JP2020176214A - Amide-imide resin composition, curable resin composition, cured product, insulating material, resin material for solder resist and resist member - Google Patents

Abstract

To provide an amide-imide resin composition which has excellent alkali developability and high photosensitivity, and excellent heat resistance and base material adhesion, a curable resin composition containing the same, and a cured product, an insulating material, and a resin material for solder resist formed of the curable resin composition, and a resist member.SOLUTION: An amide-imide resin composition contains an amide-imide resin (A) having an acid group and a polymerizable unsaturated group, and an amide-imide resin (B) other than the amide-imide resin (A), in which the amide-imide resin (A) contains an amide-imide resin (a1) having an acid group and/or an acid anhydride group and a hydroxyl group-containing (meth)acrylate compound (a2) as essential reaction raw materials.SELECTED DRAWING: None

Description

The present invention comprises an amidoimide resin composition having excellent alkali developability and high photosensitivity, excellent heat resistance and substrate adhesion, a curable resin composition containing the same, and the curable resin composition. The present invention relates to a cured product, an insulating material, a resin material for solder resist, and a resist member.

In recent years, an acid group-containing epoxy acrylate resin obtained by reacting an epoxy resin with acrylic acid and then reacting with an acid anhydride has been widely used as a resin material for solder resist for a printed wiring board. The required performance for resin materials for solder resists is that they can be cured with a small exposure amount, that they have excellent alkali developability, and that they have excellent heat resistance, strength, flexibility, elongation, dielectric properties, substrate adhesion, etc. in the cured product. There are various things.

As a conventionally known resin material for solder resist, active energy ray-curable obtained by reacting a reaction product of a novolak type epoxy resin and an unsaturated monocarboxylic acid with a saturated or unsaturated polybasic acid anhydride. Although resins are known (see, for example, Patent Document 1 below), the cured product of the active energy ray-curable resin has good heat resistance, but the substrate adhesion is not sufficient, and the heat resistance In terms of sex, it did not satisfy the ever-increasing demand characteristics, and was not sufficient for the recent market demands.

Therefore, there has been a demand for a material that has excellent alkali developability and high light sensitivity, and is more excellent in heat resistance and substrate adhesion in a cured product.

JP-A-61-243869

The problem to be solved by the present invention is an amidimide resin composition having excellent alkali developability and high photosensitivity, excellent heat resistance and substrate adhesion, and a curable resin composition containing the same. It is an object of the present invention to provide a cured product made of a curable resin composition, an insulating material, a resin material for solder resist, and a resist member.

As a result of diligent studies to solve the above problems, the present inventors have contained an amideimide resin having an acid group and a polymerizable unsaturated group using a specific amideimide resin as an essential reaction raw material, and other amideimide resins. The present invention has been completed by finding that the above problems can be solved by using an amidoimide resin composition characterized by the above.

That is, the present invention is an amideimide resin composition containing an amideimide resin (A) having an acid group and a polymerizable unsaturated group and an amideimide resin (B) other than the amideimide resin (A). The resin (A) is an amideimide resin (a1) having an acid group and / or an acid anhydride group, and a hydroxyl group-containing (meth) acrylate compound (a2) as essential reaction raw materials. The present invention relates to a resin composition, a curable resin composition containing the same, a cured product composed of the curable resin composition, an insulating material, a resin material for solder resist, and a resist member.

Since the amidoimide resin composition of the present invention can form a cured product having excellent alkali developability and high photosensitivity, and excellent heat resistance and substrate adhesion, it is possible to form an insulating material and a resin material for solder resist. And can be suitably used for a resist member.

The amideimide resin composition of the present invention is characterized by containing an amideimide resin (A) having an acid group and a polymerizable unsaturated group, and an amideimide resin (B) other than the amideimide resin (A). To do.

As the amideimide resin (A), a resin having an acid group and a polymerizable unsaturated group is used. In the present invention, the "polymerizable unsaturated group" means a functional group having a polymerizable unsaturated bond capable of radical polymerization.

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

Examples of the polymerizable unsaturated group include a vinyl group, a (meth) acryloyl group, a (meth) acryloyloxy group, a propenyl group and the like. In the present invention, the acid anhydride group is not treated as the polymerizable unsaturated group.

Further, the amideimide resin (A) may have an acid anhydride group in addition to the acid group and the polymerizable unsaturated group, and the acid anhydride group includes, for example, a carboxylic acid anhydride group and a sulfone. Examples thereof include an acid anhydride group and a phosphoric acid anhydride group.

As the amideimide resin (A), an amideimide resin (a1) having an acid group and / or an acid anhydride group and a hydroxyl group-containing (meth) acrylate compound (a2) as essential reaction raw materials are used.

The amideimide resin (a1) may have only one of an acid group and an acid anhydride group, or may have both. Among them, it is preferable to have an acid anhydride group from the viewpoint of reactivity with the hydroxyl group-containing (meth) acrylate compound (a2) and reaction control, and it has both an acid group and an acid anhydride group. Is more preferable.

Examples of the acid group include the same as the above-mentioned acid group.

Examples of the acid anhydride group include a carboxylic acid anhydride group, a sulfonic acid anhydride group, and a phosphoric acid anhydride group.

As the amideimide resin (a1), for example, a polyisocyanate compound (a1-1) and a polybasic acid anhydride (a1-2) as essential reaction raw materials can be used.

Examples of the polyisocyanate compound (a1-1) include aliphatic polyisocyanate compounds such as butane diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and 2,4,4-trimethylhexamethylene diisocyanate; Alicyclic polyisocyanate compounds such as norbornenan diisocyanate, isophorone diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated diphenylmethane diisocyanate; tolylene diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, diphenylmethane diisocyanate, 1,5-naphthalenedi isocyanate, 4 , 4'-Diisocyanato-3,3'-Dimethylbiphenyl, o-trizine diisocyanate and other aromatic polyisocyanates; Polymethylene polyphenyl polyisocyanates having a repeating structure represented by the following structural formula (1); these isocyanates Examples thereof include nurate modified products, biuret modified products, and allophanate modified products. In addition, these polyisocyanate compounds can be used alone or in combination of two or more. Among these, an alicyclic polyisocyanate compound can be obtained because an amidimide resin composition having excellent alkali developability and high photosensitivity and capable of forming a cured product having excellent heat resistance and substrate adhesion can be obtained. Is preferable.

［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), R ¹ is independently either 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 bond point connected to a structural site represented by the structural formula (1) via a methylene group marked with *. is there. l is an integer of 0 or 1-3 and m is an integer of 1-15. ]

Examples of the polybasic acid anhydride (a1-2) include aliphatic polybasic acid anhydrides, alicyclic polybasic acid anhydrides, and aromatic polybasic acid anhydrides.

Examples of the aliphatic polybasic acid anhydride include oxalic acid, malonic acid, succinic acid, glutaconic acid, adipic acid, pimelli 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. Further, as the aliphatic polybasic acid anhydride, the aliphatic hydrocarbon group may be either a linear type or a branched type, and may have an unsaturated bond in the structure.

As the alicyclic polybasic acid anhydride, in the present invention, an alicyclic polybasic acid anhydride having an acid anhydride group bonded to an alicyclic structure is used as an alicyclic polybasic acid anhydride, and the aromatic ring at other structural sites. It does not matter whether it is present or not. Examples of the alicyclic polybasic acid anhydride include tetrahydrophthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, cyclohexanetricarboxylic acid, cyclohexanetetracarboxylic acid, and bicyclo [2.2.1] heptane-2. 3-Dicarboxylic acid, methylbicyclo [2.2.1] heptane-2,3-dicarboxylic acid, 4- (2,5-dioxo tetrahydrofuran-3-yl) -1,2,3,4-tetrahydronaphthalene- Examples thereof include acid anhydrides of 1,2-dicarboxylic acid.

Examples of the aromatic polybasic acid anhydride include phthalic acid, trimellitic acid, pyromellitic acid, naphthalenedicarboxylic acid, naphthalenetricarboxylic acid, naphthalenetetracarboxylic acid, biphenyldicarboxylic acid, biphenyltricarboxylic acid and biphenyltetracarboxylic acid. Examples thereof include acid anhydrides of benzophenone tetracarboxylic acids.

These polybasic acid anhydrides (a1-2) can be used alone or in combination of two or more. Further, among these, the alicyclic type can be obtained because an amidoimide resin composition having excellent alkali developability and high photosensitivity and capable of forming a cured product having excellent heat resistance and substrate adhesion can be obtained. Polybasic acid anhydrides or the aromatic polybasic acid anhydrides are preferred. Of these, it is preferable to use a tricarboxylic acid anhydride having both a carboxyl group and an acid anhydride group in the molecular structure, and it is particularly preferable to use a cyclohexanetricarboxylic acid anhydride or a trimellitic acid anhydride. At this time, the content of the tricarboxylic acid anhydride in the polybasic acid anhydride (a1-2) is preferably 70% by mass or more, more preferably 90% by mass or more.

Further, as the amidimide resin (a1), in addition to the polyisocyanate compound (a1-1) and the polybasic acid anhydride (a1-2), other compounds may be used as a reaction raw material, if necessary. You can also. When the other compounds are used in combination, the effects of the present invention are sufficiently exhibited. Therefore, the polyisocyanate compound (a1-1) and the polybasic acid anhydride in the reaction raw material of the amidimide resin (a1). The total content of (a1-2) is preferably 80% by mass or more, more preferably 85% by mass.

Examples of the other compound include polybasic acids and the like.

As the polybasic acid, any compound having two or more carboxyl groups in one molecule can be used. 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-dioxotetra-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 and the like can be mentioned. Be done. Further, 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.

As a polymer of the conjugated diene vinyl monomer and acrylonitrile and having a carboxyl group in the molecule, for example, a butadiene-acrylonitrile copolymer represented by the following structural formula (2-1). A half of a polymer having a carboxyl group or a polymer having a hydroxyl group in the molecule of a butadiene-acrylonitrile copolymer represented by the following structural formula (2-2) and a polybasic acid anhydride such as maleic anhydride. Examples include ester. The position of the carboxyl group may be located on either the side chain or the terminal of the molecule, but the terminal is preferable.

［構造式（２−１）中、Ｘは１〜５０の整数であり、Ｙは１〜５０の整数であり、Ｚは１〜２０の整数である。］

[In the structural formula (2-1), X is an integer of 1 to 50, Y is an integer of 1 to 50, and Z is an integer of 1 to 20. ]

［構造式（２−２）中、Ｘは１〜５０の整数であり、Ｙは１〜５０の整数であり、Ｚは１〜２０の整数である。］

[In the structural formula (2-2), X is an integer of 1 to 50, Y is an integer of 1 to 50, and Z is an integer of 1 to 20. ]

The acid value of the amideimide resin (a1) is such that an amideimide resin composition capable of forming a cured product having excellent alkali developability and high photosensitivity, excellent heat resistance and substrate adhesion can be obtained. The measured value under neutral conditions, that is, under the condition that the acid anhydride group is not opened, is preferably in the range of 60 to 350 mgKOH / g, and the acid anhydride group is opened in the presence of water or the like. The measured value under the conditions is preferably in the range of 61-360 mgKOH / g. In the present invention, the acid value is a value measured by the neutralization titration method of JIS K 0070 (1992).

When the amideimide resin (a1) uses a polyisocyanate compound (a1-1) and a polybasic acid anhydride (a1-2) as reaction raw materials, the production method thereof is not particularly limited, and any It may be manufactured by a method. For example, it can be produced by the same method as a general amidoimide resin. Specifically, 0.8 to 3.5 mol of the polybasic acid anhydride (a1-2) is used with respect to 1 mol of the isocyanate group contained in the polyisocyanate compound (a1-1), and the temperature is 100 to 180 ° C. Examples thereof include a method of stirring and mixing under moderate temperature conditions for reaction.

The reaction may be carried out in an organic solvent if necessary, or a basic catalyst may be used if necessary.

Examples of the organic solvent 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. Aromatic solvents such as naphtha; alicyclic solvents such as cyclohexane and methylcyclohexane; alcohol solvents such as carbitol, cellosolve, methanol, isopropanol, butanol and propylene glycol monomethyl ether; alkylene glycol monoalkyl ethers and dialkylene glycol monoalkyl ethers. , Glycol ether solvent such as dialkylene glycol monoalkyl ether acetate; methoxypropanol, cyclohexanone, methyl cellosolve, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate and the like. These organic solvents can be used alone or in combination of two or more. Further, the amount of the organic solvent used is preferably in the range of about 0.1 to 5 times the total mass of the reaction raw materials because the reaction efficiency is good.

Examples of the basic catalyst include N-methylmorpholin, pyridine, 1,8-diazabicyclo [5.4.0] undecene-7 (DBU), and 1,5-diazabicyclo [4.3.0] nonen-. 5 (DBN), 1,4-diazabicyclo [2.2.2] octane (DABCO), tri-n-butylamine or dimethylbenzylamine, butylamine, octylamine, monoethanolamine, diethanolamine, triethanolamine, imidazole, 1 -Methylimidazole, 2,4-dimethylimidazole, 1,4-diethylimidazole, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3- (N-phenyl) aminopropyltrimethoxysilane, 3-( Amine compounds such as 2-aminoethyl) aminopropyltrimethoxysilane, 3- (2-aminoethyl) aminopropylmethyldimethoxysilane and tetramethylammonium hydroxide; and four such as trioctylmethylammonium chloride and trioctylmethylammonium acetate. Class ammonium salts; phosphines such as trimethylphosphine, tributylphosphine, triphenylphosphine; tetramethylphosphonium chloride, tetraethylphosphonium chloride, tetrapropylphosphonium chloride, tetrabutylphosphonium chloride, tetrabutylphosphonium bromide, trimethyl (2-hydroxypropyl) phosphonium Phosphonium salts such as chloride, triphenylphosphonium chloride, benzylphosphonium chloride; dibutyltin dilaurate, octyltin trilaurate, octyltin diacetate, dioctyltin diacetate, dioctyltin dineodecanoate, dibutyltin diacetate, tin octylate, Organic tin compounds such as 1,1,3,3-tetrabutyl-1,3-dodecanoyl distanoxane; organic metal compounds such as zinc octylate and bismuth octylate; inorganic tin compounds such as tin octanate; inorganic metal compounds And so on. These basic catalysts can be used alone or in combination of two or more.

The hydroxyl group-containing (meth) acrylate compound (a2) is not particularly limited as long as it is a compound having a hydroxyl group and a (meth) acryloyl group in its molecular structure, and a wide variety of compounds can be used. it can. As an example, for example, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, trimethylolpropane (meth) acrylate, trimethylrolpropandi (meth) acrylate, pentaerythritol (meth) acrylate, pentaerythritol di (meth). ) Acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol (meth) acrylate, dipentaerythritol di (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta Examples thereof include (meth) acrylate, ditrimethylol propane (meth) acrylate, ditrimethylol propane di (meth) acrylate, and ditrimethylol propanetri (meth) acrylate. In addition, (poly) oxyalkylene chains such as (poly) oxyethylene chains, (poly) oxypropylene chains, and (poly) oxytetramethylene chains were introduced into the molecular structures of the various hydroxyl group-containing (meth) acrylate compounds (). Poly) oxyalkylene modified products, lactone modified products in which a (poly) lactone structure is introduced into the molecular structure of the various hydroxyl group-containing (meth) acrylate compounds, and the like can also be used. These hydroxyl group-containing (meth) acrylate compounds (a2) can be used alone or in combination of two or more. Further, 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 (a2) is such that an amideimide resin composition capable of forming a cured product having excellent alkali developability and high photosensitivity, and excellent heat resistance and substrate adhesion. Since it can be obtained, it is preferably 1,000 or less. When the hydroxyl group-containing (meth) acrylate compound (a2) is an oxyalkylene modified product or a lactone modified product, the weight average molecular weight (Mw) is preferably 1,000 or less.

As the amideimide resin (A), an epoxy group-containing (meth) acrylate compound (a3) is used as a reaction raw material in addition to the amideimide resin (a1) and the hydroxyl group-containing (meth) acrylate compound (a2), if necessary. It can also be used together as. Further, as the amideimide resin (A), if necessary, in addition to the amideimide resin (a1) and the hydroxyl group-containing (meth) acrylate compound (a2), an epoxy group-containing (meth) acrylate compound (a3) and the like. Polybasic acid anhydride (a4) can also be used in combination as a reaction raw material.

When the epoxy group-containing (meth) acrylate compound (a3) or the epoxy group-containing (meth) acrylate compound (a3) and the polybasic acid anhydride (a4) are used in combination, the effects of the present invention are sufficiently exhibited. Therefore, the total content of the amideimide resin (a1) and the hydroxyl group-containing (meth) acrylate compound (a2) in the reaction raw material of the amideimide resin (A) is preferably 50% by mass or more.

The epoxy group-containing (meth) acrylate compound (a3) is not particularly limited as long as it has a (meth) acryloyl group and an epoxy group in its molecular structure, and a wide variety of compounds are used. Can be used. For example, glycidyl group-containing (meth) acrylate monomers such as glycidyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether, and epoxycyclohexylmethyl (meth) acrylate; dihydroxybenzene diglycidyl ether, dihydroxynaphthalenedi glycidyl ether, etc. Examples thereof include mono (meth) acrylate compounds of diglycidyl ether compounds such as biphenol diglycidyl ether and bisphenol diglycidyl ether. These epoxy group-containing (meth) acrylate compounds may be used alone or in combination of two or more.

As the polybasic acid anhydride (a4), those exemplified as the above-mentioned polybasic acid anhydride (a1-2) can be used, and the polybasic acid anhydride (a4) may be used alone. Two or more types can be used together.

The method for producing the amideimide resin (A) is not particularly limited, and any method may be used for production. For example, it may be produced by a method of reacting all of the reaction raw materials containing the amidimide resin (a1) and the hydroxyl group-containing (meth) acrylate compound (a2) at once, or by a method of sequentially reacting the reaction raw materials. You may.

The reaction between the amideimide resin (a1) and the hydroxyl group-containing (meth) acrylate compound (a2) is mainly carried out by using the acid group and / or the acid anhydride group in the amideimide resin (a1) and the hydroxyl group-containing (meth) acrylate. It reacts with the hydroxyl group in the compound (a2). Since the hydroxyl group-containing (meth) acrylate compound (a2) is particularly excellent in reactivity with an acid anhydride group, it is preferable that the amidimide resin (a1) has an acid anhydride group as described above. The content of the acid anhydride group in the amideimide resin (a1) is the difference between the two measured acid values described above, that is, the acid value under the condition that the acid anhydride group is 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 amideimide resin (a1) and the hydroxyl group-containing (meth) acrylate compound (a2) is such that the amideimide resin (a1) has an acid group and an acid anhydride group, and the amideimide resin (a1) has an acid group and an acid anhydride group. When it has an acid anhydride group, the number of moles of the hydroxyl group of the hydroxyl group-containing (meth) acrylate compound (a2) is 0.9 to 1.1 with respect to 1 mol of the acid anhydride group of the amideimide resin (a1). It is preferable to use it within the range of. When the amidimide resin (a1) has an acid group, the number of moles of hydroxyl groups of the hydroxyl group-containing (meth) acrylate compound (a2) is 0, relative to 1 mole of the acid group of the amidimide resin (a1). It is preferable to use it in the range of 01 to 0.5.

The reaction between the amidimide resin (a1) and the hydroxyl group-containing (meth) acrylate compound (a2) is carried out by heating and stirring under a temperature condition of about 80 to 140 ° C. in the presence of an appropriate esterification catalyst, for example. Can be done. 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 thereof 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. The amount of the esterification catalyst added is preferably in the range of 0.001 to 5 parts by mass with respect to 100 parts by mass of the total mass of the reaction raw materials.

The reaction may be carried out in an organic solvent if necessary, or an acidic catalyst may be used if necessary.

As the organic solvent, the same solvent as the above-mentioned organic solvent can be used, and the organic solvent can be used alone or in combination of two or more. When the reaction is carried out continuously with the production of the amide imide resin (a1), the reaction may be continued as it is in the organic solvent used in the production of the amide imide resin (a1).

Examples of the acidic catalyst include inorganic acids such as hydrochloric acid, sulfuric acid and phosphoric acid, organic acids such as methanesulfonic acid, paratoluenesulfonic acid and oxalic acid, and Lewis acids such as boron trifluoride, anhydrous aluminum chloride and zinc chloride. And so on. These acidic catalysts can be used alone or in combination of two or more.

When the amideimide resin (A) uses an epoxy group-containing (meth) acrylate compound (a3) in addition to the amideimide resin (a1) and the hydroxyl group-containing (meth) acrylate compound (a2) as a reaction raw material, the above. It may be produced by a method in which all of the reaction raw materials containing the amidimide resin (a1), the hydroxyl group-containing (meth) acrylate compound (a2), and the epoxy group-containing (meth) acrylate compound (a3) are reacted at once. , The reaction raw material may be produced by a method of sequentially reacting. Among them, since the reaction is easy to control, the product obtained by reacting the amidimide resin (a1) with the hydroxyl group-containing (meth) acrylate compound (a2) (hereinafter, “product (1)). It is preferable to produce the compound by reacting the epoxy group-containing (meth) acrylate compound (a3) with the above.

The reaction between the product (1) and the epoxy group-containing (meth) acrylate compound (a3) is mainly carried out mainly by the acid group in the product (1) and the epoxy group-containing (meth) acrylate compound (a3). It reacts with. The reaction ratio is in the range in which the number of moles of the epoxy group contained in the epoxy group-containing (meth) acrylate compound (a3) is 0.05 to 1.1 with respect to 1 mole of the acid group contained in the product (1). It is preferable to use in. The reaction can be carried out, for example, by heating and stirring under a temperature condition of about 90 to 140 ° C. in the presence of a suitable esterification catalyst. When the reaction of the amidimide resin (a1) and the hydroxyl group-containing (meth) acrylate compound (a2) is carried out continuously, the esterification catalyst may not be added or may be added as appropriate. Moreover, the reaction may be carried out in an organic solvent if necessary. As the esterification catalyst and the organic solvent, the same ones as those of the esterification catalyst and the organic solvent can be used, and they can be used alone or in combination of two or more.

In addition to the amideimide resin (a1) and the hydroxyl group-containing (meth) acrylate compound (a2), the amideimide resin (A) contains an epoxy group-containing (meth) acrylate compound (a3) and polybasic acid anhydride as reaction raw materials. When the substance (a4) is used, the amidimide resin (a1), the hydroxyl group-containing (meth) acrylate compound (a2), the epoxy group-containing (meth) acrylate compound (a3), and the polybasic acid anhydride (a4) are used. It may be produced by a method of reacting all of the reaction raw materials contained therein at once, or by a method of sequentially reacting the reaction raw materials. Among them, since the reaction is easy to control, the product (1) obtained by reacting the amidimide resin (a1) with the hydroxyl group-containing (meth) acrylate compound (a2) contains the epoxy group. By reacting the (meth) acrylate compound (a3) and reacting the obtained product (hereinafter, may be referred to as “product (2)”) with the polybasic acid anhydride (a4). It is preferable to manufacture.

The reaction between the product (2) and the polybasic acid anhydride (a4) is mainly a reaction between the hydroxyl group in the product (2) and the polybasic acid anhydride. At this time, in the product (2), the reaction ratio of the product (1) to the epoxy group-containing (meth) acrylate compound (a3) is based on 1 mol of the acid group of the product (1). The number of moles of the epoxy group contained in the epoxy group-containing (meth) acrylate compound (a3) is preferably in the range of 0.1 to 1.2, and more preferably 0.2 to 1.1. .. Here, in the product (2), for example, a hydroxyl group generated by ring-opening of the epoxy group in the epoxy group-containing (meth) acrylate compound (a3) is present. The reaction ratio of the polybasic acid anhydride (a4) is preferably adjusted so that the acid value of the produced amideimide resin (A) is about 50 to 120 mgKOH / g. The reaction can be 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. When the reaction of the product (1) with the epoxy group-containing (meth) acrylate compound (a3) is carried out continuously, the esterification catalyst may not be added or may be added as appropriate. Moreover, the reaction may be carried out in an organic solvent if necessary. As the esterification catalyst and the organic solvent, the same ones as those of the esterification catalyst and the organic solvent can be used, and they can be used alone or in combination of two or more.

The acid value of the amideimide resin (A) is such that an amideimide resin composition capable of forming a cured product having excellent alkali developability and high photosensitivity, excellent heat resistance and substrate adhesion can be obtained. , 50-160 mgKOH / g, more preferably 60-150 mgKOH / g. In the present invention, the acid value of the acid group-containing (meth) acrylate resin is a value measured by the neutralization titration method of JIS K 0070 (1992).

The weight average molecular weight (Mw) of the amidimide resin (A) is preferably in the range of 1,000 to 20,000. In the present invention, the weight average molecular weight (Mw) indicates a value measured by a gel permeation chromatography (GPC) method.

As the amideimide resin (B), an amideimide resin other than the amideimide resin (A) is used.

The amideimide resin (B) may have only one of an acid group and an acid anhydride group, or may have both, but from the viewpoint of reactivity and reaction control, it may be used. It preferably has an acid anhydride group, and more preferably has both an acid group and an acid anhydride group.

Examples of the acid group and the acid anhydride group include the same as the above-mentioned acid group and acid anhydride group.

As the amideimide resin (B), for example, a polyisocyanate compound (b1) and a polybasic acid anhydride (b2) as essential reaction raw materials can be used.

As the polyisocyanate compound (b1), those exemplified as the above-mentioned polyisocyanate compound (a1-1) can be used, and the polyisocyanate compound (b1) may be used alone or in combination of two or more. You can also do it. As the polyisocyanate compound (b1), the same compound as the polyisocyanate compound (a1-1) may be used, or a different compound may be used, but the polyisocyanate compound (b1) and the above. When at least one of the polyisocyanate compound (a1-1) is an alicyclic polyisocyanate compound, the cured product has excellent alkali developability and high photosensitivity, and has excellent heat resistance and substrate adhesion. It is preferable because an amidoimide resin composition capable of forming the above can be obtained.

As the polybasic acid anhydride (b2), those exemplified as the above-mentioned polybasic acid anhydride (a1-2) can be used, and the polybasic acid anhydride may be used alone or in combination of two or more. Can also be used together. As the polybasic acid anhydride (b2), the same one as the polybasic acid anhydride (a1-2) may be used, or a different one may be used.

The acid value of the amideimide resin (B) is such that an amideimide resin composition capable of forming a cured product having excellent alkali developability and high photosensitivity, excellent heat resistance and substrate adhesion can be obtained. The measured value of the solid content under neutral conditions, that is, under the condition that the acid anhydride group is not opened, is preferably in the range of 60 to 350 mgKOH / g, and the acid anhydride group is opened in the presence of water or the like. It is preferable that the measured value of the solid content under the ringed condition is in the range of 61 to 360 mgKOH / g. In the present invention, the acid value is a value measured by the neutralization titration method of JIS K 0070 (1992).

As the amideimide resin (B), an alcohol compound (b3) can be used in combination as a reaction raw material, if necessary.

Examples of the alcohol compound (b3) include methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, t-butyl alcohol, ethylene glycol, propylene glycol, trimethylolpropane, and benzyl alcohol. Alcohols having 10 or less carbon atoms such as 2-methoxyethyl alcohol, 2-ethoxyethyl alcohol, 1-methoxy-2-propyl alcohol, 1-ethoxy-2-propyl alcohol, 3-methoxy-1-butyl alcohol, 2 -Alcohols with 10 or less carbon atoms containing ether bonds such as isopropoxyethyl alcohol; alcohols having 10 or less carbon atoms containing ketone groups such as 3-hydroxy-2-butanone; containing ester groups such as methyl hydroxyisobutyrate Examples include alcohols having 10 or less carbon atoms. These alcohol compounds may be used alone or in combination of two or more.

Since the effects of the present invention are sufficiently exhibited, the total content of the polyisocyanate compound (b1) and the polybasic acid anhydride (b2) in the reaction raw material of the amidimide resin (B) is determined to be the total content. 80% by mass or more is preferable, and 85% by mass is more preferable.

The method for producing the amidimide resin (B) is not particularly limited, and any method may be used for producing the amideimide resin (B). For example, it can be produced by the method exemplified as the above-mentioned method for producing the amidoimide resin (a1).

When the amidimide resin (B) uses the alcohol compound (b3) as a reaction raw material, the polyisocyanate compound (b1), the polybasic acid anhydride (b2), and the alcohol compound (b3) are used. It may be produced by a method of reacting all of the reaction raw materials contained therein at once, or by a method of sequentially reacting the reaction raw materials. Among them, since the reaction is easy to control, the product obtained by reacting the polyisocyanate compound (b1) with the polybasic acid anhydride (b2) (hereinafter, “product (3)””. It is preferable to produce by a method of reacting the alcohol compound (b3) with (may be referred to as).

The reaction between the product (3) and the alcohol compound (b3) mainly involves the acid groups and / or acid anhydride groups in the product (3) and the hydroxyl groups in the alcohol compound (b3). It is something that reacts. Since the alcohol compound (b3) is particularly excellent in reactivity with an acid anhydride group, the product (3) preferably has an acid anhydride group. The content of the acid anhydride group in the product (3) is the difference between the two measured acid values described above, that is, the acid value under the condition that the acid anhydride group is 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 product (3) and the alcohol compound (b3) is such that when the product (3) has an acid group and an acid anhydride group, and when the product (3) has an acid anhydride group. When it is contained, it is preferable to use it in a range in which the number of moles of the hydroxyl group of the alcohol compound (b3) is 0.9 to 1.1 with respect to 1 mol of the acid anhydride group of the product (3). When the product (3) has an acid group, the number of moles of the hydroxyl group of the alcohol compound (b3) is 0.01 to 0.5 with respect to 1 mol of the acid group of the product (3). It is preferable to use it in the range of.

The mass ratio of the solid content between the amideimide resin (A) and the amideimide resin (B) [(A) / (B)] has excellent alkali developability and high photosensitivity, and has excellent heat resistance and heat resistance. The range of 50/50 to 95/5 is preferable, and the range of 55/45 to 90/10 is more preferable, because an amidoimide resin composition capable of forming a cured product having adhesion to a substrate can be obtained.

The amideimide resin composition of the present invention may contain other resin components other than the amideimide resin (A) and the amideimide resin (B). Examples of the other resin component include a resin (C) having an acid group and a polymerizable unsaturated bond, various (meth) acrylate monomers, and the like.

The resin (C) having an acid group and a polymerizable unsaturated bond may be any resin (C) having an acid group and a polymerizable unsaturated bond in the resin, for example, an acid group and a polymerizable unsaturated bond. Examples thereof include an epoxy resin having an acid group and a urethane resin having a polymerizable unsaturated bond, an acrylic resin having an acid group and a polymerizable unsaturated bond, and an acrylamide resin having an acid group and a polymerizable unsaturated bond. In the present invention, the "polymerizable unsaturated bond" means an unsaturated bond capable of radical polymerization.

Examples of the acid group include those exemplified as the above-mentioned acid group.

Examples of the epoxy resin having an acid group and a polymerizable unsaturated bond include an acid group-containing epoxy (meth) acrylate resin containing an epoxy resin, an unsaturated monobasic acid, and a polybasic acid anhydride as essential reaction raw materials. , Epoxy resin, unsaturated monobasic acid, polybasic acid anhydride, polyisocyanate compound, acid group containing hydroxyl group (meth) acrylate compound as a reaction raw material, and epoxy (meth) acrylate resin containing urethane group.

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, and cresol novolac type epoxy resin. Bisphenol novolac type epoxy resin, naphthol novolac type epoxy resin, naphthol-phenol co-shrink novolak type epoxy resin, naphthol-cresol co-shrink novolak type epoxy resin, phenol aralkyl type epoxy resin, naphthol aralkyl type epoxy resin, dicyclopentadiene-phenol addition Examples thereof include a reactive epoxy resin, a biphenyl aralkyl type epoxy resin, a fluorene type epoxy resin, a xanthene type epoxy resin, a dihydroxybenzene type epoxy resin, and a trihydroxybenzene type epoxy resin. These epoxy resins can be used alone or in combination of two or more.

The unsaturated monobasic acid refers to a compound having an acid group and a polymerizable unsaturated bond in one molecule. Examples of the acid group include those exemplified as the above-mentioned acid group. Examples of the unsaturated monobasic acid include acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, α-cyanocinnamic acid, β-styrylacrylic acid, β-fulfurylacrylic acid and the like. Further, an esterified product of the unsaturated monobasic acid, an acid halide, an acid anhydride and the like can also be used. These unsaturated monobasic acids can be used alone or in combination of two or more.

As the polybasic acid anhydride, those exemplified as the above-mentioned polybasic acid anhydride (a1-2) can be used, and the polybasic acid anhydride may be used alone or in combination of two or more. You can also do it.

As the polyisocyanate compound, those exemplified as the above-mentioned polyisocyanate compound (a1-1) can be used, and the polyisocyanate compound may be used alone or in combination of two or more.

As the hydroxyl group-containing (meth) acrylate compound, those exemplified as the above-mentioned hydroxyl group-containing (meth) acrylate compound (a2) can be used, and the hydroxyl group-containing (meth) acrylate compound (a2) may be used alone. It is also possible to use two or more kinds together.

The method for producing the epoxy resin having the acid group and the polymerizable unsaturated bond is not particularly limited, and any method may be used for producing the epoxy resin. In the production of the epoxy resin having an acid group and a polymerizable unsaturated bond, it may be carried out in an organic solvent if necessary, or a basic catalyst may be used if necessary.

As the organic solvent, the same solvent as the above-mentioned organic solvent can be used, and the organic solvent can be used alone or in combination of two or more.

As the basic catalyst, the same catalyst as the above-mentioned basic catalyst can be used, and the basic catalyst may be used alone or in combination of two or more.

Examples of the urethane resin having an acid group and a polymerizable unsaturated bond include a polyisocyanate compound, a hydroxyl group-containing (meth) acrylate compound, a carboxyl group-containing polyol compound, and if necessary, a polybasic acid anhydride and the carboxyl group. It is obtained by reacting with a polyol compound other than the contained 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. The ones obtained from the above can be mentioned.

As the polyisocyanate compound, the same compound as the above-mentioned polyisocyanate compound (a1-1) can be used, and the polyisocyanate compound may be used alone or in combination of two or more.

As the hydroxyl group-containing (meth) acrylate compound, the same compound as the above-mentioned hydroxyl group-containing (meth) acrylate compound (a2) can be used, and the hydroxyl group-containing (meth) acrylate compound may be used alone. The above can be used together.

Examples of the carboxyl group-containing polyol compound include 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, and 2,2-dimethylolpropane valeric acid. The carboxyl group-containing polyol compound may be used alone or in combination of two or more.

As the polybasic acid anhydride, those exemplified as the above-mentioned polybasic acid anhydride (a1-2) can be used, and the polybasic acid anhydride may be used alone or in combination of two or more. You can also do it.

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 biphenol and bisphenol; (poly) oxyalkylene chains such as (poly) oxyethylene chain, (poly) oxypropylene chain, and (poly) oxytetramethylene chain are included in the molecular structure of the various polyol compounds. Introduced (poly) oxyalkylene modified product; a lactone modified product in which a (poly) lactone structure is introduced into the molecular structure of the various polyol compounds can be mentioned. The polyol compounds other than the carboxyl group-containing polyol compound may be used alone or in combination of two or more.

The method for producing the urethane resin having the acid group and the polymerizable unsaturated bond is not particularly limited, and any method may be used for producing the urethane resin. In the production of the urethane resin having an acid group and a polymerizable unsaturated bond, it may be carried out in an organic solvent if necessary, or a basic catalyst may be used if necessary.

As the organic solvent, the same solvent as the above-mentioned organic solvent can be used, and the organic solvent can be used alone or in combination of two or more.

As the basic catalyst, the same catalyst as the above-mentioned basic catalyst can be used, and the basic catalyst may be used alone or in combination of two or more.

As the acrylic resin having an acid group and a polymerizable unsaturated bond, for example, 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 is polymerized as an essential component. A reaction obtained by introducing a (meth) acryloyl group by further reacting a (meth) acrylate compound (β) having a reactive functional group capable of reacting with these functional groups with the acrylic resin intermediate thus obtained. Examples thereof include a product and a product obtained by reacting a hydroxyl group in the reaction product with a polybasic acid anhydride.

The acrylic resin intermediate may be a copolymer of the (meth) acrylate compound (α) and other polymerizable unsaturated group-containing compounds, if necessary. The other polymerizable unsaturated group-containing compound is, for example, (meth) 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, isobolonyl (meth) acrylate, dicyclopentanyl (meth) acrylate; phenyl (meth) acrylate, benzyl (meth) acrylate, phenoxy Aromatic ring-containing (meth) acrylates such as ethyl acrylate; silyl group-containing (meth) acrylates such as 3-methacryloxypropyltrimethoxysilane; styrene derivatives such as styrene, α-methylstyrene and chlorostyrene can be mentioned. These can 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 the combination is as follows from the viewpoint of reactivity. Is preferable. That is, when a hydroxyl group-containing (meth) acrylate is used as the (meth) acrylate compound (α), it is preferable to use an isocyanate group-containing (meth) acrylate 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), it is preferable to use a hydroxyl group-containing (meth) acrylate 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). The (meth) acrylate compound (β) can be used alone or in combination of two or more.

As the polybasic acid anhydride, those exemplified as the above-mentioned polybasic acid anhydride (a1-2) can be used, and the polybasic acid anhydride may be used alone or in combination of two or more. You can also.

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 for producing the acrylic resin. In the production of the acrylic resin having an acid group and a polymerizable unsaturated bond, it may be carried out in an organic solvent if necessary, or a basic catalyst may be used if necessary.

As the organic solvent, the same solvent as the above-mentioned organic solvent can be used, and the organic solvent can be used alone or in combination of two or more.

As the basic catalyst, the same catalyst as the above-mentioned basic catalyst can be used, and the basic catalyst may be used alone or in combination of two or more.

Examples of the acrylamide resin having an acid group and a polymerizable unsaturated bond include a phenolic hydroxyl group-containing compound, an alkylene oxide or an alkylene carbonate, an N-alkoxyalkyl (meth) acrylamide compound, and a polybasic acid anhydride. Examples thereof include those obtained by reacting with unsaturated monobasic acid, if necessary.

The 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 (2-1) to (2-4).

In the above structural formulas (2-1) to (2-4), R ¹ is any one of an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group, and a halogen atom. , R ² are independently hydrogen atoms or methyl groups. Further, p is 0 or an integer of 1 or more, preferably an integer of 0 or 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. For example, in the naphthalene ring of the structural formula (2-2), it may be substituted on any ring, and the structural formula (2-2) may be substituted. In 2-3), it may be substituted on any ring of the benzene ring existing in one molecule, and in the structural formula (2-4), on any ring of the benzene ring existing in one molecule. It is shown that it may be substituted with, and it is shown that the number of substituents in one molecule is p and q.

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 indispensable. An essential reaction between the reaction product used as the reaction raw material of the above, 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). Reaction products used as raw materials can also be used. In addition, a novolak-type phenol resin using one or more compounds having one phenolic hydroxyl group in the molecule as a reaction raw material, and one or more compounds having at least two phenolic hydroxyl groups in the molecule. A novolak type phenol resin or the like as a reaction raw material can also be used.

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

Examples of the compound having one phenolic hydroxyl group in the molecule include compounds represented by the following structural formulas (3-1) to (3-4).

In the above structural formulas (3-1) to (3-4), R ⁴ is any one of an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group, and a halogen atom. , R ⁵ are independently hydrogen atoms or methyl groups. Further, p is 0 or an integer of 1 or more, preferably an integer of 0 or 1 to 3, more preferably 0 or 1, and further preferably 0. The position of the substituent on the aromatic ring in the above structural formula is arbitrary. For example, in the naphthalene ring of the structural formula (3-2), it may be substituted on any ring, and the structural formula (3-2) may be substituted. In 3-3), it may be substituted on any ring of the benzene ring existing in one molecule, and in the structural formula (3-4), it may be substituted on any ring of the benzene ring existing in one molecule. Indicates that it may be replaced with.

As the compound having at least two phenolic hydroxyl groups in the molecule, the compounds represented by the above-mentioned structural formulas (2-1) to (2-4) can be used.

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

Examples of the alkylene oxide include ethylene oxide, propylene oxide, butylene oxide, and pentylene oxide. Among these, ethylene oxide or propylene oxide can be obtained because a curable resin composition having excellent alkali developability and high photosensitivity and capable of forming a cured product having excellent heat resistance and substrate adhesion can be obtained. Is preferable. The alkylene oxide can be used alone or in combination of two or more.

Examples of the alkylene carbonate include ethylene carbonate, propylene carbonate, butylene carbonate, pentylene carbonate and the like. Among these, ethylene carbonate or propylene carbonate can be obtained because a curable resin composition having excellent alkali developability and high photosensitivity and capable of forming a cured product having excellent heat resistance and substrate adhesion can be obtained. Is preferable. The alkylene carbonate can be used alone or in combination of two or more.

Examples of the N-alkoxyalkyl (meth) acrylamide compound include N-methoxymethyl (meth) acrylamide, N-ethoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, and N-methoxyethyl (meth) acrylamide. , N-ethoxyethyl (meth) acrylamide, N-butoxyethyl (meth) acrylamide and the like. The N-alkoxyalkyl (meth) acrylamide compound may be used alone or in combination of two or more.

As the polybasic acid anhydride, those exemplified as the above-mentioned polybasic acid anhydride (a1-2) can be used, and the polybasic acid anhydride may be used alone or in combination of two or more. You can also do it.

As the unsaturated monobasic acid, those exemplified as the above-mentioned unsaturated monobasic acid can be used, and the unsaturated monobasic acid can be used alone or in combination of two or more.

The method for producing the acrylamide resin having the acid group and the polymerizable unsaturated bond is not particularly limited, and any method may be used for producing the acrylamide resin. In the production of the acrylamide resin having an acid group and a polymerizable unsaturated bond, it may be carried out in an organic solvent if necessary, and a basic catalyst and an acidic catalyst may be used if necessary.

As the organic solvent, the same solvent as the above-mentioned organic solvent can be used, and the organic solvent can be used alone or in combination of two or more.

As the basic catalyst, the same catalyst as the above-mentioned basic catalyst can be used, and the basic catalyst may be used alone or in combination of two or more.

As the acidic catalyst, the same catalyst as the above-mentioned acidic catalyst can be used, and the acidic catalyst can be used alone or in combination of two or more.

The amount of the resin (C) having an acid group and a polymerizable unsaturated bond is preferably in the range of 10 to 900 parts by mass with respect to 100 parts by mass of the amidimide resin (A) of the present invention.

Examples of the various (meth) acrylate monomers include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, and hexyl (meth) acrylate, 2 -Alipid mono (meth) acrylate compounds such as ethylhexyl (meth) acrylate and octyl (meth) acrylate; alicyclic mono (meth) such as cyclohexyl (meth) acrylate, isobornyl (meth) acrylate and adamantyl mono (meth) acrylate. Acrylate compounds; 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. Mono (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. A (poly) oxyalkylene-modified mono (meth) acrylate compound having a polyoxyalkylene chain such as a tetramethylene chain introduced; a lactone-modified mono having a (poly) lactone structure introduced into the molecular structure of the various mono (meth) acrylate compounds. (Meta) 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, norbornandi (meth) acrylate, norbornan dimethanol di (meth) acrylate, dicyclopentanyldi (meth) acrylate, tricyclodecandy Alicyclic di (meth) acrylate compounds such as methanol di (meth) acrylate; biphenol di (meth) acrylate, bisfe Aromatic di (meth) acrylate compounds such as nourdi (meth) acrylate; (poly) oxyethylene chain, (poly) oxypropylene chain, (poly) oxytetramethylene in the molecular structure of the various di (meth) acrylate compounds. Polyoxyalkylene-modified di (meth) acrylate compound into which a (poly) oxyalkylene chain such as a chain has been introduced; a lactone-modified di (meth) having a (poly) lactone structure introduced into the molecular structure of the various di (meth) acrylate compounds. ) Acrylic compound; an aliphatic tri (meth) acrylate compound such as trimethylolpropantri (meth) acrylate and glycerin tri (meth) acrylate; a (poly) oxyethylene chain in the molecular structure of the aliphatic tri (meth) acrylate compound. , (Poly) oxyalkylene-modified tri (meth) acrylate compound introduced with (poly) oxyalkylene chain such as (poly) oxypropylene chain, (poly) oxytetramethylene chain; molecule of the aliphatic tri (meth) acrylate compound. A lactone-modified tri (meth) acrylate compound in which a (poly) lactone structure is introduced into the structure; tetrafunctional or higher such as pentaerythritol tetra (meth) acrylate, ditrimethylolpropantetra (meth) acrylate, and dipentaerythritol hexa (meth) acrylate. (Poly) such as (poly) oxyethylene chain, (poly) oxypropylene chain, (poly) oxytetramethylene chain in the molecular structure of the aliphatic poly (meth) acrylate compound. A tetrafunctional or higher (poly) oxyalkylene-modified poly (meth) acrylate compound having an oxyalkylene chain introduced; a tetrafunctional or higher 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. The various (meth) acrylate monomers may be used alone or in combination of two or more.

Since the amideimide resin composition of the present invention contains an amideimide resin (A) having a polymerizable (meth) acryloyl group in its molecular structure, for example, a curable resin composition can be obtained by adding a photopolymerization initiator. Can be used as.

As the photopolymerization initiator, an appropriate one may be selected and used depending on the type of active energy ray to be irradiated and the like. 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 1-hydroxy-cyclohexyl-phenyl-ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2- (dimethylamino). Alkylphenone-based photopolymerization initiators such as -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone; 2,4,6-trimethylbenzoyl-diphenyl- Examples thereof include an acylphosphine oxide-based photopolymerization initiator such as phosphenyl oxide; and an intramolecular hydrogen abstraction type photopolymerization initiator such as a benzophenone compound. Each of these may be used alone, or two or more types may be used in combination.

Examples of the photopolymerization initiator include 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, and 1- [4- (2-hydroxyethoxy) phenyl] -2-. Hydroxy-2-methyl-1-propane-1-one, thioxanthone and thioxanthone derivatives, 2,2'-dimethoxy-1,2-diphenylethane-1-one, diphenyl (2,4,6-trimethoxybenzoyl) phosphine Oxide, 2,4,6-trimethylbenzoyldiphenylphosphenyl oxide, bis (2,4,6-trimethylbenzoyl) phenylphosphenyl oxide, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1- On, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone and the like can be mentioned.

Examples of commercially available products of the other photopolymerization initiator 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" (Wordbrenkinsop), "Runtecure-1104" (Runtec) (Manufactured by the company), etc. These photopolymerization initiators can be used alone or in combination of two or more.

The amount of the photopolymerization initiator added is preferably in the range of 0.05 to 15% by mass, preferably in the range of 0.1 to 10% by mass, based on, for example, the total amount of the components other than the solvent in the curable resin composition. Is more preferable.

Further, the curable resin composition of the present invention contains, if necessary, a curing agent, a curing accelerator, an organic solvent, inorganic fine particles and polymer fine particles, pigments, defoaming agents, viscosity modifiers, leveling agents, flame retardants, etc. It can also contain various additives such as a storage stabilizer.

Examples of the curing agent include epoxy resins. 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, and cresol novolac type epoxy resin. Bisphenol novolac type epoxy resin, naphthol novolac type epoxy resin, naphthol-phenol co-shrink novolak type epoxy resin, naphthol-cresol co-shrink novolak type epoxy resin, phenol aralkyl type epoxy resin, naphthol aralkyl type epoxy resin, dicyclopentadiene-phenol addition Examples thereof include a reactive epoxy resin, a biphenyl aralkyl type epoxy resin, a fluorene type epoxy resin, a xanthene type epoxy resin, a dihydroxybenzene type epoxy resin, and a trihydroxybenzene type epoxy resin. These epoxy resins can be used alone or in combination of two or more. Among these, phenol novolac type epoxy resin, cresol novolac type epoxy resin, and cresol novolac type epoxy resin, because a cured product having excellent alkali developability and high light sensitivity, and excellent heat resistance and substrate adhesion can be obtained. Novolac type epoxy resins such as bisphenol novolac type epoxy resin, naphthol novolac type epoxy resin, naphthol-phenol co-shrink novolak type epoxy resin, and naphthol-cresol co-shrink novolak type epoxy resin are preferable, and the softening point is in the range of 20 to 120 ° C. Some are particularly preferred.

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, an amine compound, an imidazole, an organic acid metal salt, a Lewis acid, etc. Examples include amine complex salts. These curing accelerators can be used alone or in combination of two or more. The amount of the curing accelerator added is preferably in the range of 1 to 10 parts by mass with respect to 100 parts by mass of the curing agent, for example.

As the organic solvent, the same solvent as the above-mentioned organic solvent can be used, and the organic solvent can be used alone or in combination of two or more.

The cured product of the present invention can be obtained by irradiating the curable resin composition with active energy rays. Examples of the active energy ray include ionizing radiation such as ultraviolet rays, electron beams, α rays, β rays, and γ rays. When ultraviolet rays are used as the active energy rays, they may be irradiated in an atmosphere of an inert gas such as nitrogen gas or in an air atmosphere in order to efficiently carry out the curing reaction by ultraviolet rays.

As the ultraviolet source, an ultraviolet lamp is generally used from the viewpoint of practicality and economy. Specific examples thereof include low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, xenon lamps, gallium lamps, metal halide lamps, sunlight, and LEDs.

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 in the above range, it is preferable because the generation of the uncured portion can be prevented or suppressed.

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

Further, since the cured product of the present invention has excellent alkali developability and high light sensitivity, and has excellent heat resistance and substrate adhesion, for example, a solder resist, an interlayer insulating material, etc. in semiconductor device applications. It can be suitably used as a package adhesive layer for a package material, an underfill material, a circuit element, etc., or as an adhesive layer between an integrated circuit element and a circuit board. Further, it can be suitably used as a thin film transistor protective film, a liquid crystal color filter protective film, a pigment resist for a color filter, a resist for a black matrix, a spacer and the like in thin display applications typified by LCD and OELD. Among these, it can be particularly preferably used for solder resist applications.

The resin material for solder resist of the present invention comprises the curable resin composition.

The resist member of the present invention is, for example, a photomask in which the resin material for solder resist is applied onto a substrate, an organic solvent is volatile-dried in a temperature range of about 60 to 100 ° C., and then a desired pattern is formed. It can be obtained by exposing the unexposed portion with an active energy ray, developing the unexposed portion with an alkaline aqueous solution, and further heating and curing 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 values of the amidimide resin and the acid group-containing acrylate resin were measured by the neutralization titration method of JIS K 0070 (1992).

In the examples of the present application, the molecular weights of the amidimide resin and the acid group-containing acrylate resin were measured by GPC under the following conditions.

Measuring device: "HLC-8220 GPC" manufactured by Tosoh Corporation,
Column: Guard column "HXL-L" manufactured by Tosoh Corporation
+ "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 velocity 1.0 ml / min Standard: The following monodisperse polystyrene with a known molecular weight was used in accordance with the measurement manual of "GPC-8020 Model II Version 4.10".
(Polystyrene used)
"A-500" manufactured by Tosoh Corporation
"A-1000" manufactured by Tosoh Corporation
"A-2500" manufactured by Tosoh Corporation
"A-5000" manufactured by Tosoh Corporation
"F-1" manufactured by Tosoh Corporation
"F-2" manufactured by Tosoh Corporation
"F-4" manufactured by Tosoh Corporation
"F-10" manufactured by Tosoh Corporation
"F-20" manufactured by Tosoh Corporation
"F-40" manufactured by Tosoh Corporation
"F-80" manufactured by Tosoh Corporation
"F-128" manufactured by Tosoh Corporation
Sample: A solution obtained by filtering 1.0% by mass of a tetrahydrofuran solution in terms of resin solid content with a microfilter (50 μl).

(Synthesis Example 1: Production of Amidoimide Resin (A-1))
In 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 Co., Ltd., isocyanate group content 17. 2% by mass) (hereinafter, abbreviated as "T-1890") 244 parts by mass, 192 parts by mass of trimellitic anhydride, and 1.0 part 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. The solid acid value measured under the acid anhydride group non-ring-opening condition was 160 mgKOH / g. 0.3 parts by mass of methquinone, pentaerythritol polyacrylate mixture (“Aronix M-306” manufactured by Toa Synthetic Co., Ltd., pentaerythritol triacrylate content: about 67%, hydroxyl value: 159.7 mgKOH / g) (hereinafter, “M-306” 172 parts by mass and 3.6 parts by mass of triphenylphosphine were added, and the mixture was reacted at 110 ° C. for 5 hours while blowing air. Then, 163 parts by mass of glycidyl methacrylate was added and reacted at 110 ° C. for 5 hours. Further, 112 parts by mass of succinic anhydride and 122 parts by mass of diethylene glycol monomethyl ether acetate were added and reacted at 110 ° C. for 5 hours, and an amideimide resin having an acid group having a solid content of 62.1% by mass and a polymerizable unsaturated group (A). -1) was obtained. The solid acid value of the amidimide resin (A-1) was 79 mgKOH / g, and the weight average molecular weight was 3790.

(Synthesis Example 2: Production of Amidoimide Resin (A-2))
In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 355.0 parts by mass of diethylene glycol monomethyl ether acetate, 188.0 parts by mass of "T-1890" and cyclohexane-1,3,4-tricarboxylic acid-3, 160.8 parts by mass of 4-anhydride and 1.6 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. The solid acid value measured under the acid anhydride group non-ring-opening condition was 156 mgKOH / g. 0.3 parts by mass of methquinone, 39.9 parts by mass of "M-306" and 3.2 parts by mass of triphenylphosphine were added, and the mixture was reacted at 110 ° C. for 5 hours while blowing air. Then, 154.0 parts by mass of glycidyl methacrylate was added, and the mixture was reacted at 110 ° C. for 10 hours. Further, 136.3 parts by mass of tetrahydrophthalic anhydride was added and reacted at 110 ° C. for 5 hours to obtain an amidoimide resin (A-2) having an acid group having a solid content of 64.5% by mass and a polymerizable unsaturated group. It was. The solid acid value of the amidimide resin (A-2) was 80 mgKOH / g, and the weight average molecular weight was 4020.

(Synthesis Example 3: Production of Amidoimide Resin (A-3))
Diethylene glycol monomethyl ether acetate 374.4 parts by mass, "T-1890" 172.1 parts by mass, trimellitic anhydride 135.2 parts by mass, dibutylhydroxytoluene 1 in a flask equipped with a thermometer, a stirrer, and a reflux condenser. .6 parts 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. The solid acid value measured under the acid anhydride group non-ring-opening condition was 162 mgKOH / g. 0.3 parts by mass of methquinone, 104.0 parts by mass of "M-306" and 3.1 parts by mass of triphenylphosphine were added, and the mixture was reacted at 110 ° C. for 5 hours while blowing air. Then, 166.4 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, 78.8 parts by mass of succinic anhydride was added and reacted at 110 ° C. for 5 hours to obtain an amidoimide resin (A-3) having an acid group having a solid content of 62.4% by mass and a polymerizable unsaturated group. .. The solid acid value of the amidimide resin (A-3) was 74 mgKOH / g, and the weight average molecular weight was 4040.

(Synthesis Example 4: Production of Amidoimide Resin (A-4))
1103 parts by mass of diethylene glycol monomethyl ether acetate, 198 parts by mass of "T-1890" and 507 parts by mass of cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride in a flask equipped with a thermometer, a stirrer, and a reflux condenser. Added a part. The temperature was raised to 140 ° C. over 2 hours, and the reaction was carried out at the same temperature for another 2 hours. In the infrared spectrum, it was confirmed that the absorption of 2270 cm ^-1 , which is the characteristic absorption of the isocyanate group, was completely eliminated. Then, 198 parts by mass of "T-1890" was added to continue the reaction, and it was confirmed in the infrared spectrum that the absorption of 2270 cm ^-1 , which is the characteristic absorption of the isocyanate group, was completely eliminated. Further, 198 parts by mass of "T-1890" was added to continue the reaction, and the absorption of 2270 cm-1 which was the characteristic absorption of the isocyanate group disappeared completely in the infrared spectrum, and the imide was set to 1780 cm ^-1 and 1720 cm ^-1 . The characteristic absorption of the group was confirmed. The solid acid value measured under the acid anhydride group non-ring-opening condition was 190 mgKOH / g. Then, 189 parts by mass of "M-306", 3.8 parts by mass of triphenylphosphine, and 0.6 parts by mass of methquinone were added, and the mixture was reacted at 120 ° C. for 7 hours. It was confirmed in the infrared spectrum that the absorption of 1860 cm ^-1 , which is the characteristic absorption of the acid anhydride group, was completely eliminated, and the amideimide resin having an acid group having a solid content of 51.7% by mass and a polymerizable unsaturated group. (A-4) was obtained. The solid acid value of this amidoimide (A-4) was 140 mgKOH / g, and the weight average molecular weight was 3550.

(Synthesis Example 5: Production of Amidoimide Resin (A-5))
In a flask equipped with a thermometer, a stirrer, and a reflux cooler, 377.5 parts by mass of diethylene glycol monomethyl ether acetate, isocyanurate modified product of 1,3-bis (isocyanatomethyl) cyclohexane (Mitsui Chemicals Co., Ltd. "Takenate D" -127N ”, isocyanate group content 13.8% by mass, solid content 75.5% by mass) 304.0 parts by mass, trimellitic anhydride 192.0 parts by mass, dibutylhydroxytoluene 0.9 parts by mass are added and dissolved. I let you. 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. The solid acid value measured under the acid anhydride group non-ring-opening condition was 125 mgKOH / g. 0.2 parts by mass of methquinone, 94.7 parts by mass of "M-306" and 1.4 parts by mass of triphenylphosphine were added, and the mixture was reacted at 110 ° C. for 5 hours while blowing air. Then. 136.0 parts by mass of glycidyl methacrylate was added and reacted at 110 ° C. for 7 hours. Further, 91.0 parts by mass of succinic anhydride was added and reacted at 110 ° C. for 5 hours to obtain an amidoimide resin (A-5) having an acid group having a solid content of 64.7% by mass and a polymerizable unsaturated group. .. The solid acid value of this amidimide resin (A-5) was 76 mgKOH / g, and the weight average molecular weight was 2050.

(Synthesis Example 6: Production of Amidoimide Resin (A-6))
Dissolve 276 parts by mass of diethylene glycol monomethyl ether acetate, 214 parts by mass of isophorone diisocyanate, 277 parts by mass of trimellitic anhydride, and 1.9 parts by mass of dibutylhydroxytoluene in a flask equipped with a thermometer, a stirrer, and a reflux condenser. I let you. 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. The solid acid value measured under the acid anhydride group non-ring-opening condition was 134 mgKOH / g. 0.4 parts by mass of methquinone, 85 parts by mass of "M-306" and 3.9 parts by mass of triphenylphosphine were added, and the mixture was reacted at 110 ° C. for 5 hours while blowing air. Then, 138 parts by mass of glycidyl methacrylate was added and reacted at 110 ° C. for 5 hours. Further, 94 parts by mass of succinic anhydride and 162 parts by mass of diethylene glycol monomethyl ether acetate were added and reacted at 110 ° C. for 5 hours to form an amidimide resin having an acid group having a solid content of 62.5% by mass and a polymerizable unsaturated group (A). -6) was obtained. The solid content acid value of this amidoimide resin (A-6) was 75 mgKOH / g, and the weight average molecular weight was 1750.

(Synthesis Example 7: Production of Amidoimide Resin (A-7))
To a flask equipped with a thermometer, a stirrer, and a reflux condenser, 100 parts by mass of the amidimide resin (A-4) obtained in Synthesis Example 4 and 5.2 parts by mass of glycidyl methacrylate were added, and the temperature was 110 ° C. for 5 hours. The reaction was carried out to obtain an amidoimide resin (A-7) having an acid group having a solid content of 54.1% by mass and a polymerizable unsaturated group. The solid acid value of the amidimide resin (A-7) was 98 mgKOH / g, and the weight average molecular weight was 3670.

(Synthesis Example 8: Production of Amidoimide Resin (A-8))
In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 468 parts by mass of dimethylacetamide and 174 parts by mass of toluenediisocyanate (“Coronate T-100” manufactured by Toso Co., Ltd.) Cyclohexane-1,3,4-tricarboxylic acid- 297 parts by mass of 3,4-anhydrous and 1.0 part 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. The solid acid value measured under the acid anhydride group non-ring-opening condition was 189 mgKOH / g. 0.3 parts by mass of methquinone, 107 parts by mass of "M-306" and 3.4 parts by mass of triphenylphosphine were added, and the mixture was reacted at 110 ° C. for 5 hours while blowing air. Then, 184 parts by mass of glycidyl methacrylate was added and reacted at 110 ° C. for 5 hours. Further, 123 parts by mass of succinic anhydride was added and reacted at 110 ° C. for 5 hours to obtain an amidoimide resin (A-8) having an acid group having a solid content of 62.8% by mass and a polymerizable unsaturated group. The solid content acid value of this amidoimide resin (A-8) was 90 mgKOH / g, and the weight average molecular weight was 2080.

(Synthesis Example 9: Production of Amidoimide Resin (A-9))
In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 300.2 parts by mass of diethylene glycol monomethyl ether acetate, a nulate modified product of hexamethylene diisocyanate (“Barnock DN901S” manufactured by DIC Co., Ltd., isocyanate group content 23.5). (% by Mass) 197.9 parts by mass, 219.7 parts by mass of trimellitic anhydride, and 1.8 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. The solid acid value measured under the acid anhydride group non-ring-opening condition was 187 mgKOH / g. 0.4 parts by mass of methquinone, "M-306", 11.9 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. Then, 221.7 parts by mass of glycidyl methacrylate was added and reacted at 120 ° C. for 10 hours. Further, 97.3 parts by mass of succinic anhydride was added and reacted at 110 ° C. for 5 hours to obtain an amidoimide resin (A-9) having an acid group having a solid content of 70.0% by mass and a polymerizable unsaturated group. .. The solid acid value of the amidimide resin (A-9) was 80 mgKOH / g, and the weight average molecular weight was 4350.

(Synthesis Example 10: Production of Amidoimide Resin (B-1))
Propylene glycol monomethyl ether acetate 1086 parts by mass, "T-1890" 587.3 parts by mass and cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride 499 in a flask equipped with a stirrer, a thermometer and a condenser. .1 part by mass was added and the temperature was raised to 140 ° C. The reaction proceeded with foaming. The reaction was carried out at this temperature for 8 hours. Results The characteristic absorption was measured by the infrared spectrum, 2270 cm ^-1 which is the characteristic absorption of an isocyanate group was disappeared ^completely, 1780 cm -1, from the absorption of the imide group in 1720 cm ^-1 was confirmed, the solid content 47.4% by mass of amidoimide resin (B-1) was obtained. The solid content acid value of this amideimide resin (B-1) was 212 mgKOH / g, and the concentration of the acid anhydride group was 1.14 mmol / g in terms of solid content.

(Synthesis Example 11: Production of Amidoimide Resin (B-2))
To the amidoimide resin (B-1) obtained in Synthesis Example 1, 96.3 parts by mass of n-butanol was added, and the mixture was reacted at 120 ° C. for 2 hours. As a result of measuring the characteristic absorption by the infrared spectrum, it was confirmed that the mass absorption of 1860 cm ^-1 , which is the characteristic absorption of the acid anhydride group, was completely eliminated, and the amideimide resin (B) having a solid content of 49.2% by mass was confirmed. -2) was obtained. The solid acid value of this amidimide resin (B-2) was 148 mgKOH / g, and the weight average molecular weight was 4800.

(Synthesis Example 12: Production of Amidoimide Resin (B-3))
4628 parts by mass of diethylene glycol monomethyl ether acetate, 2070 parts by mass of "T-1890" and 1386 parts by mass of cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride in a flask equipped with a stirrer, a thermometer and a condenser. In addition, the temperature was raised to 140 ° C. The reaction proceeded with foaming. The reaction was carried out at this temperature for 8 hours. As a result of measuring the characteristic absorption in the infrared spectrum, the characteristic absorption of the isocyanate group of 2270 cm ^-1 was completely eliminated, and the absorption of the imide group was confirmed at 1780 cm ^-1 and 1720 cm ^{-1, so} that the imide group was intermediate. Obtained body (1). The solid content acid value of this amidoimide resin intermediate (1) was 140 mgKOH / g, the concentration of the acid anhydride group was 0.75 mmol / g in terms of solid content, and the solid content was 40.0% by mass. Then, 326 parts by mass of 2-ethylhexanol was added, and the mixture was reacted at 120 ° C. for 2 hours. As a result of measuring the characteristic absorption by the infrared spectrum, it was confirmed that the absorption of 1860 cm ^-1 , which is the characteristic absorption of the acid anhydride group, was completely eliminated, and the amideimide resin (B-) having a solid content of 40.9% by mass was confirmed. 3) was obtained. The solid acid value of this amidoimide resin (B-3) was 98 mgKOH / g, and the weight average molecular weight was 6000.

(Synthesis Example 13: Production of Amidoimide Resin (B-4))
To the amidimide resin (B-1) obtained in Synthesis Example 1, 153.7 parts by mass of butyl cellosolve was added, and the mixture was reacted at 120 ° C. for 2 hours. As a result of measuring the characteristic absorption by the infrared spectrum, it was confirmed that the mass absorption of 1860 cm ^-1 , which is the characteristic absorption of the acid anhydride group, was completely eliminated, and the amideimide resin (B) having a solid content of 50.2% by mass was confirmed. -4) was obtained. The solid acid value of this amidoimide resin (B-4) was 145 mgKOH / g, and the weight average molecular weight was 4900.

(Synthesis Example 14: Production of Amidoimide Resin (B-5))
1569 parts by mass of propylene glycol monomethyl ether acetate, 959 parts by mass of "T-1890" and 791 parts by mass of trimellitic anhydride were added to a flask equipped with a stirrer, a thermometer and a condenser, and the temperature was raised to 140 ° C. The reaction proceeded with foaming. The reaction was carried out at this temperature for 8 hours. As a result of measuring the characteristic absorption by the infrared spectrum, the characteristic absorption of the isocyanate group of 2270 cm ^-1 was completely eliminated, and the absorption of the imide group was confirmed at 1780 cm ^-1 and 1720 cm ^{-1, so} that the imide group was intermediate. Obtained body (2). The solid content acid value of this amidoimide resin intermediate (2) was 185 mgKOH / g, the concentration of the acid anhydride group was 0.57 mmol / g in terms of solid content, and the solid content was 50.2% by weight. Then, 79.9 parts by mass of n-butanol was added, and the mixture was reacted at 120 ° C. for 5 hours. As a result of measuring the characteristic absorption by the infrared spectrum, it was confirmed that the absorption of 1860 cm ^-1 , which is the characteristic absorption of the acid anhydride group, was completely eliminated, and the amideimide resin (B-) having a solid content of 51.1% by mass was confirmed. 5) was obtained. The solid content acid value of this amidoimide resin (B-5) was 153 mgKOH / g, and the weight average molecular weight was 5800.

(Synthesis Example 15: Production of Acid Group-Containing Acrylate Resin (1))
101 parts by mass of diethylene glycol monomethyl ether acetate was placed in a flask equipped with a thermometer, a stirrer, and a reflux cooler, and an orthocresol novolac type epoxy resin (“EPICLON N-680” manufactured by DIC Co., Ltd., epoxy equivalent: 214) 428. After dissolving 4 parts by mass of dibutylhydroxytoluene as an antioxidant and 0.4 parts by mass of methquinone as a thermal polymerization inhibitor, 144 parts by mass of acrylic acid and 1.6 parts by mass of triphenylphosphine were added. The esterification reaction was carried out at 120 ° C. for 10 hours while blowing air. Then, 311 parts by mass of diethylene glycol monomethyl ether acetate and 160 parts by mass of tetrahydrophthalic anhydride were added and reacted at 110 ° C. for 2.5 hours to obtain an acid group-containing acrylate resin (1) having a solid content of 64.0% by mass. .. The solid acid value of the acid group-containing acrylate resin (1) was 85 mgKOH / g.

(Example 1: Preparation of curable resin composition (1))
The amideimide resin (A-1) obtained in Synthesis Example 1 and the amideimide resin (B-1) obtained in Synthesis Example 10 were mixed to obtain an amideimide resin composition (1). Next, as a curing agent, orthocresol novolac type epoxy resin (“EPICLON N-680” manufactured by DIC Co., Ltd.), dipentaerythritol hexaacrylate, diethylene glycol monoethyl ether acetate, and a photopolymerization initiator (“Omnirad 907” manufactured by IGM Co., Ltd.) ”), 2-Ethyl-4-methylimidazole, and phthalocyanine green were blended in parts by mass shown in Table 1 and kneaded with a roll mill to obtain a curable resin composition (1).

(Examples 2 to 21: Preparation of curable resin compositions (2) to (21))
Curable resin compositions (2) to (21) were obtained in the same manner as in Example 1 with the compositions and formulations shown in Tables 1 and 2.

(Comparative Example 1: Preparation of curable resin compositions (C1) to (C4))
Curable resin compositions (C1) to (C4) were obtained in the same manner as in Example 1 with the compositions and formulations shown in Tables 1 and 2.

The following evaluations were carried out using the curable resin compositions (2) to (21) and (C1) to (C4) obtained in the above Examples and Comparative Examples.

[Evaluation method of light sensitivity]
The curable resin compositions obtained in each Example and Comparative Example were applied to a glass substrate using an applicator so as to have a film thickness of 50 μm, and then dried at 80 ° C. for 30 minutes. Next, Kodak's step tablet No. Ultraviolet rays of 1000 mJ / cm ² were irradiated through ² using a metal halide lamp. This was developed with a 1% by mass aqueous sodium carbonate solution for 180 seconds and evaluated by the number of remaining stages. The larger the number of remaining stages, the higher the light sensitivity.

[Evaluation method of alkali developability]
The curable resin compositions obtained in each Example and Comparative Example were applied to a glass substrate using an applicator so as to have a film thickness of 50 μm, and then at 80 ° C. for 30 minutes, 40 minutes, and 50 minutes, respectively. The samples were dried for 60 minutes, 70 minutes, 80 minutes, 90 minutes, 100 minutes, and 110 minutes to prepare samples having different drying times. These were developed with a 1% aqueous sodium carbonate solution at 30 ° C. for 180 seconds, and the drying time at 80 ° C. of the sample in which no residue remained on the substrate was evaluated as the drying control range. It should be noted that the longer the drying control range, the better the alkali developability.

Table 1 shows the compositions and evaluation results of the curable resin compositions (1) to (21) prepared in Examples 1 to 21 and the curable resin compositions (C1) to (C4) prepared in Comparative Examples 1 to 4. And 2.

(Example 22: Preparation of curable resin composition (22))
The amideimide resin (A-1) obtained in Synthesis Example 1 and the amideimide resin (B-1) obtained in Synthesis Example 10 were mixed to obtain an amideimide resin composition (1). Next, an orthocresol novolac type epoxy resin (“EPICLON N-680” manufactured by DIC Co., Ltd.) was used as a curing agent, and 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1- was used as a photopolymerization initiator. On (“Omnirad-907” manufactured by IGM), diethylene glycol monomethyl ether acetate as an organic solvent was blended in parts by mass shown in Table 2 to obtain a curable resin composition (22).

(Examples 23 to 42: Preparation of curable resin compositions (23) to (42))
Curable resin compositions (23) to (42) were obtained in the same manner as in Example 22 with the compositions and formulations shown in Tables 3 and 4.

(Comparative Examples 5 to 8: Preparation of curable resin compositions (C5) to (C8))
Curable resin compositions (C5) to (C8) were obtained in the same manner as in Example 22 with the compositions and formulations shown in Tables 3 and 4.

The following evaluations were carried out using the curable resin compositions (22) to (42) and (C5) to (C8) obtained in the above Examples and Comparative Examples.

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

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 Leometric Co., Ltd., tensile method: frequency 1 Hz, temperature rise rate 3 ° C./min) was used. The temperature at which the change in viscoelasticity was maximum (the rate of change in tan δ was the largest) was evaluated as the glass transition temperature (Tg).

[Evaluation method of substrate adhesion]
The substrate adhesion was evaluated by measuring the peel strength.

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

Table 2 shows the compositions and evaluation results of the curable resin compositions (22) to (42) prepared in Examples 22 to 42 and the curable resin compositions (C5) to (C8) prepared in Comparative Examples 5 to 8. Shown in.

The amounts of the amidimide resins (A-1) to (A-9), (B-1) to (B-5), and the acid group-containing acrylate resin (1) in Tables 1 to 4 are the solid content. The value.

The "curing agent" in Tables 1 to 4 indicates an orthocresol novolac type epoxy resin ("EPICLON N-680" manufactured by DIC Corporation, epoxy equivalent: 214).

“Organic solvent” in Tables 1 to 4 represents diethylene glycol monomethyl ether acetate.

“Photopolymerization initiator” in Tables 1 to 4 indicates “Omnirad-907” manufactured by IGM.

Examples 1 to 42 shown in Tables 1 to 4 are examples of a curable resin composition using the amideimide resin composition of the present invention. It was confirmed that this curable resin composition has excellent photosensitivity and alkali developability, and also has excellent heat resistance and substrate adhesion in the cured product.

On the other hand, Comparative Examples 1, 2, 4, 5, 6 and 8 are examples of a curable resin composition having no amidoimide resin (A) having an acid group and a polymerizable unsaturated group specified in the present invention. .. It was confirmed that this curable resin composition could not have the performances of light sensitivity, alkali developability, heat resistance, and substrate adhesion.

Comparative Examples 3 and 7 are examples of curable resin compositions having no amideimide resin (B) other than the amideimide resin (A) defined in the present invention. It was confirmed that this curable resin composition could not have the performances of light sensitivity, alkali developability, heat resistance, and substrate adhesion.

Claims (14)

Amidimide resin (A) having an acid group and a polymerizable unsaturated group,
An amideimide resin composition containing an amideimide resin (B) other than the amideimide resin (A).
The amidimide resin (A)
An amideimide resin composition comprising an amideimide resin (a1) having an acid group and / or an acid anhydride group and a hydroxyl group-containing (meth) acrylate compound (a2) as essential reaction raw materials. The amidimide resin (B) uses a polyisocyanate compound (b1) and a polybasic acid anhydride (b2) as essential reaction raw materials.
The amideimide resin composition according to claim 1, wherein the amideimide resin (a1) contains a polyisocyanate compound (a1-1) and a polybasic acid anhydride (a1-2) as essential reaction raw materials. The amidimide resin composition according to claim 2, wherein at least one of the polyisocyanate compound (b1) and the polyisocyanate compound (a1-1) is an alicyclic polyisocyanate compound. The amide imide resin according to claim 1, wherein the mass ratio [(A) / (B)] of the solid content between the amide imide resin (A) and the amide imide resin (B) is in the range of 50/50 to 95/5. Composition. The amide imide resin composition according to claim 1, wherein the amide imide resin (A) further contains an epoxy group-containing (meth) acrylate compound (a3) as a reaction raw material. The amide imide resin composition according to claim 5, wherein the amide imide resin (A) further contains a polybasic acid anhydride (a4) as a reaction raw material. The amide imide resin composition according to claim 2, wherein the amide imide resin (B) further contains an alcohol compound (b3) as a reaction raw material. The amideimide resin composition according to claim 1, further comprising a resin (C) having an acid group other than the amideimide resin (A) and the amideimide resin (B) and a polymerizable unsaturated bond. A curable resin composition containing the amidimide resin composition according to any one of claims 1 to 8 and a photopolymerization initiator. The curable resin composition according to claim 9, further comprising an organic solvent and a curing agent. A cured product according to claim 9 or 10, which is a cured reaction product of the curable resin composition. An insulating material comprising the curable resin composition according to claim 9 or 10. A resin material for a solder resist, which comprises the curable resin composition according to claim 9 or 10. A resist member comprising the resin material for solder resist according to claim 13.