is preferable, and the range of 0.05 to 0.8 is more preferable.
• the acid value of the (meth) acrylate resin having an acid group of the present invention is excellent in alkali developability, and a (meth) acrylate resin having an acid group having elongation in a cured product and adhesion to a substrate can be obtained. Therefore, the range of 50 to 150 mgKOH / g is preferable, and the range of 60 to 120 mgKOH / g is more preferable.
• the acid value of the (meth) acrylate resin having an acid group is a value measured by the neutralization titration method of JIS K0070 (1992).
• the (meth) acrylate resin having an acid group of the present invention a polymerization inhibitor, an antioxidant, or the like can be used, if necessary.
• polymerization inhibitor examples include p-methoxyphenol, p-methoxycresol, 4-methoxy-1-naphthol, 4,4'-dialkoxy-2,2'-bi-1-naphthol, 3- (N).
• -Salicyloyl amino-1,2,4-triazole, N'1, N'12-bis (2-hydroxybenzoyl) dodecanedihydrazide, styrenated phenol, N-isopropyl-N'-phenylbenzene-1,4-diamine , 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline and other phenolic compounds, hydroquinone, methylhydroquinone, p-benzoquinone, methyl-p-benzoquinone, 2,5-diphenylbenzoquinone, 2-hydroxy- Kinone compounds such as 1,4-naphthoquinone, anthraquinone and diphenoquinone, melamine, p-phenylenediamine, 4-aminodiphenylamine, N.I.
• N'-diphenyl-p-phenylenediamine, N-i-propyl-N'-phenyl-p-phenylenediamine, N- (1.3-dimethylbutyl) -N'-phenyl-p-phenylenediamine, diphenylamine, 4 , 4'-dicumyl-diphenylamine, 4,4'-dioctyl-diphenylamine, poly (2,2,4-trimethyl-1,2-dihydroquinoline), sylated diphenylamine, sylated diphenylamine and 2,4,4-trimethyl Penten reaction products, amine compounds such as diphenylamine and 2,4,4-trimethylpenten reaction products, phenothiazine, distearylthiodipropionate, 2,2-bis ( ⁇ [3- (dodecylthio) propionyl] oxy ⁇ Methyl) -1,3-propanediyl bis [3- (
• the same compounds as those exemplified for the polymerization inhibitor can be used, and the antioxidant may be used alone or in combination of two or more.
• Examples of commercially available products of the polymerization inhibitor and the antioxidant include "Q-1300” and “Q-1301” manufactured by Wako Pure Chemical Industries, Ltd. and “Smilizer BBM-S” manufactured by Sumitomo Chemical Industries, Ltd. , “Smilizer GA-80 is” and the like.
• the (meth) acrylate resin having an acid group of the present invention has a polymerizable (meth) acryloyl group in its molecular structure, it can be used as a curable resin composition by adding, for example, a photopolymerization initiator. be able to.
• photopolymerization initiator examples include 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- [4- (2-hydroxyethoxy) phenyl] -2-. Hydroxy-2-methyl-1-propane-1-one, thioxanthone and thioxanthone derivatives, 2,2'-dimethoxy-1,2-diphenylethan-1-one, diphenyl (2,4,6-trimethoxybenzoyl) phosphenyl Oxide, 2,4,6-trimethylbenzoyldiphenylphosphenyl oxide, bis (2,4,6-trimethylbenzoyl) phenylphosphenyl oxide, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1- Examples thereof include photoradical polymerization initiators such as on, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone.
• Examples of commercially available products of the other photopolymerization initiators include “Omnirad 1173”, “Omnirad 184”, “Omnirad 127”, “Omnirad 2959”, “Omnirad 369”, “Omnirad 379”, “Omnirad 90".
• the amount of the photopolymerization initiator added is preferably in the range of 0.05 to 15% by mass, preferably in the range of 0.1 to 10% by mass, in the total of the components other than the solvent of the curable resin composition, for example. Is more preferable.
• a photosensitizer such as an amine compound, a urea compound, a sulfur-containing compound, a phosphorus-containing compound, a chlorine-containing compound, and a nitrile compound can be used in combination, if necessary.
• the curable resin composition of the present invention may contain other resin components other than the (meth) acrylate resin having an acid group described above.
• the other resin components include a resin (E) having an acid group and a polymerizable unsaturated group, various (meth) acrylate monomers, and the like.
• the resin (E) having an acid group and a polymerizable unsaturated group may be any resin (E) having an acid group and a polymerizable unsaturated group in the resin, and for example, an acid group and a polymerizable unsaturated group may be used.
• Examples thereof include an acrylamide resin having a group, an ester resin having an acid group and a polymerizable unsaturated group, and the like.
• Examples of the acid group include those exemplified as the above-mentioned acid group.
• Examples of the epoxy resin having an acid group and a polymerizable unsaturated group include an epoxy resin, an unsaturated monobasic acid, and an epoxy (meth) acrylate resin having an acid group using a polybasic acid anhydride as an essential reaction raw material.
• Epoxy resin, unsaturated monobasic acid, polybasic acid anhydride, polyisocyanate compound, and epoxy (meth) acrylate resin having an acid group and urethane bond using a (meth) acrylate compound having a hydroxyl group as a reaction raw material Can be mentioned.
• epoxy resin the same ones as those exemplified as the above-mentioned epoxy resin (A) can be used, and the epoxy resin can be used alone or in combination of two or more.
• unsaturated monobasic acid the same ones as those exemplified as the above-mentioned unsaturated monobasic acid (B) can be used, and the unsaturated monobasic acid may be used alone or in combination of two or more. It can also be used together.
• polybasic acid anhydride the same ones as those exemplified as the above-mentioned polybasic acid anhydride (D) can be used, and the polybasic acid anhydride may be used alone or in combination of two or more. It can also be used together.
• polyisocyanate compound examples include aliphatic diisocyanate compounds such as butane diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and 2,4,4-trimethylhexamethylene diisocyanate; norbornan diisocyanate and isophorone diisocyanate.
• Alicyclic diisocyanate compounds such as hydrogenated xylylene diisocyanate and hydrogenated diphenylmethane diisocyanate; tolylene diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, diphenylmethane diisocyanate, 1,5-naphthalenedi isocyanate, 4,4'-diisocyanato-3 , 3'-Aromatic diisocyanate compounds such as dimethylbiphenyl and o-trizine diisocyanate; polymethylenepolyphenylpolyisocyanate having a repeating structure represented by the following structural formula (2); these isocyanurate modified products, biuret modified products, Examples thereof include allophanate denatured compounds. Further, these polyisocyanate compounds may be used alone or in combination of two or more.
• R 1 is either a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, respectively.
• R 2 is an independently alkyl group having 1 to 4 carbon atoms.
• l is an integer of 0 or 1 to 3
• m is an integer of 1 to 15.
• Examples of the (meth) acrylate compound having a hydroxyl group include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, trimethylolpropane (meth) acrylate, trimethylolpropanedi (meth) acrylate, and pentaerythritol (meth).
• a (poly) oxyalkylene chain such as a (poly) oxyethylene chain, a (poly) oxypropylene chain, or a (poly) oxytetramethylene chain was introduced into the molecular structure of the (meth) acrylate compound having various hydroxyl groups.
• a (poly) oxyalkylene modified product, a lactone modified product in which a (poly) lactone structure is introduced into the molecular structure of the (meth) acrylate compound having various hydroxyl groups, or the like can also be used.
• These (meth) acrylate compounds having a hydroxyl group may be used alone or in combination of two or more.
• the method for producing the epoxy resin having the acid group and the polymerizable unsaturated group is not particularly limited, and any method may be used for producing the epoxy resin.
• it may be carried out in an organic solvent if necessary, or a basic catalyst may be used if necessary.
• organic solvent the same ones as those exemplified as the above-mentioned organic solvent can be used, and the organic solvent can be used alone or in combination of two or more.
• the same catalysts as those exemplified as the above-mentioned basic catalyst can be used, and the basic catalyst may be used alone or in combination of two or more.
• Examples of the urethane resin having an acid group and a polymerizable unsaturated group include a polyisocyanate compound, a (meth) acrylate compound having a hydroxyl group, a polyol compound having a carboxyl group, and, if necessary, a polybasic acid anhydride.
• polyisocyanate compound the same one as exemplified as the above-mentioned polyisocyanate compound can be used, and the polyisocyanate compound may be used alone or in combination of two or more.
• the same compounds as those exemplified for the (meth) acrylate compound having a hydroxyl group can be used, and the (meth) acrylate compound having a hydroxyl group is used alone. It is also possible to use two or more kinds together.
• polyol compound having a carboxyl group examples include 2,2-dimethylol propionic acid, 2,2-dimethylol butanoic acid, and 2,2-dimethylol valeric acid.
• the polyol compound having a carboxyl group may be used alone or in combination of two or more.
• polybasic acid anhydride the same ones as those exemplified as the above-mentioned polybasic acid anhydride (D) can be used, and the polybasic acid anhydride may be used alone or in combination of two or more. It can also be used together.
• polyol compound other than the polyol compound having a carboxyl group examples include aliphatic polyol compounds such as ethylene glycol, propylene glycol, butanediol, hexanediol, glycerin, trimethylolpropane, ditrimethylolpropane, pentaerythritol and dipentaerythritol.
• Aromatic polyol compounds such as biphenol and bisphenol; (poly) oxyalkylene chains such as (poly) oxyethylene chain, (poly) oxypropylene chain and (poly) oxytetramethylene chain in the molecular structure of the various polyol compounds.
• polystyrene foam in which (poly) lactone structure is introduced into the molecular structure of the various polyol compounds, and the like can be mentioned.
• the polyol compound other than the polyol compound having a carboxyl group may be used alone or in combination of two or more.
• the method for producing the urethane resin having the acid group and the polymerizable unsaturated group is not particularly limited, and any method may be used for producing the urethane resin.
• it may be carried out in an organic solvent if necessary, or a basic catalyst may be used if necessary.
• organic solvent the same ones as those exemplified as the above-mentioned organic solvent can be used, and the organic solvent can be used alone or in combination of two or more.
• the same catalysts as those exemplified as the above-mentioned basic catalyst can be used, and the basic catalyst may be used alone or in combination of two or more.
• the acrylic resin having an acid group and a polymerizable unsaturated group for example, a (meth) acrylate compound ( ⁇ ) having a reactive functional group such as a hydroxyl group, a carboxyl group, an isocyanate group or a glycidyl group is polymerized as an essential component.
• the acrylic resin intermediate may be a copolymer of the (meth) acrylate compound ( ⁇ ) and other compounds having a polymerizable unsaturated group, if necessary.
• the other compounds having a polymerizable unsaturated group include (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate.
• Acrylic acid alkyl ester (meth) acrylate having an alicyclic structure such as cyclohexyl (meth) acrylate, isoboronyl (meth) acrylate, dicyclopentanyl (meth) acrylate; phenyl (meth) acrylate, benzyl (meth) acrylate , (Meta) acrylate having an aromatic ring such as phenoxyethyl acrylate; (meth) acrylate having a silyl group such as 3-methacryloxypropyltrimethoxysilane; styrene derivatives such as styrene, ⁇ -methylstyrene and chlorostyrene. Be done. These can be used alone or in combination of two or more.
• the (meth) acrylate compound ( ⁇ ) is not particularly limited as long as it can react with the reactive functional group of the (meth) acrylate compound ( ⁇ ), but the combination is as follows from the viewpoint of reactivity. Is preferable. That is, when a (meth) acrylate having a hydroxyl group is used as the (meth) acrylate compound ( ⁇ ), it is preferable to use a (meth) acrylate having an isocyanate group as the (meth) acrylate compound ( ⁇ ).
• a (meth) acrylate having a carboxyl group is used as the (meth) acrylate compound ( ⁇ )
• a (meth) acrylate having an isocyanate group is used as the (meth) acrylate compound ( ⁇ )
• the (meth) acrylate compound ( ⁇ ) When a (meth) acrylate having a glycidyl group is used as the (meth) acrylate compound ( ⁇ ), it is preferable to use a (meth) acrylate having a carboxyl group as the (meth) acrylate compound ( ⁇ ).
• the (meth) acrylate compound ( ⁇ ) can be used alone or in combination of two or more.
• polybasic acid anhydride the same ones as those exemplified as the above-mentioned polybasic acid anhydride (D) can be used, and the polybasic acid anhydride may be used alone or in combination of two or more. You can also do it.
• the method for producing the acrylic resin having the acid group and the polymerizable unsaturated group is not particularly limited, and any method may be used for producing the acrylic resin.
• it may be carried out in an organic solvent if necessary, or a basic catalyst may be used if necessary.
• organic solvent the same ones as those exemplified as the above-mentioned organic solvent can be used, and the organic solvent can be used alone or in combination of two or more.
• the same catalysts as those exemplified as the above-mentioned basic catalyst can be used, and the basic catalyst may be used alone or in combination of two or more.
• Examples of the amideimide resin having an acid group and a polymerizable unsaturated group include an amideimide resin having an acid group and / or an acid anhydride group, and a (meth) acrylate compound having a hydroxyl group and / or an epoxy group (meth).
• the compound having a reactive functional group may or may not have a (meth) acryloyl group.
• the amidimide resin may have only one of an acid group and an acid anhydride group, or may have both. From the viewpoint of reactivity with a (meth) acrylate compound having a hydroxyl group and an epoxy compound having a (meth) acryloyl group and reaction control, it is preferable that the compound has an acid anhydride group, and the acid group and the acid anhydride group are used. It is more preferable that the compound has both of the above.
• the solid acid value of the amideimide resin is preferably in the range of 60 to 350 mgKOH / g under neutral conditions, that is, under conditions where the acid anhydride group is not opened. On the other hand, the measured value under the condition that the acid anhydride group is opened, such as in the presence of water, is preferably in the range of 61 to 360 mgKOH / g.
• amidoimide resin examples include those obtained by using a polyisocyanate compound and a polybasic acid anhydride as reaction raw materials.
• polyisocyanate compound the same one as exemplified as the above-mentioned polyisocyanate compound can be used, and the polyisocyanate compound may be used alone or in combination of two or more.
• polybasic acid anhydride the same ones as those exemplified as the above-mentioned polybasic acid anhydride (D) can be used, and the polybasic acid anhydride may be used alone or in combination of two or more. It can also be used together.
• amidoimide resin a polybasic acid can be used as a reaction raw material in addition to the polyisocyanate compound and the polybasic acid anhydride, if necessary.
• any compound having two or more carboxyl groups in one molecule can be used.
• Phthalic acid methylhexahydrophthalic acid, citraconic acid, itaconic acid, glutaconic acid, 1,2,3,4-butanetetracarboxylic acid, cyclohexanetricarboxylic acid, cyclohexanetetracarboxylic acid, bicyclo [2.2.1] heptane- 2,3-Dicarboxylic acid, methylbicyclo [2.2.1] heptane-2,3-dicarboxylic acid, 4- (2,5-dioxotetratetra-3-yl) -1,2,3,4-tetrahydro Naphthalene-1,2-dicarboxylic acid, trimellitic acid, pyromellitic acid, naphthalenedicarboxylic acid, naphthalenetricarboxylic acid, naphthalenetetracarboxylic acid, biphenyldicarboxylic acid, biphenyltricarboxylic acid, biphenyltetracar
• polybasic acid for example, a copolymer of a conjugated diene vinyl monomer and acrylonitrile, which has a carboxyl group in its molecule, can also be used.
• These polybasic acids can be used alone or in combination of two or more.
• the same compounds as those exemplified for the (meth) acrylate compound having a hydroxyl group can be used, and the (meth) acrylate compound having a hydroxyl group is used alone. It is also possible to use two or more kinds together.
• the (meth) acrylate compound having an epoxy group is not particularly limited as long as it has a (meth) acryloyl group and an epoxy group in its molecular structure, and a wide variety of compounds can be used.
• (meth) acrylate monomers having a glycidyl group such as glycidyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether, and epoxycyclohexylmethyl (meth) acrylate; dihydroxybenzene diglycidyl ether, dihydroxynaphthalenedi glycidyl ether.
• Mono (meth) acrylates of diglycidyl ether compounds such as biphenol diglycidyl ether and bisphenol diglycidyl ether.
• These epoxy group-containing (meth) acrylate compounds may be used alone or in combination of two or more.
• a (meth) acrylate compound having one epoxy group is preferable because the reaction can be easily controlled, and a cured product having excellent alkali developability, excellent elongation and substrate adhesion.
• a (meth) acrylate monomer having a glycidyl group is preferable because a curable resin composition capable of forming the above can be obtained.
• the molecular weight of the (meth) acrylate monomer having a glycidyl group is preferably 500 or less.
• the ratio of the (meth) acrylate monomer having a glycidyl group to the total mass of the (meth) acrylate compound having an epoxy group is preferably 70% by mass or more, and more preferably 90% by mass or more.
• the method for producing the amidoimide resin having the acid group and the polymerizable unsaturated group is not particularly limited, and any method may be used for production. In the production of the amidoimide resin having an acid group and a polymerizable unsaturated group, it may be carried out in an organic solvent if necessary, or a basic catalyst may be used if necessary.
• organic solvent the same ones as those exemplified as the above-mentioned organic solvent can be used, and the organic solvent can be used alone or in combination of two or more.
• the same catalysts as those exemplified as the above-mentioned basic catalyst can be used, and the basic catalyst may be used alone or in combination of two or more.
• Examples of the acrylamide resin having an acid group and a polymerizable unsaturated group include a compound having a phenolic hydroxyl group, an alkylene oxide or an alkylene carbonate, an N-alkoxyalkyl (meth) acrylamide compound, and a polybasic acid anhydride. , If necessary, those obtained by reacting with unsaturated monobasic acid can be mentioned.
• the compound having a phenolic hydroxyl group means a compound having at least one phenolic hydroxyl group in the molecule.
• Examples of the compound having at least one phenolic hydroxyl group in the molecule include compounds represented by the following structural formulas (3-1) to (3-4).
• R 1 is any one of an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group, and a halogen atom.
• R 2 are independently hydrogen atoms or methyl groups.
• p is an integer of 0 or 1 or more, preferably an integer of 0 or 1 to 3, and more preferably 0 or 1 of 1.
• the position of the substituent on the aromatic ring in the above structural formula is arbitrary, and for example, in the naphthalene ring of the structural formula (3-2), it may be substituted on any ring, and the structural formula ( In 3-3), it may be substituted on any ring of the benzene ring present in one molecule, and in the structural formula (3-4), it may be substituted on any ring of the benzene ring present in one molecule. It is shown that it may be substituted with, and it is shown that the number of substituents in one molecule is p and q.
• the compound having a phenolic hydroxyl group includes, for example, a compound having at least one phenolic hydroxyl group in the molecule and a compound represented by any of the following structural formulas (x-1) to (x-5).
• a reaction product or the like using the above as an essential reaction raw material can also be used.
• a novolak type phenol resin or the like using one or more of compounds having at least one phenolic hydroxyl group in the molecule as a reaction raw material can also be used.
• h is 0 or 1.
• R 3 is any one of an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group, and a halogen atom, and i. Is 0 or an integer from 1 to 4.
• Z is any one of a vinyl group, a halomethyl group, a hydroxymethyl group and an alkyloxymethyl group.
• Y is any of an alkylene group having 1 to 4 carbon atoms, an oxygen atom, a sulfur atom, and a carbonyl group, and j is an integer of 1 to 4.
• alkylene oxide examples include ethylene oxide, propylene oxide, butylene oxide, and pentylene oxide.
• ethylene oxide or propylene oxide is preferable because a curable resin composition having excellent alkali developability and capable of forming a cured product having excellent elongation and substrate adhesion can be obtained.
• the alkylene oxide can be used alone or in combination of two or more.
• alkylene carbonate examples include ethylene carbonate, propylene carbonate, butylene carbonate, pentylene carbonate and the like.
• ethylene carbonate or propylene carbonate is preferable because a curable resin composition having excellent alkali developability and capable of forming a cured product having excellent elongation and substrate adhesion can be obtained.
• the alkylene carbonate can be used alone or in combination of two or more.
• N-alkoxyalkyl (meth) acrylamide compound examples include N-methoxymethyl (meth) acrylamide, N-ethoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, and N-methoxyethyl (meth) acrylamide. , N-ethoxyethyl (meth) acrylamide, N-butoxyethyl (meth) acrylamide and the like.
• the N-alkoxyalkyl (meth) acrylamide compound may be used alone or in combination of two or more.
• polybasic acid anhydride the same ones as those exemplified as the above-mentioned polybasic acid anhydride (D) can be used, and the polybasic acid anhydride may be used alone or in combination of two or more. It can also be used together.
• unsaturated monobasic acid the same as those exemplified as the above-mentioned unsaturated monobasic acid (B) can be used, and the unsaturated monobasic acid may be used alone or in combination of two or more. You can also do it.
• the method for producing the acrylamide resin having the acid group and the polymerizable unsaturated group is not particularly limited, and any method may be used for producing the acrylamide resin.
• the acrylamide resin having an acid group and a polymerizable unsaturated group it may be carried out in an organic solvent if necessary, and a basic catalyst and an acidic catalyst may be used as necessary.
• organic solvent the same ones as those exemplified as the above-mentioned organic solvent can be used, and the organic solvent can be used alone or in combination of two or more.
• the same catalysts as those exemplified as the above-mentioned basic catalyst can be used, and the basic catalyst may be used alone or in combination of two or more.
• the acidic catalyst examples include inorganic acids such as hydrochloric acid, sulfuric acid and phosphoric acid, organic acids such as methanesulfonic acid, paratoluenesulfonic acid and oxalic acid, and Lewis acids such as boron trifluoride, anhydrous aluminum chloride and zinc chloride. And so on. Further, a solid acid catalyst having a strong acid such as a sulfonyl group can also be used. These acidic catalysts can be used alone or in combination of two or more.
• ester resin having an acid group and a polymerizable unsaturated group for example, a compound having a phenolic hydroxyl group, an alkylene oxide or an alkylene carbonate, an unsaturated monobasic acid, and a polybasic acid anhydride are reacted with each other.
• the obtained ones can be mentioned.
• the same compounds as those exemplified as the above-mentioned compound having a phenolic hydroxyl group can be used, and the compound having the phenolic hydroxyl group may be used alone or in combination of two or more. It can also be used together.
• alkylene oxide the same ones as those exemplified as the above-mentioned alkylene oxide can be used.
• ethylene oxide or propylene oxide is preferable because a curable resin composition having excellent alkali developability and capable of forming a cured product having excellent elongation and substrate adhesion can be obtained.
• the alkylene oxide can be used alone or in combination of two or more.
• alkylene carbonate the same ones as those exemplified as the above-mentioned alkylene carbonate can be used.
• ethylene carbonate or propylene carbonate is preferable because a curable resin composition having excellent alkali developability and capable of forming a cured product having excellent elongation and substrate adhesion can be obtained.
• the alkylene carbonate can be used alone or in combination of two or more.
• unsaturated monobasic acid the same as those exemplified as the above-mentioned unsaturated monobasic acid (B) can be used, and the unsaturated monobasic acid may be used alone or in combination of two or more. You can also do it.
• polybasic acid anhydride the same ones as those exemplified as the above-mentioned polybasic acid anhydride (D) can be used, and the polybasic acid anhydride may be used alone or in combination of two or more. It can also be used together.
• the method for producing the ester resin having the acid group and the polymerizable unsaturated group is not particularly limited, and any method may be used for producing the ester resin.
• the ester resin having an acid group and a polymerizable unsaturated group it may be carried out in an organic solvent if necessary, or a basic catalyst and an acidic catalyst may be used if necessary.
• organic solvent the same ones as those exemplified as the above-mentioned organic solvent can be used, and the organic solvent can be used alone or in combination of two or more.
• the same catalysts as those exemplified as the above-mentioned basic catalyst can be used, and the basic catalyst may be used alone or in combination of two or more.
• the same ones as those exemplified as the above-mentioned acidic catalyst can be used, and the acidic catalyst can be used alone or in combination of two or more.
• the amount of the resin (E) having an acid group and a polymerizable unsaturated group is preferably in the range of 10 to 900 parts by mass with respect to 100 parts by mass of the (meth) acrylate resin having an acid group of the present invention.
• Examples of the various (meth) acrylate monomers include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, and hexyl (meth) acrylate, 2 -Alipid mono (meth) acrylate compounds such as ethylhexyl (meth) acrylate and octyl (meth) acrylate; alicyclic mono (meth) such as cyclohexyl (meth) acrylate, isobornyl (meth) acrylate and adamantyl mono (meth) acrylate.
• Acrylate compounds such as glycidyl (meth) acrylate and tetrahydrofurfuryl acrylate; benzyl (meth) acrylate, phenyl (meth) acrylate, phenylbenzyl (meth) acrylate, phenoxy (meth) acrylate, Aromatic mono (meth) such as phenoxyethyl (meth) acrylate, phenoxyethoxyethyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, phenoxybenzyl (meth) acrylate, and phenylphenoxyethyl (meth) acrylate.
• heterocyclic mono (meth) acrylate compounds such as glycidyl (meth) acrylate and tetrahydrofurfuryl acrylate
• benzyl (meth) acrylate phenyl (meth) acrylate, phenylbenzyl (meth
• Mono (meth) acrylate compounds such as acrylate compounds: Polyoxy such as (poly) oxyethylene chain, (poly) oxypropylene chain, and (poly) oxytetramethylene chain in the molecular structure of the various mono (meth) acrylate monomers.
• An aliphatic di (meth) acrylate compound such as glycol di (meth) acrylate, propylene glycol di (meth) acrylate, butanediol di (meth) acrylate, hexanediol di (meth) acrylate, and neopentyl glycol di (meth) acrylate; 1,4-Cyclohexanedimethanol di (meth) acrylate, norbornandi (meth) acrylate, norbornan dimethanol di (meth) acrylate, dicyclopentanyldi (meth) acrylate, tricyclodecanedimethanol di (meth) acrylate, etc.
• a chain-introduced polyoxyalkylene-modified di (meth) acrylate compound a lactone-modified di (meth) acrylate compound in which a (poly) lactone structure is introduced into the molecular structure of the various di (meth) acrylate compounds;
• An aliphatic tri (meth) acrylate compound such as (meth) acrylate and glycerin tri (meth) acrylate; a (poly) oxyethylene chain, a (poly) oxypropylene chain, etc. in the molecular structure of the aliphatic tri (meth) acrylate compound.
• a (poly) oxyalkylene chain such as a (poly) oxytetramethylene chain
• a (poly) lactone structure in the molecular structure of the aliphatic tri (meth) acrylate compound Introduced lactone-modified tri (meth) acrylate compound; tetrafunctional or higher aliphatic poly (meth) acrylate such as pentaerythritol tetra (meth) acrylate, ditrimethylolpropanetetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, etc.
• the above (poly) oxyalkylene-modified poly (meth) acrylate compound; a tetrafunctional or higher functional lactone-modified poly (meth) acrylate compound in which a (poly) lactone structure is introduced into the molecular structure of the aliphatic poly (meth) acrylate compound, etc. Can be mentioned.
• a (meth) acrylate monomer containing a phenol compound, a cyclic carbonate compound or a cyclic ether compound, and an unsaturated monocarboxylic acid as essential reaction raw materials can be used.
• phenol compound examples include cresol, xylenol, catechol, resorcinol, hydroquinone, 3-methylcatechol, 4-methylcatechol, 4-allylpyrocatechol, 1,2,3-trihydroxybenzene, 1,2,4-.
• Trihydroxybenzene 1-naphthol, 2-naphthol, 1,3-naphthalenediol, 1,5-naphthalenediol, 2,6-naphthalenediol, 2,7-naphthalenediol, hydrogenated bisphenol, hydrogenated biphenol, polyphenylene ether
• type diols polynaphthylene ether type diols, phenol novolac resins, cresol novolak resins, bisphenol novolak type resins, naphthol novolak type resins, phenol aralkyl type resins, naphthol aralkyl type resins, phenol resins having a cycloring structure and the like.
• cyclic carbonate compound examples include ethylene carbonate, propylene carbonate, butylene carbonate, and pentylene carbonate. These cyclic carbonate compounds may be used alone or in combination of two or more.
• cyclic ether compound examples include ethylene oxide, propylene oxide, and tetrahydrofuran. These cyclic ether compounds may be used alone or in combination of two or more.
• unsaturated monocarboxylic acid the same one as exemplified as the unsaturated monocarboxylic acid (B) described above can be used.
• the content of the other (meth) acrylate monomer is preferably 90% by mass or less in the curable resin composition of the present invention.
• the curable resin composition of the present invention contains, if necessary, a curing agent, a curing accelerator, an ultraviolet absorber, an organic solvent, an inorganic filler, polymer fine particles, a pigment, a defoaming agent, a viscosity modifier, and leveling. It can also contain various additives such as an agent, a flame retardant, and a storage stabilizer.
• curing agent examples include epoxy resins, polybasic acids, unsaturated monobasic acids, amine compounds, amide compounds, azo compounds, organic peroxides, polyol compounds, epoxy resins and the like.
• epoxy resin the same ones as those exemplified as the above-mentioned epoxy resin (A) can be used, and the epoxy resin can be used alone or in combination of two or more.
• polybasic acid examples include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, and terephthalic acid.
• Tetrahydrophthalic acid Tetrahydrophthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, citraconic acid, itaconic acid, glutaconic acid, 1,2,3,4-butanetetracarboxylic acid, cyclohexanetricarboxylic acid, cyclohexanetetracarboxylic acid, bicyclo [2 .2.1] Heptane-2,3-dicarboxylic acid, methylbicyclo [2.2.1] heptane-2,3-dicarboxylic acid, 4- (2,5-dioxotetraxoxy-3-yl) -1, 2,3,4-Tetrahydronaphthalene-1,2-dicarboxylic acid, trimellitic acid, pyromellitic acid, naphthalenedicarboxylic acid, naphthalenetricarboxylic acid, naphthalenetetracarboxylic acid, biphenyldicarboxylic
• polybasic acid for example, a copolymer of a conjugated diene vinyl monomer and acrylonitrile, which has a carboxyl group in its molecule, can also be used.
• polybasic acids can be used alone or in combination of two or more.
• unsaturated monobasic acid the same ones as those exemplified as the above-mentioned unsaturated monobasic acid (B) can be used, and the unsaturated monobasic acid may be used alone or in combination of two or more. It can also be used together.
• amine compound examples include diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, imidazole, BF3-amine complex, guanidine derivative and the like. These amine compounds may be used alone or in combination of two or more.
• amide compound examples include a polyamide resin synthesized from a dimer of dicyandiamide and linolenic acid and ethylenediamine. These amide compounds may be used alone or in combination of two or more.
• azo compound examples include azobisisobutyronitrile.
• organic peroxide examples include ketone peroxides, peroxyketals, hydroperoxides, dialkyl peroxides, diacyl peroxides, peroxyesters, peroxydicarbonates, alkyl peroxycarbonates and the like. These organic peroxides can be used alone or in combination of two or more.
• polyol compound examples include ethylene glycol, diethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 3-methyl-1,3-butanediol, 1, 5-Pentanediol, Neopentylglycol, 1,6-hexanediol, Glycerin, Glycerin mono (meth) acrylate, Trimethylol ethane, Trimethylol methanemono (meth) acrylate, Trimethylol propane, Trimethylol propane mono (meth) acrylate , Pentaerythritol mono (meth) acrylate, pentaerythritol di (meth) acrylate and other polyol monomers; , Hexahydrophthalic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, polyester polyol obtained by coco
• epoxy resin the same ones as those exemplified as the above-mentioned epoxy resin (A) can be used, and the epoxy resin can be used alone or in combination of two or more.
• the curing accelerator examples include phosphorus-based compounds, amine-based compounds, imidazoles, organic acid metal salts, Lewis acids, amine complex salts, and the like, which promote the curing reaction. These curing accelerators can be used alone or in combination of two or more.
• the amount of the curing accelerator added is preferably in the range of 0.01 to 10% by mass in the solid content of the curable resin composition, for example.
• UV absorber examples include 2- [4- ⁇ (2-hydroxy-3-dodecyloxypropyl) oxy ⁇ -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1. , 3,5-Triazine, 2- [4- ⁇ (2-Hydroxy-3-tridecyloxypropyl) oxy ⁇ -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1, Triazine derivatives such as 3,5-triazine, 2- (2'-xanthencarboxy-5'-methylphenyl) benzotriazole, 2- (2'-o-nitrobenzyloxy-5'-methylphenyl) benzotriazole, 2 -Xanthenecarboxy-4-dodecyloxybenzophenone, 2-o-nitrobenzyloxy-4-dodecyloxybenzophenone and the like can be mentioned. These UV absorbers can be used alone or in combination of two or more.
• organic solvent the same ones as those exemplified as the above-mentioned organic solvent can be used, and the organic solvent can be used alone or in combination of two or more.
• inorganic filler examples include fused silica, crystalline silica, alumina, silicon nitride, aluminum hydroxide and the like.
• the pigment a known and commonly used inorganic pigment or organic pigment can be used.
• inorganic pigment examples include white pigment, antimony red, red iron oxide, cadmium red, cadmium yellow, cobalt blue, navy blue, ultramarine blue, carbon black, graphite and the like. These inorganic pigments can be used alone or in combination of two or more.
• white pigment examples include titanium oxide, zinc oxide, magnesium oxide, zirconium oxide, aluminum oxide, barium sulfate, silica, talc, mica, aluminum hydroxide, calcium silicate, aluminum silicate, hollow resin particles, and zinc sulfide. And so on.
• organic pigment examples include quinacridone pigment, quinacridone quinone pigment, dioxazine pigment, phthalocyanine pigment, anthrapyrimidine pigment, anthanthrone pigment, indanslon pigment, flavanthron pigment, perylene pigment, diketopyrrolopyrrole pigment, perinone pigment, and the like.
• organic pigments examples include quinophthalone pigments, anthraquinone pigments, thioindigo pigments, benzimidazolone pigments, and azo pigments. These organic pigments can be used alone or in combination of two or more.
• the flame retardant examples include red phosphorus, monoammonium phosphate, diammonium phosphate, triammonium phosphate, ammonium phosphate such as ammonium polyphosphate, and inorganic phosphorus compounds such as phosphoric acid amide; phosphoric acid ester compounds and phosphones.
• the cured product of the present invention can be obtained by irradiating the curable resin composition with active energy rays.
• active energy ray include ionizing radiation such as ultraviolet rays, electron beams, ⁇ rays, ⁇ rays, and ⁇ rays.
• ultraviolet rays When ultraviolet rays are used as the active energy rays, they may be irradiated in an atmosphere of an inert gas such as nitrogen gas or in an air atmosphere in order to efficiently carry out the curing reaction by the ultraviolet rays.
• an ultraviolet lamp As a source of ultraviolet rays, an ultraviolet lamp is generally used from the viewpoint of practicality and economy. Specific examples thereof include low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, xenon lamps, gallium lamps, metal halide lamps, sunlight, and LEDs.
• the integrated light amount of the active energy rays is not particularly limited, but is preferably 0.1 to 50 kJ / m 2 , and more preferably 0.5 to 10 kJ / m 2 .
• the integrated light amount is in the above range, it is preferable because the generation of the uncured portion can be prevented or suppressed.
• the irradiation of the active energy beam may be performed in one step or may be divided into two or more steps.
• the cured product of the present invention has high photosensitivity, excellent alkali developability, and excellent elongation and dielectric properties. Therefore, for example, solder resists, interlayer insulating materials, packaging materials, and undercoats in semiconductor device applications. It can be suitably used as a package adhesive layer for a fill material, a circuit element, or the like, or as an adhesive layer between an integrated circuit element and a circuit board. Further, it can be suitably used as a thin film transistor protective film, a liquid crystal color filter protective film, a pigment resist for a color filter, a resist for a black matrix, a spacer and the like in a thin display application typified by LCD and OELD. Among these, it can be particularly preferably used for solder resist applications.
• the resin material for solder resist of the present invention comprises the curable resin composition.
• the resist member of the present invention is, for example, a photomask in which the resin material for solder resist is applied onto a substrate, an organic solvent is volatilized and dried in a temperature range of about 60 to 100 ° C., and then a desired pattern is formed. It can be obtained by exposing the unexposed portion with an active energy ray, developing the unexposed portion with an alkaline aqueous solution, and further heating and curing the unexposed portion in a temperature range of about 140 to 200 ° C.
• Examples of the base material include metal-clad laminates such as copper and aluminum.
• the solid content acid value measured under the acid anhydride group non-ring-opening condition was 160 mgKOH / g. 0.3 parts by mass of methquinone, pentaerythritol polyacrylate mixture (“Aronix M-306” manufactured by Toa Synthetic Co., Ltd., pentaerythritol triacrylate content of about 67%, hydroxyl value 159.7 mgKOH / g) 172 parts by mass and triphenylphosphine 3.6 parts by mass was added, and the mixture was reacted at 110 ° C. for 5 hours while blowing air.
• Equivalent amount 214 g / eq,) (hereinafter abbreviated as "epoxy resin (1)”) 214 parts by mass is dissolved, 0.9 parts by mass of dibutylhydroxytoluene and 0.2 parts by mass of methquinone are added, and then acrylic acid 72. A mass part and 1.4 parts by mass of triphenylphosphine were added, and the reaction was carried out at 120 ° C. for 10 hours while blowing air. Next, 72 parts by mass of diethylene glycol monomethyl ether acetate and 76 parts by mass of tetrahydrophthalic anhydride were added and reacted at 110 ° C. for 3 hours to obtain a resin (2) having an acid group and a polymerizable unsaturated group. The non-volatile content of the resin (2) having an acid group and a polymerizable unsaturated group was 65% by mass, and the solid content acid value was 80 mgKOH / g.
• Example 1 Preparation of acrylate resin (1) having an acid group
• a flask equipped with a thermometer, a stirrer, and a reflux cooler 131 parts by mass of diethylene glycol monomethyl ether acetate was placed, 214 parts by mass of the epoxy resin (1) was dissolved, 0.9 part by mass of dibutylhydroxytoluene, and 0.
• After adding 2 parts by mass 50 parts by mass of acrylic acid, 40 parts by mass of dimethylolpropionic acid and 1.5 parts by mass of triphenylphosphine were added, and the reaction was carried out at 120 ° C. for 12 hours while blowing air.
• an acrylate resin (1) having an acid group was obtained by 78 parts by mass of diethylene glycol monomethyl ether acetate and 82 parts by mass of tetrahydrophthalic anhydride.
• the non-volatile content of the acrylate resin (1) having an acid group was 65% by mass, and the solid content acid value was 80 mgKOH / g.
• the number of moles of dimethylolpropionic acid is 0.3 with respect to 1 mol of the epoxy group of the epoxy resin (1), and tetrahydrophthalic anhydride is obtained with respect to 1 mol of the epoxy group of the epoxy resin (1).
• the number of moles of the epoxy resin (1) was 0.54, and the total number of moles of the carboxyl groups of the acrylic acid and the dimethylolpropionic acid was 1.0 with respect to 1 mol of the epoxy group of the epoxy resin (1).
• Example 2 Preparation of acrylate resin (2) having an acid group
• the number of moles of dimethylolpropionic acid is 0.3 with respect to 1 mol of the epoxy group contained in the orthocresol novolac type epoxy resin, and tetrahydroanhydrogen is obtained with respect to 1 mol of the epoxy group possessed by the orthocresol novolac type epoxy resin.
• the number of moles of phthalic acid is 0.54, and the total number of moles of carboxyl groups of acrylic acid and dimethylolpropionic acid is 1.0 with respect to 1 mol of epoxy groups of orthocresol novolak type epoxy resin. rice field.
• Example 3 Preparation of acrylate resin (3) having an acid group
• 207 g / eq 207 parts by mass was dissolved, 0.9 parts by mass of dibutylhydroxytoluene and 0.1 parts by mass of methquinone were added, and then 50 parts by mass of acrylic acid, 40 parts by mass of dimethylol propionic acid, and 1 part of triphenylphosphine. .5 parts by mass was added, and the reaction was carried out at 120 ° C. for 12 hours while blowing air. Next, 42 parts by mass of diethylene glycol monomethyl ether acetate and 81 parts by mass of tetrahydrophthalic anhydride were added and reacted at 110 ° C. for 3 hours to obtain an acrylate resin (3) having an acid group.
• the non-volatile content of the acrylate resin (3) having an acid group was 69% by mass, and the solid content acid value was 81 mgKOH / g.
• the number of moles of dimethylolpropionic acid is 0.3 with respect to 1 mol of the epoxy group contained in the orthocresol novolac type epoxy resin, and tetrahydroanhydrogen is obtained with respect to 1 mol of the epoxy group possessed by the orthocresol novolac type epoxy resin.
• the number of moles of phthalic acid is 0.53, and the total number of moles of carboxyl groups of acrylic acid and dimethylolpropionic acid is 1.0 with respect to 1 mol of epoxy groups of orthocresol novolak type epoxy resin. rice field.
• Example 4 Preparation of acrylate resin (4) having an acid group
• a flask equipped with a thermometer, a stirrer, and a reflux cooler 128 parts by mass of diethylene glycol monomethyl ether acetate was placed, 214 parts by mass of the epoxy resin (1) was dissolved, and 0.9 parts by mass of dibutylhydroxytoluene and 0.
• 58 parts by mass of acrylic acid, 27 parts by mass of dimethylol propionic acid and 1.5 parts by mass of triphenylphosphine were added, and the reaction was carried out at 120 ° C. for 12 hours while blowing air.
• an acrylate resin (4) having an acid group 75 parts by mass of diethylene glycol monomethyl ether acetate and 79 parts by mass of tetrahydrophthalic anhydride were added and reacted at 110 ° C. for 3 hours to obtain an acrylate resin (4) having an acid group.
• the non-volatile content of the acrylate resin (4) having an acid group was 65% by mass, and the solid content acid value was 79 mgKOH / g.
• the number of moles of dimethylolpropionic acid is 0.2 with respect to 1 mol of the epoxy group of the epoxy resin (1), and tetrahydrophthalic anhydride is obtained with respect to 1 mol of the epoxy group of the epoxy resin (1).
• the number of moles of the epoxy resin (1) was 0.52, and the total number of moles of the carboxyl groups of the acrylic acid and the dimethylolpropionic acid was 1.0 with respect to 1 mol of the epoxy group of the epoxy resin (1).
• Example 5 Preparation of acrylate resin (5) having an acid group
• a flask equipped with a thermometer, a stirrer, and a reflux cooler 133 parts by mass of diethylene glycol monomethyl ether acetate was placed, 214 parts by mass of the epoxy resin (1) was dissolved, 0.9 part by mass of dibutylhydroxytoluene, and 0.
• After adding 2 parts by mass 43 parts by mass of acrylic acid, 54 parts by mass of dimethylol propionic acid and 1.6 parts by mass of triphenylphosphine were added, and the reaction was carried out at 120 ° C. for 12 hours while blowing air.
• an acrylate resin (5) having an acid group was obtained by 79 parts by mass of diethylene glycol monomethyl ether acetate and 84 parts by mass of tetrahydrophthalic anhydride.
• the non-volatile content of the acrylate resin (5) having an acid group was 65% by mass, and the solid content acid value was 79 mgKOH / g.
• the number of moles of dimethylolpropionic acid is 0.4 with respect to 1 mol of the epoxy group contained in the epoxy resin (1), and tetrahydrophthalic anhydride with respect to 1 mol of the epoxy group contained in the epoxy resin (1).
• the number of moles of the epoxy resin (1) was 0.55, and the total number of moles of the carboxyl groups of the acrylic acid and the dimethylolpropionic acid was 1.0 with respect to 1 mol of the epoxy group of the epoxy resin (1).
• Example 6 Preparation of acrylate resin (6) having an acid group
• a flask equipped with a thermometer, a stirrer, and a reflux cooler 119 parts by mass of diethylene glycol monomethyl ether acetate was placed, and the phenol novolac type epoxy resin "EPICLON N-775" (manufactured by DIC Co., Ltd., softening point 74 ° C., epoxy equivalent) was placed.
• the non-volatile content of the acrylate resin (6) having an acid group was 65% by mass, and the solid content acid value was 80 mgKOH / g.
• the number of moles of dimethylolpropionic acid is 0.3 with respect to 1 mol of the epoxy group of the phenol novolac type epoxy resin, and tetrahydrophthalic anhydride is obtained with respect to 1 mol of the epoxy group of the phenol novolak type epoxy resin.
• the number of moles was 0.49, and the total number of moles of carboxyl groups of acrylic acid and dimethylolpropionic acid was 1.0 with respect to 1 mol of epoxy groups of the phenol novolac type epoxy resin.
• Example 7 Preparation of acrylate resin (7) having an acid group
• a flask equipped with a thermometer, a stirrer, and a reflux cooler 113 parts by mass of diethylene glycol monomethyl ether acetate was placed, and a naphthalene-type epoxy resin "EPICLON HP-4710" (manufactured by DIC Co., Ltd., softening point 99 ° C., epoxy equivalent: 173 g / eq,) 173 parts by mass was dissolved, 0.8 parts by mass of dibutyl hydroxytoluene and 0.1 parts by mass of methquinone were added, and then 50 parts by mass of acrylic acid, 40 parts by mass of dimethylol propionic acid, and triphenylphosphine 1.
• the number of moles of dimethylolpropionic acid is 0.3 with respect to 1 mol of the epoxy group contained in the naphthalene type epoxy resin, and the molar number of tetrahydrophthalic anhydride is obtained with respect to 1 mol of the epoxy group contained in the naphthalene type epoxy resin.
• the number was 0.47, and the total number of moles of the carboxyl groups of the acrylic acid and the dimethylolpropionic acid was 1.0 with respect to 1 mol of the epoxy group of the naphthalene type epoxy resin.
• Example 8 Preparation of acrylate resin (8) having an acid group
• a flask equipped with a thermometer, a stirrer, and a reflux cooler 131 parts by mass of diethylene glycol monomethyl ether acetate was placed, 214 parts by mass of the epoxy resin (1) was dissolved, 0.9 part by mass of dibutylhydroxytoluene, and 0.
• 50 parts by mass of acrylic acid, 40 parts by mass of dimethylolpropionic acid and 1.5 parts by mass of triphenylphosphine were added, and the reaction was carried out at 120 ° C. for 12 hours while blowing air.
• an acrylate resin (8) having an acid group was obtained by reacting 62 parts by mass of diethylene glycol monomethyl ether acetate and 53 parts by mass of tetrahydrophthalic anhydride and reacted at 110 ° C. for 3 hours to obtain an acrylate resin (8) having an acid group.
• the non-volatile content of the acrylate resin (8) having an acid group was 65% by mass, and the solid content acid value was 57 mgKOH / g.
• the number of moles of dimethylolpropionic acid is 0.3 with respect to 1 mol of the epoxy group of the epoxy resin (1), and tetrahydrophthalic anhydride is obtained with respect to 1 mol of the epoxy group of the epoxy resin (1).
• the number of moles of the epoxy resin (1) was 0.35, and the total number of moles of the carboxyl groups of the acrylic acid and the dimethylolpropionic acid was 1.0 with respect to 1 mol of the epoxy group of the epoxy resin (1).
• Example 9 Preparation of acrylate resin (9) having an acid group
• a flask equipped with a thermometer, a stirrer, and a reflux cooler 131 parts by mass of diethylene glycol monomethyl ether acetate was placed, 214 parts by mass of the epoxy resin (1) was dissolved, 0.9 part by mass of dibutylhydroxytoluene, and 0.
• 50 parts by mass of acrylic acid, 40 parts by mass of dimethylolpropionic acid and 1.5 parts by mass of triphenylphosphine were added, and the reaction was carried out at 120 ° C. for 12 hours while blowing air.
• an acrylate resin (9) having an acid group 60 parts by mass of diethylene glycol monomethyl ether acetate and 49 parts by mass of tetrahydrophthalic anhydride were added and reacted at 110 ° C. for 3 hours to obtain an acrylate resin (9) having an acid group.
• the non-volatile content of the acrylate resin (9) having an acid group was 65% by mass, and the solid content acid value was 51 mgKOH / g.
• the number of moles of dimethylolpropionic acid is 0.3 with respect to 1 mol of the epoxy group of the epoxy resin (1), and tetrahydrophthalic anhydride is obtained with respect to 1 mol of the epoxy group of the epoxy resin (1).
• the number of moles of the epoxy resin (1) was 0.32, and the total number of moles of the carboxyl groups of the acrylic acid and the dimethylolpropionic acid was 1.0 with respect to 1 mol of the epoxy group of the epoxy resin (1).
• Example 10 Preparation of acrylate resin (10) having an acid group
• a flask equipped with a thermometer, a stirrer, and a reflux cooler 131 parts by mass of diethylene glycol monomethyl ether acetate was placed, 214 parts by mass of the epoxy resin (1) was dissolved, 0.9 part by mass of dibutylhydroxytoluene, and 0.
• 50 parts by mass of acrylic acid, 40 parts by mass of dimethylolpropionic acid and 1.5 parts by mass of triphenylphosphine were added, and the reaction was carried out at 120 ° C. for 12 hours while blowing air.
• an acrylate resin (10) having an acid group was obtained by 169 parts by mass of diethylene glycol monomethyl ether acetate and 144 parts by mass of tetrahydrophthalic anhydride.
• the non-volatile content of the acrylate resin (10) having an acid group was 60%, and the solid content acid value was 121 mgKOH / g.
• the number of moles of dimethylolpropionic acid is 0.3 with respect to 1 mol of the epoxy group of the epoxy resin (1), and tetrahydrophthalic anhydride is obtained with respect to 1 mol of the epoxy group of the epoxy resin (1).
• the number of moles of the epoxy resin (1) was 0.95, and the total number of moles of the carboxyl groups of the acrylic acid and the dimethylolpropionic acid was 1.0 with respect to 1 mol of the epoxy group of the epoxy resin (1).
• Example 11 Preparation of acrylate resin (11) having an acid group
• a flask equipped with a thermometer, a stirrer, and a reflux cooler 131 parts by mass of diethylene glycol monomethyl ether acetate was placed, 214 parts by mass of the epoxy resin (1) was dissolved, 0.9 part by mass of dibutylhydroxytoluene, and 0.
• 50 parts by mass of acrylic acid, 40 parts by mass of dimethylolpropionic acid and 1.5 parts by mass of triphenylphosphine were added, and the reaction was carried out at 120 ° C. for 12 hours while blowing air.
• an acrylate resin (11) having an acid group was obtained by 174 parts by mass of diethylene glycol monomethyl ether acetate and 152 parts by mass of tetrahydrophthalic anhydride.
• the non-volatile content of the acrylate resin (11) having an acid group was 60% by mass, and the solid content acid value was 125 mgKOH / g.
• the number of moles of dimethylolpropionic acid is 0.3 with respect to 1 mol of the epoxy group of the epoxy resin (1), and tetrahydrophthalic anhydride is obtained with respect to 1 mol of the epoxy group of the epoxy resin (1).
• the number of moles of the epoxy resin (1) was 1.0, and the total number of moles of the carboxyl groups of the acrylic acid and the dimethylolpropionic acid was 1.0 with respect to 1 mol of the epoxy group of the epoxy resin (1).
• Example 12 Preparation of acrylate resin (12) having an acid group
• a flask equipped with a thermometer, a stirrer, and a reflux cooler 131 parts by mass of diethylene glycol monomethyl ether acetate was placed, 214 parts by mass of the epoxy resin (1) was dissolved, 0.9 part by mass of dibutylhydroxytoluene, and 0.
• 50 parts by mass of acrylic acid, 40 parts by mass of dimethylolpropionic acid and 1.5 parts by mass of triphenylphosphine were added, and the reaction was carried out at 120 ° C. for 12 hours while blowing air.
• an acrylate resin (12) having an acid group was obtained by 177 parts by mass of diethylene glycol monomethyl ether acetate and 157 parts by mass of tetrahydrophthalic anhydride.
• the non-volatile content of the acrylate resin (12) having an acid group was 60% by mass, and the solid content acid value was 127 mgKOH / g.
• the number of moles of dimethylolpropionic acid is 0.3 with respect to 1 mol of the epoxy group of the epoxy resin (1), and tetrahydrophthalic anhydride is obtained with respect to 1 mol of the epoxy group of the epoxy resin (1).
• the number of moles of the epoxy resin (1) was 1.03, and the total number of moles of the carboxyl groups of the acrylic acid and the dimethylolpropionic acid was 1.0 with respect to 1 mol of the epoxy group of the epoxy resin (1).
• Example 13 Preparation of acrylate resin (13) having an acid group
• a flask equipped with a thermometer, a stirrer, and a reflux cooler 131 parts by mass of diethylene glycol monomethyl ether acetate was placed, 214 parts by mass of the epoxy resin (1) was dissolved, 0.9 part by mass of dibutylhydroxytoluene, and 0.
• 50 parts by mass of acrylic acid, 40 parts by mass of dimethylolpropionic acid and 1.5 parts by mass of triphenylphosphine were added, and the reaction was carried out at 120 ° C. for 12 hours while blowing air.
• acrylate resin (13) having an acid group 78 parts by mass of diethylene glycol monomethyl ether acetate and 83 parts by mass of cyclohexane-1,2-dicarboxylic acid anhydride were added and reacted at 110 ° C. for 3 hours to obtain an acrylate resin (13) having an acid group.
• the non-volatile content of the acrylate resin (13) having an acid group was 65% by mass, and the solid content acid value was 80 mgKOH / g.
• the number of moles of dimethylolpropionic acid is 0.3 with respect to 1 mol of the epoxy group contained in the epoxy resin (1), and cyclohexane-1,
• the number of moles of 2-dicarboxylic acid anhydride is 0.54, and the total number of moles of carboxyl groups of acrylic acid and dimethylolpropionic acid is 1.0 with respect to 1 mole of epoxy group of epoxy resin (1).
• Example 14 Preparation of acrylate resin (14) having an acid group
• a flask equipped with a thermometer, a stirrer, and a reflux cooler 131 parts by mass of diethylene glycol monomethyl ether acetate was placed, 214 parts by mass of the epoxy resin (1) was dissolved, 0.9 part by mass of dibutylhydroxytoluene, and 0.
• 50 parts by mass of acrylic acid, 40 parts by mass of dimethylolpropionic acid and 1.5 parts by mass of triphenylphosphine were added, and the reaction was carried out at 120 ° C. for 12 hours while blowing air.
• an acrylate resin (14) having an acid group 60 parts by mass of diethylene glycol monomethyl ether acetate and 49 parts by mass of anhydrous shavings were added and reacted at 110 ° C. for 3 hours to obtain an acrylate resin (14) having an acid group.
• the non-volatile content of the acrylate resin (14) having an acid group was 65% by mass, and the solid content acid value was 79 mgKOH / g.
• the number of moles of dimethylolpropionic acid is 0.3 with respect to 1 mol of the epoxy group contained in the epoxy resin (1), and succinic anhydride is used with respect to 1 mol of the epoxy group contained in the epoxy resin (1).
• the number of moles was 0.49, and the total number of moles of the carboxyl groups of acrylic acid and dimethylolpropionic acid was 1.0 with respect to 1 mole of the epoxy group of the epoxy resin (1).
• Example 15 Preparation of acrylate resin (15) having an acid group
• a flask equipped with a thermometer, a stirrer, and a reflux cooler 129 parts by mass of diethylene glycol monomethyl ether acetate was placed, 214 parts by mass of the epoxy resin (1) was dissolved, and 0.9 parts by mass of dibutylhydroxytoluene and 0.
• After adding 2 parts by mass 48 parts by mass of acrylic acid, 40 parts by mass of dimethylolpropionic acid and 1.5 parts by mass of triphenylphosphine were added, and the reaction was carried out at 120 ° C. for 10 hours while blowing air.
• an acrylate resin (15) having an acid group was obtained by 81 parts by mass of diethylene glycol monomethyl ether acetate and 88 parts by mass of tetrahydrophthalic anhydride.
• the non-volatile content of the acrylate resin (15) having an acid group was 65% by mass, and the solid content acid value was 80 mgKOH / g.
• the number of moles of dimethylolpropionic acid is 0.3 with respect to 1 mol of the epoxy group of the epoxy resin (15), and tetrahydrophthalic anhydride is obtained with respect to 1 mol of the epoxy group of the epoxy resin (1).
• the number of moles of the epoxy resin (1) was 0.58, and the total number of moles of the carboxyl groups of the acrylic acid and the dimethylolpropionic acid was 0.96 with respect to 1 mol of the epoxy group of the epoxy resin (1).
• Example 16 Preparation of acrylate resin (16) having an acid group
• a flask equipped with a thermometer, a stirrer, and a reflux cooler 128 parts by mass of diethylene glycol monomethyl ether acetate was placed, 214 parts by mass of the epoxy resin (1) was dissolved, and 0.9 parts by mass of dibutylhydroxytoluene and 0.
• an acrylate resin (16) having an acid group was obtained by 82 parts by mass of diethylene glycol monomethyl ether acetate and 91 parts by mass of tetrahydrophthalic anhydride.
• the non-volatile content of the acrylate resin (16) having an acid group was 65% by mass, and the solid content acid value was 80 mgKOH / g.
• the number of moles of dimethylolpropionic acid is 0.3 with respect to 1 mol of the epoxy group of the epoxy resin (16), and tetrahydrophthalic anhydride is obtained with respect to 1 mol of the epoxy group of the epoxy resin (1).
• the number of moles of the epoxy resin (1) was 0.60, and the total number of moles of the carboxyl groups of the acrylic acid and the dimethylolpropionic acid was 0.93 with respect to 1 mol of the epoxy group of the epoxy resin (1).
• Example 17 Preparation of acrylate resin (17) having an acid group
• a flask equipped with a thermometer, a stirrer, and a reflux cooler 132 parts by mass of diethylene glycol monomethyl ether acetate was placed, 214 parts by mass of the epoxy resin (1) was dissolved, 0.9 part by mass of dibutylhydroxytoluene, and 0.
• After adding 2 parts by mass 53 parts by mass of acrylic acid, 40 parts by mass of dimethylolpropionic acid and 1.5 parts by mass of triphenylphosphine were added, and the reaction was carried out at 120 ° C. for 11 hours while blowing air.
• an acrylate resin (17) having an acid group 76 parts by mass of diethylene glycol monomethyl ether acetate and 79 parts by mass of tetrahydrophthalic anhydride were added and reacted at 110 ° C. for 3 hours to obtain an acrylate resin (17) having an acid group.
• the non-volatile content of the acrylate resin (17) having an acid group was 65% by mass, and the solid content acid value was 80 mgKOH / g.
• the number of moles of dimethylolpropionic acid is 0.3 with respect to 1 mol of the epoxy group of the epoxy resin (1), and tetrahydrophthalic anhydride is obtained with respect to 1 mol of the epoxy group of the epoxy resin (1).
• the number of moles of the epoxy resin (1) was 0.52, and the total number of moles of the carboxyl groups of the acrylic acid and the dimethylolpropionic acid was 1.04 with respect to 1 mol of the epoxy group of the epoxy resin (1).
• Example 18 Preparation of acrylate resin (18) having an acid group
• 133 parts by mass of diethylene glycol monomethyl ether acetate was placed, 214 parts by mass of the epoxy resin (1) was dissolved, 0.9 part by mass of dibutylhydroxytoluene, and 0.
• an acrylate resin (18) having an acid group 75 parts by mass of diethylene glycol monomethyl ether acetate and 76 parts by mass of tetrahydrophthalic anhydride were added and reacted at 110 ° C. for 3 hours to obtain an acrylate resin (18) having an acid group.
• the non-volatile content of the acrylate resin (18) having an acid group was 65% by mass, and the solid content acid value was 80 mgKOH / g.
• the number of moles of dimethylolpropionic acid is 0.3 with respect to 1 mol of the epoxy group of the epoxy resin (18), and tetrahydrophthalic anhydride is obtained with respect to 1 mol of the epoxy group of the epoxy resin (1).
• the number of moles of the epoxy resin (1) was 0.5, and the total number of moles of the carboxyl groups of the acrylic acid and the dimethylolpropionic acid was 1.07 with respect to 1 mol of the epoxy group of the epoxy resin (1).
• Example 19 Preparation of acrylate resin (19) having an acid group
• a flask equipped with a thermometer, a stirrer, and a reflux cooler 132 parts by mass of diethylene glycol monomethyl ether acetate was placed, 214 parts by mass of the epoxy resin (1) was dissolved, 0.9 part by mass of dibutylhydroxytoluene, and 0.
• 50 parts by mass of acrylic acid, 44 parts by mass of dimethylolbutanoic acid and 1.5 parts by mass of triphenylphosphine were added, and the reaction was carried out at 120 ° C. for 12 hours while blowing air.
• Example 20 Preparation of methacrylate resin (1) having an acid group
• a flask equipped with a thermometer, a stirrer, and a reflux cooler 135 parts by mass of diethylene glycol monomethyl ether acetate was placed, 214 parts by mass of the epoxy resin (1) was dissolved, 0.9 part by mass of dibutylhydroxytoluene, and 0.
• After adding 2 parts by mass 60 parts by mass of methacrylic acid, 40 parts by mass of dimethylol propionic acid, and 1.6 parts by mass of triphenylphosphine were added, and the reaction was carried out at 120 ° C. for 10 hours while blowing air.
• a methacrylate resin (1) having an acid group 80 parts by mass of diethylene glycol monomethyl ether acetate and 84 parts by mass of tetrahydrophthalic anhydride were added and reacted at 110 ° C. for 3 hours to obtain a methacrylate resin (1) having an acid group.
• the non-volatile content of the methacrylate resin (1) having an acid group was 65% by mass, and the solid content acid value was 79 mgKOH / g.
• the number of moles of dimethylolpropionic acid is 0.3 with respect to 1 mol of the epoxy group of the epoxy resin (1), and tetrahydrophthalic anhydride is obtained with respect to 1 mol of the epoxy group of the epoxy resin (1).
• the number of moles of the epoxy resin (1) was 0.55, and the total number of moles of the carboxyl groups of methacrylic acid and dimethylolpropionic acid was 1.0 with respect to 1 mole of the epoxy group of the epoxy resin (1).
• an acrylate resin (R1) having an acid group was obtained by 74 parts by mass of diethylene glycol monomethyl ether acetate and 78 parts by mass of tetrahydrophthalic anhydride were added and reacted at 110 ° C. for 3 hours to obtain an acrylate resin (R1) having an acid group.
• the non-volatile content of the acrylate resin (R1) having an acid group was 65% by mass, and the solid content acid value was 80 mgKOH / g.
• the number of moles of dimethylol propionic acid is 0.1 with respect to 1 mol of the epoxy group contained in the epoxy resin (1), and acrylic acid and dimethylol propionic acid and the dimethylol propionic acid are contained with respect to 1 mol of the epoxy group contained in the epoxy resin (1).
• the total number of moles of carboxyl groups contained in methylol propionic acid was 1.0.
• an acrylate resin (R2) having an acid group was obtained by 81 parts by mass of diethylene glycol monomethyl ether acetate and 85 parts by mass of tetrahydrophthalic anhydride were added and reacted at 110 ° C. for 3 hours to obtain an acrylate resin (R2) having an acid group.
• the non-volatile content of the acrylate resin (R2) having an acid group was 65% by mass, and the solid content acid value was 80 mgKOH / g.
• the number of moles of dimethylol propionic acid is 0.5 with respect to 1 mol of the epoxy group contained in the epoxy resin (1), and methacrylic acid and dimethylol propionic acid and the dimethylol propionic acid are contained with respect to 1 mol of the epoxy group contained in the epoxy resin (1).
• the total number of moles of carboxyl groups contained in methylol propionic acid was 1.0.
• Example 21 Preparation of curable resin composition (1)
• Ether acetate, a photopolymerization initiator (“Omnirad 907” manufactured by IGM), 2-ethyl-4-methylimidazole, and phthalocyanine green are blended in parts by mass shown in Tables 1 and 2, and kneaded by a roll mill.
• the curable resin composition (1) was obtained.
• Curable resin compositions (R1) and (R2) were obtained in the same manner as in Example 21 with the compositions and formulations shown in Table 2.
• Table 1 shows the compositions and evaluation results of the curable resin compositions (2) to (22) prepared in Examples 21 to 42 and the curable resin compositions (R1) and (R2) prepared in Comparative Examples 3 and 4. And 2 show.
• Example 43 Preparation of curable resin composition (23)
• 4-Methylthiophenyl) -2-morpholinopropane-1-one (“Omnirad 907” manufactured by IGM Resins) and diethylene glycol monomethyl ether acetate as an organic solvent are blended in parts by mass shown in Table 3 to form a curable resin composition. I got the thing (22).
• Curable resin compositions (R3) and (R4) were obtained in the same manner as in Example 43 with the compositions and formulations shown in Table 4.
• ⁇ Tensile test> The test piece 1 was cut into a size of 10 mm ⁇ 80 mm, and a tensile test was performed on the test piece 1 under the following measurement conditions using a precision universal testing machine Autograph “AG-IS” manufactured by Shimadzu Corporation. The elongation (%) until the test piece broke was measured and evaluated according to the following criteria.
• Measurement conditions temperature 23 ° C, humidity 50%, distance between marked lines 20 mm, distance between fulcrums 20 mm, tensile speed 10 mm / min
• the substrate adhesion was evaluated by measuring the peel strength.
• ⁇ Preparation of test piece 2> The curable resin composition obtained in Examples and Comparative Examples was applied onto a copper foil (manufactured by Furukawa Sangyo Co., Ltd., electrolytic copper foil "F2-WS" 18 ⁇ m) with a 50 ⁇ m applicator, and 1000 mJ / using a metal halide lamp. After irradiating with ultraviolet rays of cm 2 , the test piece 2 was obtained by heating at 160 ° C. for 1 hour.
• the test piece 2 was cut into a size of 1 cm in width and 12 cm in length, and the 90 ° peel strength was measured using a peeling tester (“A & D Tensilon” manufactured by A & D Co., Ltd., peeling speed 50 mm / min).
• compositions and evaluation results of the curable resin compositions (23) to (44) prepared in Examples 43 to 64 and the curable resin compositions (R3) and (R4) prepared in Comparative Examples 5 and 6 are shown in the table. Shown in 3 and 4.
• the description of the mass portion of the acrylate resin having an acid group, the methacrylate resin having an acid group, and the resin having an acid group and a polymerizable unsaturated group in Tables 1 to 4 is a solid content value.
• “Curing agent” in Tables 1 to 4 indicates an orthocresol novolak type epoxy resin ("EPICLON N-680" manufactured by DIC Corporation).
• Organic solvent in Tables 1 to 4 indicates diethylene glycol monomethyl ether acetate.
• Photopolymerization initiator in Tables 1 to 4 indicates “Omnirad-907” manufactured by IGM Resins.
• Examples 21 to 42 shown in Tables 1 and 2 are examples of curable resin compositions using the acrylate resin having an acid group of the present invention. It was confirmed that these curable resin compositions have excellent alkali developability.
• Examples 43 to 64 shown in Tables 3 and 4 are examples of the curable resin composition using the acrylate resin having an acid group of the present invention. It was confirmed that the cured product of these curable resin compositions had excellent elongation and adhesion.
• the amount of the compound (C) having a hydroxyl group and a carboxyl group specified in the present invention is 0.2 to 0.2 with respect to 1 mol of the epoxy group of the epoxy resin (A).
• This is an example of a curable resin composition using an acrylate resin having an acid group outside the range of 0.4 mol. It was confirmed that these curable resin compositions were remarkably insufficient in elongation and substrate adhesion.

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