WO2020129667A1 - 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

Info

Publication number
WO2020129667A1
WO2020129667A1 PCT/JP2019/047584 JP2019047584W WO2020129667A1 WO 2020129667 A1 WO2020129667 A1 WO 2020129667A1 JP 2019047584 W JP2019047584 W JP 2019047584W WO 2020129667 A1 WO2020129667 A1 WO 2020129667A1
Authority
WO
WIPO (PCT)
Prior art keywords
meth
acrylate
group
acid
mass
Prior art date
Application number
PCT/JP2019/047584
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
駿介 山田
康介 桑田
Original Assignee
Dic株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dic株式会社 filed Critical Dic株式会社
Priority to JP2020537671A priority Critical patent/JP6780809B1/ja
Priority to CN201980084081.9A priority patent/CN113195574B/zh
Priority to KR1020217014292A priority patent/KR102500020B1/ko
Publication of WO2020129667A1 publication Critical patent/WO2020129667A1/ja

Links

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
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/04—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polycarbonamides, polyesteramides or polyimides
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
    • 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
    • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
    • 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
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • 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
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1003—Preparatory processes
    • C08G73/1035—Preparatory processes from tetracarboxylic acids or derivatives and diisocyanates
    • 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
    • H05K3/30—Assembling printed circuits with electric components, e.g. with resistor
    • H05K3/32—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits
    • H05K3/34—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits by soldering
    • H05K3/3452—Solder masks

Definitions

  • the present invention provides an acid group-containing (meth)acrylate resin having excellent photosensitivity and alkali developability and excellent heat resistance in a cured product, a curable resin composition containing the same, and an insulating material comprising the curable resin composition.
  • a solder resist resin material, a resist member, and a method for producing an acid group-containing (meth)acrylate resin are examples of solder resist resin material, a resist member, and a method for producing an acid group-containing (meth)acrylate resin.
  • acid group-containing epoxy acrylate resins obtained by reacting an acid anhydride after acrylate conversion of epoxy resin with acrylic acid are widely used as resin materials for solder resists for printed wiring boards.
  • resin materials for solder resists There are various requirements for the resin material for a solder resist, such as curing with a small amount of exposure, excellent alkali developability, and excellent heat resistance in the cured product.
  • 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), although it has excellent heat resistance in a cured product, it does not satisfy the ever-increasing required properties and is sufficient for the recent market demands. Was not.
  • the problem to be solved by the present invention is to provide an acid group-containing (meth)acrylate resin having excellent photosensitivity and alkali developability and excellent heat resistance in a cured product, a curable resin composition containing the same,
  • An object of the present invention is to provide an insulating material comprising a curable resin composition, a resin material for solder resist, a resist member, and a method for producing an acid group-containing (meth)acrylate resin.
  • an amide imide resin having an acid group and/or an acid anhydride group, a hydroxyl group-containing (meth)acrylate compound, an epoxy group-containing (meth)acrylate compound and a polycarboxylic acid An acid group-containing (meth)acrylate resin using an acid anhydride as an essential reaction raw material, wherein the amide imide resin is a reaction product of a polyisocyanate compound and a polycarboxylic acid anhydride, or a polyisocyanate compound, a polycarboxylic acid anhydride.
  • a hydroxyl group-containing (meth)acrylate compound used as a raw material of an acid group-containing (meth)acrylate resin or a hydroxyl group-containing (meth)acrylate compound used as a raw material of an amideimide resin One or both contain a (meth)acrylate compound having two hydroxyl groups, and/or a (meth)acrylate compound having three hydroxyl groups. The inventors have found that the above problems can be solved by using them, and completed the present invention.
  • the present invention relates to an amide imide resin (A) having an acid group and/or an acid anhydride group, a hydroxyl group-containing (meth)acrylate compound (B), an epoxy group-containing (meth)acrylate compound (C), and An acid group-containing (meth)acrylate resin containing a carboxylic acid anhydride (D) as an essential reaction raw material, wherein the amideimide resin (A) is a polyisocyanate compound (a1) and a polycarboxylic acid anhydride (a2). Or a reaction product (A-2) of the polyisocyanate compound (a1), the polycarboxylic acid anhydride (a2) and the hydroxyl group-containing (meth)acrylate compound (a3).
  • Either or both of the containing (meth)acrylate compound (B) and the hydroxyl group-containing (meth)acrylate compound (a3) have (meth)acrylate compound having two hydroxyl groups, and/or have three hydroxyl groups (meth ) Acid group-containing (meth)acrylate resin containing an acrylate compound, a curable resin composition containing the same, a cured product of the curable resin composition, an insulating material, and a solder resist
  • the present invention relates to a resin material, a resist member, and a method for producing an acid group-containing (meth)acrylate resin.
  • the acid group-containing (meth)acrylate resin of the present invention is excellent in photosensitivity and alkali developability, and is excellent in heat resistance in a cured product, and thus can be suitably used for an insulating material, a resin material for solder resist and a resist member. ..
  • the acid group-containing (meth)acrylate resin of the present invention includes an amide imide resin (A) having an acid group and/or an acid anhydride group, a hydroxyl group-containing (meth)acrylate compound (B), and an epoxy group-containing (meth)acrylate compound ( C) and polycarboxylic acid anhydride (D) are 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 amide-imide resin (A) having an acid group and/or an acid anhydride group may have only one of an acid group and an acid anhydride group, or may have both. Good. Among them, it is preferable to have an acid anhydride group from the viewpoint of reactivity and reaction control with the hydroxyl group-containing (meth)acrylate compound (B) and the epoxy group-containing (meth)acrylate compound (C). It is preferable to have both an acid group and an acid anhydride group.
  • Examples of the acid group include a carboxyl group, a sulfonic acid group, a phosphoric acid group and the like.
  • Examples of the acid anhydride group include a carboxylic acid anhydride group, a sulfonic acid anhydride group, and a phosphoric acid anhydride group.
  • amide-imide resin (A) As the amide-imide resin (A), [1] a reaction product (A-1) of a polyisocyanate compound (a1) and a polycarboxylic acid anhydride (a2) (hereinafter referred to as "amide-imide resin (A-1)" Or [2] a reaction product (A-2) of a polyisocyanate compound (a1), a polycarboxylic acid anhydride (a2) and a hydroxyl group-containing (meth)acrylate compound (a3) (hereinafter referred to as an amide imide resin (A -2) is sometimes used).
  • the amide imide resin (A-1) is obtained by reacting a polyisocyanate compound (a1) and a polycarboxylic acid anhydride (a2).
  • polyisocyanate compound (a1) examples include, butane diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, and other aliphatic diisocyanate compounds; norbornane diisocyanate, Alicyclic diisocyanate compounds such as isophorone diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated diphenylmethane diisocyanate; tolylene diisocyanate, xylylene diisocyanate, tetramethyl xylylene diisocyanate, diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, 4,4'- Aromatic diisocyanate compounds such as diisocyanato-3,3'-dimethylbiphenyl and o-tolidine diisocyanate; polymethylene polyphenyl polyis
  • these polyisocyanate compounds may be used alone or in combination of two or more kinds.
  • These polyisocyanate compounds (a1) have excellent photosensitivity and alkali developability, and are capable of forming an acid group-containing (meth)acrylate resin capable of forming a cured product having excellent heat resistance. Nurate modified products are preferred.
  • 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 the structural site represented by the structural formula (1) and the methylene group marked with *. is there.
  • l is 0 or an integer of 1 to 3
  • m is an integer of 1 to 15.
  • the alicyclic diisocyanate compound or its modified product is preferable, and the alicyclic diisocyanate is preferable, in terms of the acid group-containing (meth)acrylate resin having excellent solvent solubility. Further, the aliphatic diisocyanate compound or a modified product thereof is preferable in that an acid group-containing (meth)acrylate resin capable of forming a cured product having excellent heat sensitivity and excellent photosensitivity and alkali developability can be obtained. , Aliphatic diisocyanates are preferred.
  • the ratio of the total mass of the alicyclic diisocyanate compound or a modified product thereof and the aliphatic diisocyanate compound or a modified product thereof to the total mass of the polyisocyanate compound (a1) is preferably 70% by mass or more, It is more preferably 90 mass% or more.
  • the mass ratio of both is preferably in the range of 20/80 to 80/20.
  • polycarboxylic acid anhydride (a2) examples include aliphatic polycarboxylic acid anhydride, alicyclic polycarboxylic acid anhydride, aromatic polycarboxylic acid anhydride and the like.
  • aliphatic polycarboxylic acid anhydrides examples include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, citraconic acid, and itacone.
  • examples thereof include acids, glutaconic acid, and acid anhydrides of 1,2,3,4-butanetetracarboxylic acid.
  • the aliphatic hydrocarbon group may be linear or branched and may have an unsaturated bond in the structure.
  • the acid anhydride group is bonded to the alicyclic structure as an alicyclic polycarboxylic acid anhydride, the aromatic ring of the other structural site It does not matter whether it is present or not.
  • Examples of the alicyclic polycarboxylic acid anhydride include tetrahydrophthalic acid, hexahydrophthalic acid, methylhexahydrophthalic 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-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene- Examples thereof include acid anhydrides of 1,2-dicarboxylic acid.
  • aromatic polycarboxylic acid anhydrides examples include phthalic acid, trimellitic acid, pyromellitic acid, naphthalene dicarboxylic acid, naphthalene tricarboxylic acid, naphthalene tetracarboxylic acid, biphenyl dicarboxylic acid, biphenyl tricarboxylic acid, biphenyl tetracarboxylic acid, Examples thereof include acid anhydrides of benzophenone tetracarboxylic acid.
  • polycarboxylic acid anhydrides (a2) can be used alone or in combination of two or more kinds.
  • the acid group-containing (meth)acrylate resin capable of forming a cured product having excellent photosensitivity and alkali developability and having excellent heat resistance is obtained, the alicyclic polycarboxylic acid An acid anhydride or the aromatic polycarboxylic acid anhydride is preferable.
  • an acid group-containing (meth)acrylate resin capable of forming a cured product having excellent heat sensitivity and excellent photosensitivity and alkali developability it is possible to obtain a carboxyl group and an acid anhydride in the molecular structure.
  • the content of the tricarboxylic acid anhydride in the polycarboxylic acid anhydride (a2) is preferably 70% by mass or more, and more preferably 90% by mass or more.
  • the amide-imide resin (A-1) if necessary, other compounds may be used in combination as a reaction raw material in addition to the polyisocyanate compound (a1) and the polycarboxylic acid anhydride (a2). ..
  • the other compound when used in combination, the effects of the present invention are sufficiently exhibited, and therefore, the polyisocyanate compound (a1) and the polycarboxylic acid anhydride in the reaction raw material of the amide imide resin (A-1) are used.
  • the total content of (a2) is preferably 80% by mass or more, and more preferably 85% by mass.
  • Examples of the other compounds include polycarboxylic acid and the like.
  • 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-
  • polycarboxylic 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.
  • polycarboxylic acids (a2) can be used alone or in combination of two or more kinds.
  • the copolymer of the conjugated diene vinyl monomer and acrylonitrile, which has a carboxyl group in its molecule is, for example, a butadiene-acrylonitrile copolymer represented by the following structural formula (2-1).
  • the position of the carboxyl group may be located on either the side chain or the terminal of the molecule, but the terminal is preferred.
  • X is an integer of 1 to 50
  • Y is an integer of 1 to 50
  • Z is an integer of 1 to 20.
  • X is an integer of 1 to 50
  • Y is an integer of 1 to 50
  • Z is an integer of 1 to 20.
  • the acid value of the amide-imide resin (A-1) has excellent photosensitivity and alkali developability, an acid group-containing (meth)acrylate resin capable of forming a cured product having excellent heat resistance can be obtained.
  • the measured value under a neutral condition that is, under the condition that the acid anhydride group is not ring-opened is in the range of 60 to 350 mgKOH/g, and the acid anhydride group was ring-opened in the presence of water.
  • the measured value under the condition is preferably in the range of 61 to 360 mgKOH/g.
  • the acid value is a value measured by the neutralization titration method of JIS K0070 (1992).
  • the method for producing the amide-imide resin (A-1) is not particularly limited and may be produced by any method.
  • it can be produced by a method similar to that of a general amide-imide resin.
  • 0.8 to 3.5 mol of the polycarboxylic acid anhydride (a2) is used with respect to 1 mol of the isocyanate group contained in the polyisocyanate compound (a1), and the temperature condition is about 100 to 180° C.
  • the method of stirring and mixing under the reaction is mentioned.
  • the reaction may be carried out in an organic solvent if necessary, and a basic catalyst may be used if necessary.
  • 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 kinds. 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 becomes good.
  • Examples of the basic catalyst include N-methylmorpholine, pyridine, 1,8-diazabicyclo[5.4.0]undecene-7 (DBU), 1,5-diazabicyclo[4.3.0]nonene- 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-amin
  • the amide imide resin (A-2) is obtained by reacting a polyisocyanate compound (a1), a polycarboxylic acid anhydride (a2) and a hydroxyl group-containing (meth)acrylate compound (a3).
  • polyisocyanate compound (a1) the same ones as the above polyisocyanate compound (a1) can be used, and the polyisocyanate compound can be used alone or in combination of two or more kinds.
  • polycarboxylic acid anhydride (a2) the same polycarboxylic acid anhydride (a2) as described above can be used.
  • the polycarboxylic acid anhydride (a2) is used in such an amount that an acid group-containing (meth)acrylate resin capable of forming a cured product having excellent photosensitivity and alkali developability and excellent heat resistance can be obtained. Therefore, it is preferably used in the range of 0.8 to 3.5 mol with respect to 1 mol of the isocyanate group contained in the polyisocyanate compound (a1).
  • hydroxyl group-containing (meth)acrylate compound (a3) other specific structures are not particularly limited as long as it is a compound having a hydroxyl group and a (meth)acryloyl group in the molecular structure, and various compounds can be used. it can. Examples thereof include hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, trimethylolpropane (meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol (meth)acrylate, pentaerythritol di(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 obtained by introducing a (poly)lactone structure into the molecular structure of each of the various hydroxyl group-containing (meth)acrylate compounds.
  • These hydroxyl group-containing (meth)acrylate compounds (a3) can be used alone or in combination of two or more kinds.
  • the amide imide resin (A-2) if necessary, other than the polyisocyanate compound (a1), the polycarboxylic acid anhydride (a2) and the hydroxyl group-containing (meth)acrylate compound (a3), Other compounds can be used together as a reaction raw material. When the other compound is used in combination, the effect of the present invention is sufficiently exhibited, and therefore, the polyisocyanate compound (a1) and the polycarboxylic acid anhydride in the reaction raw material of the amide imide resin (A-2) are used.
  • the total content of (a2) and the hydroxyl group-containing (meth)acrylate compound (a3) is preferably 80% by mass or more, and more preferably 85% by mass.
  • Examples of the other compounds include polycarboxylic acid and the like.
  • polycarboxylic acid As the polycarboxylic acid, the same polycarboxylic acid as described above can be used.
  • the polycarboxylic acids may be used alone or in combination of two or more.
  • the acid value of the amide-imide resin (A-2) has excellent photosensitivity and alkali developability, an acid group-containing (meth)acrylate resin capable of forming a cured product having excellent heat resistance can be obtained.
  • the measured value under a neutral condition that is, under the condition that the acid anhydride group is not ring-opened is in the range of 60 to 350 mgKOH/g, and the acid anhydride group was ring-opened in the presence of water.
  • the measured value under the condition is preferably in the range of 61 to 360 mgKOH/g.
  • the method for producing the amide-imide resin (A-2) is not particularly limited and may be produced by any method.
  • it may be produced by a method of reacting all the reaction raw materials at once, or may be produced by a method of sequentially reacting the reaction raw materials.
  • the polycarboxylic acid anhydride (a2) is reacted with the hydroxyl group-containing (meth)acrylate compound (a3) (step A1) to obtain the intermediate obtained in the step A1. It is preferable that the reaction product and the polyisocyanate compound (a1) are reacted (step A2).
  • the step A1 is a step of reacting the polycarboxylic acid anhydride (a2) with the hydroxyl group-containing (meth)acrylate compound (a3) to obtain an intermediate reaction product.
  • the reaction is mainly to react the acid anhydride group of the polycarboxylic acid anhydride (a2) with the hydroxyl group of the hydroxyl group-containing (meth)acrylate compound (a3).
  • the reaction ratio of the reaction is preferably such that the number of moles of the polycarboxylic acid anhydride (a2) is 1 to 8 with respect to 1 mole of the hydroxyl group contained in the hydroxyl group-containing (meth)acrylate compound (a3).
  • the reaction of step A1 can be carried out, for example, in the presence of a suitable esterification catalyst while heating and stirring under a temperature condition of about 80 to 140°C. Further, the reaction may be carried out in an organic solvent, if necessary.
  • esterification catalyst examples include phosphorus compounds such as trimethylphosphine, tributylphosphine and triphenylphosphine, amine compounds such as triethylamine, tributylamine and dimethylbenzylamine, 2-methylimidazole, 2-heptadecylimidazole and 2-ethyl.
  • esterification catalysts can be used alone or in combination of two or more kinds.
  • 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 step A2 is a reaction between the intermediate reaction product obtained in the step A1 and the polyisocyanate compound (a1).
  • the reaction is mainly to react the acid group and/or acid anhydride group of the intermediate reaction product obtained in step A1 with the isocyanate group of the polyisocyanate compound (a1).
  • the reaction of step A2 can be carried out, for example, in the presence of a suitable basic catalyst, with heating and stirring under a temperature condition of about 100 to 180°C. Further, the reaction may be carried out in an organic solvent, if necessary. When step A1 and step A2 are continuously performed, the basic catalyst and the organic solvent may not be added, or may be appropriately added.
  • the same basic catalysts as described above can be used, and the organic solvent can be used alone or in combination of two or more kinds.
  • the hydroxyl group-containing (meth)acrylate compound (B) As the hydroxyl group-containing (meth)acrylate compound (B), the same as the above-mentioned hydroxyl group-containing (meth)acrylate compound (a3) can be used, and the hydroxyl group-containing (meth)acrylate compound (B) is independent. Can also be used in combination with two or more kinds.
  • the amide imide resin (A-1) is used as the amide imide resin (A)
  • the hydroxyl group-containing (meth)acrylate compound (B) is a (meth)acrylate compound having two hydroxyl groups, and/or A (meth)acrylate compound having three hydroxyl groups is used as an essential component.
  • the hydroxyl group-containing (meth)acrylate compound (a3) which is a raw material of the amide imide resin (A-2), or the hydroxyl group containing A (meth)acrylate compound having two hydroxyl groups and/or a (meth)acrylate compound having three hydroxyl groups is essentially used for either or both of the (meth)acrylate compound (B).
  • the molecular weight of the hydroxyl group-containing (meth)acrylate compound (B) has excellent photosensitivity and alkali developability, and an acid group-containing (meth)acrylate resin capable of forming a cured product having excellent heat resistance is obtained. Therefore, 1,000 or less is preferable. Further, when the hydroxyl group-containing (meth)acrylate compound (B) is an oxyalkylene modified product or a lactone modified product, the weight average molecular weight (Mw) is preferably 1,000 or less.
  • epoxy group-containing (meth)acrylate compound (C) other specific structures are not particularly limited as long as it has a (meth)acryloyl group and an epoxy group in the molecular structure, and various compounds are used. be able to. Examples thereof include glycidyl group-containing (meth)acrylate monomers such as glycidyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate glycidyl ether, and epoxycyclohexylmethyl (meth)acrylate; dihydroxybenzene diglycidyl ether and dihydroxy.
  • Examples thereof include mono(meth)acrylate compounds of diglycidyl ether compounds such as naphthalene diglycidyl ether, 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 kinds.
  • a (meth)acrylate compound having one epoxy group is preferable because the reaction can be easily controlled, and it forms a cured product having excellent photosensitivity and alkali developability and excellent heat resistance.
  • Glycidyl group-containing (meth)acrylate monomers are preferred because they give possible acid group-containing (meth)acrylate resins.
  • the molecular weight of the glycidyl group-containing (meth)acrylate monomer is preferably 500 or less. Furthermore, the ratio of the glycidyl group-containing (meth)acrylate monomer to the total mass of the epoxy group-containing (meth)acrylate compound (C) is preferably 70% by mass or more, and more preferably 90% by mass or more. ..
  • polycarboxylic acid anhydride (D) the same polycarboxylic acid anhydride (a3) as described above can be used.
  • an acid group-containing (meth)acrylate resin having excellent photosensitivity and alkali developability and capable of forming a cured product having excellent heat resistance can be obtained, an aliphatic polycarboxylic acid anhydride or an alicyclic resin can be obtained.
  • Formula polycarboxylic acid anhydrides are preferred, and aliphatic dicarboxylic acid anhydrides or alicyclic dicarboxylic acid anhydrides are more preferred.
  • These polycarboxylic acid anhydrides (D) can be used alone or in combination of two or more kinds.
  • Examples of the acid group-containing (meth)acrylate resin of the present invention include the amideimide resin (A), the hydroxyl group-containing (meth)acrylate compound (B), and the epoxy group-containing (meth)acrylate depending on desired resin performance and the like.
  • other reaction raw materials can be used in combination.
  • the total content of the above components (A) to (D) in the reaction raw materials of the acid group-containing (meth)acrylate resin is included.
  • the amount is preferably 80% by mass or more, more preferably 85% by mass or more.
  • the method for producing the acid group-containing (meth)acrylate resin of the present invention is not particularly limited, and any method may be used. For example, it may be produced by a method of reacting all the reaction raw materials at once, or may be produced by a method of sequentially reacting the reaction raw materials. Among them, since the reaction can be easily controlled, the amide-imide resin (A) is reacted with the hydroxyl group-containing (meth)acrylate compound (B) (step 1), and the product of step 1 and the epoxy group-containing ( It is preferably produced by a method of reacting a (meth)acrylate compound (C) (step 2) and reacting the product of step 2 with the polycarboxylic acid anhydride (D) (step 3).
  • the step 1 is a reaction between the amide imide resin (A) and the hydroxyl group-containing (meth)acrylate compound (B).
  • the reaction mainly reacts the acid group and/or acid anhydride group in the amide-imide resin (A) with the hydroxyl group in the hydroxyl group-containing (meth)acrylate compound (B). Since the hydroxyl group-containing (meth)acrylate compound (B) is particularly excellent in reactivity with the acid anhydride group, it is preferable that the amide imide resin (A) has an acid anhydride group as described above.
  • the content of the acid anhydride group in the amide imide resin (A) is the difference between the above-mentioned two measured values of the acid value, that is, the acid value under the condition where the acid anhydride group is ring-opened, It can be calculated from the difference from the acid value under the condition that the acid anhydride group is not opened.
  • the reaction ratio between the amide imide resin (A) and the hydroxyl group-containing (meth)acrylate compound (B) is such that when the amide imide resin (A) has an acid group and an acid anhydride group, and the amide imide resin (A) is When it has an acid anhydride group, the number of moles of the hydroxyl group of the hydroxyl group-containing (meth)acrylate compound (B) is 0.9 to 1.1 with respect to 1 mole of the acid anhydride group of the amide imide resin (A). It is preferable to use it within the range. When the amide imide resin (A) has an acid group, the number of moles of the hydroxyl group of the hydroxyl group-containing (meth)acrylate compound (B) is 0. 1 mole of the acid group of the amide imide resin (A). It is preferably used in the range of 1 to 0.5.
  • the reaction between the amide-imide resin (A) and the hydroxyl group-containing (meth)acrylate compound (B) is carried out, for example, by heating and stirring under a temperature condition of about 80 to 140° C. in the presence of a suitable esterification catalyst.
  • a suitable esterification catalyst You can As the esterification catalyst, the same esterification catalyst as described above can be used.
  • the esterification catalysts may be used alone or in combination of two or more.
  • the esterification catalyst is preferably added in an amount of 0.001 to 5 parts by mass with respect to 100 parts by mass of the total amount of the reaction raw materials.
  • the reaction may be carried out in an organic solvent if necessary, and an acidic catalyst may be used if necessary.
  • the 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 reaction may be continued as it is in the organic solvent used in the production of the amide imide resin (A).
  • 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, boron trifluoride, anhydrous aluminum chloride, Lewis acids such as zinc chloride. And so on. These acidic catalysts can be used alone or in combination of two or more kinds.
  • the step 2 is a reaction between the product of the step 1 and the epoxy group-containing (meth)acrylate compound (C).
  • the reaction is mainly to react the acid group in the product obtained in the step 1 with the epoxy group-containing (meth)acrylate compound.
  • the reaction ratio is such that the number of moles of the epoxy group contained in the epoxy group-containing (meth)acrylate compound (C) is 0.7 to 1.2 with respect to 1 mole of the acid group in the product obtained in step 1. It is preferable to use the above range, more preferably to the range of 0.9 to 1.1.
  • the reaction of step 2 can be carried out, for example, in the presence of a suitable esterification catalyst with heating and stirring under temperature conditions of about 90 to 140°C.
  • the esterification catalyst may not be added, or may be added appropriately. Further, the reaction may be carried out in an organic solvent, if necessary.
  • the esterification catalyst and the organic solvent may be the same as the above-mentioned esterification catalyst and the organic solvent, and they may be used alone or in combination of two or more kinds.
  • the step 3 is a reaction between the product of the step 2 and the polycarboxylic acid anhydride (D).
  • the reaction is mainly to react the hydroxyl group in the product obtained in the step 2 with the polycarboxylic acid anhydride (D).
  • a hydroxyl group generated by ring opening of the epoxy group in the epoxy group-containing (meth)acrylate compound (C) is present.
  • the reaction ratio of the polycarboxylic acid anhydride (D) is preferably adjusted so that the acid value of the product (meth)acrylate resin containing an acid group is about 60 to 120 mgKOH/g.
  • step 3 can be carried out, for example, in the presence of a suitable esterification catalyst while heating and stirring under a temperature condition of about 80 to 140°C.
  • the esterification catalyst may not be added, or may be added appropriately.
  • the reaction may be carried out in an organic solvent, if necessary.
  • the esterification catalyst and the organic solvent may be the same as the above-mentioned esterification catalyst and the organic solvent, and they may be used alone or in combination of two or more kinds.
  • the acid value of the acid group-containing (meth)acrylate resin of the present invention has excellent photosensitivity and alkali developability, and an acid group-containing (meth)acrylate resin capable of forming a cured product having excellent heat resistance is obtained. Therefore, the range of 50 to 120 mgKOH/g is preferable, and the range of 60 to 110 mgKOH/g is more preferable.
  • the acid value of the acid group-containing (meth)acrylate resin in the present invention 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 may be appropriately selected and used depending on 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. 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 initiator 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; 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” and “Omnirad-2100".
  • Omnirad-754 "Omnirad-784", “Omnirad-500”, “Omnirad-81” (manufactured by IGM), "Kayacure-DETX”, “Kayacure-MBP”, “Kayacure-DMBI”, “Kayacure-EPA”.
  • photopolymerization initiators can be used alone or in combination of two or more kinds.
  • the amount of the photopolymerization initiator added is, for example, preferably in the range of 0.05 to 15% by mass, and in the range of 0.1 to 10% by mass, based on the total amount of the components other than the solvent of 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 (E) having an acid group and a polymerizable unsaturated bond, various (meth)acrylate monomers, and the like.
  • the resin (E) having an acid group and a polymerizable unsaturated bond may be any resin having an acid group and a polymerizable unsaturated bond in the resin, for example, an acid group and a polymerizable unsaturated bond Epoxy resin having, urethane resin having acid group and polymerizable unsaturated bond, acrylic resin having acid group and polymerizable unsaturated bond, amide imide resin having acid group and polymerizable unsaturated bond, acid group and polymerizable unsaturated Examples thereof include an acrylamide resin having a 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 that uses polybasic acid anhydride as an essential reaction raw material.
  • epoxy resin 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
  • examples thereof include reactive epoxy resins, biphenylaralkyl epoxy resins, fluorene epoxy resins, xanthene epoxy resins, dihydroxybenzene epoxy resins, trihydroxybenzene epoxy resins and the like. These epoxy resins can be used alone or in combination of two or more kinds.
  • the unsaturated monobasic acid means 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 (D) include acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, ⁇ -cyanocinnamic acid, ⁇ -styrylacrylic acid and ⁇ -furfurylacrylic acid.
  • esterified products of unsaturated monobasic acids, acid halides, acid anhydrides and the like can also be used. These unsaturated monobasic acids can be used alone or in combination of two or more kinds.
  • polybasic acid anhydrides examples include phthalic anhydride, succinic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic acid anhydride, and hexahydro.
  • examples thereof include phthalic anhydride, methylhexahydrophthalic anhydride, octenyl succinic anhydride and tetrapropenyl succinic anhydride.
  • These polybasic acid anhydrides can be used alone or in combination of two or more kinds. Further, among these, since a curable resin composition having excellent photosensitivity and alkali developability and capable of forming a cured product having excellent heat resistance is obtained, tetrahydrophthalic anhydride and succinic anhydride are preferable.
  • the same polyisocyanate compound (a1) as described above can be used as the polyisocyanate compound, and the polyisocyanate compound can be used alone or in combination of two or more kinds.
  • the hydroxyl group-containing (meth)acrylate compound may be the same as the above-mentioned hydroxyl group-containing (meth)acrylate compound (a3), and the hydroxyl group-containing (meth)acrylate compound may be used alone or in two kinds. The above can also be used together.
  • 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.
  • the production of the epoxy 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 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 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 optionally a polybasic acid anhydride, the carboxyl group Those 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 And the like.
  • the same polyisocyanate compound (a1) as described above can be used as the polyisocyanate compound, and the polyisocyanate compound can be used alone or in combination of two or more kinds.
  • the hydroxyl group-containing (meth)acrylate compound may be the same as the above-mentioned hydroxyl group-containing (meth)acrylate compound (a3), and the hydroxyl group-containing (meth)acrylate compound may be used alone or in two kinds. The above can also be used together.
  • 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 the same polybasic acid anhydride as described above can be used, and the polybasic acid anhydride can be used alone or in combination of two or more kinds.
  • 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 biphenol and bisphenol; (Poly)oxyethylene chains such as (poly)oxyethylene chains, (poly)oxypropylene chains, and (poly)oxytetramethylene chains in the molecular structures of the various polyol compounds Modified (poly)oxyalkylene modified products; lactone modified products 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 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 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, and 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 ( ⁇ ), an isocyanate group-containing (meth)acrylate is preferably used 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 ( ⁇ )
  • a carboxyl group-containing (meth)acrylate is preferably used as the (meth)acrylate compound ( ⁇ ).
  • the (meth)acrylate compound ( ⁇ ) can be used alone or in combination of two or more kinds.
  • polybasic acid anhydride the same polybasic acid anhydride as described above 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 an acid group and a polymerizable unsaturated bond is not particularly limited, and any method may be used.
  • 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 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.
  • Examples of the amide imide resin having an acid group and a polymerizable unsaturated bond include an amide imide 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 at least one reactive functional group selected from the group consisting of a hydroxyl group, a carboxyl group, an isocyanate group, a glycidyl group, and an acid anhydride group.
  • 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 opened. On the other hand, the measured value under the condition that the acid anhydride group is ring-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.
  • the same polyisocyanate compound (a1) as described above can be used as the polyisocyanate compound.
  • polybasic acid anhydride the same polybasic acid anhydride as described above can be used, and the polybasic acid anhydride can be used alone or in combination of two or more kinds.
  • a polybasic acid may be used as a reaction raw material in combination with the amide-imide resin, 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 kinds.
  • the hydroxyl group-containing (meth)acrylate compound may be the same as the above-mentioned hydroxyl group-containing (meth)acrylate compound (a3), and the hydroxyl group-containing (meth)acrylate compound may be used alone or in two kinds. The above can also be used together.
  • epoxy group-containing (meth)acrylate compound as the above-mentioned epoxy group-containing (meth)acrylate compound (C) can be used, and the epoxy group-containing (meth)acrylate compound can be used alone. It is also possible to use two or more kinds in combination.
  • 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 amide-imide resin having an acid group and a polymerizable unsaturated bond may be produced 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 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.
  • 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 alkylene carbonate, an N-alkoxyalkyl (meth)acrylamide compound, and a polybasic acid anhydride. Examples thereof include those obtained by reacting with an 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 (3-1) to (3-4).
  • 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 each independently a hydrogen atom or a methyl group.
  • 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, and for example, in the naphthalene ring of the structural formula (3-2), it may be substituted on any ring, and In 3-3), it may be substituted on any ring of the benzene ring present in one molecule, and in structural formula (3-4), it may be substituted on any ring of the benzene ring present in one molecule. It indicates that they 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 one of the following structural formulas (x-1) to (x-5) are essential.
  • An essential reaction between the reaction product used as the reaction raw material, the compound having at least two phenolic hydroxyl groups in the molecule, and the compound represented by any of the following structural formulas (x-1) to (x-5) A reaction product as a raw material can also be used.
  • 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 It is also possible to use a novolac-type phenol resin as a reaction raw material.
  • 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 (2-1) to (2-4).
  • 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 each independently a hydrogen atom or a methyl group.
  • 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, and for example, in the naphthalene ring of the structural formula (4-2), the substituent may be substituted on any ring.
  • the compounds represented by the above structural formulas (3-1) to (3-4) 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 photosensitivity and alkali developability and capable of forming a cured product having excellent heat resistance can be obtained.
  • the alkylene oxides may 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 photosensitivity and alkali developability and capable of forming a cured product having excellent heat resistance can be obtained.
  • the alkylene carbonates may 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.
  • polybasic acid anhydride the same polybasic acid anhydride as described above can be used, and the polybasic acid anhydride can be used alone or in combination of two or more kinds.
  • the same unsaturated monobasic acid as described above can be used, and the organic solvent can be used alone or in combination of two or more kinds.
  • 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 same acidic catalyst as described above can be used, and the acidic catalyst can be used alone or in combination of two or more kinds.
  • the amount of the resin (E) 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 and octyl(meth)acrylate; cycloaliphatic (meth)acrylate, isobornyl(meth)acrylate, adamantyl mono(meth)acrylate and other alicyclic mono(meth)acrylates Acrylate compounds; Heterocyclic mono(meth)acrylate compounds such as glycidyl (meth)acrylate and tetrahydrofurfuryl acrylate; benzyl (meth)acrylate, phenyl (meth)acrylate, phenylbenzyl (meth)
  • (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 may also 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 kinds. Further, among these, since a curable resin composition having excellent photosensitivity and alkali developability and capable of forming a cured product having excellent heat resistance is obtained, a phenol novolac type epoxy resin, a cresol novolac type is obtained.
  • Novolak type epoxy resins such as epoxy resin, bisphenol novolac type epoxy resin, naphthol novolak type epoxy resin, naphthol-phenol co-contracting novolac type epoxy resin, naphthol-cresol co-contracting novolac type epoxy resin are preferable, and the softening point is 20 to 120°C. The range of is particularly preferable.
  • 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 kinds. Further, the addition amount of the curing accelerator is preferably, for example, in the 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 with the active energy rays may be performed in one step or in two or more steps.
  • the cured product of the present invention has excellent heat resistance, for example, in a semiconductor device application, a solder resist, an interlayer insulating material, a package material, an underfill material, a package adhesive layer such as a circuit element, or an integrated circuit. It can be suitably used as an adhesive layer between an 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 color filter pigment resist, a black matrix resist, a spacer and the like in a thin display application represented by LCD and OELD. Among them, 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 on which a desired pattern is formed after applying the resin material for solder resist on a substrate and evaporating and drying an organic solvent in a temperature range of about 60 to 100°C. Through exposure with an active energy ray, the unexposed area is developed with an alkaline aqueous solution, and then heat-cured in a temperature range of about 140 to 200° C.
  • 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.
  • Measuring device "HLC-8220 GPC” manufactured by Tosoh Corporation, Column: Tosoh Co., Ltd. guard column “HXL-L” + “TSK-GEL G2000HXL” manufactured by Tosoh Corporation + “TSK-GEL G2000HXL” manufactured by Tosoh Corporation + “TSK-GEL G3000HXL” manufactured by Tosoh Corporation + “TSK-GEL G4000HXL” manufactured by Tosoh Corporation Detector: RI (differential refractometer) Data processing: "GPC-8020 model II version 4.10" manufactured by Tosoh Corporation Measurement conditions: Column temperature 40°C Developing solvent Tetrahydrofuran Flow rate 1.0 ml/min Standard: The following monodisperse polystyrene having a known molecular weight was used according to the measurement manual of “GPC-8020 Model II Version 4.10”.
  • the hydroxyl value of this pentaerythritol polyacrylate (A1) is 290 mgKOH/g
  • the content of pentaerythritol tetraacrylate (a1) calculated from the area ratio of the liquid chromatography chart is 16% by mass
  • the pentaerythritol triacrylate (a2) content is 50% by mass
  • the content of pentaerythritol diacrylate (a3) is 29% by mass
  • the content of pentaerythritol monoacrylate (a4) is 3% by mass
  • the content of the other high molecular weight component (a') is 2%. It was mass %.
  • the obtained aqueous layer was extracted with ethyl acetate and washed with a saturated aqueous solution of sodium hydrogen carbonate until the pH reached 7.
  • the organic layer was dehydrated with magnesium sulfate and then concentrated under reduced pressure at room temperature to obtain pentaerythritol diacrylate (A2).
  • dipentaerythritol acrylate (A3) was 140 mgKOH/g.
  • dipentaerythritol tetraacrylate (b1) calculated from the area ratio of the liquid chromatography chart is 28% by mass
  • the content of dipentaerythritol pentaacrylate (b2) is 42% by mass
  • dipentaerythritol hexaacrylate is 28% by mass
  • the content of (b3) was 22% by mass
  • the content of the high molecular weight component (b') was 8% by mass.
  • Example 1 Production of acid group-containing (meth)acrylate resin (1)
  • a flask equipped with a thermometer, a stirrer, and a reflux condenser 288 parts by mass of diethylene glycol monomethyl ether acetate, 168 parts by mass of trimellitic anhydride, 53 parts by mass of pentaerythritol polyacrylate (A1) obtained in Synthesis Example 1, dibutyl. Hydroxytoluene (0.7 parts by mass), metoquinone (0.3 parts by mass) and triphenylphosphine (0.7 parts by mass) were added, and the mixture was reacted at 120° C. for 6 hours while blowing air.
  • the acid value of the solid content of the acid group-containing (meth)acrylate resin (1) was 87 mgKOH/g, and the weight average molecular weight was 2,390.
  • Example 2 Production of acid group-containing (meth)acrylate resin (2)
  • a flask equipped with a thermometer, a stirrer, and a reflux condenser 288 parts by mass of diethylene glycol monomethyl ether acetate, 168 parts by mass of trimellitic anhydride, 53 parts by mass of pentaerythritol polyacrylate (A1) obtained in Synthesis Example 1, dibutyl. Hydroxytoluene (0.7 parts by mass), metoquinone (0.3 parts by mass) and triphenylphosphine (0.7 parts by mass) were added, and the mixture was reacted at 120° C. for 6 hours while blowing air.
  • Example 3 Production of acid group-containing (meth)acrylate resin (3)
  • a flask equipped with a thermometer, a stirrer, and a reflux condenser 288 parts by mass of diethylene glycol monomethyl ether acetate, 168 parts by mass of trimellitic anhydride, 53 parts by mass of pentaerythritol polyacrylate (A1) obtained in Synthesis Example 1, dibutyl. 0.7 parts by mass of hydroxytoluene, 0.3 parts by mass of methoquinone, and 0.7 parts by mass of triphenylphosphine were added and the reaction was carried out at 120° C. for 6 hours while blowing air.
  • Example 4 Production of acid group-containing (meth)acrylate resin (4)
  • a flask equipped with a thermometer, a stirrer, and a reflux condenser 275 parts by mass of diethylene glycol monomethyl ether acetate, 144 parts by mass of trimellitic anhydride, 44 parts by mass of pentaerythritol polyacrylate (A1) obtained in Synthesis Example 1, dibutyl. 0.7 parts by mass of hydroxytoluene, 0.2 parts by mass of metoquinone, and 0.6 parts by mass of triphenylphosphine were added, and the mixture was reacted at 120° C. for 6 hours while blowing air.
  • the acid value of the solid content of the acid group-containing (meth)acrylate resin (4) was 85 mgKOH/g, and the weight average molecular weight was 2,440.
  • Example 5 Production of acid group-containing (meth)acrylate resin (5)
  • a flask equipped with a thermometer, a stirrer, and a reflux condenser 275 parts by mass of diethylene glycol monomethyl ether acetate, 144 parts by mass of trimellitic anhydride, 44 parts by mass of pentaerythritol polyacrylate (A1) obtained in Synthesis Example 1, dibutyl. Hydroxytoluene (0.7 parts by mass), metoquinone (0.3 parts by mass) and triphenylphosphine (0.6 parts by mass) were added, and the mixture was reacted at 120° C. for 6 hours while blowing air.
  • Example 6 Production of acid group-containing (meth)acrylate resin (6)
  • 374 parts by mass of diethylene glycol monomethyl ether acetate 173 parts by mass of cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride, obtained in Synthesis Example 1
  • 53 parts by mass of pentaerythritol polyacrylate (A1), 0.7 parts by mass of dibutylhydroxytoluene, 0.3 parts by mass of methoquinone, and 0.7 parts by mass of triphenylphosphine were added, and the mixture was reacted at 120° C.
  • Example 7 Production of acid group-containing (meth)acrylate resin (7)
  • 341 parts by mass of diethylene glycol monomethyl ether acetate 341 parts by mass of diethylene glycol monomethyl ether acetate, 149 parts by mass of cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride, obtained in Synthesis Example 1
  • 44 parts by mass of pentaerythritol polyacrylate (A1), 0.7 parts by mass of dibutylhydroxytoluene, 0.3 parts by mass of methoquinone, and 0.6 parts by mass of triphenylphosphine were added and reacted at 120° C. for 6 hours while blowing air.
  • Example 8 Production of acid group-containing (meth)acrylate resin (8)
  • a flask equipped with a thermometer, a stirrer, and a reflux condenser 211 parts by mass of diethylene glycol monomethyl ether acetate, 111 parts by mass of isophorone diisocyanate, 144 parts by mass of trimellitic anhydride, and 0.5 parts by mass of dibutylhydroxytoluene were added and dissolved.
  • the reaction was carried out at 160° C. for 8 hours in a nitrogen atmosphere, and it was confirmed that the isocyanate group content was 0.1% by mass or less.
  • Example 9 Production of acid group-containing (meth)acrylate resin (9)
  • a flask equipped with a thermometer, a stirrer, and a reflux condenser 211 parts by mass of diethylene glycol monomethyl ether acetate, 111 parts by mass of isophorone diisocyanate, 144 parts by mass of trimellitic anhydride, and 0.5 parts by mass of dibutylhydroxytoluene were added and dissolved.
  • the reaction was carried out at 160° C. for 8 hours in a nitrogen atmosphere, and it was confirmed that the isocyanate group content was 0.1% by mass or less.
  • Example 10 Production of acid group-containing (meth)acrylate resin (10)
  • a flask equipped with a thermometer, a stirrer, and a reflux condenser 269 parts by mass of diethylene glycol monomethyl ether acetate, 168 parts by mass of trimellitic anhydride, 34 parts by mass of pentaerythritol diacrylate (A2) obtained in Synthesis Example 2, dibutyl. 0.7 parts by mass of hydroxytoluene, 0.2 parts by mass of metoquinone, and 0.6 parts by mass of triphenylphosphine were added, and the mixture was reacted at 120° C. for 6 hours while blowing air.
  • the acid value of the solid content of the acid group-containing (meth)acrylate resin (10) was 92 mgKOH/g, and the weight average molecular weight was 2,590.
  • Example 11 Production of acid group-containing (meth)acrylate resin (11)
  • a flask equipped with a thermometer, a stirrer, and a reflux condenser 288 parts by mass of diethylene glycol monomethyl ether acetate, 168 parts by mass of trimellitic anhydride, 53 parts by mass of pentaerythritol polyacrylate (A1) obtained in Synthesis Example 1, dibutyl. 0.7 parts by mass of hydroxytoluene, 0.2 parts by mass of methoquinone, and 0.7 parts by mass of triphenylphosphine were added and the reaction was carried out at 120° C. for 6 hours while blowing air.
  • Example 12 Production of acid group-containing (meth)acrylate resin (12)
  • a flask equipped with a thermometer, a stirrer, and a reflux condenser 269 parts by mass of diethylene glycol monomethyl ether acetate, 168 parts by mass of trimellitic anhydride, 34 parts by mass of pentaerythritol diacrylate (A2) obtained in Synthesis Example 2, dibutyl. 0.7 parts by mass of hydroxytoluene, 0.2 parts by mass of metoquinone, and 0.6 parts of triphenylphosphine were added and the reaction was carried out at 120° C. for 6 hours while blowing air.
  • the acid value of the solid content of the acid group-containing (meth)acrylate resin (12) was 105 mgKOH/g, and the weight average molecular weight was 2990.
  • Example 13 Production of acid group-containing (meth)acrylate resin (13)
  • a flask equipped with a thermometer, a stirrer, and a reflux condenser 269 parts by mass of diethylene glycol monomethyl ether acetate, 168 parts by mass of trimellitic anhydride, 34 parts by mass of pentaerythritol diacrylate (A2) obtained in Synthesis Example 2, dibutyl. 0.7 parts by mass of hydroxytoluene, 0.2 parts by mass of metoquinone, and 0.6 parts by mass of triphenylphosphine were added, and the mixture was reacted at 120° C. for 6 hours while blowing air.
  • the acid value of the solid content of the acid group-containing (meth)acrylate resin (13) was 101 mgKOH/g, and the weight average molecular weight was 2,590.
  • Example 14 Production of acid group-containing (meth)acrylate resin (14)
  • a flask equipped with a thermometer, a stirrer, and a reflux condenser 332 parts by mass of diethylene glycol monomethyl ether acetate, 168 parts by mass of trimellitic anhydride, 97 parts by mass of "Aronix M-306", 0.8 part by mass of dibutylhydroxytoluene.
  • 0.3 parts by mass of methoquinone and 0.8 part of triphenylphosphine were added and the reaction was carried out at 120° C. for 6 hours while blowing air.
  • 111 parts by mass of isophorone diisocyanate was added and reacted at 120° C.
  • Example 15 Production of acid group-containing (meth)acrylate resin (15)
  • a flask equipped with a thermometer, a stirrer, and a reflux condenser 332 parts by mass of diethylene glycol monomethyl ether acetate, 168 parts by mass of trimellitic anhydride, 97 parts by mass of "Aronix M-306", 0.8 part by mass of dibutylhydroxytoluene.
  • 0.3 parts by mass of methoquinone and 0.8 part of triphenylphosphine were added and the reaction was carried out at 120° C. for 6 hours while blowing air.
  • 111 parts by mass of isophorone diisocyanate was added and reacted at 120° C.
  • Example 16 Production of acid group-containing (meth)acrylate resin (16)
  • a flask equipped with a thermometer, a stirrer, and a reflux condenser 392 parts by mass of diethylene glycol monomethyl ether acetate, an isocyanurate modified product of isophorone diisocyanate (“VESTANAT T-1890/100” manufactured by EVONIK, isocyanate group content 17. (2 mass %) 244 mass parts, trimellitic anhydride 192 mass parts, and dibutyl hydroxytoluene 1.0 mass part were added and dissolved. The reaction was carried out at 160° C. for 5 hours in a nitrogen atmosphere, and it was confirmed that the isocyanate group content was 0.1% by mass or less.
  • VESTANAT T-1890/100 manufactured by EVONIK
  • the acid value of the solid content of the acid group-containing (meth)acrylate resin (16) was 86 mgKOH/g, and the weight average molecular weight was 7,450.
  • Example 17 Production of acid group-containing (meth)acrylate resin (17)
  • a flask equipped with a thermometer, a stirrer, and a reflux condenser 418 parts by mass of diethylene glycol monomethyl ether acetate, 192 parts by mass of trimellitic anhydride, 26 parts by mass of pentaerythritol polyacrylate (A1) obtained in Synthesis Example 1, dibutyl. 1.0 parts by mass of hydroxytoluene, 0.3 parts by mass of methoquinone, and 0.7 parts by mass of triphenylphosphine were added and the reaction was carried out at 120° C. for 6 hours while blowing air.
  • the acid value of the solid content of the acid group-containing (meth)acrylate resin (17) was 84 mgKOH/g, and the weight average molecular weight was 7,390.
  • Example 18 Production of acid group-containing (meth)acrylate resin (18)
  • a flask equipped with a thermometer, a stirrer, and a reflux condenser 211 parts by mass of diethylene glycol monomethyl ether acetate, 111 parts by mass of isophorone diisocyanate, 144 parts by mass of trimellitic anhydride, and 0.5 parts by mass of dibutylhydroxytoluene were added and dissolved.
  • the reaction was carried out at 160° C. for 8 hours in a nitrogen atmosphere, and it was confirmed that the isocyanate group content was 0.1% by mass or less.
  • Example 19 Production of acid group-containing (meth)acrylate resin (19)
  • a flask equipped with a thermometer, a stirrer, and a reflux condenser 345 parts by mass of diethylene glycol monomethyl ether acetate, 168 parts by mass of trimellitic anhydride, 110 parts by mass of dipentaerythritol polyacrylate (A3) obtained in Synthesis Example 3, 0.9 parts by mass of dibutylhydroxytoluene, 0.3 parts by mass of metoquinone, and 0.8 parts by mass of triphenylphosphine were added and the reaction was carried out at 120° C. for 6 hours while blowing air.
  • A3 dipentaerythritol polyacrylate
  • Example 20 Production of acid group-containing (meth)acrylate resin (20)
  • a flask equipped with a thermometer, a stirrer, and a reflux condenser 258 parts by mass of diethylene glycol monomethyl ether acetate, 139 parts by mass of trimellitic anhydride, 52 parts by mass of pentaerythritol diacrylate (A2) obtained in Synthesis Example 2, dibutyl. Hydroxytoluene (0.6 parts by mass), methoquinone (0.2 parts by mass) and triphenylphosphine (0.6 parts by mass) were added, and the mixture was reacted at 120° C. for 6 hours while blowing air.
  • 111 parts by mass of isophorone diisocyanate was added and reacted at 120° C. for 12 hours, and it was confirmed that the isocyanate group content was 0.1% by mass or less.
  • 65 parts by mass of “Aronix M-306” was added, and the mixture was reacted at 110° C. for 3 hours.
  • 111 parts by mass of glycidyl methacrylate and 1.6 parts by mass of triphenylphosphine were added and reacted at 110° C. for 5 hours.
  • 74 parts by mass of succinic anhydride and 53 parts by mass of diethylene glycol monomethyl ether acetate were added and reacted at 110° C. for 5 hours to obtain a target acid group-containing (meth)acrylate resin (20).
  • the acid value of the solid content of the acid group-containing (meth)acrylate resin (20) was 85 mgKOH/g, and the weight average molecular weight was 2340.
  • Example 21 Production of acid group-containing (meth)acrylate resin (21)
  • a flask equipped with a thermometer, a stirrer, and a reflux condenser 279 parts by mass of diethylene glycol monomethyl ether acetate, 197 parts by mass of trimellitic anhydride, 15 parts by mass of pentaerythritol diacrylate (A2) obtained in Synthesis Example 2, dibutyl. Hydroxytoluene (0.7 parts by mass), metoquinone (0.3 parts by mass) and triphenylphosphine (0.6 parts by mass) were added, and the mixture was reacted at 120° C. for 6 hours while blowing air.
  • Example 22 Production of acid group-containing (meth)acrylate resin (22)
  • a flask equipped with a thermometer, a stirrer, and a reflux condenser 254 parts by mass of diethylene glycol monomethyl ether acetate, 168 parts by mass of trimellitic anhydride, 53 parts by mass of pentaerythritol polyacrylate (A1) obtained in Synthesis Example 1, dibutyl. Hydroxytoluene (0.6 parts by mass), methoquinone (0.2 parts by mass) and triphenylphosphine (0.7 parts by mass) were added, and the mixture was reacted at 120° C. for 6 hours while blowing air.
  • Example 23 Production of acid group-containing (meth)acrylate resin (23)
  • 271 parts by mass of dimethylacetamide 271 parts by mass of trimellitic anhydride, 53 parts by mass of pentaerythritol polyacrylate (A1) obtained in Synthesis Example 1, dibutylhydroxytoluene.
  • 0.7 parts by mass, 0.2 parts by mass of metoquinone, and 0.7 parts by mass of triphenylphosphine were added, and the mixture was reacted at 120° C. for 6 hours while blowing air.
  • the acid value of the solid content of the acid group-containing acrylate resin (C1) was 85 mgKOH/g.
  • Example 24 Preparation of curable resin composition (1)
  • Curable resin composition (1) was obtained.
  • Examples 25 to 46 Preparation of curable resin compositions (2) to (23)
  • the acid group-containing (meth)acrylate resins (2) to (23) obtained in Examples 2 to 23 were used, respectively.
  • Curable resin compositions (2) to (23) were obtained in the same manner as in Example 24.
  • Tables 1 and 2 show the compositions and evaluation results of the curable resin compositions (1) to (23) produced in Examples 24 to 46 and the curable resin composition (C2) produced in Comparative Example 2.
  • Example 47 Preparation of curable resin composition (24)
  • the acid group-containing (meth)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 as a photopolymerization initiator.
  • -(4-Methylthiophenyl)-2-morpholinopropan-1-one (“OMNIRAD-907” manufactured by IGM) and diethylene glycol monomethyl ether acetate as an organic solvent were mixed in a mass ratio shown in Table 1 to prepare a curable resin.
  • a composition (24) was obtained.
  • Example 48 to 69 Preparation of curable resin compositions (25) to (46)
  • the acid group-containing (meth)acrylate resins (2) to (23) obtained in Examples 2 to 23 were used instead of the acid group-containing (meth)acrylate resin (1) used in Example 47, respectively.
  • Curable resin compositions (25) to (46) were obtained in the same manner as in Example 47.
  • the test piece was cut into a size of 6 mm ⁇ 40 mm, and a viscoelasticity measuring device (DMA: solid viscoelasticity measuring device “RSAII” manufactured by Rheometric Co., tension method: frequency 1 Hz, temperature rising rate 3° C./min) was used.
  • DMA solid viscoelasticity measuring device “RSAII” manufactured by Rheometric Co., tension method: frequency 1 Hz, temperature rising rate 3° C./min
  • Tg glass transition temperature
  • Tables 3 and 4 show the compositions and evaluation results of the curable resin compositions (24) to (46) produced in Examples 47 to 69 and the curable resin composition (C3) produced in Comparative Example 3.
  • the parts by mass of the “acid group-containing (meth)acrylate resin” in Tables 1 to 4 are solution values.
  • “Curing agent” in Tables 1 to 4 indicates an ortho-cresol novolac type epoxy resin (“EPICLON N-680” manufactured by DIC Corporation, epoxy equivalent: 214).
  • Organic solvent in Tables 1 to 4 indicates diethylene glycol monomethyl ether acetate.
  • Examples 22 to 63 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 had excellent photosensitivity and alkali developability, and that the cured product had excellent heat resistance.
  • Comparative Examples 2 and 3 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 remarkably insufficient heat resistance in the cured product.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Materials For Photolithography (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Organic Insulating Materials (AREA)
  • Non-Metallic Protective Coatings For Printed Circuits (AREA)
PCT/JP2019/047584 2018-12-19 2019-12-05 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 WO2020129667A1 (ja)

Priority Applications (3)

Application Number Priority Date Filing Date Title
JP2020537671A JP6780809B1 (ja) 2018-12-19 2019-12-05 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
CN201980084081.9A CN113195574B (zh) 2018-12-19 2019-12-05 含酸基(甲基)丙烯酸酯树脂、固化性树脂组合物、固化物、绝缘材料、阻焊剂用树脂材料及抗蚀构件
KR1020217014292A KR102500020B1 (ko) 2018-12-19 2019-12-05 산기 함유 (메타)아크릴레이트 수지, 경화성 수지 조성물, 경화물, 절연 재료, 솔더 레지스트용 수지 재료 및 레지스트 부재

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2018237342 2018-12-19
JP2018-237342 2018-12-19

Publications (1)

Publication Number Publication Date
WO2020129667A1 true WO2020129667A1 (ja) 2020-06-25

Family

ID=71100851

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2019/047584 WO2020129667A1 (ja) 2018-12-19 2019-12-05 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

Country Status (5)

Country Link
JP (1) JP6780809B1 (zh)
KR (1) KR102500020B1 (zh)
CN (1) CN113195574B (zh)
TW (1) TWI797403B (zh)
WO (1) WO2020129667A1 (zh)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7183761B2 (ja) * 2018-12-19 2022-12-06 Dic株式会社 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

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000344889A (ja) * 1999-03-30 2000-12-12 Dainippon Ink & Chem Inc イミド（アミド）樹脂の製造方法及びその樹脂を使用したエネルギー線硬化型樹脂組成物
JP2015155500A (ja) * 2014-02-20 2015-08-27 Dic株式会社 硬化性アミドイミド樹脂およびアミドイミド樹脂の製造方法
WO2018230144A1 (ja) * 2017-06-14 2018-12-20 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
WO2018230428A1 (ja) * 2017-06-14 2018-12-20 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

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61243869A (ja) 1985-04-19 1986-10-30 Taiyo Ink Seizo Kk レジストインキ組成物
JP4565293B2 (ja) * 1999-03-30 2010-10-20 Ｄｉｃ株式会社 硬化性イミド樹脂の製造方法及びその組成物
JP2001323036A (ja) * 2000-05-16 2001-11-20 Nippon Kayaku Co Ltd 樹脂組成物、ソルダーレジスト樹脂組成物及びこれらの硬化物
JP6877202B2 (ja) * 2016-12-28 2021-05-26 太陽インキ製造株式会社 ネガ型光硬化性樹脂組成物、ドライフィルム、硬化物およびプリント配線板

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000344889A (ja) * 1999-03-30 2000-12-12 Dainippon Ink & Chem Inc イミド（アミド）樹脂の製造方法及びその樹脂を使用したエネルギー線硬化型樹脂組成物
JP2015155500A (ja) * 2014-02-20 2015-08-27 Dic株式会社 硬化性アミドイミド樹脂およびアミドイミド樹脂の製造方法
WO2018230144A1 (ja) * 2017-06-14 2018-12-20 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
WO2018230428A1 (ja) * 2017-06-14 2018-12-20 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

Also Published As

Publication number Publication date
JPWO2020129667A1 (ja) 2021-02-15
KR102500020B1 (ko) 2023-02-16
CN113195574A (zh) 2021-07-30
TW202031703A (zh) 2020-09-01
TWI797403B (zh) 2023-04-01
CN113195574B (zh) 2023-10-20
JP6780809B1 (ja) 2020-11-04
KR20210076076A (ko) 2021-06-23

Similar Documents

Publication Publication Date Title
JP7172555B2 (ja) 酸基含有（メタ）アクリレート樹脂組成物、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
JP6780809B1 (ja) 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
JP6797354B2 (ja) 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
JP7310253B2 (ja) アミドイミド樹脂組成物、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
JP7188053B2 (ja) 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
JP6813135B1 (ja) 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
JP7183761B2 (ja) 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
JP7192521B2 (ja) 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
JP7196587B2 (ja) 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
JP7228093B2 (ja) 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
JP7151411B2 (ja) 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
JP7192480B2 (ja) 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
JP7264004B2 (ja) 酸基含有（メタ）アクリレート樹脂組成物、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
JP7275898B2 (ja) 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
JP6838692B1 (ja) 酸基含有（メタ）アクリレート樹脂、酸基含有（メタ）アクリレート樹脂組成物、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
TWI811384B (zh) 含酸基之（甲基）丙烯酸酯樹脂組成物、硬化性樹脂組成物、硬化物、及阻焊劑用樹脂材料
JP7215105B2 (ja) 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
WO2021220922A1 (ja) 酸基含有（メタ）アクリレート樹脂、硬化性樹脂組成物、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
WO2021065318A1 (ja) 酸基含有（メタ）アクリレート樹脂、酸基含有（メタ）アクリレート樹脂組成物、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
JP2022006901A (ja) 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

Legal Events

Date Code Title Description
ENP Entry into the national phase

Ref document number: 2020537671

Country of ref document: JP

Kind code of ref document: A

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 19897622

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 20217014292

Country of ref document: KR

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 19897622

Country of ref document: EP

Kind code of ref document: A1