JP2020083986A - Acid group-containing (meth)acrylate resin, curable resin composition, cured product, insulating material, resin material for solder resist, and resist member - Google Patents

Abstract

To provide an acid group-containing (meth)acrylate resin giving a cured product excellent in heat resistance and adhesion to a substrate, a curable resin composition containing the same, and an insulating material, a resin material for a solder resist, and a resist member comprising the curable resin composition.SOLUTION: The acid group-containing (meth)acrylate resin is used which uses an amide-imide resin (A) having an acid group or an acid anhydride group, a hydroxyl group-containing (meth)acrylate compound (B), an epoxy group-containing (meth)acrylate compound (C), a polycarboxylic acid anhydride (D), and an isocyanate group-containing (meth)acrylate compound (E) as essential reaction raw materials.SELECTED DRAWING: None

Description

The present invention relates to an acid group-containing (meth)acrylate resin having excellent heat resistance and substrate adhesion in a cured product, a curable resin composition containing the same, an insulating material comprising the curable resin composition, and a solder resist. The present invention relates to a resin material and a resist member.

In recent years, an acid group-containing epoxy acrylate resin obtained by acrylate conversion of an epoxy resin with acrylic acid and then reaction with an acid anhydride has been widely used as a resin material for a solder resist for a printed wiring board. There are various requirements for the resin material for the solder resist, such as excellent heat resistance of the cured product and excellent adhesion to the substrate.

As a conventionally known resin material for solder resist, an active energy ray curable product 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 Resins are known (see, for example, Patent Document 1 below), but although the cured product is excellent in heat resistance, it does not satisfy the ever-increasing required properties in substrate adhesion. It was not sufficient for the market demand.

Therefore, there has been a demand for a material having excellent heat resistance and substrate adhesion in the cured product.

JP-A-61-243869

The problem to be solved by the present invention comprises an acid group-containing (meth)acrylate resin having excellent heat resistance and substrate adhesion in a cured product, a curable resin composition containing the same, and the curable resin composition. An object is to provide an insulating material, a resin material for a solder resist, and a resist member.

As a result of intensive studies to solve the above problems, the present inventors have found that an amide imide resin (A) having an acid group or an acid anhydride group, a hydroxyl group-containing (meth)acrylate compound (B), and an epoxy group-containing (meth). By using an acid group-containing (meth)acrylate resin characterized by using an acrylate compound (C), a polycarboxylic acid anhydride (D) and an isocyanate group-containing (meth)acrylate compound (E) as essential reaction raw materials. The inventors have found that the above problems can be solved and completed the present invention.

That is, the present invention provides an amide-imide resin (A) having an acid group or an acid anhydride group, a hydroxyl group-containing (meth)acrylate compound (B), an epoxy group-containing (meth)acrylate compound (C), a polycarboxylic acid anhydride ( D) and an isocyanate group-containing (meth)acrylate compound (E) as essential reaction raw materials, an acid group-containing (meth)acrylate resin, a curable resin composition containing the same, and the curable resin composition The present invention relates to a cured product made of a material, an insulating material, a resin material for solder resist, and a resist member.

The acid group-containing (meth)acrylate resin of the present invention is excellent in heat resistance and substrate adhesion in a cured product, and therefore can be suitably used for an insulating material, a solder resist resin material and a resist member.

Hereinafter, the present invention will be described in detail.
The acid group-containing (meth)acrylate resin of the present invention is an amide imide resin (A) having an acid group or an acid anhydride group, a hydroxyl group-containing (meth)acrylate compound (B), and an epoxy group-containing (meth)acrylate compound (C). The polycarboxylic acid anhydride (D) and the isocyanate group-containing (meth)acrylate compound (E) are used as essential reaction raw materials.

In addition, in this invention, "(meth)acrylate" means an acrylate and/or a methacrylate. Moreover, "(meth)acryloyl" means acryloyl and/or methacryloyl. Furthermore, "(meth)acrylic" means acrylic and/or methacrylic.

The amide-imide resin (A) having an acid group or an acid anhydride group may have only one of the acid group and the acid anhydride group, or may have both. 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. The acid value of the amide-imide resin (A) is preferably in the range of 60 to 350 mgKOH/g, as 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. The acid value in the present invention is a value measured by the neutralization titration method of JIS K 0070 (1992).

The specific structure and manufacturing method of the amide imide resin (A) are not particularly limited, and general amide imide resins and the like can be widely used. Specific examples include those in which the polyisocyanate compound (a1) and the polycarboxylic acid or its acid anhydride (a2) are used as reaction raw materials.

Examples of the polyisocyanate compound (a1) include aliphatic diisocyanate compounds such as butane diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate and 2,4,4-trimethylhexamethylene diisocyanate; norbornane diisocyanate, Aliphatic diisocyanate compounds such as isophorone diisocyanate, hydrogenated xylylene diisocyanate and 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 polyisocyanate having a repeating structure represented by the following structural formula (1); these isocyanurate modified products, biuret Examples include modified products and allophanate modified products. In addition, these polyisocyanate compounds can be used alone or in combination of two or more kinds.

［式（１）中、Ｒ^１はそれぞれ独立して、水素原子、または炭素原子数１〜６の炭化水素基の何れかである。Ｒ^２はそれぞれ独立して、炭素原子数１〜４のアルキル基、または構造式（１）で表される構造部位と＊印が付されたメチレン基を介して連結する結合点の何れかである。ｌは０または１〜３の整数であり、ｍは１〜１５の整数である。］

[In the formula (1), 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 moiety represented by the structural formula (1) and a methylene group marked with *. is there. l is 0 or an integer of 1 to 3, and m is an integer of 1 to 15. ]

Among these, the alicyclic diisocyanate compound or a modified product thereof is preferable, and the alicyclic diisocyanate or a modified isocyanurate thereof is preferable, from the viewpoint of providing an acid group-containing (meth)acrylate resin having excellent solvent solubility. Further, the aliphatic diisocyanate compound or a modified product thereof is preferable in that it becomes an acid group-containing (meth)acrylate resin having excellent heat resistance and substrate adhesion in a cured product, and an aliphatic diisocyanate or a modified isocyanurate thereof is preferable. Is preferred. Furthermore, 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% by mass or more. When the alicyclic diisocyanate compound or modified product thereof and the aliphatic diisocyanate compound or modified product thereof are used in combination, the mass ratio of the two is preferably in the range of 20/80 to 80/20.

The polycarboxylic acid or its acid anhydride (a2) is not particularly limited in its specific structure as long as it is a compound having a plurality of carboxyl groups in its molecular structure or its acid anhydride, and various compounds can be used. .. Moreover, the polycarboxylic acid or its acid anhydride (a2) can be used alone or in combination of two or more kinds. In addition, in order for the amide-imide resin (A) to have both an amide group and an imide group, it is necessary that both a carboxyl group and an acid anhydride group be present in the system, but in the present invention, A compound having both a carboxyl group and an acid anhydride group in the molecule may be used, or a compound having a carboxyl group and a compound having an acid anhydride group may be used in combination.

Examples of the polycarboxylic acid or its acid anhydride (a2) include, for example, an aliphatic polycarboxylic acid compound or its acid anhydride, an alicyclic polycarboxylic acid compound or its acid anhydride, and an aromatic polycarboxylic acid compound. Or the acid anhydride etc. are mentioned.

In the aliphatic polycarboxylic acid compound or the acid anhydride thereof, the aliphatic hydrocarbon group may be linear or branched, and may have an unsaturated bond in the structure. Examples of the aliphatic polycarboxylic acid compound or an acid anhydride thereof include, for example, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid. Examples thereof include acids, citraconic acid, itaconic acid, glutaconic acid, 1,2,3,4-butanetetracarboxylic acid, and acid anhydrides thereof.

As the alicyclic polycarboxylic acid compound or an anhydride thereof, in the present invention, a carboxyl group or an acid anhydride group bonded to an alicyclic structure is an alicyclic polycarboxylic acid compound or an anhydride thereof, The presence or absence of an aromatic ring in the other structural parts is irrelevant. Examples of the alicyclic polycarboxylic acid compound or its anhydride include, for example, 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)-1,2,3,3 Examples include 4-tetrahydronaphthalene-1,2-dicarboxylic acid and acid anhydrides thereof.

Examples of the aromatic polycarboxylic acid compound or an acid anhydride thereof include, for example, phthalic acid, trimellitic acid, pyromellitic acid, naphthalene dicarboxylic acid, naphthalene tricarboxylic acid, naphthalene tetracarboxylic acid, biphenyl dicarboxylic acid, biphenyl tricarboxylic acid. , Biphenyltetracarboxylic acid, benzophenonetetracarboxylic acid, and acid anhydrides thereof.

Among these, since an acid group-containing (meth)acrylate compound capable of forming a cured product having excellent heat resistance and substrate adhesion is obtained, the alicyclic polycarboxylic acid compound or an acid anhydride thereof, or The aromatic polycarboxylic acid compound or its acid anhydride is preferable. Further, since the amide imide resin (A) can be efficiently produced, it is preferable to use a tricarboxylic acid anhydride having both a carboxyl group and an acid anhydride group in the molecular structure, and cyclohexanetricarboxylic acid anhydride or trimellitic acid is used. It is particularly preferable to use an acid anhydride. Further, the ratio of the total amount of the alicyclic tricarboxylic acid anhydride and the aromatic tricarboxylic acid anhydride to the total mass of the polycarboxylic acid or its acid anhydride (a2) is preferably 70% by mass or more, 90 It is preferably at least mass %.

When the amide imide resin (A) uses the polyisocyanate compound (a1) and the polycarboxylic acid or its acid anhydride (a2) as reaction raw materials, other than these, depending on desired resin performance and the like. You may use reaction raw materials together. In this case, since the effect of the present invention is sufficiently exerted, the polyisocyanate compound (a1) and the polycarboxylic acid or its acid anhydride (a2) with respect to the total mass of the reaction raw material of the amideimide resin (A) are The ratio of the total mass is preferably 90% by mass or more, and more preferably 95% by mass or more.

When the amide-imide resin (A) is prepared by using the polyisocyanate compound (a1) and the polycarboxylic acid or its acid anhydride (a2) as reaction raw materials, the production method thereof is not particularly limited, and any method May be manufactured in. For example, it can be produced by a method similar to that of a general amide-imide resin. Specifically, with respect to 1 mol of the isocyanate group contained in the polyisocyanate compound (a1), 0.8 to 3.5 mol of the polycarboxylic acid or its acid anhydride (a2) is used, and the temperature is about 100 to 180°C. A method of stirring and mixing under the temperature conditions of (1) and reacting can be mentioned.

The reaction may be carried out in an organic solvent if necessary. The selection of the organic solvent to be used is appropriately selected depending on the reaction raw material and the solubility of the acid group-containing (meth)acrylate resin which is a product, the reaction temperature conditions, and the like, and examples thereof include methyl ethyl ketone, acetone, dimethylformamide, and methyl isobutyl ketone. Methoxypropanol, cyclohexanone, methyl cellosolve, dialkylene glycol monoalkyl ether acetate, dialkylene glycol acetate and the like can be mentioned. These organic solvents can be used alone or in combination of two or more kinds. 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 will be good.

As the hydroxyl group-containing (meth)acrylate compound (B), 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 di(meth)acrylate, pentaerythritol (meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate. ) Acrylate, dipentaerythritol (meth)acrylate, dipentaerythritol di(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, ditrimethylolpropane Examples thereof include tri(meth)acrylate. Further, 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 ( It is also possible to use a modified poly)oxyalkylene or a modified lactone in which a (poly)lactone structure is introduced into the molecular structure of each of the various hydroxyl group-containing (meth)acrylate compounds. These hydroxyl group-containing (meth)acrylate compounds may be used alone or in combination of two or more kinds. Among these, a (meth)acrylate compound having one hydroxyl group is preferable because the reaction can be easily controlled.

The molecular weight of the hydroxyl group-containing (meth)acrylate compound (B) is 1,000 or less because an acid group-containing (meth)acrylate compound capable of forming a cured product having excellent heat resistance and substrate adhesion is obtained. Is preferred. 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.

As the 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)acrylates 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. Among these, a (meth)acrylate compound having one epoxy group is preferable because the reaction is easily controlled, and an acid group-containing compound (meta) capable of forming a cured product having excellent heat resistance and substrate adhesion (meta) is preferable. ) A glycidyl group-containing (meth)acrylate monomer is preferable because an acrylate compound is obtained. 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. ..

Examples of the polycarboxylic acid anhydride (D) include phthalic anhydride, succinic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, and methylnazic anhydride. Acid, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, octenyl succinic anhydride, tetrapropenyl succinic anhydride and the like can be mentioned. Further, an aliphatic polycarboxylic acid anhydride, an alicyclic polycarboxylic acid anhydride, an aromatic polycarboxylic acid anhydride, or the like among the compounds exemplified as the polycarboxylic acid or its acid anhydride (a2) is also used. You can These polycarboxylic acid anhydrides (D) can be used alone or in combination of two or more kinds. Further, among these, since an acid group-containing (meth)acrylate compound capable of forming a cured product having excellent heat resistance and substrate adhesion is obtained, an aliphatic polycarboxylic acid anhydride or an alicyclic polycarboxylic acid is obtained. An acid anhydride is preferable, and an aliphatic dicarboxylic acid anhydride or an alicyclic dicarboxylic acid anhydride is more preferable.

As the isocyanate group-containing (meth)acrylate compound (E), other specific structures are not particularly limited as long as it has a (meth)acryloyl group and an isocyanate group in the molecular structure, and various compounds are used. be able to. Examples thereof include 2-acryloyloxyethyl isocyanate, 2-methacryloyloxyethyl isocyanate, and 1,1-bis(acryloyloxymethyl)ethyl isocyanate. Examples of commercially available isocyanate group-containing (meth)acrylate compounds include "Karenzu AOI", "Karenzu MOI", and "AOI-VM" manufactured by Showa Denko KK. Further, as the isocyanate group-containing (meth)acrylate compound (E), an isocyanate compound having at least two isocyanate groups and a hydroxyl group-containing (meth)acrylate compound are used, wherein the hydroxyl group is 1 mole of the isocyanate group contained in the isocyanate compound. A compound obtained by reacting the contained (meth)acrylate compound under the condition that the number of moles of hydroxyl groups is in the range of 0.3 to 0.7 mol can also be used.

As the isocyanate compound having at least two isocyanate groups, the same ones as the above-mentioned polyisocyanate compound (a1) can be used.

As the hydroxyl group-containing (meth)acrylate compound, the same compounds as the above-mentioned hydroxyl group-containing (meth)acrylate compound (B) can be used.

In the acid group-containing (meth)acrylate resin of the present invention, the acid group-containing (meth)acrylate resin may be the amideimide resin (A) or the hydroxyl group-containing (meth)acrylate compound (B ), the epoxy group-containing (meth)acrylate compound (C), the polycarboxylic acid anhydride (D), and the isocyanate group-containing (meth)acrylate compound (E), other reaction raw materials may be used in combination. .. In this case, since the effect of the present invention is sufficiently exhibited, the ratio of the total mass of the components (A) to (E) to the total mass of the reaction raw material of the acid group-containing (meth)acrylate resin is 80% by mass or more. Is preferable, and 90% by mass or more is more preferable.

The method for producing the acid group-containing (meth)acrylate resin 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 is 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 ( (Meth)acrylate compound (C) is reacted (step 2), the product of step 2 is reacted with the polycarboxylic acid anhydride (D) (step 3), the product of step 3 is reacted with the isocyanate group. It is preferably produced by a method of reacting with a (meth)acrylate compound (E) (step 4).

In the step 1, in the reaction of the amide imide resin (A) with the hydroxyl group-containing (meth)acrylate compound (B), the acid group or the acid anhydride group and the hydroxyl group-containing group in the amide imide resin (A) are mainly contained ( The hydroxyl group in the (meth)acrylate compound (B) is reacted. 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. Further, the reaction ratio of the amide imide resin (A) and the hydroxyl group (meth)acrylate compound (B) is such that the hydroxyl group-containing (meth) group is included with respect to the total of acid groups and acid anhydride groups in the amide imide resin (A). ) It is preferable to use the acrylate compound (B) in the range of 0.9 to 1.1 mol. 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 between the amide-imide resin (A) and the hydroxyl group-containing (meth)acrylate compound (B) is performed, for example, in the presence of an appropriate esterification catalyst while heating and stirring under a temperature condition of about 90 to 140°C. You can Examples of the esterification catalyst include phosphorus compounds such as trimethylphosphine, tributylphosphine and triphenylphosphine, amine compounds such as triethylamine, tributylamine and dimethylbenzylamine, 2-methylimidazole, 2-heptadecylimidazole and 2-ethyl. Examples include imidazole compounds such as -4-methylimidazole, 1-benzyl-2-methylimidazole and 1-isobutyl-2-methylimidazole. These esterification catalysts can be used alone or in combination of two or more kinds. The esterification catalyst is preferably added in an amount of 0.001 to 5 parts by mass based on 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. The selection of the organic solvent to be used is appropriately selected depending on the reaction raw material and the solubility of the acid group-containing (meth)acrylate resin which is a product, the reaction temperature conditions, and the like, and examples thereof include methyl ethyl ketone, acetone, dimethylformamide, and methyl isobutyl ketone. Methoxypropanol, cyclohexanone, methyl cellosolve, dialkylene glycol monoalkyl ether acetate, dialkylene glycol acetate and the like can be mentioned. These organic solvents can be used alone or in combination of two or more kinds. When the production of the amide-imide resin (A) and step 1 are carried out continuously, the reaction may be continued as it is in the organic solvent used in the production of the amide-imide resin (A).

Regarding the step 2, the epoxy group-containing (meth)acrylate compound (C) mainly reacts with the carboxyl group in the product of the step 1. With respect to the reaction ratio, it is preferable to use the epoxy group-containing (meth)acrylate compound (C) in the range of 0.5 to 1.2 mol, and 0.9 to the carboxyl group in the product of Step 1. It is more preferable to use it in the range of 1.1 mol. The reaction of step 2 can be carried out, for example, by heating and stirring under the temperature condition of about 90 to 140° C. in the presence of a suitable esterification catalyst. When step 1 and step 2 are carried out continuously, 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.

Regarding the step 3, the polycarboxylic acid anhydride (D) mainly reacts with the hydroxyl group in the product of the step 2. In the product of the step 2, for example, 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. The reaction of 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 90 to 140°C. When step 2 and step 3 are carried out continuously, 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.

Regarding the step 4, the isocyanate group-containing (meth)acrylate compound (E) reacts with the remaining hydroxyl group. The isocyanate group-containing (meth)acrylate compound (E) is preferably adjusted such that the acid group-containing (meth)acrylate resin as a product has an acid value of about 60 to 120 mgKOH/g. The reaction of the step 4 can be carried out, for example, in the presence of a suitable urethanization catalyst while heating and stirring under a temperature condition of about 50 to 100°C. Further, the reaction may be carried out in an organic solvent, if necessary.

Examples of the urethanization catalyst include amines such as pyridine, pyrrole, triethylamine, diethylamine and dibutylamine, phophines such as triphenylphosphine and triethylphosphine, dibutyltin dilaurate, octyltin trilaurate, octyltin diacetate and dioctyltin. Organotin compounds such as diacetate, dioctyltin dineodecanoate, dibutyltin diacetate, tin octylate, 1,1,3,3-tetrabutyl-1,3-dodecanoyldistanoxane, zinc octylate, octyl Examples thereof include organic metal compounds such as bismuth acid salt, inorganic tin compounds such as tin octoate, and inorganic metal compounds.

The acid value of the acid group-containing (meth)acrylate resin of the present invention is 50 to 120 mgKOH because an acid group-containing (meth)acrylate resin capable of forming a cured product having excellent heat resistance and substrate adhesion is obtained. The range of /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 K 0070 (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. In addition, in this invention, a weight average molecular weight (Mw) shows the value measured by the gel permeation chromatography (GPC) method.

Since 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

As the photopolymerization initiator, an appropriate one may be 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). 2-[(4-Methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone and other alkylphenone photoinitiators; 2,4,6-trimethylbenzoyl-diphenyl- Examples thereof include acylphosphine oxide-based photopolymerization initiators such as phosphine oxide; and intramolecular hydrogen abstraction type photopolymerization initiators such as benzophenone compounds. These may be used alone or in combination of two or more.

Examples of the photopolymerization initiator include 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, and 1-[4-(2-hydroxyethoxy)phenyl]-2-. Hydroxy-2-methyl-1-propan-1-one, thioxanthone and thioxanthone derivatives, 2,2'-dimethoxy-1,2-diphenylethan-1-one, diphenyl(2,4,6-trimethoxybenzoyl)phosphine Oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropane-1- On, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone and the like.

Examples of commercial products of the other photopolymerization initiators include "Omnirad-1173", "Omnirad-184", "Omnirad-127", "Omnirad-2959", "Omnirad-369", and "Omnirad-379". , "Omnirad-907", "Omnirad-4265", "Omnirad-1000", "Omnirad-651", "Omnirad-TPO", "Omnirad-819", "Omnirad-2022", "Omnirad-2100", "Omnirad-2100". Omnirad-754", "Omnirad-784", "Omnirad-500", "Omnirad-81" (manufactured by IGM), "Kayacure-DETX", "Kayacure-MBP", "Kayacure-DMBI", "Kayacure-EPA". , "Kayacure-OA" (manufactured by Nippon Kayaku Co., Ltd.), "Vicure-10", "Vicure-55" (manufactured by Stofa Chemical Co., Ltd.), "Trigonal P1" (manufactured by Akzo), "Sandray 1000" ( Sands), "Deep" (Apjon), "Quantacure-PDO", "Quantacure-ITX", "Quantacure-EPD" (Word Brenkinsop), "Runtecure-1104" (Runtec) Manufactured by the company) and the like. These 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 components other than the solvent of the curable resin composition. Is more preferable.

The curable resin composition of the present invention may contain a resin component other than the acid group-containing (meth)acrylate resin described above. Examples of the other resin component include acid group-containing (meth)acrylate resin (F) and various (meth)acrylate monomers.

The acid group-containing (meth)acrylate resin (F) may be any as long as it has an acid group and a (meth)acryloyl group in the resin, and examples thereof include an acid group-containing epoxy (meth)acrylate resin and an acid group. Examples of the urethane-containing (meth)acrylate resin, acid group-containing acrylic (meth)acrylate resin, acid group-containing amide imide (meth)acrylate resin, acid group-containing acrylamide resin, and the like.

Examples of the acid group include a carboxyl group, a sulfonic acid group, a phosphoric acid group and the like.

Examples of the acid group-containing epoxy (meth)acrylate resin include an epoxy group, an unsaturated monobasic acid, and an acid group-containing epoxy (meth)acrylate resin that uses polybasic acid anhydride as an essential reaction raw material, and an epoxy resin. , Unsaturated monobasic acid, polybasic acid anhydride, polyisocyanate compound, and acid group- and urethane group-containing epoxy (meth)acrylate resin using a hydroxyl group-containing (meth)acrylate compound as a reaction raw material.

Examples of 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 Examples thereof include reactive epoxy resins, biphenylaralkyl epoxy resins, fluorene epoxy resins, xanthene 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 a (meth)acryloyl group and a carboxyl group in one molecule, for example, acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, α-cyanocinnamic acid, β- Examples thereof include styryl acrylic acid and β-furfuryl acrylic acid. Further, 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.

Examples of the polybasic acid anhydrides include phthalic anhydride, succinic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic 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. Among these, tetrahydrophthalic anhydride and succinic anhydride are preferable because a curable resin composition capable of forming a cured product having excellent heat resistance and substrate adhesion can be obtained.

As the polyisocyanate compound, the same polyisocyanate compound (a1) as described above can be used.

As the hydroxyl group-containing (meth)acrylate compound, the same compounds as the above-mentioned hydroxyl group-containing (meth)acrylate compound (B) can be used.

As the acid group-containing urethane (meth)acrylate resin, 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-containing polyol compound Obtained by reacting with a polyol compound other than, polyisocyanate compound, hydroxyl group-containing (meth) acrylate compound, polybasic acid anhydride, and obtained by reacting with a polyol compound other than the carboxyl group-containing polyol compound There are things like

As the polyisocyanate compound, the same polyisocyanate compound (a1) as described above can be used.

As the hydroxyl group-containing (meth)acrylate compound, the same compounds as the above-mentioned hydroxyl group-containing (meth)acrylate compound (B) can be used.

Examples of the carboxyl group-containing polyol compound include 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, and 2,2-dimethylolvaleric acid.

As the polybasic acid anhydride, the same polybasic acid anhydride as described above can be used.

Examples of the polyol compound other than the carboxyl group-containing polyol compound include aliphatic polyol compounds such as ethylene glycol, propylene glycol, butanediol, hexanediol, glycerin, trimethylolpropane, ditrimethylolpropane, pentaerythritol, and dipentaerythritol; Aromatic polyol compounds such as biphenols and bisphenols; (poly)oxyalkylene chains such as (poly)oxyethylene chains, (poly)oxypropylene chains, and (poly)oxytetramethylene chains in the molecular structures of the various polyol compounds. Introduced (poly)oxyalkylene modified products; lactone modified products in which a (poly)lactone structure is introduced into the molecular structure of each of the various polyol compounds are included.

The acid group-containing acrylic (meth)acrylate resin is obtained, for example, by polymerizing a (meth)acrylate compound (α) having a reactive functional group such as a hydroxyl group, a carboxyl group, an isocyanate group, or a glycidyl group as an essential component. A reaction product obtained by introducing a (meth)acryloyl group by further reacting the resulting acrylic resin intermediate with a (meth)acrylate compound (β) having a reactive functional group capable of reacting with these functional groups, Examples thereof include those obtained by reacting a polybasic acid anhydride with the hydroxyl group in the reaction product.

The acrylic resin intermediate may be a copolymer of the (meth)acrylate compound (α) and other polymerizable unsaturated group-containing compound, if necessary. Examples of the other polymerizable unsaturated group-containing compounds 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; and styrene derivatives such as styrene, α-methylstyrene, and chlorostyrene. These may be used alone or in combination of two or more.

The (meth)acrylate compound (β) is not particularly limited as long as it can react with the reactive functional group of the (meth)acrylate compound (α), 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 (α), an isocyanate group-containing (meth)acrylate is preferably used as the (meth)acrylate compound (β). When a carboxyl group-containing (meth)acrylate is used as the (meth)acrylate compound (α), it is preferable to use a glycidyl group-containing (meth)acrylate as the (meth)acrylate compound (β). When an isocyanate group-containing (meth)acrylate is used as the (meth)acrylate compound (α), a hydroxyl group-containing (meth)acrylate is preferably used as the (meth)acrylate compound (β). When a glycidyl group-containing (meth)acrylate is used as the (meth)acrylate compound (α), it is preferable to use a carboxyl group-containing (meth)acrylate as the (meth)acrylate compound (β).

As the polybasic acid anhydride, the same polybasic acid anhydride as described above can be used.

Examples of the acid group-containing amide imide (meth)acrylate resin include an amide imide resin having an acid group or an acid anhydride group, a hydroxyl group-containing (meth)acrylate compound and/or a (meth)acryloyl group-containing epoxy compound, and Accordingly, those obtained by reacting 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 can be mentioned. 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, those having an acid anhydride group are preferable, and both an acid group and an acid anhydride group are included. 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 when 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 opened, such as in the presence of water, is preferably in the range of 61 to 360 mgKOH/g.

The specific structure and manufacturing method of the amide-imide resin are not particularly limited, and general amide-imide resins and the like can be widely used. For example, those obtained by using a polyisocyanate compound and a polybasic acid or a polybasic acid anhydride as reaction raw materials can be mentioned.

As the polyisocyanate compound, the same polyisocyanate compound (a1) as described above can be used.

As the polybasic acid, any compound can be used as long as it is a compound having two or more carboxyl groups in one molecule. For example, 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-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydro Naphthalene-1,2-dicarboxylic acid, trimellitic acid, pyromellitic acid, naphthalenedicarboxylic acid, naphthalenetricarboxylic acid, naphthalenetetracarboxylic acid, biphenyldicarboxylic acid, biphenyltricarboxylic acid, biphenyltetracarboxylic acid, benzophenonetetracarboxylic acid, etc. Be done. As the 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.

As the polybasic acid anhydride, the same polybasic acid anhydride as described above can be used.

As the hydroxyl group-containing (meth)acrylate compound, the same compounds as the above-mentioned hydroxyl group-containing (meth)acrylate compound (B) can be used.

As the (meth)acryloyl group-containing epoxy compound, the same epoxy group-containing (meth)acrylate compound (C) as described above can be used.

Examples of the acid group-containing acrylamide resin include, for example, a phenolic hydroxyl group-containing compound, an alkylene oxide or an alkylene carbonate, an N-alkoxyalkyl (meth)acrylamide compound, a polybasic acid anhydride, and optionally an unsaturated monocarboxylic acid. Examples thereof include those obtained by reacting with a basic acid.

The phenolic hydroxyl group-containing compound refers to 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 (1-1) to (1-4).

In the above structural formulas (1-1) to (1-4), 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. Further, 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 Structural Formula (1-2), the substituent may be substituted on any ring, and In 1-3), it may be substituted on any ring of the benzene ring present in one molecule, and in structural formula (1-4), it may be substituted on any ring of the benzene ring present in one molecule. It indicates that it may be substituted, and the number of substituents in one molecule is p and q.

Further, as the phenolic hydroxyl group-containing compound, for example, a compound having one phenolic hydroxyl group in the molecule and a compound represented by any of the following structural formulas (x-1) to (x-5) are essential. Of the reaction product used as the reaction raw material, a compound having at least two phenolic hydroxyl groups in the molecule, and a 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. In addition, 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 of 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.

［式（ｘ−１）中、ｈは０または１である。式（ｘ−２）〜（ｘ−５）中、Ｒ^３は、炭素原子数１〜２０のアルキル基、炭素原子数１〜２０のアルコキシ基、アリール基、ハロゲン原子の何れかであり、ｉは、０または１〜４の整数である。式（ｘ−２）、（ｘ−３）及び（ｘ−５）中、Ｚは、ビニル基、ハロメチル基、ヒドロキシメチル基、アルキルオキシメチル基の何れかである。式（ｘ−５）中、Ｙは、炭素原子数１〜４のアルキレン基、酸素原子、硫黄原子、カルボニル基の何れかであり、ｊは１〜４の整数である。］

[In formula (x-1), h is 0 or 1. In formulas (x-2) to (x-5), 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. In formulas (x-2), (x-3) and (x-5), Z is any of a vinyl group, a halomethyl group, a hydroxymethyl group and an alkyloxymethyl group. In formula (x-5), Y is an alkylene group having 1 to 4 carbon atoms, an oxygen atom, a sulfur atom, or 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).

In the above 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. Further, 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 (2-2), it may be substituted on any ring, and the structural formula ( In 2-3), it may be substituted on any ring of the benzene ring present in one molecule, and in structural formula (2-4), it may be substituted on any ring of the benzene ring present in one molecule. It indicates that they may be replaced.

As the compound having at least two phenolic hydroxyl groups in the molecule, the compounds represented by the above structural formulas (1-1) to (1-4) can be used.

These phenolic hydroxyl group-containing compounds can be used alone or in combination of two or more kinds.

Examples of the alkylene oxide include ethylene oxide, propylene oxide, butylene oxide, pentylene oxide and the like. Among these, ethylene oxide or propylene oxide is preferable because a curable resin composition capable of forming a cured product having excellent heat resistance and substrate adhesion can be obtained.

Examples of the alkylene carbonate include ethylene carbonate, propylene carbonate, butylene carbonate, pentylene carbonate and the like. Among these, ethylene carbonate or propylene carbonate is preferable because a curable resin composition capable of forming a cured product having excellent heat resistance and substrate adhesion can be obtained.

Examples of the N-alkoxyalkyl(meth)acrylamide compound 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.

As the polybasic acid anhydride, the same polybasic acid anhydride as described above can be used.

As the unsaturated monobasic acid, the same unsaturated monobasic acid as described above can be used.

The amount of the acid group-containing (meth)acrylate resin (F) 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 and adamantyl mono(meth)acrylate Acrylate compounds; Heterocyclic mono(meth)acrylate compounds such as glycidyl (meth)acrylate and tetrahydrofurfuryl acrylate; benzyl (meth)acrylate, phenyl (meth)acrylate, phenylbenzyl (meth)acrylate, phenoxy (meth)acrylate, Phenoxyethyl (meth)acrylate, phenoxyethoxyethyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, phenoxybenzyl (meth)acrylate, benzylbenzyl (meth)acrylate, phenylphenoxyethyl (meth)acrylate, etc. (Meth)acrylate compound such as aromatic mono(meth)acrylate compound: (poly)oxyethylene chain, (poly)oxypropylene chain, (poly)oxy in the molecular structure of the various mono(meth)acrylate monomers A (poly)oxyalkylene-modified mono(meth)acrylate compound having a polyoxyalkylene chain such as a tetramethylene chain introduced therein; a lactone-modified mono compound having a (poly)lactone structure introduced into the molecular structure of each of the various mono(meth)acrylate compounds (Meth)acrylate compound; aliphatic such as ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, butanediol di(meth)acrylate, hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate Di(meth)acrylate compound; 1,4-cyclohexanedimethanol di(meth)acrylate, norbornane di(meth)acrylate, norbornane dimethanol di(meth)acrylate, dicyclopentanyl di(meth)acrylate, tricyclodecane di Alicyclic di(meth)acrylate compounds such as methanol di(meth)acrylate; biphenol di(meth)acrylate, bisphe Aromatic di(meth)acrylate compounds such as diol (meth)acrylate; (poly)oxyethylene chains, (poly)oxypropylene chains, (poly)oxytetramethylene in the molecular structures of the various di(meth)acrylate compounds. A polyoxyalkylene-modified di(meth)acrylate compound having a (poly)oxyalkylene chain such as a chain introduced therein; a lactone-modified di(meth) having a (poly)lactone structure introduced into the molecular structure of each of the various di(meth)acrylate compounds ) Acrylate compound; Aliphatic tri(meth)acrylate compound such as trimethylolpropane tri(meth)acrylate, glycerin tri(meth)acrylate; (Poly)oxyethylene chain in the molecular structure of the aliphatic tri(meth)acrylate compound. A (poly)oxyalkylene-modified tri(meth)acrylate compound introduced with a (poly)oxyalkylene chain such as a (poly)oxypropylene chain or a (poly)oxytetramethylene chain; a molecule of the aliphatic tri(meth)acrylate compound A lactone-modified tri(meth)acrylate compound having a (poly)lactone structure introduced therein; pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, etc. An aliphatic poly(meth)acrylate compound of (poly)oxyethylene chain, (poly)oxypropylene chain, (poly)oxytetramethylene chain or the like (poly) in the molecular structure of the aliphatic poly(meth)acrylate compound Tetra- or more-functional (poly)oxyalkylene-modified poly(meth)acrylate compound having an oxyalkylene chain introduced therein; tetra- or more-functional lactone having a (poly)lactone structure introduced into the molecular structure of the aliphatic poly(meth)acrylate compound Examples thereof include modified poly(meth)acrylate compounds.

Further, the curable resin composition of the present invention, if necessary, a curing agent, a curing accelerator, an organic solvent, inorganic fine particles or polymer fine particles, a pigment, a defoaming agent, a viscosity modifier, a leveling agent, a flame retardant, It is also possible to contain various additives such as a storage stabilizer.

The curing agent is not particularly limited as long as it has a functional group capable of reacting with the carboxy group in the acid group-containing (meth)acrylate resin, and examples thereof include an epoxy resin. Examples of 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 Examples thereof include reactive epoxy resins, biphenylaralkyl epoxy resins, fluorene epoxy resins, xanthene epoxy resins and the like. These epoxy resins can be used alone or in combination of two or more kinds. Further, among these, since a curable resin composition capable of forming a cured product having excellent heat resistance and substrate adhesion is obtained, a phenol novolac type epoxy resin, a cresol novolac type epoxy resin, and a bisphenol novolac type epoxy resin are obtained. Novolak type epoxy resins such as resins, naphthol novolac type epoxy resins, naphthol-phenol co-condensed novolac type epoxy resins, naphthol-cresol co-condensed novolac type epoxy resins are preferable, and those having a softening point in the range of 50 to 120° C. are particularly preferable. preferable.

The curing accelerator accelerates the curing reaction of the curing agent, and when an epoxy resin is used as the curing agent, a phosphorus compound, a tertiary amine, imidazole, an organic acid metal salt, a Lewis acid. , Amine complex salts and the like. 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.

The organic solvent is not particularly limited as long as it can dissolve various components such as the acid group-containing (meth)acrylate resin and the curing agent, and examples thereof include ketones such as methyl ethyl ketone, acetone, dimethylformamide, and methyl isobutyl ketone. Solvents; cyclic ether solvents such as tetrahydrofuran and dioxolane; ester solvents such as methyl acetate, ethyl acetate and butyl acetate; aromatic solvents such as toluene, xylene and solvent naphtha; alicyclic solvents such as cyclohexane and methylcyclohexane; carbitol, Alcohol solvent such as cellosolve, methanol, isopropanol, butanol, propylene glycol monomethyl ether; glycol ether solvent such as alkylene glycol monoalkyl ether, dialkylene glycol monoalkyl ether, 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.

The cured product of the present invention can be obtained by irradiating the curable resin composition with an active energy ray. Examples of the active energy rays include ionizing radiation such as ultraviolet rays, electron rays, α rays, β rays, and γ rays. When ultraviolet rays are used as the active energy 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.

As a source of ultraviolet rays, ultraviolet lamps are generally used in terms 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.

Integrated light quantity of the active energy ray is not particularly limited, it is preferably from 10~5,000mJ / cm ^2, more preferably 50~1,000mJ / cm ^2. When the integrated light amount is within the above range, it is possible to prevent or suppress the generation of an uncured portion, which is preferable.

The irradiation of the active energy ray may be performed in one step or may be performed in two or more steps.

Further, since the cured product of the present invention has excellent heat resistance and substrate adhesion, for example, in semiconductor device applications, solder resist, interlayer insulating material, package material, underfill material, package adhesion of circuit elements, etc. It can be suitably used as a layer or an adhesive layer between an integrated circuit element and a circuit board. Further, it can be suitably used as a thin film transistor protective film, a liquid crystal color filter protective film, a color filter pigment resist, a black matrix resist, a spacer and the like in thin display applications 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 portion is developed with an alkaline aqueous solution, and further cured by heating 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.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples.

In the examples of the present application, the acid value of the acid group-containing (meth)acrylate resin was measured by the neutralization titration method of JIS K 0070 (1992).

In the examples of the present application, 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
+ Tosoh Corporation “TSK-GEL G4000HXL”
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".
(Polystyrene used)
Tosoh Corporation "A-500"
Tosoh Corporation "A-1000"
Tosoh Corporation "A-2500"
Tosoh Corporation "A-5000"
Tosoh Corporation "F-1"
Tosoh Corporation "F-2"
Tosoh Corporation "F-4"
Tosoh Corporation “F-10”
Tosoh Corporation "F-20"
Tosoh Corporation "F-40"
Tosoh Corporation “F-80”
Tosoh Corporation "F-128"
Sample: 1.0% by mass tetrahydrofuran solution in terms of resin solid content filtered through a microfilter (50 μl)

(Example 1: Production of acid group-containing (meth)acrylate resin (1))
In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 399.8 parts by mass of diethylene glycol monomethyl ether acetate, a modified isocyanurate of isophorone diisocyanate (“VESTANAT T-1890/100” manufactured by EVONIK, isocyanate group content) (17.2 mass %) 174.8 mass parts, 137.4 mass parts of trimellitic anhydride, and 1.5 mass parts of dibutylhydroxytoluene 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. Next, 0.3 parts by mass of methoquinone, pentaerythritol polyacrylate mixture ("Aronix M-306" manufactured by Toagosei Co., Ltd., pentaerythritol triacrylate content of about 67%, hydroxyl value of 159.7 mg KOH/g) 105.7 parts by mass. And 3.0 parts by mass of triphenylphosphine were added, and the mixture was reacted at 110° C. for 5 hours while blowing air. Next, 118.1 parts by mass of glycidyl methacrylate was added and reacted at 110° C. for 5 hours. Further, 74.8 parts by mass of succinic anhydride was added and the reaction was carried out at 110° C. for 5 hours. Next, 8.4 parts by mass of 2-isocyanatoethyl acrylate and 0.1 parts by mass of dioctyltin dineodecanoate (“Neostan U-830” manufactured by Nitto Kasei Co., Ltd.) were added and reacted at 80° C. for 3 hours. A desired acid group-containing (meth)acrylate resin (1) was obtained. The acid value of the solid content of the acid group-containing (meth)acrylate resin (1) was 73 mgKOH/g, and the weight average molecular weight was 3,700.

(Example 2: Production of acid group-containing (meth)acrylate resin (2))
In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 399.9 parts by mass of diethylene glycol monomethyl ether acetate, a modified isocyanurate of isophorone diisocyanate (“VESTANAT T-1890/100” manufactured by EVONIK, isocyanate group content) 17.2 mass%) 178.5 mass parts, trimellitic anhydride 140.3 mass parts, and dibutylhydroxytoluene 1.5 mass parts 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. Next, 0.3 parts by mass of methoquinone, pentaerythritol polyacrylate mixture ("Aronix M-306" manufactured by Toagosei Co., Ltd., pentaerythritol triacrylate content of about 67%, hydroxyl value of 159.7 mg KOH/g) 108.0 parts by mass. And 3.0 parts by mass of triphenylphosphine were added, and the mixture was reacted at 110° C. for 5 hours while blowing air. Next, 120.6 parts by mass of glycidyl methacrylate was added and reacted at 110° C. for 5 hours. Further, 76.4 parts by mass of succinic anhydride was added and the reaction was carried out at 110° C. for 5 hours. Then, 21.3 parts by mass of a reaction product of isophorone diisocyanate and hydroxyethyl acrylate (“VESTANAT EP-DC 1241” manufactured by EVONIK), dioctyltin dineodecanoate (“Neostan U-830” manufactured by Nitto Kasei Co., Ltd.) 0 0.1 part by mass was added and the mixture was reacted at 80° C. for 3 hours to obtain the desired acid group-containing acid group-containing (meth)acrylate resin (2). The acid value of the solid content of the acid group-containing (meth)acrylate resin (2) was 75 mgKOH/g, and the weight average molecular weight was 3630.

(Example 3: Production of acid group-containing (meth)acrylate resin (3))
In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 349.0 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 72.2 parts by mass, 72.2 parts by mass, a hexanomethylene diisocyanate nurate modified product (“Bernock DN901S” manufactured by DIC Corporation, isocyanate group content 23.5% by mass) 72.2 parts by mass, trimellitic anhydride 176 0.2 parts by mass and 1.5 parts by mass of dibutylhydroxytoluene 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. Next, 0.36 parts by mass of methoquinone, pentaerythritol polyacrylate mixture ("Aronix M-306" manufactured by Toagosei Co., Ltd., pentaerythritol triacrylate content of about 67%, hydroxyl value of 159.7 mg KOH/g) 106.6 parts by mass. And 3.3 parts by mass of triphenylphosphine were added, and the mixture was reacted at 110° C. for 5 hours while blowing air. Then, 149.2 parts by mass of glycidyl methacrylate was added, and the mixture was reacted at 110° C. for 5 hours. Further, 90.4 parts by mass of succinic anhydride was added and reacted at 110° C. for 5 hours for reaction. Then, 14.8 parts by mass of 2-isocyanatoethyl acrylate and 0.1 part by mass of dioctyltin dineodecanoate (“Neostan U-830” manufactured by Nitto Kasei Co., Ltd.) were added and reacted at 80° C. for 3 hours. The desired acid group-containing (meth)acrylate resin (3) was obtained. The acid value of the solid content of the acid group-containing (meth)acrylate resin (3) was 80 mgKOH/g, and the weight average molecular weight was 3250.

(Example 4: Production of acid group-containing (meth)acrylate resin (4))
In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 301.4 parts by mass of diethylene glycol monomethyl ether acetate, a nurate modified product of hexamethylene diisocyanate ("Bernock DN901S" manufactured by DIC Corporation, an isocyanate group content of 23.5). Mass%) 167.4 parts by mass, trimellitic anhydride 185.8 parts by mass, and dibutylhydroxytoluene 1.8 parts by mass 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. Next, 0.4 parts by mass of methquinone, pentaerythritol polyacrylate mixture ("Aronix M-306" manufactured by Toagosei Co., Ltd., pentaerythritol triacrylate content of about 67%, hydroxyl value of 159.7 mg KOH/g) 53.3 parts by mass. And 3.5 parts by mass of triphenylphosphine were added, and the mixture was reacted at 110° C. for 5 hours while blowing air. Next, 192.8 parts by mass of glycidyl methacrylate was added and reacted at 110° C. for 5 hours. Further, 96.4 parts by mass of succinic anhydride was added and the reaction was carried out at 110° C. for 5 hours. Next, 44.0 parts by mass of 2-isocyanatoethyl acrylate and 0.1 part by mass of dioctyltin dineodecanoate (“Neostan U-830” manufactured by Nitto Kasei Co., Ltd.) were added and reacted at 80° C. for 3 hours. Thus, the desired acid group-containing (meth)acrylate resin (4) was obtained. The acid value of the solid content of the acid group-containing (meth)acrylate resin (4) was 80 mgKOH/g, and the weight average molecular weight was 2770.

(Example 5: Production of acid group-containing (meth)acrylate resin (5))
In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 300.1 parts by mass of diethylene glycol monomethyl ether acetate, 207.7 parts by mass of isophorone diisocyanate, 269.4 parts by mass of trimellitic anhydride, and 1.8 parts of dibutylhydroxytoluene. Part by mass was 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. Next, 0.4 parts by mass of methoquinone, pentaerythritol polyacrylate mixture ("Aronix M-306" manufactured by Toagosei Co., Ltd., pentaerythritol triacrylate content of about 67%, hydroxyl value of 159.7 mg KOH/g) 79.0 parts by mass. And 3.5 parts by mass of triphenylphosphine were added, and the mixture was reacted at 110° C. for 5 hours while blowing air. Next, 132.3 parts by mass of glycidyl methacrylate was added, and the mixture was reacted at 110° C. for 5 hours. Further, 84.8 parts by mass of succinic anhydride was added and the reaction was carried out at 110° C. for 5 hours. Then, 9.2 parts by mass of 2-isocyanatoethyl acrylate and 0.1 parts by mass of dioctyltin dineodecanoate (“Neostan U-830” manufactured by Nitto Kasei Co., Ltd.) were added and reacted at 80° C. for 3 hours. Thus, the desired acid group-containing (meth)acrylate resin (5) was obtained. The acid value of the solid content of the acid group-containing (meth)acrylate resin (5) was 71 mgKOH/g, and the weight average molecular weight was 2,190.

(Example 6: Production of acid group-containing (meth)acrylate resin (6))
In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 382.7 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 175.2 parts by mass), cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride 150.3 parts by mass, and dibutylhydroxytoluene 1.2 parts by mass 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. Next, 0.2 parts by mass of methoquinone, pentaerythritol polyacrylate mixture (“Aronix M-306” manufactured by Toagosei Co., Ltd., pentaerythritol triacrylate content of about 67%, hydroxyl value of 159.7 mg KOH/g) 37.3 parts by mass. 2.3 parts by mass of triphenylphosphine were added, and the mixture was reacted at 110° C. for 5 hours while blowing air. Then, 144.0 parts by mass of glycidyl methacrylate was added, and the mixture was reacted at 110° C. for 10 hours. Further, 98.7 parts by mass of tetrahydrophthalic anhydride was added and the reaction was carried out at 110° C. for 5 hours. Next, 42.9 parts by mass of 2-isocyanatoethyl acrylate and 0.1 part by mass of dioctyltin dineodecanoate (“Neostan U-830” manufactured by Nitto Kasei Co., Ltd.) were added and reacted at 80° C. for 3 hours. Thus, the desired acid group-containing (meth)acrylate resin (6) was obtained. The acid value of the solid content of the acid group-containing (meth)acrylate resin (6) was 80 mgKOH/g, and the weight average molecular weight was 3650.

(Example 7: Production of acid group-containing (meth)acrylate resin (7))
In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 399.9 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 16 4.7 parts by mass, 129.4 parts by mass of trimellitic anhydride, and 1.5 parts by mass of dibutylhydroxytoluene 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. Next, 0.3 parts by mass of methoquinone, pentaerythritol triacrylate mixture ("Aronix M-306" manufactured by Toagosei Co., Ltd., pentaerythritol triacrylate content of about 67%, hydroxyl value of 159.7 mg KOH/g) 99.5 parts by mass. And 3.0 parts by mass of triphenylphosphine were added, and the mixture was reacted at 110° C. for 5 hours while blowing air. Next, 159.3 parts by mass of 3,4-epoxycyclohexylmethyl methacrylate (“Cyclomer M100” manufactured by Daicel Corporation, epoxy group equivalent 207 g/equivalent) was added, and the mixture was reacted at 110° C. for 7 hours. Further, 71.5 parts by mass of succinic anhydride was added and the reaction was carried out at 110° C. for 5 hours. Then, 5.4 parts by mass of 2-isocyanatoethyl acrylate and 0.1 parts by mass of dioctyltin dineodecanoate (“Neostan U-830” manufactured by Nitto Kasei Co., Ltd.) were added and reacted at 80° C. for 3 hours. Thus, the desired acid group-containing (meth)acrylate resin (7) was obtained. The acid value of the solid content of the acid group-containing (meth)acrylate resin (7) was 70 mgKOH/g, and the weight average molecular weight was 3820.

(Comparative Example 1: Production of acid group-containing (meth)acrylate resin (C1))
A flask equipped with a thermometer, a stirrer, and a reflux condenser was charged with 101 parts by mass of diethylene glycol monomethyl ether acetate, and orthocresol novolac type epoxy resin (“EPICLON N-680” manufactured by DIC Corporation, epoxy equivalent: 214) 428. After dissolving 4 parts by mass of dibutylhydroxytoluene as an antioxidant and 0.4 parts by mass of methoquinone as a thermal polymerization inhibitor, 144 parts by mass of acrylic acid and 1.6 parts by mass of triphenylphosphine were added. Then, the esterification reaction was carried out at 120° C. for 10 hours while blowing air. After that, 311 parts by mass of diethylene glycol monomethyl ether acetate and 160 parts by mass of tetrahydrophthalic anhydride were added and reacted at 110° C. for 2.5 hours to obtain a desired acid group-containing (meth)acrylate resin (C1). The acid value of the solid content of the acid group-containing (meth)acrylate resin (C1) was 85 mgKOH/g.

(Example 8: Preparation of curable resin composition (1))
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 (1) was obtained.

(Examples 9 to 14: Preparation of curable resin compositions (2) to (7))
Instead of using the acid group-containing (meth)acrylate resin (1) used in Example 8, the acid group-containing (meth)acrylate resins (2) to (7) obtained in Examples 2 to 7 were used, respectively. The curable resin compositions (2) to (7) were obtained in the same manner as in Example 8.

(Comparative Example 2: Preparation of curable resin composition (C2))
The same procedure as in Example 8 was repeated except that the acid group-containing (meth)acrylate resin (C1) obtained in Comparative Example 1 was used instead of the acid group-containing (meth)acrylate resin (1) used in Example 8. Thus, a curable resin composition (C2) was obtained.

The following evaluations were performed using the curable resin compositions (1) to (7) and (C2) obtained in the above Examples and Comparative Examples.

[Heat resistance evaluation method]
<Preparation of test piece 1>
The curable resin compositions obtained in Examples and Comparative Examples were applied onto a copper foil (manufactured by Furukawa Sangyo Co., Ltd., electrolytic copper foil “F2-WS” 18 μm) with an applicator of 50 μm and dried at 80° C. for 30 minutes. It was After irradiating with 1000 mJ/cm< ² > ultraviolet rays using a metal halide lamp, it heated at 160 degreeC for 1 hour. The cured product was peeled off from the copper foil to obtain a test piece 1 (cured product).

The test piece 1 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. The glass transition temperature (Tg) was evaluated as the temperature at which the change in elastic modulus was maximum (the change rate of tan δ was the largest).

[Substrate adhesion evaluation method]
The substrate adhesion was evaluated by measuring the peel strength.

<Creation of test piece 2>
The curable resin compositions obtained in Examples and Comparative Examples were applied onto a copper foil (manufactured by Furukawa Sangyo Co., Ltd., electrolytic copper foil “F2-WS” 18 μm) with an applicator of 50 μm and dried at 80° C. for 30 minutes. It was After irradiating with 1000 mJ/cm< ² > ultraviolet rays using a metal halide lamp, it heated at 160 degreeC for 1 hour, and obtained the test piece 2.

<Peel strength measurement method>
The test piece 2 was cut into a size of 1 cm in width and 12 cm in length, and 90° peel strength was measured using a peeling tester (“A&D Tensilon” manufactured by A&D Co., Ltd., peeling speed 50 mm/min).

Table 1 shows the compositions and evaluation results of the curable resin compositions (1) to (7) produced in Examples 8 to 14 and the curable resin composition (C2) produced in Comparative Example 2.

In addition, the "curing agent" in Table 1 shows an ortho-cresol novolac type epoxy resin ("EPICLON N-680" manufactured by DIC Corporation, epoxy equivalent: 214).

"Organic solvent" in Table 1 indicates diethylene glycol monomethyl ether acetate.

"Photoinitiator" in Table 1 indicates "Omnirad-907" manufactured by IGM.

Examples 8 to 14 shown in Table 1 are examples of curable resin compositions using the acid group-containing (meth)acrylate resin of the present invention. It was confirmed that the cured product of this curable resin composition had excellent heat resistance and substrate adhesion.

On the other hand, Comparative Example 2 is an example of a curable resin composition that does not use the acid group-containing (meth)acrylate resin of the present invention. It was confirmed that the cured product of this curable resin composition had remarkably insufficient heat resistance and substrate adhesion.

Claims (11)

Amidoimide resin (A) having acid group or acid anhydride group, hydroxyl group-containing (meth)acrylate compound (B), epoxy group-containing (meth)acrylate compound (C), polycarboxylic acid anhydride (D) and isocyanate group-containing An acid group-containing (meth)acrylate resin, which comprises a (meth)acrylate compound (E) as an essential reaction raw material. The amide-imide resin (A) having an acid group or an acid anhydride group uses a polyisocyanate compound (a1) and a polycarboxylic acid or an acid anhydride thereof (a2) as essential reaction raw materials,
The polyisocyanate compound (a1) contains an alicyclic diisocyanate compound or a modified product thereof as an essential component, and the polycarboxylic acid or acid anhydride (a2) thereof contains a tricarboxylic acid anhydride as an essential component. The acid group-containing (meth)acrylate resin according to claim 1, wherein The amide-imide resin (A) having an acid group or an acid anhydride group uses a polyisocyanate compound (a1) and a polycarboxylic acid or an acid anhydride thereof (a2) as essential reaction raw materials,
The polyisocyanate compound (a1) has an aliphatic diisocyanate compound or a modified product thereof as an essential component, and the polycarboxylic acid or its acid anhydride (a2) has a tricarboxylic acid anhydride as an essential component. The acid group-containing (meth)acrylate resin according to claim 1, wherein The acid group-containing (meth)acrylate resin according to claim 1, wherein the polycarboxylic acid anhydride (D) is an aliphatic polycarboxylic acid anhydride or an alicyclic polycarboxylic acid anhydride. A curable resin composition comprising the acid group-containing (meth)acrylate resin according to any one of claims 1 to 4 and a photopolymerization initiator. The curable resin composition according to claim 5, further comprising an organic solvent and a curing agent. The curable resin composition according to claim 5, further comprising an acid group-containing (meth)acrylate resin (F) other than the acid group-containing (meth)acrylate resin according to any one of claims 1 to 4. object. A cured product, which is a curing reaction product of the curable resin composition according to any one of claims 5 to 7. An insulating material comprising the curable resin composition according to any one of claims 5 to 7. A resin material for a solder resist, comprising the curable resin composition according to any one of claims 5 to 7. A resist member comprising the resin material for solder resist according to claim 10.