WO2020179287A1 - 酸基含有（メタ）アクリレート樹脂、硬化性樹脂組成物、硬化物、絶縁材料、ソルダーレジスト用樹脂材料及びレジスト部材 - Google Patents

酸基含有（メタ）アクリレート樹脂、硬化性樹脂組成物、硬化物、絶縁材料、ソルダーレジスト用樹脂材料及びレジスト部材 Download PDF

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WO2020179287A1
WO2020179287A1 PCT/JP2020/002901 JP2020002901W WO2020179287A1 WO 2020179287 A1 WO2020179287 A1 WO 2020179287A1 JP 2020002901 W JP2020002901 W JP 2020002901W WO 2020179287 A1 WO2020179287 A1 WO 2020179287A1
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mass
parts
acid
meth
resin
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PCT/JP2020/002901
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English (en)
French (fr)
Japanese (ja)
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駿介 山田
亀山　裕史
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Dic株式会社
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Priority to KR1020217020463A priority Critical patent/KR102516535B1/ko
Priority to CN202080018777.4A priority patent/CN113544179B/zh
Priority to JP2020535670A priority patent/JP6813135B1/ja
Publication of WO2020179287A1 publication Critical patent/WO2020179287A1/ja

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    • 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
    • C08F290/144—Polymers containing more than one epoxy group per molecule
    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • 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
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • 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
    • 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 has an acid group-containing (meth)acrylate resin having excellent alkali developability and high photosensitivity and having excellent elongation in a cured product, a curable resin composition containing the same, and the curable resin composition.
  • the present invention relates to a cured product of an object, an insulating material, a resin material for a solder resist, and a resist member.
  • solder resist resin materials include active energy ray curable products obtained by reacting a reaction product of a novolac type epoxy resin and an unsaturated monocarboxylic acid with a saturated or unsaturated polybasic acid anhydride.
  • a resin is known (for example, refer to Patent Document 1 below)
  • the elongation of the cured product does not satisfy the ever-increasing required properties and is not sufficient for the recent market demand. ..
  • the problem to be solved by the present invention is to provide an acid group-containing (meth)acrylate resin having excellent alkali developability and high photosensitivity and having excellent elongation in a cured product, and a curable resin composition containing the same.
  • a cured product made of the curable resin composition, an insulating material, a resin material for solder resist, and a resist member.
  • an epoxy resin, a reaction product (I) of an unsaturated monobasic acid, and a polybasic acid anhydride, an epoxy resin, and an unsaturated monobasic acid The present invention has been completed by finding that the above-mentioned problems can be solved by using an acid group-containing (meth) acrylate resin characterized by using, as an essential reaction raw material.
  • the present invention relates to a reaction product (I) of an epoxy resin (A), an unsaturated monobasic acid (B), and a polybasic acid anhydride (C), an epoxy resin (D), and an unsaturated monobasic acid.
  • the acid group-containing (meth)acrylate resin of the present invention has excellent alkali developability and high photosensitivity and can form a cured product having excellent elongation, it is used as an insulating material, a resin material for solder resist and It can be suitably used for a resist member.
  • the acid group-containing (meth)acrylate resin of the present invention is a reaction product (I) of an epoxy resin (A), an unsaturated monobasic acid (B), and a polybasic acid anhydride (C), and an epoxy resin (D). And unsaturated monobasic acid (E) as essential reaction raw materials.
  • (meth)acrylate means acrylate and/or methacrylate.
  • (meth) acryloyl means acryloyl and / or methacryloyl.
  • (meth) acrylic means acrylic and / or methacrylic.
  • the reaction product (I) is obtained by reacting an epoxy resin (A), an unsaturated monobasic acid (B), and a polybasic acid anhydride (C).
  • epoxy resin (A) examples 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, cresol novolac type.
  • Epoxy resin bisphenol novolac type epoxy resin, naphthol novolac type epoxy resin, naphthol-phenol co-contracting novolac type epoxy resin, naphthol-cresol co-contracting novolac type epoxy resin, phenol aralkyl type epoxy resin, naphthol aralkyl type epoxy resin, dicyclopentadiene -Phenol addition reaction type epoxy resin, biphenylaralkyl type epoxy resin, fluorene type epoxy resin, xanthene type epoxy resin, dihydroxybenzene type epoxy resin, trihydroxybenzene type epoxy resin, and the like. These epoxy resins can be used alone or in combination of two or more.
  • the acid group-containing (meth)acrylate resin capable of forming a cured product having excellent alkali developability and high photosensitivity and having excellent elongation
  • a bisphenol type epoxy resin Phenylene ether type epoxy resin, naphthylene ether type epoxy resin, biphenyl type epoxy resin and dihydroxybenzene type epoxy resin are preferable.
  • the unsaturated monobasic acid (B) refers to a compound having an acid group and a polymerizable unsaturated bond in one molecule.
  • the acid group include a carboxyl group, a sulfonic acid group, a phosphoric acid group and the like.
  • the unsaturated monobasic acid (B) include acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, ⁇ -cyanocinnamic acid, ⁇ -styrylacrylic acid and ⁇ -furfurylacrylic acid. Further, esterified products of unsaturated monobasic acids, acid halides, acid anhydrides and the like can also be used.
  • unsaturated monobasic acids can be used alone or in combination of two or more kinds. Further, among these, since an acid group-containing (meth)acrylate resin capable of forming a cured product having excellent alkali developability and high photosensitivity and having excellent elongation is obtained, acrylic acid and methacrylic acid Is preferable.
  • polybasic acid anhydride (C) examples include phthalic anhydride, succinic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, and methylnazic anhydride. Acid, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, octenyl succinic anhydride, tetrapropenyl succinic anhydride and the like can be mentioned. These polybasic acid anhydrides can be used alone or in combination of two or more.
  • the method for producing the reaction product (I) is not particularly limited, and any method may be used. For example, it may be produced by a method of reacting all of the reaction raw materials at once, or by a method of sequentially reacting the reaction raw materials. Among them, since the reaction is easily controlled, the epoxy resin (A) is reacted with the unsaturated monobasic acid (B) (step A1), and the intermediate reaction product obtained in the step A1 and the above It is preferably produced by a method of reacting with a polybasic acid anhydride (C) (step A2).
  • the step A1 is a step of reacting the epoxy resin (A) with the unsaturated monobasic acid (B).
  • the reaction mainly reacts the epoxy group of the epoxy resin (A) with the acid group of the unsaturated monobasic acid (B).
  • the reaction ratio of the reaction is such that an acid group-containing (meth) acrylate resin having excellent alkali developability and high photosensitivity and capable of forming a cured product having excellent elongation can be obtained.
  • the number of moles of the acid group of the unsaturated monobasic acid (B) is preferably in the range of 0.9 to 1.1 with respect to 1 mol of the epoxy group of A). It is more preferable to use the ratio in the range of 95 to 1.05.
  • the reaction in the step A1 can be carried out by heating and stirring under a temperature condition of about 80 to 150°C.
  • the reaction in step A1 may be carried out in an organic solvent, if necessary, or a basic catalyst may be used.
  • organic solvent examples include ketone solvents such as methyl ethyl ketone, acetone, dimethylformamide and methyl isobutyl ketone; cyclic ether solvents such as tetrahydrofuran and dioxolane; 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 dioxolane
  • 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, propylene glycol monomethyl ether; alkylene glycol monoalkyl ether, dialkylene glycol monoalkyl ether And glycol ether solvents 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 can be used alone or in combination of two or more.
  • 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 becomes good.
  • the step A2 is a step of reacting the intermediate reaction product obtained in the step A1 with the polybasic acid anhydride (C).
  • the reaction mainly reacts the hydroxyl group contained in the intermediate reaction product with the polybasic acid anhydride (C).
  • the intermediate reaction product has a hydroxyl group generated by ring opening of the epoxy group of the epoxy resin (A).
  • the reaction ratio of the polybasic acid anhydride (C) is preferably adjusted so that the acid value of the reaction product (I) as a product is about 70 to 160 mgKOH/g.
  • the reaction in the step A2 can be carried out, for example, in the presence of a suitable basic catalyst while heating and stirring under a temperature condition of about 70 to 140°C. Further, the reaction may be carried out in an organic solvent, if necessary.
  • a suitable basic catalyst while heating and stirring under a temperature condition of about 70 to 140°C.
  • the reaction may be carried out in an organic solvent, if necessary.
  • the basic catalyst and the organic solvent the same basic catalysts and organic solvents as those described above can be used, and they can be used alone or in combination of two or more kinds.
  • unsaturated monobasic acid (E) those exemplified above as the unsaturated monobasic acid (B) can be used, and the unsaturated monobasic acid (E) can be used alone or in two kinds. The above can also be used together.
  • the unsaturated monobasic acid (B) and the unsaturated monobasic acid (E) may be the same or different.
  • reaction product (II) may be produced by the method of reacting with I) (step 2b).
  • the reaction product (II) since the acid group-containing (meth)acrylate resin capable of forming a cured product having excellent alkali developability and high photosensitivity and having excellent elongation is obtained, the reaction product (II) is previously prepared. It is preferable to obtain it, and then produce it by a method of reacting the reaction product (II) with the reaction product (I).
  • the step 1a is a step of reacting the reaction product (I) with the epoxy resin (D).
  • the reaction mainly reacts the acid group of the reaction product (I) with the epoxy group of the epoxy resin (D).
  • the reaction ratio of the reaction is such that an acid group-containing (meth)acrylate resin capable of forming a cured product having excellent alkali developability and high photosensitivity and having excellent elongation can be obtained.
  • the epoxy resin (D) is preferably used in such a ratio that the number of moles of the epoxy group contained in the epoxy resin (D) is in the range of 0.3 to 0.8 with respect to 1 mole of the acid group contained in I). It is more preferable to use it in a ratio of 0.8.
  • reaction between the reaction product (I) and the epoxy resin (D) can be carried out by heating and stirring under a temperature condition of about 80 to 150 ° C. in the presence of a suitable basic catalyst. Moreover, the reaction may be carried out in an organic solvent if necessary.
  • a suitable basic catalyst e.g., sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium sulfate, sodium bicarbonate, sodium sulfate, sodium bicarbonate, sodium sulfate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium sulfate, sodium bicarbonate, sodium sul
  • the step 2a is a reaction between the product obtained in the step 1a and the unsaturated monobasic acid (E).
  • the reaction mainly reacts the epoxy group of the product with the acid group of the unsaturated monobasic acid (E).
  • the reaction ratio of the reaction is such that the number of moles of the acid group of the unsaturated monobasic acid (E) is in the range of 0.9 to 1.1 with respect to 1 mole of the epoxy group of the product. Is preferably used.
  • the reaction in the step 2a can be carried out by heating and stirring in the presence of a suitable basic catalyst under a temperature condition of about 80 to 150°C.
  • a suitable basic catalyst When step 1a and step 2a are carried out continuously, the basic catalyst may not be added or may be added as appropriate.
  • the reaction may be carried out in an organic solvent if necessary.
  • the basic catalyst and the organic solvent the same ones as those of the basic catalyst and the organic solvent can be used, and they can be used alone or in combination of two or more.
  • the step 1b is a step of producing the reaction product (II).
  • the reaction product (II) is obtained by reacting the epoxy resin (D) with the unsaturated monobasic acid (E).
  • the reaction between the epoxy resin (D) and the unsaturated monobasic acid (E) contains an acid group capable of forming a cured product having excellent alkali developability and high photosensitivity and excellent elongation. Since the (meth) acrylate resin is obtained, the number of moles of the acid group of the unsaturated monobasic acid (E) is 0.25 to 0 with respect to 1 mol of the epoxy group of the epoxy resin (D). It is preferably used in a ratio of 0.75, and more preferably in a ratio of 0.3 to 0.7.
  • the reaction of the above step 1b can be carried out by heating and stirring under a temperature condition of about 70 to 150°C.
  • the reaction in step 1b may be carried out in an organic solvent, if necessary, or a basic catalyst may be used.
  • a basic catalyst may be used as the basic catalyst and the organic solvent, the same ones as those of the basic catalyst and the organic solvent can be used, and they can be used alone or in combination of two or more.
  • reaction product (II) an acid group-containing (meth) acrylate resin having excellent alkali developability and high photosensitivity and capable of forming a cured product having excellent elongation can be obtained, and thus the same molecule. It is preferable that it has an epoxy group and a (meth)acryloyl group.
  • the step 2b is a step of reacting the reaction product (II) with the reaction product (I).
  • the reaction mainly reacts the acid group of the reaction product (I) with the epoxy group of the reaction product (II).
  • the reaction ratio of the reaction is such that an acid group-containing (meth)acrylate resin capable of forming a cured product having excellent alkali developability and high photosensitivity and having excellent elongation can be obtained.
  • the number of moles of the epoxy group of the reaction product (II) is preferably in the range of 0.03 to 0.4 with respect to 1 mol of the acid group of I), preferably 0.05 to 0. It is more preferable to use the ratio in the range of 0.4.
  • reaction of the step 2b can be carried out by heating and stirring under a temperature condition of about 90 to 150 ° C.
  • the reaction in step 2b may be carried out in an organic solvent, if necessary, or a basic catalyst may be used.
  • the basic catalyst and the organic solvent the same ones as those of the basic catalyst and the organic solvent can be used, and they can be used alone or in combination of two or more.
  • the acid value of the acid group-containing (meth)acrylate resin of the present invention is such that the acid group-containing (meth)acrylate resin capable of forming a cured product having excellent alkali developability and high photosensitivity and excellent elongation is From the above, the range of 50 to 140 mgKOH / g is preferable, and the range of 60 to 120 mgKOH / g is more preferable.
  • the acid value of the acid group-containing (meth) acrylate resin is a value measured by the neutralization titration method of JIS K0070 (1992).
  • the weight average molecular weight (Mw) of the acid group-containing (meth)acrylate resin is preferably in the range of 1,000 to 20,000.
  • a weight average molecular weight (Mw) shows the value measured by the gel permeation chromatography (GPC) method.
  • the acid group-containing (meth)acrylate resin 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 a photopolymerization initiator, for example. You can
  • the photopolymerization initiator an appropriate one may be selected and used according to the type of active energy ray to be irradiated. Further, it may be used in combination with 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.
  • 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.
  • Specific examples of the photopolymerization initiator include, for example, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1,2-(dimethylamino).
  • Alkylphenone-based photopolymerization initiators such as 2-[[4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone; 2,4,6-trimethylbenzoyl-diphenyl- Examples thereof include acylphosphine oxide-based photopolymerization initiators such as phosphine oxide; and intramolecular hydrogen abstraction type photopolymerization initiators such as benzophenone compounds. These may be used alone or in combination of two or more.
  • photopolymerization initiator examples include 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2- Hydroxy-2-methyl-1-propan-1-one, thioxanthone and thioxanthone derivatives, 2,2′-dimethoxy-1,2-diphenylethan-1-one, diphenyl(2,4,6-trimethoxybenzoyl)phosphine Oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropane-1- On, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone and the like.
  • Examples of commercial products of the other photopolymerization initiators include “Omnirad-1173”, “Omnirad-184", “Omnirad-127”, “Omnirad-2959”, “Omnirad-369”, and “Omnirad-379”. , “Omnirad-907”, “Omnirad-4265”, “Omnirad-1000”, “Omnirad-651”, “Omnirad-TPO", “Omnirad-819", “Omnirad-2022”, “Omnirad-2100", “Omnirad-2100”, “Omnirad-2100".
  • photopolymerization initiators can be used alone or in combination of two or more.
  • 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, based on, for example, the total amount of the components other than the solvent in the curable resin composition. Is more preferable.
  • the curable resin composition of the present invention may contain other resin components other than the acid group-containing (meth) acrylate resin described above.
  • the other resin components include a resin (F) having an acid group and a polymerizable unsaturated bond, various (meth)acrylate monomers, and the like.
  • the resin (F) having an acid group and a polymerizable unsaturated bond may be any resin (F) having an acid group and a polymerizable unsaturated bond in the resin, for example, an acid group and a polymerizable unsaturated bond.
  • Examples of the acid group include a carboxyl group, a sulfonic acid group, a phosphoric acid group and the like.
  • Examples of the epoxy resin having an acid group and a polymerizable unsaturated bond include, for example, an epoxy resin, an unsaturated monobasic acid, and an acid group-containing epoxy (meth)acrylate resin containing polybasic acid anhydride as an essential reaction raw material, , An epoxy resin, an unsaturated monobasic acid, a polybasic acid anhydride, a polyisocyanate compound, and an acid group- and urethane group-containing epoxy (meth)acrylate resin using a hydroxyl group-containing (meth)acrylate compound as a reaction raw material.
  • unsaturated monobasic acid 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 kinds. it can.
  • each R 1 is independently a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms.
  • Each R 2 is independently an alkyl group having 1 to 4 carbon atoms, or a bonding point connecting with the structural moiety represented by the structural formula (1) through a methylene group marked with *.
  • l is an integer of 0 or 1 to 3
  • m is an integer of 1 to 15.
  • hydroxyl group-containing (meth)acrylate compound examples include hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, trimethylolpropane (meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol (meth)acrylate.
  • a (poly)oxyalkylene chain such as a (poly)oxyethylene chain, a (poly)oxypropylene chain, or a (poly)oxytetramethylene chain is introduced into the molecular structure of each of the various hydroxyl group-containing (meth)acrylate compounds
  • a modified poly)oxyalkylene a modified lactone in which a (poly)lactone structure is introduced into the molecular structure of each of the various hydroxyl group-containing (meth)acrylate compounds.
  • These hydroxyl group-containing (meth)acrylate compounds 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 bond is not particularly limited and may be produced by any method. In the production of the epoxy resin having an acid group and a polymerizable unsaturated bond, it may be carried out in an organic solvent if necessary, or a basic catalyst may be used if necessary.
  • organic solvent the same one 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 basic catalyst the same one as the above-mentioned basic catalyst can be used, and the basic catalyst can be used alone or in combination of two or more.
  • the urethane resin having an acid group and a polymerizable unsaturated bond for example, a polyisocyanate compound, a hydroxyl group-containing (meth) acrylate compound, a carboxyl group-containing polyol compound, and if necessary polybasic acid anhydride, the carboxyl group What was obtained by reacting with a polyol compound other than the containing polyol compound, a polyisocyanate compound, a hydroxyl group-containing (meth)acrylate compound, a polybasic acid anhydride, and a polyol compound other than the carboxyl group-containing polyol compound were reacted. And the like.
  • polyisocyanate compound the same compound as the above-mentioned polyisocyanate compound can be used, and the polyisocyanate compound can be used alone or in combination of two or more.
  • hydroxyl group-containing (meth)acrylate compound the same as the above-mentioned hydroxyl group-containing (meth)acrylate compound can be used, and the hydroxyl group-containing (meth)acrylate compound can be used alone or in combination of two or more kinds. You can also do it.
  • carboxyl group-containing polyol compound examples include 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, and 2,2-dimethylolvaleric acid.
  • the carboxyl group-containing polyol compound may be used alone or in combination of two or more kinds.
  • polybasic acid anhydride those exemplified above as the polybasic acid anhydride (C) can be used, and the polybasic acid anhydride can be used alone or in combination of two or more kinds. it can.
  • polyol compound other than the carboxyl group-containing polyol compound examples include aliphatic polyol compounds such as ethylene glycol, propylene glycol, butanediol, hexanediol, glycerin, trimethylolpropane, ditrimethylolpropane, pentaerythritol, and dipentaerythritol; Aromatic polyol compounds such as biphenols and bisphenols; (poly)oxyalkylene chains such as (poly)oxyethylene chains, (poly)oxypropylene chains, and (poly)oxytetramethylene chains in the molecular structures of the various polyol compounds.
  • aliphatic polyol compounds such as ethylene glycol, propylene glycol, butanediol, hexanediol, glycerin, trimethylolpropane, ditrimethylolpropane, pentaerythritol, and dipentaerythr
  • Modified (poly)oxyalkylene modified products lactone modified compounds in which a (poly)lactone structure is introduced into the molecular structures of the various polyol compounds are included.
  • the polyol compounds other than the carboxyl group-containing polyol compound may be used alone or in combination of two or more kinds.
  • the method for producing the urethane resin having an acid group and a polymerizable unsaturated bond is not particularly limited and may be produced by any method.
  • the production of the urethane resin having an acid group and a polymerizable unsaturated bond may be carried out in an organic solvent if necessary, and a basic catalyst may be used if necessary.
  • organic solvent the same one 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 basic catalyst the same one as the above-mentioned basic catalyst can be used, and the basic catalyst can be used alone or in combination of two or more.
  • the acrylic resin having an acid group and a polymerizable unsaturated bond 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, if necessary, other polymerizable unsaturated group-containing compound.
  • the other polymerizable unsaturated group-containing compound 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 alicyclic structure-containing (meth)acrylate such as cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate; phenyl (meth)acrylate, benzyl (meth)acrylate, phenoxy Examples thereof include aromatic ring-containing (meth)acrylates such as ethyl acrylate; silyl group-containing (meth)acrylates such as 3-methacryloxypropyltrimethoxysilane; styrene derivatives such as styrene, ⁇ -methylstyrene and chlorostyrene. These may 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 contained in the (meth)acrylate compound ( ⁇ ), but from the viewpoint of reactivity, it is the following combination. Is preferred. That is, when a hydroxyl group-containing (meth)acrylate is used as the (meth)acrylate compound ( ⁇ ), it is preferable to use an isocyanate group-containing (meth)acrylate as the (meth)acrylate compound ( ⁇ ). When a carboxyl group-containing (meth)acrylate is used as the (meth)acrylate compound ( ⁇ ), it is preferable to use a glycidyl group-containing (meth)acrylate as the (meth)acrylate compound ( ⁇ ).
  • an isocyanate group-containing (meth)acrylate is used as the (meth)acrylate compound ( ⁇ )
  • a hydroxyl group-containing (meth)acrylate is preferably used as the (meth)acrylate compound ( ⁇ ).
  • a glycidyl group-containing (meth)acrylate is used as the (meth)acrylate compound ( ⁇ )
  • the (meth)acrylate compound ( ⁇ ) may be used alone or in combination of two or more kinds.
  • polybasic acid anhydride those exemplified as the above-mentioned polybasic acid anhydride (C) can be used, and the polybasic acid anhydride can be used alone or in combination of two or more kinds. ..
  • the method for producing the acrylic resin having the acid group and the polymerizable unsaturated bond is not particularly limited and may be produced by any method.
  • the production of the acrylic resin having an acid group and a polymerizable unsaturated bond may be carried out in an organic solvent if necessary, and a basic catalyst may be used if necessary.
  • organic solvent the same one 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 basic catalyst the same one as the above-mentioned basic catalyst can be used, and the basic catalyst can be used alone or in combination of two or more.
  • Examples of the amideimide resin having an acid group and a polymerizable unsaturated bond include an amideimide resin having an acid group and/or an acid anhydride group, a hydroxyl group-containing (meth)acrylate compound and/or an epoxy group-containing (meth)acrylate.
  • Examples thereof include those obtained by reacting a compound with a compound having one or more reactive functional groups selected from the group consisting of a hydroxyl group, a carboxyl group, an isocyanate group, a glycidyl group, and an acid anhydride group, if necessary. Be done.
  • the compound having a reactive functional group may or may not have a (meth) acryloyl group.
  • the amide-imide resin may have either an acid group or an acid anhydride group, or may have both. From the viewpoint of reactivity and reaction control with a hydroxyl group-containing (meth)acrylate compound or a (meth)acryloyl group-containing epoxy compound, it is preferable to have an acid anhydride group, and both an acid group and an acid anhydride group It is more preferable to have
  • the acid value of the amide-imide resin is preferably in the range of 60 to 350 mgKOH/g measured under neutral conditions, that is, under conditions where the acid anhydride group is not ring-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.
  • Examples of the amide-imide resin include those obtained by using a polyisocyanate compound and a polybasic acid anhydride as reaction raw materials.
  • polyisocyanate compound the same compound as the above-mentioned polyisocyanate compound can be used, and the polyisocyanate compound can be used alone or in combination of two or more.
  • polybasic acid anhydride those exemplified above as the polybasic acid anhydride (C) can be used, and the polybasic acid anhydride can be used alone or in combination of two or more kinds. it can.
  • 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 can be used as long as it is a compound having two or more carboxyl groups in one molecule.
  • 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, terephthalic acid, tetrahydrophthalic acid, hexahydro 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,
  • 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.
  • hydroxyl group-containing (meth)acrylate compound the same as the above-mentioned hydroxyl group-containing (meth)acrylate compound can be used, and the hydroxyl group-containing (meth)acrylate compound can be used alone or in combination of two or more kinds. You can also do it.
  • epoxy group-containing (meth)acrylate compound examples include glycidyl group-containing (meth)acrylate monomers such as glycidyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate glycidyl ether, and epoxycyclohexylmethyl (meth)acrylate; Examples thereof include mono(meth)acrylate compounds of diglycidyl ether compounds such as dihydroxybenzene diglycidyl ether, dihydroxynaphthalene diglycidyl ether, biphenol diglycidyl ether, and bisphenol diglycidyl ether. These epoxy group-containing (meth)acrylate compounds can be used alone or in combination of two or more kinds.
  • the method for producing the amide-imide resin having the acid group and the polymerizable unsaturated bond is not particularly limited and may be produced by any method.
  • the production of the amide-imide resin having an acid group and a polymerizable unsaturated bond may be carried out in an organic solvent, if necessary, and a basic catalyst may be used, if necessary.
  • organic solvent the same organic solvents as described above can be used, and the organic solvent can be used alone or in combination of two or more kinds.
  • the basic catalyst the same one as the above-mentioned basic catalyst can be used, and the basic catalyst can be used alone or in combination of two or more.
  • Examples of the acrylamide resin having an acid group and a polymerizable unsaturated bond include a phenolic hydroxyl group-containing compound, an alkylene oxide or an alkylene carbonate, an N-alkoxyalkyl (meth)acrylamide compound, and a polybasic acid anhydride. Examples thereof include those obtained by reacting with unsaturated monobasic acid, if necessary.
  • the above-mentioned phenolic hydroxyl group-containing compound means a compound having at least two phenolic hydroxyl groups in the molecule.
  • Examples of the compound having at least two phenolic hydroxyl groups in the molecule include compounds represented by the following structural formulas (2-1) to (2-4).
  • R 1 is any 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 0 or an integer of 1 or more, preferably 0 or an integer of 1 to 3, more preferably 0 or 1, and further preferably 0.
  • q is an integer of 2 or more, preferably 2 or 3.
  • the position of the substituent on the aromatic ring in the above structural formula is arbitrary.
  • the substituent in the naphthalene ring of the structural formula (2-2), the substituent may be substituted on any ring, and the structural formula ( In 2-3), it may be substituted on any ring of the benzene ring present in one molecule, and in structural formula (2-4), it may be substituted on any ring of the benzene ring present in one molecule. It indicates that it may be substituted, and the number of substituents in one molecule is p and q.
  • phenolic hydroxyl group-containing compound for example, a compound having one phenolic hydroxyl group in the molecule and a compound represented by any of the following structural formulas (x-1) to (x-5) are indispensable.
  • a novolac type phenol resin using one or more compounds having one phenolic hydroxyl group in the molecule as a reaction raw material, and one or more compounds having at least two phenolic hydroxyl groups in the molecule
  • a novolak type phenol resin or the like as a reaction raw material can also be used.
  • h is 0 or 1.
  • R 3 is any 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 of 1 to 4.
  • Z is any 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.
  • Examples of the compound having one phenolic hydroxyl group in the molecule include compounds represented by the following structural formulas (3-1) to (3-4).
  • R 4 is any 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 5 are independently hydrogen atoms or methyl groups.
  • p is 0 or an integer of 1 or more, preferably 0 or an integer of 1 to 3, more preferably 0 or 1, and further preferably 0.
  • the position of the substituent on the aromatic ring in the above structural formula is arbitrary. For example, in the naphthalene ring of the structural formula (3-2), it may be substituted on any ring, and the structural formula (3-2) may be substituted.
  • the compounds represented by the above structural formulas (2-1) to (2-4) can be used.
  • phenolic hydroxyl group-containing compounds can be used alone or in combination of two or more kinds.
  • alkylene oxide examples include ethylene oxide, propylene oxide, butylene oxide, pentylene oxide and the like.
  • ethylene oxide or propylene oxide is preferable because a curable resin composition having excellent alkali developability and high photosensitivity and capable of forming a cured product having excellent elongation 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 high photosensitivity and capable of forming a cured product having excellent elongation 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, N-methoxyethyl(meth)acrylamide. , N-ethoxyethyl (meth)acrylamide, N-butoxyethyl (meth)acrylamide and the like.
  • the N-alkoxyalkyl(meth)acrylamide compounds may be used alone or in combination of two or more kinds.
  • polybasic acid anhydride those exemplified above as the polybasic acid anhydride (C) can be used, and the polybasic acid anhydride can be used alone or in combination of two or more kinds. it can.
  • unsaturated monobasic acid 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 kinds. it can.
  • the method for producing the acrylamide resin having the acid group and the polymerizable unsaturated bond is not particularly limited and may be produced by any method.
  • the production of the acrylamide resin having an acid group and a polymerizable unsaturated bond may be carried out in an organic solvent if necessary, and a basic catalyst and an acidic catalyst may be used if necessary.
  • organic solvent the same organic solvents as described above can be used, and the organic solvent can be used alone or in combination of two or more kinds.
  • the same basic catalysts as described above can be used, and the basic catalyst can be used alone or in combination of two or more kinds.
  • the acidic catalyst examples include inorganic acids such as hydrochloric acid, sulfuric acid and phosphoric acid, organic acids such as methanesulfonic acid, p-toluenesulfonic acid and oxalic acid, Lewis acids such as boron trifluoride, anhydrous aluminum chloride and zinc chloride. And so on. These acidic catalysts can be used alone or in combination of two or more.
  • the amount of the resin (F) having an acid group and a polymerizable unsaturated bond used is preferably in the range of 10 to 900 parts by mass with respect to 100 parts by mass of the acid group-containing (meth)acrylate resin 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, hexyl (meth)acrylate, 2 -Aliphatic mono(meth)acrylate compounds such as ethylhexyl(meth)acrylate, octyl(meth)acrylate; cyclohexyl(meth)acrylate, isobornyl(meth)acrylate, adamantyl mono(meth)acrylate, etc.
  • Acrylate compounds such as glycidyl (meth)acrylate and tetrahydrofurfuryl acrylate; benzyl (meth)acrylate, phenyl (meth)acrylate, phenylbenzyl (meth)acrylate, phenoxy (meth)acrylate, Phenoxyethyl (meth)acrylate, phenoxyethoxyethyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, phenoxybenzyl (meth)acrylate, benzylbenzyl (meth)acrylate, phenylphenoxyethyl (meth)acrylate, etc.
  • (Meth)acrylate compounds such as aromatic mono(meth)acrylate compounds: (poly)oxyethylene chain, (poly)oxypropylene chain, (poly)oxy in the molecular structure of the various mono(meth)acrylate monomers
  • An aliphatic poly(meth)acrylate compound of (poly)oxyethylene chain, (poly)oxypropylene chain, (poly)oxytetramethylene chain or the like in the molecular structure of the aliphatic poly(meth)acrylate compound A tetra- or higher functional (poly)oxyalkylene-modified poly(meth)acrylate compound having an oxyalkylene chain introduced; a tetra-functional or higher functional lactone having a (poly)lactone structure introduced into the molecular structure of the aliphatic poly(meth)acrylate compound Examples include modified poly(meth)acrylate compounds.
  • the various (meth)acrylate monomers may be used alone or in combination of two or more.
  • the curable resin composition of the present invention if necessary, a curing agent, a curing accelerator, an organic solvent, inorganic fine particles or polymer fine particles, a pigment, a defoaming agent, a viscosity modifier, a leveling agent, a flame retardant, It is also possible to contain various additives such as a storage stabilizer.
  • the curing agent is not particularly limited as long as it has a functional group capable of reacting with the carboxy group in the acid group-containing (meth)acrylate resin, and examples thereof include an epoxy resin.
  • the epoxy resin 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, cresol novolac type epoxy resin, Bisphenol novolac type epoxy resin, naphthol novolac type epoxy resin, naphthol-phenol co-contracting novolac type epoxy resin, naphthol-cresol co-contracting novolac type epoxy resin, phenol aralkyl type epoxy resin, naphthol aralkyl type epoxy resin, dicyclopentadiene-phenol addition
  • epoxy resins can be used alone or in combination of two or more. Further, among these, a curable resin composition having excellent alkali developability and high photosensitivity and capable of forming a cured product having excellent elongation can be obtained, and therefore, a phenol novolac type epoxy resin, cresol novolac Type epoxy resin, bisphenol novolac type epoxy resin, naphthol novolac type epoxy resin, naphthol-phenol co-condensed novolac type epoxy resin, naphthol-cresol co-condensed novolac type epoxy resin and the like are preferable, and the softening point is 20 to 120. Those in the range of °C are particularly preferred.
  • the curing accelerator is for promoting a curing reaction of the curing agent, and when an epoxy resin is used as the curing agent, a phosphorus compound, an amine compound, an imidazole, an organic acid metal salt, a Lewis acid, Examples thereof include amine complex salts. These curing accelerators can be used alone or in combination of two or more. The amount of the curing accelerator added is preferably within a range of 1 to 10 parts by mass with respect to 100 parts by mass of the curing agent.
  • organic solvent the same organic solvents as described above can be used, and the organic solvent can be used alone or in combination of two or more kinds.
  • the cured product of the present invention can be obtained by irradiating the curable resin composition with an active energy ray.
  • the active energy rays include ionizing radiation such as ultraviolet rays, electron rays, ⁇ rays, ⁇ rays, and ⁇ rays.
  • the irradiation may be performed 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.
  • ultraviolet lamps are generally used from the viewpoint of practicality and economy. Specific examples thereof include a low pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a xenon lamp, a gallium lamp, a metal halide lamp, sunlight, and an LED.
  • the cumulative light amount of the active energy rays is not particularly limited, but is preferably 10 to 5,000 mJ/cm 2 , and more preferably 50 to 1,000 mJ/cm 2 .
  • the integrated light amount is within the above range, it is possible to prevent or suppress the generation of an uncured portion, which is preferable.
  • the irradiation of the active energy rays may be performed in one step or in two or more steps.
  • the resin material for solder resist of the present invention comprises the curable resin composition.
  • Examples of the base material include metal foils such as copper foil and aluminum foil.
  • the acid value of the acid group-containing (meth)acrylate resin was measured by the neutralization titration method of JIS K0070 (1992).
  • the molecular weight of the acid group-containing (meth)acrylate resin was measured by GPC under the following conditions.
  • reaction product (II-1) was 478 g / equivalent.
  • the number of moles of acid groups contained in acrylic acid was 0.5 with respect to 1 mole of epoxy groups contained in the bisphenol A type epoxy resin (2).
  • reaction product (II-3) was 241 g / equivalent.
  • the number of moles of acid groups contained in acrylic acid was 0.15 with respect to 1 mole of epoxy groups contained in the bisphenol A type epoxy resin (2).
  • reaction product (II-5) was 785 g / equivalent.
  • the number of moles of acid groups contained in acrylic acid was 0.7 with respect to 1 mole of epoxy groups contained in the bisphenol A type epoxy resin (2).
  • reaction product (II-6) was 1603 g / equivalent.
  • the number of moles of the acid group of acrylic acid was 0.85 with respect to 1 mole of the epoxy group of the bisphenol A type epoxy resin (2).
  • reaction product (II-8) was 388 g / equivalent.
  • the number of moles of acid groups contained in acrylic acid was 0.5 with respect to 1 mole of epoxy groups contained in the naphthalene-type epoxy resin (1).
  • the esterification reaction was carried out for 10 hours. Then, 311 parts by mass of diethylene glycol monomethyl ether acetate and 160 parts by mass of tetrahydrophthalic anhydride were added and reacted at 110° C. for 2.5 hours to obtain a target acid group-containing acrylate resin (P).
  • the acid value of the solid content of this acid group-containing acrylate resin (P) was 85 mgKOH/g, and the weight average molecular weight was 8540.
  • Example 1 Production of acid group-containing acrylate resin (1)
  • a flask equipped with a thermometer, a stirrer, and a reflux condenser 188 parts by mass of bisphenol A type epoxy resin (1), 41 parts by mass of bisphenol A, and 0.5 parts by mass of triphenylphosphine were added, and the mixture was heated under a nitrogen atmosphere to 140 The reaction was carried out at ° C. for 2 hours.
  • Resin (1) was obtained.
  • the acid value of the solid content of the acid group-containing acrylate resin (1) was 89 mgKOH/g, and the weight average molecular weight was 5,670.
  • the number of moles of the epoxy group of the bisphenol A type epoxy resin (2) was 0.56, relative to 1 mole of the acid group of the reaction product (I-1).
  • Example 2 Production of acid group-containing acrylate resin (2)
  • a flask equipped with a thermometer, a stirrer, and a reflux condenser 188 parts by mass of bisphenol A type epoxy resin (1), 41 parts by mass of bisphenol A, and 0.5 parts by mass of triphenylphosphine were added, and the mixture was heated under a nitrogen atmosphere to 140 The reaction was carried out at ° C. for 2 hours.
  • the resin (2) was obtained.
  • the solid acid value of the acid group-containing acrylate resin (2) was 69 mgKOH / g, and the weight average molecular weight was 6070.
  • the number of moles of the epoxy group of the bisphenol A type epoxy resin (2) was 0.80, relative to 1 mole of the acid group of the reaction product (I-2).
  • Example 3 Production of acid group-containing acrylate resin (3)
  • a thermometer a thermometer
  • a stirrer a stirrer
  • a reflux condenser 188 parts by mass of bisphenol A type epoxy resin (1)
  • 41 parts by mass of bisphenol A 41 parts by mass of bisphenol A
  • 0.5 parts by mass of triphenylphosphine were added, and the mixture was heated under a nitrogen atmosphere to 140
  • the reaction was carried out at 0°C for 2 hours.
  • Resin (3) was obtained.
  • the solid acid value of the acid group-containing acrylate resin (3) was 115 mgKOH / g, and the weight average molecular weight was 5180.
  • the number of moles of the epoxy group of the bisphenol A type epoxy resin (2) was 0.28, relative to 1 mole of the acid group of the reaction product (I-3).
  • Example 5 Production of acid group-containing acrylate resin (5)
  • a flask equipped with a thermometer, a stirrer, and a reflux condenser 188 parts by mass of bisphenol A type epoxy resin (1), 41 parts by mass of bisphenol A, and 0.5 parts by mass of triphenylphosphine were added, and the mixture was heated under a nitrogen atmosphere to 140 The reaction was carried out at 0°C for 2 hours.
  • the target acid group-containing acrylate resin (5) was obtained by 5 hours to obtain the target acid group-containing acrylate resin (5).
  • the solid acid value of the acid group-containing acrylate resin (5) was 87 mgKOH / g, and the weight average molecular weight was 5090.
  • the number of moles of the epoxy group contained in the reaction product (II-1) was 0.26 with respect to 1 mol of the acid group contained in the reaction product (I-5).
  • Example 7 Production of acid group-containing acrylate resin (7)
  • a flask equipped with a thermometer, a stirrer, and a reflux condenser 188 parts by mass of bisphenol A type epoxy resin (1), 41 parts by mass of bisphenol A, and 0.5 parts by mass of triphenylphosphine were added, and the mixture was heated under a nitrogen atmosphere to 140 The reaction was carried out at ° C. for 2 hours.
  • the solid acid value of the acid group-containing acrylate resin (7) was 68 mgKOH / g, and the weight average molecular weight was 5880.
  • the number of moles of the epoxy group of the reactant (II-2) was 0.37 with respect to 1 mole of the acid group of the reactant (I-7).
  • Example 8 Production of acid group-containing acrylate resin (8)
  • a flask equipped with a thermometer, a stirrer, and a reflux condenser 188 parts by mass of bisphenol A type epoxy resin (1), 41 parts by mass of bisphenol A, and 0.5 parts by mass of triphenylphosphine were added, and the mixture was heated under a nitrogen atmosphere to 140 The reaction was carried out at ° C. for 2 hours.
  • the target acid group-containing acrylate resin (8) was obtained by 3 hours to obtain the target acid group-containing acrylate resin (8).
  • the acid value of the solid content of the acid group-containing acrylate resin (8) was 116 mgKOH/g, and the weight average molecular weight was 5020.
  • the number of moles of the epoxy group of the reactant (II-2) was 0.13 with respect to 1 mole of the acid group of the reactant (I-8).
  • Example 9 Production of acid group-containing acrylate resin (9)
  • a flask equipped with a thermometer, a stirrer, and a reflux condenser 188 parts by mass of bisphenol A type epoxy resin (1), 41 parts by mass of bisphenol A, and 0.5 parts by mass of triphenylphosphine were added, and the mixture was heated under a nitrogen atmosphere to 140 The reaction was carried out at 0°C for 2 hours.
  • the target acid group-containing acrylate resin (9) was obtained by 6 hours to obtain the target acid group-containing acrylate resin (9).
  • the acid value of the solid content of the acid group-containing acrylate resin (9) was 63 mgKOH/g, and the weight average molecular weight was 6,290.
  • the number of moles of the epoxy group of the reactant (II-2) was 0.41 with respect to 1 mole of the acid group of the reactant (I-9).
  • Example 10 Production of acid group-containing acrylate resin (10)
  • a flask equipped with a thermometer, a stirrer, and a reflux condenser 188 parts by mass of bisphenol A type epoxy resin (1), 41 parts by mass of bisphenol A, and 0.5 parts by mass of triphenylphosphine were added, and the mixture was heated under a nitrogen atmosphere to 140 The reaction was carried out at ° C. for 2 hours.
  • a target acid group-containing acrylate resin (10) The acid value of the solid content of this acid group-containing acrylate resin (10) was 98 mgKOH/g, and the weight average molecular weight was 6030. The number of moles of the epoxy group of the reactant (II-3) was 0.26 with respect to 1 mole of the acid group of the reactant (I-10).
  • the solid acid value of the acid group-containing acrylate resin (11) was 95 mgKOH / g, and the weight average molecular weight was 5890.
  • the number of moles of the epoxy group of the reaction product (II-4) was 0.26 with respect to 1 mole of the acid group of the reaction product (I-11).
  • Example 12 Production of acid group-containing acrylate resin (12)
  • a flask equipped with a thermometer, a stirrer, and a reflux condenser 188 parts by mass of bisphenol A type epoxy resin (1), 41 parts by mass of bisphenol A, and 0.5 parts by mass of triphenylphosphine were added, and the mixture was heated under a nitrogen atmosphere to 140 The reaction was carried out at ° C. for 2 hours.
  • the solid acid value of the acid group-containing acrylate resin (12) was 75 mgKOH / g, and the weight average molecular weight was 5310.
  • the number of moles of the epoxy group contained in the reaction product (II-5) was 0.26 with respect to 1 mol of the acid group contained in the reaction product (I-12).
  • Example 13 Production of acid group-containing acrylate resin (13)
  • a flask equipped with a thermometer, a stirrer, and a reflux condenser 188 parts by mass of bisphenol A type epoxy resin (1), 41 parts by mass of bisphenol A, and 0.5 parts by mass of triphenylphosphine were added, and the mixture was heated under a nitrogen atmosphere to 140 The reaction was carried out at ° C. for 2 hours.
  • the solid acid value of the acid group-containing acrylate resin (13) was 73 mgKOH / g, and the weight average molecular weight was 5060.
  • the number of moles of the epoxy group contained in the reaction product (II-6) was 0.18, relative to 1 mol of the acid group contained in the reaction product (I-13).
  • Example 14 Production of acid group-containing acrylate resin (14)
  • a bisphenol F type epoxy resin (“EPICLON 830-S” manufactured by DIC Corporation, epoxy equivalent 169 g/equivalent.
  • bisphenol F type epoxy resin (2) 169 parts by mass, bisphenol F 42 parts by mass, and triphenylphosphine 0.4 parts by mass were added and reacted at 140° C. for 2 hours in a nitrogen atmosphere.
  • the acid value of the solid content of this acid group-containing acrylate resin (14) was 94 mgKOH/g, and the weight average molecular weight was 4,880.
  • the number of moles of the epoxy group contained in the reaction product (II-7) was 0.26, relative to 1 mol of the acid group contained in the reaction product (I-14).
  • the target acid group-containing acrylate resin (15) was 86 mgKOH/g, and the weight average molecular weight was 4,890.
  • the number of moles of the epoxy group contained in the reaction product (II-7) was 0.26 with respect to 1 mol of the acid group contained in the reaction product (I-15).
  • the acid value of the solid content of the acid group-containing acrylate resin (17) was 92 mgKOH/g, and the weight average molecular weight was 49000.
  • the number of moles of the epoxy group of the reaction product (II-2) was 0.26 with respect to 1 mole of the acid group of the reaction product (I-17).
  • the target acid group-containing acrylate resin (18) was 94 mgKOH / g, and the weight average molecular weight was 4750.
  • the number of moles of the epoxy group of the reactant (II-8) was 0.3 with respect to 1 mole of the acid group of the reactant (I-18).
  • Example 19 Production of acid group-containing acrylate resin (19)
  • a flask equipped with a thermometer, a stirrer, and a reflux condenser 188 parts by mass of bisphenol A type epoxy resin (1), 41 parts by mass of bisphenol A, and 0.5 parts by mass of triphenylphosphine were added, and the mixture was heated under a nitrogen atmosphere to 140 The reaction was carried out at ° C. for 2 hours.
  • the target acid group-containing acrylate resin (19) was 90 mgKOH / g, and the weight average molecular weight was 4870.
  • the number of moles of the epoxy group contained in the reaction product (II-8) was 0.26 with respect to 1 mol of the acid group contained in the reaction product (I-19).
  • Example 20 Production of acid group-containing acrylate resin (20)
  • a flask equipped with a thermometer, a stirrer, and a reflux condenser 188 parts by mass of bisphenol A type epoxy resin (1), 41 parts by mass of bisphenol A, and 0.5 parts by mass of triphenylphosphine were added, and the mixture was heated under a nitrogen atmosphere to 140 The reaction was carried out at ° C. for 2 hours.
  • reaction product (II-2) obtained in Synthesis Example 2 23 parts by mass of the reaction product (II-2) obtained in Synthesis Example 2 and 35 parts by mass of the bisphenol A type epoxy resin (2) were added and reacted at 120 ° C. for 5 hours to obtain the desired acid group-containing acrylate resin. (21) was obtained.
  • the acid value of the solid content of the acid group-containing acrylate resin (20) was 100 mgKOH/g, and the weight average molecular weight was 8200.
  • the number of moles of the epoxy group of the reaction product (II-2) was 0.05 with respect to 1 mole of the acid group of the reaction product (I-21).
  • Example 22 Production of acid group-containing methacrylate resin (1)
  • a flask equipped with a thermometer, a stirrer, and a reflux condenser 188 parts by mass of bisphenol A type epoxy resin (1), 41 parts by mass of bisphenol A, and 0.5 parts by mass of triphenylphosphine were added, and the mixture was heated under a nitrogen atmosphere to 140 The reaction was carried out at ° C. for 2 hours.
  • the solid acid value of the acid group-containing methacrylate resin (1) was 86 mgKOH / g, and the weight average molecular weight was 4840.
  • the number of moles of the epoxy group of the reactant (II-2) was 0.26 with respect to 1 mole of the acid group of the reactant (I-22).
  • Example 23 Preparation of curable resin composition (1)
  • the acid group-containing acrylate resin (1) obtained in Example 1 an orthocresol novolac type epoxy resin (“EPICLON N-680” manufactured by DIC Corporation) as a curing agent, dipentaerythritol hexaacrylate, and diethylene glycol monoethyl ether acetate.
  • a photopolymerization initiator (“Omnirad 907” manufactured by IGM), 2-ethyl-4-methylimidazole, and phthalocyanine green were mixed in a mass part shown in Table 1 and kneaded by a roll mill to prepare a curable resin.
  • a composition (1) was obtained.
  • Examples 24-42 Preparation of curable resin compositions (2)-(22)
  • the acid group-containing acrylate resins (2) to (21) obtained in Examples 2 to 21 or the acid group-containing methacrylate obtained in Example 22 Curable resin compositions (2) to (22) were obtained in the same manner as in Example 23 except that the resin (1) was used.
  • Example 43 Preparation of curable resin composition (23) Except that the acid group-containing acrylate resin obtained in Example 6 and the acid group-containing acrylate resin (P) obtained in Synthesis Example 9 were used instead of the acid group-containing acrylate resin (1) used in Example 23. , A curable resin composition (23) was obtained in the same manner as in Example 23.
  • compositions and evaluation results of the curable resin compositions (1) to (23) prepared in Examples 21 to 43 and the curable resin compositions (C4) to (C6) prepared in Comparative Examples 4 to 6 are shown in Table 1. And shown in Table 2.
  • Example 44 Preparation of curable resin composition (24)
  • the acid group-containing acrylate resin (1) obtained in Example 1 an orthocresol novolac type epoxy resin (“EPICLON N-680” manufactured by DIC Corporation) as a curing agent, and 2-methyl-1-(4 as a photopolymerization initiator.
  • -Methylthiophenyl)-2-morpholinopropan-1-one (“OMNIRAD-907” manufactured by IGM)
  • diethylene glycol monomethyl ether acetate as an organic solvent in an amount of parts by mass shown in Table 3 to prepare a curable resin composition ( 24) was obtained.
  • Example 45 to 65 Preparation of curable resin compositions (25) to (45)
  • the acid group-containing acrylate resins (2) to (21) obtained in Examples 2 to 21 or the acid group-containing methacrylate obtained in Example 22 Curable resin compositions (25) to (45) were obtained in the same manner as in Example 42, except that the resin (1) was used.
  • ⁇ Tensile test> The test piece 2 was cut into a size of 10 mm ⁇ 80 mm, and a tensile test of the test piece was performed 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, pulling speed 10 mm/min
  • Examples 21 to 66 shown in Tables 1 to 4 are examples of curable resin compositions using the acid group-containing (meth)acrylate resin of the present invention. It was confirmed that this curable resin composition has excellent photosensitivity and alkali developability, and also has excellent elongation in the cured product.
  • Comparative Examples 4 to 9 are examples of curable resin compositions that do not use the acid group-containing (meth)acrylate resin of the present invention. It was confirmed that this curable resin composition had remarkably insufficient photosensitivity and also had insufficient elongation in the cured product.

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PCT/JP2020/002901 2019-03-06 2020-01-28 酸基含有（メタ）アクリレート樹脂、硬化性樹脂組成物、硬化物、絶縁材料、ソルダーレジスト用樹脂材料及びレジスト部材 WO2020179287A1 (ja)

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JPH0987346A (ja) * 1995-09-19 1997-03-31 Dainippon Ink & Chem Inc エネルギ−線硬化型エポキシアクリレ−ト樹脂組成物
JP2000267275A (ja) * 1999-03-15 2000-09-29 Tamura Kaken Co Ltd 感光性樹脂組成物及びプリント配線板
JP2004131526A (ja) * 2002-10-08 2004-04-30 Great Eastern Resins Industrial Co Ltd 感光性熱硬化型樹脂およびその製造方法ならびにその樹脂を含む耐ソルダー性インク組成物
JP2007003590A (ja) * 2005-06-21 2007-01-11 Dainippon Ink & Chem Inc レジストインキ組成物

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JP4242010B2 (ja) * 1999-06-30 2009-03-18 日本化薬株式会社 感光性樹脂組成物及びその硬化物
WO2009150769A1 (ja) * 2008-06-09 2009-12-17 互応化学工業株式会社 カルボキシル基含有樹脂及びカルボキシル基含有樹脂を含有する硬化性組成物並びにその硬化物
WO2018186183A1 (ja) * 2017-04-06 2018-10-11 Dic株式会社 酸基含有（メタ）アクリレート樹脂及びソルダーレジスト用樹脂材料

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JPH0987346A (ja) * 1995-09-19 1997-03-31 Dainippon Ink & Chem Inc エネルギ−線硬化型エポキシアクリレ−ト樹脂組成物
JP2000267275A (ja) * 1999-03-15 2000-09-29 Tamura Kaken Co Ltd 感光性樹脂組成物及びプリント配線板
JP2004131526A (ja) * 2002-10-08 2004-04-30 Great Eastern Resins Industrial Co Ltd 感光性熱硬化型樹脂およびその製造方法ならびにその樹脂を含む耐ソルダー性インク組成物
JP2007003590A (ja) * 2005-06-21 2007-01-11 Dainippon Ink & Chem Inc レジストインキ組成物

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