JP2023156041A - Resin having acid group and polymerizable unsaturated group, curable resin composition, cured product, insulation material and resist member - Google Patents

Abstract

To provide a resin having excellent alkali developability and having excellent heat resistance and high elastic modulus in a cured product, a curable resin composition, a cured product of the curable resin composition, an insulation material, and a resist member.SOLUTION: There is provided a resin having an acid group and a polymerizable unsaturated group which contains a phenolic resin having at least two catechol skeletons and an epoxy resin (A) containing a glycidyl ether group-containing compound obtained by reacting epihalohydrin, an unsaturated monobasic acid (B) and a polybasic acid anhydride (C) as essential reaction raw materials.SELECTED DRAWING: Figure 1

Description

The present invention relates to a resin having an acid group and a polymerizable unsaturated group, a curable resin composition, a cured product, an insulating material, and a resist member.

In recent years, curable compositions such as active energy ray-curable compositions that can be cured by active energy rays such as ultraviolet rays and thermosetting compositions that can be cured by heat have been used for inks, paints, coatings, adhesives, optical Widely used in the field of components, etc. Among these, the coating agent is generally used because it can impart design properties to the surface of various substrates, has excellent curability, and can form a coating film that can prevent deterioration of the substrate surface. is required. Furthermore, in recent years, there has been a demand from industry for materials that can form cured coatings that have not only curability but also high elastic modulus, heat resistance, photosensitivity, and alkali developability.

Conventional curable compositions for solder resists include acid groups and polymerization obtained by further reacting tetrahydrophthalic anhydride with an intermediate obtained by reacting a cresol novolac type epoxy resin, acrylic acid, and phthalic anhydride. Although photosensitive resin compositions containing resins having sexually unsaturated groups are known (for example, see Patent Document 1), they do not satisfy the increasingly required properties in terms of elastic modulus and heat resistance, and It was not sufficient to meet recent market demands.

Therefore, there has been a need for a material that can form a cured product that has excellent alkali developability, excellent heat resistance, and high elastic modulus.

Japanese Patent Application Publication No. 8-259663

The problem to be solved by the present invention is a resin having an acid group and a polymerizable unsaturated group, which has excellent alkali developability, and has excellent heat resistance and high elastic modulus in a cured product, a curable resin composition, The present invention provides a cured product of the curable resin composition, an insulating material, and a resist member.

As a result of intensive studies to solve the above problems, the present inventors have discovered that an acid group and a polymerizable material using a specific epoxy resin, an unsaturated monobasic acid, and a polybasic acid anhydride as essential reaction raw materials. The inventors have discovered that the above problems can be solved by using a resin having an unsaturated group, and have completed the present invention.

That is, the present invention provides a phenol resin having at least two catechol skeletons derived from a catechol compound, an epoxy resin (A) containing a glycidyl ether group-containing compound obtained by reacting epihalohydrin, and an unsaturated monobasic acid ( B) and a polybasic acid anhydride (C) as essential reaction raw materials, a resin having an acid group and a polymerizable unsaturated group, a curable resin composition containing the same, and a curable resin composition containing the same; The present invention relates to a cured product made of a resin composition, an insulating material, and a resist member.

More specifically, aspect 1 of the present invention comprises a phenol resin having at least two catechol skeletons derived from a catechol compound, and an epoxy resin (A) containing a glycidyl ether group-containing compound obtained by reacting epihalohydrin. , relates to a resin having an acid group and a polymerizable unsaturated group, characterized in that an unsaturated monobasic acid (B) and a polybasic acid anhydride (C) are used as essential reaction raw materials.

Aspect 2 of the present invention relates to a resin having an acid group and a polymerizable unsaturated group according to Aspect 1, wherein the phenol resin according to Aspect 1 is a reaction product of a catechol compound and a ketone group-containing compound.

Aspect 3 of the present invention is such that the amount of unsaturated monobasic acid (B) used is the number of moles of acid groups possessed by the unsaturated monobasic acid (B) per mole of epoxy groups possessed by the epoxy resin (A). The present invention relates to a resin having an acid group and a polymerizable unsaturated group according to aspect 1 or aspect 2, wherein the amount is in a range of 0.9 to 1.1 mol.

Aspect 4 of the present invention is Aspect 1 to 1, wherein the amount of polybasic acid anhydride (C) used is in the range of 0.2 to 1.05 mol per mol of epoxy group possessed by the epoxy resin (A). The present invention relates to a resin having an acid group and a polymerizable unsaturated group according to any one of Aspect 3.

Aspect 5 of the present invention relates to a curable resin composition comprising a resin having an acid group and a polymerizable unsaturated group according to any one of Aspects 1 to 4, and a photopolymerization initiator. .

Aspect 6 of the present invention is a curable resin according to aspect 5, which further contains a resin (D) having an acid group and a polymerizable unsaturated group other than the resin having an acid group and a polymerizable unsaturated group. The present invention relates to a resin composition.

Aspect 7 of the present invention relates to a cured product of the curable resin composition according to aspect 5 or 6.

Aspect 8 of the present invention relates to an insulating material characterized by being made of the cured product according to aspect 7.

Aspect 9 of the present invention relates to a resist member characterized by being made of the cured product according to aspect 7.

The resin having an acid group and a polymerizable unsaturated group of the present invention is an alkali-soluble resin having excellent alkali developability, and has excellent heat resistance and high elastic modulus in a cured product. A curable resin composition containing an initiator can be used as a coating agent or an adhesive, and particularly as a coating agent, it can be suitably used particularly for solder resist applications.

FIG. 2 is a GPC chart of the phenol resin obtained in Synthesis Example 1. FIG. 3 is a GPC chart of an epoxy resin obtained in Synthesis Example 7.

The resin having an acid group and a polymerizable unsaturated group of the present invention is a phenol resin having at least two catechol skeletons derived from a catechol compound, and an epoxy resin containing a glycidyl ether group-containing compound obtained by reacting epihalohydrin. A), an unsaturated monobasic acid (B), and a polybasic acid anhydride (C) are used as essential reaction materials.

In the present invention, "(meth)acrylate" means acrylate and/or methacrylate. Moreover, "(meth)acryloyl" means acryloyl and/or methacryloyl. Furthermore, "(meth)acrylic" means acrylic and/or methacrylic.

[Phenol resin]
The phenol resin used for the epoxy resin (A) is characterized by having at least two catechol skeletons derived from a catechol compound.
The phenol resin is a reaction product of a catechol compound and a ketone group-containing compound, and has a catechol skeleton derived from the catechol compound (having two hydroxyl groups as substituents on the aromatic ring, and the two hydroxyl groups are in an ortho positional relationship with each other). It is preferable that at least two (2) or more of these are included as independent ring structures to make the resin polyfunctional, so that the obtained cured product exhibits high heat resistance. It should be noted that the phenolic resin has at least two catechol skeletons, and may have three or more, but it is particularly preferable to have two catechol skeletons, since this results in a low melt viscosity.

In addition, the said "phenol resin" in this invention refers to the resin containing a phenolic hydroxyl group, and the said "epoxy resin" refers to the resin containing the said glycidyl ether group. In addition, the above-mentioned "catechol skeleton" refers to a skeleton that "has two hydroxyl groups as substituents on an aromatic ring, and the two hydroxyl groups are in an ortho positional relationship with each other," or a hydrogen atom constituting the hydroxyl group. Refers to the removed skeleton.

[Catechol compound]
The phenol resin is characterized in that it is a reaction product of a catechol compound and a ketone group-containing compound. The catechol compound is dihydroxybenzene having a hydroxyl group at the 1st and 2nd positions, and may have a substituent on the aromatic ring of the catechol compound, but one without a substituent (catechol) It is particularly preferable from the viewpoint of bending properties. By using the catechol compound, the phenol resin will include a catechol skeleton, and it is assumed that the intermolecular density will increase due to the π-π interaction between molecules based on the aromatic ring, and the mechanical strength and heat resistance will increase. This method is preferable because a cured product with excellent properties can be obtained.

The substituent may be a hydrocarbon group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a halogen atom, and the substituent may be an alkyl group such as a methyl group. The positions of the substituents and the number thereof are not particularly limited. In addition, if the number of carbon atoms in the hydrocarbon group exceeds 4, steric hindrance becomes too large, and the reactivity becomes too low during the synthesis of the phenol resin or the epoxy resin described below, or the obtained cured product This is not preferable because the mechanical strength of the material decreases.

The catechol compound may be used alone, or a plurality of compounds having different substituent positions may be used in combination.

[Ketone group-containing compound]
As described above, the phenol resin is characterized by being a reaction product of a catechol compound and a ketone group-containing compound. In the phenol resin, the catechol compound and the ketone group-containing compound (for example, represented by RC(=O)-R', where R is a hydrocarbon group, and R' is a hydrocarbon group or By introducing a skeleton based on a reaction with a hydrogen atom (for example, -C(-R)(-R')-), intermolecular interactions are moderately weakened, resulting in a low melt viscosity. This is preferable because it becomes a phenolic resin with excellent handling properties. Further, the obtained cured product has an excellent balance of heat resistance and mechanical strength, which is useful. As the ketone group-containing compound, it is preferable to use an aliphatic ketone or a formyl group-containing aromatic compound.

Examples of the aliphatic ketones include acetone, methyl ethyl ketone, diethyl ketone, methyl propyl ketone, methyl isobutyl ketone, methyl amyl ketone (2-heptanone), cyclopentanone, cyclohexanone, isophorone, cycloheptanone, and cyclooctanone. Can be mentioned. Among these, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and the like are preferred from the viewpoint of reactivity during the synthesis of the phenol resin or epoxy resin, and from the viewpoint of easy availability.
The aliphatic ketone may be used alone or in combination with a plurality of compounds.

The formyl group-containing aromatic compound is preferably a compound having a benzene ring substituted with at least one aldehyde group, such as benzaldehyde, 4-methylbenzaldehyde, and 4-methoxybenzaldehyde. Among these, benzaldehyde is more preferred from the viewpoint of reactivity during epoxy resin synthesis and handling properties.

[Phenol resin 1]
The phenol resin is characterized by being a reaction product of a catechol compound and a ketone group-containing compound, and specifically, for example, a catechol compound represented by the following general formula (1) and a catechol compound represented by the following general formula ( Phenol resin 1 represented by the following general formula (3) can be obtained by reacting with the aliphatic ketone represented by 2).

In the above general formula (1), the substituent R ¹ may be a hydrogen atom, a hydrocarbon group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a halogen atom, From the viewpoint of reactivity when used as a raw material and bending properties of cured products, the hydrocarbon group having 1 to 4 carbon atoms is preferably a methyl group, ethyl group, propyl group, butyl group, or t-butyl group. Examples of the alkoxy group having 1 to 4 carbon atoms include methoxy group, ethoxy group, propyloxy group, butoxy group, and examples of the halogen atom include fluorine atom, chlorine atom, bromine atom, etc. It will be done. Among these, when R ¹ is a hydrogen atom, the melt viscosity is low, the handling properties are excellent, and the balance between bending properties and heat resistance is excellent, which is a preferred embodiment.

In the above general formula (1), m is preferably an integer of 0 to 3, and more preferably an integer of 0 or 1 from the viewpoint of reactivity when used as a raw material and bending properties of the cured product. be.

In the above general formula (2), R ² and R ³ are each independently preferably a hydrocarbon group having 1 to 4 carbon atoms, and from the viewpoint of heat resistance and bending properties of the cured product, more preferably: The R ² and R ³ are each independently a methyl group, an ethyl group, a propyl group, or a butyl group, and more preferably, both R ² and R ³ are a methyl group. When R ² and R ³ are methyl groups, it is preferable because the cured product has a well-balanced heat resistance and bending properties. Particularly, when R ² and R ³ are both methyl groups, the melt viscosity This is a preferred embodiment since it has a low resistance, excellent handling properties, and an excellent balance between bending properties and heat resistance. Further, R ² and R ³ may be combined to form a cyclic structure (the aliphatic ketone includes an alicyclic ketone).

In the above general formula (3), n is preferably an integer of 0 to 3, and the resulting phenol resin or epoxy resin is easily adjusted to a low viscosity and has excellent fluidity and handling properties. In the case, n is preferably an integer of 0 or 1, and in the case, n is preferably 0 (biscatechol A).

Note that R ¹ , R ² , R ³ , and m in the above general formula (3) are the same as in the above general formulas (1) and (2).

The reaction ratio of the catechol compound and the aliphatic ketone is such that an epoxy resin having an excellent balance between melt viscosity and heat resistance in a cured product is obtained. The amount is preferably in the range of 0.1 to 0.9 mol, more preferably 0.1 to 0.7 mol, and even more preferably 0.2 to 0.6 mol.

The reaction between the catechol compound and the aliphatic ketone is preferably carried out in the presence of an acid catalyst because the reaction proceeds efficiently. Examples of the acid catalyst include inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid, organic acids such as methanesulfonic acid, p-toluenesulfonic acid, and oxalic acid, and Lewis acids such as boron trifluoride, anhydrous aluminum chloride, and zinc chloride. can be mentioned. In addition to the acid catalyst, mercaptocarboxylic acids such as thioglycolic acid, thiolactic acid, 2-mercaptopropionic acid, and 3-mercaptopropionic acid, propyl mercaptan, butyl mercaptan, pentyl mercaptan, hexyl mercaptan, heptyl mercaptan, and octyl mercaptan can also be used. Co-catalysts such as alkyl mercaptans such as , nonyl mercaptan, decyl mercaptan, undecyl and dodecyl mercaptan can also be used. The amount of the acid catalyst used is preferably in the range of 0.01 to 5.0% by mass based on the total mass of the reaction raw materials (including the solvent).

The reaction between the catechol compound and the aliphatic ketone can usually be carried out at a temperature of 30 to 80°C for 1 to 20 hours. The reaction may be carried out in an organic solvent if necessary. The organic solvent used here is not particularly limited as long as it can be used under the above temperature conditions, and specific examples include methyl cellosolve, ethyl cellosolve, toluene, xylene, methyl isobutyl ketone, etc. . When these organic solvents are used, they are preferably used in an amount of 10 to 500% by mass based on the total mass of reaction raw materials.

After the reaction between the catechol compound and the aliphatic ketone is completed, the purified phenol resin is obtained by distilling off unreacted reaction materials, by-products, and the like.
In addition, if a part of the catechol compound remains unreacted after the reaction between the catechol compound and the aliphatic ketone is completed, it may evaporate during the production of a cured product and cause voids. It is preferable that the remaining amount of the catechol compound does not become large, since there is a possibility that the bending properties of the obtained epoxy resin may be adversely affected due to errors in stoichiometry. Therefore, the content of the remaining (unreacted) catechol compound is preferably 20 area % or less, more preferably 10 area % or less in GPC area %. Note that the GPC area % herein refers to the value obtained by dividing the GPC peak area value of the remaining (unreacted) catechol compound by the sum of the GPC peak area values of all components.

The hydroxyl equivalent of the phenolic resin 1 is preferably 50 to 110 g/equivalent, more preferably 60 to 100 g/equivalent, and even more preferably 65 to 90 g/equivalent. When the hydroxyl equivalent is within the above range, the functional group density in the cured product increases, and the obtained cured product also has excellent heat resistance and mechanical strength, which is preferable. The hydroxyl equivalent of the phenol resin 1 herein is based on the method for measuring "hydroxyl equivalent of phenol resin" in the following example.

The melt viscosity (150° C.) of the phenolic resin 1 is preferably 5.0 dPa·s or less, more preferably 0.1 to 4.0 dPa·s, and 0.5 to 3.0 dPa·s. It is more preferable that When the melt viscosity of the phenol resin is within the above range, the phenol resin has a low viscosity and has excellent fluidity and handling properties, so it is preferable because it has excellent handling properties during epoxy resin synthesis and when producing a cured product. The melt viscosity (150° C.) here is measured using an ICI viscometer in accordance with ASTM D4287.

[Phenol resin 2]
The phenol resin is characterized by being a reaction product of a catechol compound and a ketone group-containing compound, and specifically, for example, a catechol compound represented by the following general formula (4), A phenol resin having a triphenylmethane skeleton represented by the following general formula (6) can be obtained by reacting it with a formyl group-containing aromatic compound represented by the following general formula (5).

In the above general formula (4), the substituent R ² is represented by a hydrogen atom, a hydrocarbon group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a halogen atom, and as a raw material From the viewpoint of reactivity during use and bending properties of the cured product, the hydrocarbon group having 1 to 4 carbon atoms is preferably a methyl group, ethyl group, propyl group, butyl group, t-butyl group, etc. Can be mentioned. Further, examples of the alkoxy group having 1 to 4 carbon atoms include a methoxy group, an ethoxy group, a propyloxy group, a butoxy group, and the like. Furthermore, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and the like. Among these, when R ² is a hydrogen atom, the melt viscosity is low, the handling properties are excellent, and the balance between bending properties and heat resistance is excellent, which is a preferred embodiment.

In the above general formula (4), m represents an integer of 0 to 3, and is preferably an integer of 0 or 1 from the viewpoint of reactivity when used as a raw material and bending properties of a cured product.

In the above general formula (5), the substituent R ³ is represented by a hydrogen atom, a hydrocarbon group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a hydroxyl group, or a halogen atom, From the viewpoint of reactivity when used as a raw material and bending properties of cured products, the hydrocarbon group having 1 to 4 carbon atoms is preferably a methyl group, ethyl group, propyl group, butyl group, or t-butyl group. etc. Further, examples of the alkoxy group having 1 to 4 carbon atoms include a methoxy group, an ethoxy group, a propyloxy group, a butoxy group, and the like. Furthermore, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and the like. Among these, when R ³ is a hydrogen atom, the melt viscosity is low, the handling properties are excellent, and the balance between bending properties and heat resistance is excellent, which is a preferred embodiment.

In the above general formula (5), n represents an integer of 0 to 5, and is preferably an integer of 0 or 1 from the viewpoint of reactivity when used as a raw material and bending properties of a cured product.

In the above general formula (6), R ¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and from the viewpoint of bending properties of the cured product, R ¹ preferably represents a hydrogen atom, a methyl group, or an ethyl group. , a propyl group, or a butyl group, preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom. When R ¹ is a hydrogen atom or the like, it is preferable because the cured product has a well-balanced heat resistance and bending properties. Particularly, when R ¹ is a hydrogen atom, the melt viscosity is low and the handling property is improved. This is a preferable aspect.
Note that in the above general formula (6), R ² , R ³ , m, and n are the same as in the above general formulas (4) to (5).

The reaction ratio of the catechol compound and the formyl group-containing aromatic compound is such that an epoxy resin having an excellent balance between melt viscosity and heat resistance in a cured product is obtained. The amount of the aromatic compound is preferably in the range of 0.01 to 0.9 mol, more preferably in the range of 0.05 to 0.8 mol, and even more preferably in the range of 0.1 to 0.7 mol. The amount is preferably 0.1 to 0.5 mol, more preferably 0.1 to 0.5 mol.

The reaction between the catechol compound and the formyl group-containing aromatic compound is preferably carried out in the presence of an acid catalyst because the reaction proceeds efficiently. Examples of the acid catalyst include inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid, organic acids such as methanesulfonic acid, p-toluenesulfonic acid, and oxalic acid, and Lewis acids such as boron trifluoride, anhydrous aluminum chloride, and zinc chloride. can be mentioned. At this time, the amount of the reaction catalyst used is preferably in the range of 0.01 to 5% by mass based on the total mass of the reaction raw materials.

The reaction between the catechol compound and the formyl group-containing aromatic compound can usually be carried out at a temperature of 80 to 200°C for 1 to 20 hours. The reaction may be carried out in an organic solvent if necessary. The organic solvent used here is not particularly limited as long as it can be used under the above temperature conditions, and specific examples include methyl cellosolve, ethyl cellosolve, toluene, xylene, methyl isobutyl ketone, etc. . When these organic solvents are used, they are preferably used in an amount of 10 to 500% by mass based on the total mass of the reaction raw materials.

After the reaction between the catechol compound and the formyl group-containing aromatic compound is completed, the phenolic resin 2 containing the phenolic hydroxyl group-containing compound is obtained by distilling off unreacted reaction raw materials, by-products, etc. .
Note that if some of the catechol compound remains unreacted after the reaction between the catechol compound and the formyl group-containing aromatic compound is completed, it may contaminate the reactor used for the reaction or adversely affect the surrounding environment. In addition, there is a concern that the remaining catechol compound may cause a stoichiometric error, leading to a decrease in physical properties.Furthermore, the remaining catechol compound may evaporate during the production of a cured product, causing voids, etc. It is undesirable that the amount of the compound remaining increases. Therefore, the content ratio of the remaining (unreacted) catechol compound calculated by GPC measurement is preferably 5 area % or less in GPC area %. Examples of by-products other than the phenolic hydroxyl group-containing compound include compounds represented by the following general formula (7). Further, the by-products may be included to the extent that they do not impede the effects of the present invention, and specifically, it is preferable that the total value of the by-products is less than 30% in terms of GPC area %. Note that the GPC area % herein refers to the value obtained by dividing the GPC peak area value of the by-product by the sum of the GPC peak area values of all components.

The hydroxyl equivalent of the phenol resin 2 is preferably from 60 to 110 g/eq, more preferably from 70 to 100 g/eq, even more preferably from 75 to 90 g/eq. When the hydroxyl equivalent of the phenol resin 2 is within the above range, the functional group density in the cured product increases, and the obtained cured product also has excellent heat resistance and mechanical strength, which is preferable. The hydroxyl equivalent of the phenol resin 2 herein is based on the method for measuring "hydroxyl equivalent of phenol resin" in the following example.

The melt viscosity (150° C.) of the phenolic resin 2 is preferably 5.0 dPa·s or less, more preferably 0.1 to 4.5 dPa·s, and 1.0 to 4.0 dPa·s. It is more preferable that When the melt viscosity of the epoxy resin is within the above range, the epoxy resin has a low viscosity and has excellent fluidity and handling properties, so it is preferable because it has excellent handling properties during epoxy resin synthesis and when producing a cured product. The melt viscosity (150° C.) here is measured using an ICI viscometer in accordance with ASTM D4287.

The softening point of the phenolic resin 2 is preferably 50 to 110°C, more preferably 60 to 100°C. It is preferable that the softening point of the phenol resin 2 is within the above range since handling properties and storage stability are excellent. The softening point here is measured based on JIS K 7234 (ring and ball method).

<Epoxy resin (A)>
The present invention is a reaction product of a catechol compound and a ketone group-containing compound, and the glycidyl ether group is produced by a reaction between a phenol resin having at least two catechol skeletons derived from the catechol compound, and a phenolic hydroxyl group of the phenol resin and epihalohydrin. The present invention relates to an epoxy resin characterized in that it is a reactant having the following.
The epoxy resin is an epoxy resin into which a glycidyl ether group is introduced by reacting the phenolic hydroxyl group of the phenol resin with epihalohydrin (epoxidation reaction), and the cured product using the epoxy resin has a high It is preferable because it has excellent heat resistance and high elastic modulus.

Examples of the epihalohydrin include epichlorohydrin, epibromohydrin, and β-methylepichlorohydrin. These may be used alone or in combination. Among them, epichlorohydrin is preferred because it is easily available industrially.

Further, by using an organic solvent in combination during the epoxidation reaction, the reaction rate in the synthesis of the epoxy resin can be increased. Such organic solvents are not particularly limited, but include, for example, hydrocarbon solvents such as toluene, xylene, heptane, hexane, and mineral spirits, and ketone solvents such as methyl ethyl ketone, acetone, dimethyl formamide, methyl isobutyl ketone, cyclohexanone, and dimethyl acetamide. Cyclic ether solvents such as tetrahydrofuran and dioxolane; Ester solvents such as methyl acetate, ethyl acetate and butyl acetate; Aromatic solvents such as toluene, xylene and solvent naphtha; Alicyclic solvents such as cyclohexane and methylcyclohexane; Carbitol and cellosolve Alcohol solvents such as , methanol, ethanol, propanol, isopropanol, butanol, cyclohexanol, propylene glycol monomethyl ether; Ether solvents such as propyl ether, methyl cellosolve, cellosolve, butyl cellosolve, methyl carbitol; alkylene glycol monoalkyl ether, dialkylene Glycol ether solvents such as glycol monoalkyl ether and dialkylene glycol monoalkyl ether acetate; Vegetable oils and fats such as soybean oil, linseed oil, rapeseed oil, and safflower oil; Methoxypropanol, cyclohexanone, methyl cellosolve, diethylene glycol monoethyl ether acetate, propylene glycol Examples include monomethyl ether acetate. These organic solvents can be used alone or in combination of two or more.

Furthermore, as the above-mentioned organic solvent, commercially available products can also be used, and examples of the commercially available products include "No. 1 Spindle Oil", "No. 3 Solvent", "No. 4 Solvent", and "No. 5 Solvent" manufactured by ENEOS Corporation. "Solvent", "Solvent No. 6", "Naftesol H", "Alkene 56NT", "AF Solvent No. 4", "AF Solvent No. 5", "AF Solvent No. 6", "AF Solvent No. 7", manufactured by Mitsubishi Chemical Corporation "Diadol 13", "Diyaren 168";"FOxocol","F Oxocol 180" manufactured by Nissan Chemical Co., Ltd.; "Supersol LA35", "Supersol LA38" manufactured by Idemitsu Kosan Co., Ltd.; "Exsol D80" manufactured by ExxonMobil Chemical Co., Ltd. ”, “Exor D110”, “Exor D120”, “Exor D130”, “Exor D160”, “Exor D100K”, “Exor D120K”, “Exor D130K”, “Exor D280”, “Exor D300”, “Exor D320” ”; etc.
The above organic solvents can be used alone or in combination of two or more. Further, in the present embodiment, 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 improved.

Further, the organic solvent and water may be used together. At this time, the proportion of water used in the mixed solvent is preferably in the range of 5 to 60 parts by weight, more preferably 10 to 50 parts by weight, based on 100 parts by weight of the mixed solvent.

Note that when the basic catalyst used in the epoxidation reaction is an aqueous solution, the content of water contained in the aqueous solution is not included in what is defined as water in the mixed solvent.

[Epoxy resin 1]
As the epoxy resin, for example, a glycidyl ether group (formula ( Epoxy resin 1 in which the "OX group" in 9) has been introduced can be obtained.

In the above general formula (8), X is represented by the above general formula (9), and R ⁴ in the above general formula (9) is preferably a hydrogen atom or a methyl group, more preferably hydrogen It is an atom. It is preferable that R ⁴ is a hydrogen atom or the like, since this results in excellent bending properties and heat resistance. Among these, hydrogen atoms lower the melt viscosity, making this a particularly preferred embodiment. In addition, all of said X may be substituted with the glycidyl ether group represented by the said formula (9), and may be partially substituted. When unsubstituted, X represents a hydrogen atom.

Note that in the above general formula (8), R ¹ , R ² , R ³ , m, and n are the same as in the above general formulas (1) to (3).

[Epoxy resin 2]
The epoxy resin is represented by the following general formula (10) and is characterized by containing a glycidyl ether group-containing compound obtained by reacting the phenol resin 2 and epihalohydrin. By reacting the phenolic resin 2 with epihalohydrin, it is possible to obtain an epoxy resin containing a glycidyl ether group into which a glycidyl ether group has been introduced, and a cured product with low melt viscosity and excellent bending properties can be obtained. ,preferable.

In the above general formula (10), X is represented by the above general formula (9), and R ⁴ in the above general formula (9) is preferably a hydrogen atom or a methyl group, more preferably hydrogen It is an atom. It is preferable that R ⁴ is a hydrogen atom or the like, since this results in excellent bending properties and heat resistance. Among these, hydrogen atoms lower the melt viscosity, making this a particularly preferred embodiment. In addition, all of said X may be substituted with the glycidyl ether group represented by the said formula (9), and may be partially substituted. When unsubstituted, X represents a hydrogen atom.
In addition, in the above general formula (10), R ¹ , R ² , R ³ , m, and n are the same as in the above general formula (6).

The desired epoxy resin 1 and/or epoxy resin 2 can be obtained by reacting the phenol resin 1 and/or phenol resin 2 with epihalohydrin. Epihalohydrin is used in a ratio of 1 to 10 moles per mole of phenolic hydroxyl groups in 2, and 0.9 to 2.0 moles of a basic catalyst is added all at once or divided to 1 mole of phenolic hydroxyl groups. Examples include a method of reacting at a temperature of 20 to 120° C. for 0.5 to 30 hours while adding.

Specific examples of the basic catalyst include alkaline earth metal hydroxides, alkali metal carbonates, and alkali metal hydroxides. Among these, alkali metal hydroxides are preferred because of their excellent catalytic activity, and specifically, sodium hydroxide, potassium hydroxide, and the like are preferred.

After the reaction is completed, the reaction mixture is washed with water, and unreacted epihalohydrin and organic solvent are distilled off under heating and reduced pressure. In addition, in order to produce an epoxy resin with even fewer hydrolyzable halogens, the obtained epoxy resin was dissolved in an organic solvent again, and an aqueous solution of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide was added thereto for further reaction. You can also do At this time, a phase transfer catalyst such as a quaternary ammonium salt or a crown ether may be present for the purpose of improving the reaction rate. When using a phase transfer catalyst, the amount used is preferably 0.1 to 3.0 parts by mass based on 100 parts by mass of the epoxy resin. After the reaction is completed, the produced salt is removed by filtration, washing with water, etc., and the organic solvent is distilled off under heating and reduced pressure, thereby obtaining the desired epoxy resin of the present invention.

The epoxy equivalent of each of the epoxy resin 1 and the epoxy resin 2 is preferably 120 to 400 g/equivalent, more preferably 130 to 300 g/equivalent, and even more preferably 120 to 200 g/equivalent. It is preferable that the epoxy equivalent of the epoxy resin is within the above range because the crosslinking density of the cured product increases and the resulting cured product has excellent heat resistance. The epoxy equivalent here is measured based on JIS K7236.

The melt viscosity (150° C.) of each of the epoxy resin 1 and the epoxy resin 2 is preferably 2.0 dPa·s or less, more preferably 0.01 to 1.0 dPa·s, and 0.1 More preferably, it is 0.6 dPa·s. It is preferable that the melt viscosity of the epoxy resin is within the above range, since the epoxy resin has a low viscosity and is excellent in fluidity and handling properties, so that the obtained cured product is also excellent in moldability. The melt viscosity (150° C.) here is measured using an ICI viscometer in accordance with ASTM D4287.

<Unsaturated monobasic acid (B)>
Examples of the unsaturated monobasic acid (B) include acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, α-cyanocinnamic acid, β-styrylacrylic acid, β-furfurylacrylic acid, and the like. Furthermore, acid halides and esters of the unsaturated monobasic acids can also be used. Furthermore, a compound represented by the following general formula (11), etc. can also be used.

[In general formula (11), X represents an alkylene chain, polyoxyalkylene chain, (poly)ester chain, aromatic hydrocarbon chain, or (poly)carbonate chain having 1 to 10 carbon atoms, and halogen It may contain atoms, alkoxy groups, etc. Y is a hydrogen atom or a methyl group. ]

Examples of the polyoxyalkylene chain include a polyoxyethylene chain and a polyoxypropylene chain.

Examples of the (poly)ester chain include a (poly)ester chain represented by the following general formula (12).

[In general formula (12), R ¹ is an alkylene group having 1 to 10 carbon atoms, and n is an integer of 1 to 5. ]

Examples of the aromatic hydrocarbon chain include a phenylene chain, a naphthylene chain, a biphenylene chain, a phenylnaphthylene chain, and a binaphthylene chain. Further, as a partial structure, a hydrocarbon chain having an aromatic ring such as a benzene ring, a naphthalene ring, an anthracene ring, or a phenanthrene ring can also be used.

Examples of the (poly)carbonate chain include a (poly)carbonate chain represented by the following general formula (13).

[In general formula (13), R ² is an alkylene group having 1 to 10 carbon atoms, and n is an integer of 1 to 5. ]

The molecular weight of the compound represented by the general formula (11) is preferably in the range of 100 to 500, more preferably in the range of 150 to 400.

These unsaturated monobasic acids (B) can be used alone or in combination of two or more.

The amount of the unsaturated monobasic acid (B) to be used is determined as follows, since a curable resin composition having excellent alkali developability and capable of forming a cured product having excellent heat resistance and high elastic modulus is obtained. The amount of acid groups contained in the unsaturated monobasic acid (B) is preferably 0.9 to 1.1 mol per 1 mol of epoxy groups contained in the epoxy resin (A), and 0.95 to 1.1 mol is used. ~1.05 is more preferred.

<Polybasic acid anhydride (C)>
Examples of the polybasic acid anhydride (C) include aliphatic polybasic acid anhydrides, alicyclic polybasic acid anhydrides, aromatic polybasic acid anhydrides, and acid halides of aliphatic polybasic acid anhydrides. , acid halides of alicyclic polybasic acid anhydrides, acid halides of aromatic polybasic acid anhydrides, and the like.

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

In the present invention, as the alicyclic polybasic acid anhydride, an alicyclic polybasic acid anhydride is one in which an acid anhydride group is bonded to an alicyclic structure, and an alicyclic polybasic acid anhydride is one in which an acid anhydride group is bonded to an alicyclic structure, and an alicyclic polybasic acid anhydride in which an acid anhydride group is bonded to an alicyclic structure is used. It does not matter whether or not it exists. Examples of the alicyclic polybasic acid anhydride include tetrahydrophthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, cyclohexanetricarboxylic acid, cyclohexanetetracarboxylic acid, bicyclo[2.2.1]heptane-2, 3-dicarboxylic acid, methylbicyclo[2.2.1]heptane-2,3-dicarboxylic acid, 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene- Examples include acid anhydrides of 1,2-dicarboxylic acids.

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

These polybasic acid anhydrides (C) can be used alone or in combination of two or more. Among these, tetrahydrophthalic anhydride, succinic anhydride, Cyclohexanedicarboxylic anhydride is preferred.

The amount of the polybasic acid anhydride (C) to be used is determined as described above because a curable resin composition having excellent alkali developability and capable of forming a cured product having excellent heat resistance and high elastic modulus is obtained. It is preferably used in a range of 0.2 to 1.05 mol, more preferably 0.25 to 0.95 mol, per 1 mol of epoxy groups contained in the epoxy resin (A). .

The resin having an acid group and a polymerizable unsaturated group of the present invention may be used as raw materials other than the epoxy resin (A), the unsaturated monobasic acid (B), and the polybasic acid anhydride (C), if necessary. Other compounds can also be used.

Examples of the other compounds include unsaturated monobasic acid anhydrides.

Examples of the unsaturated monobasic acid anhydride include acrylic anhydride, methacrylic anhydride, and the like. These unsaturated monobasic acid anhydrides can be used alone or in combination of two or more.

The total of the epoxy resin (A), the unsaturated monobasic acid (B), and the polybasic acid anhydride (C) in the raw material (solid content) of the resin having acid groups and polymerizable unsaturated groups of the present invention The mass proportion is preferably 70 mass% or more, since a curable resin composition having excellent alkali developability and capable of forming a cured product having excellent heat resistance and high elastic modulus is obtained.

The method for producing the resin having an acid group and a polymerizable unsaturated group of the present invention is not particularly limited, and any method may be used. For example, it may be produced by a method in which all of the reaction raw materials containing the epoxy resin (A), the unsaturated monobasic acid (B), and the polybasic acid anhydride (C) are reacted at once. However, it may be produced by a method in which reaction raw materials are reacted sequentially. Among them, since the reaction can be easily controlled, the epoxy resin (A) and the unsaturated monobasic acid (B) are first reacted in the presence of a basic catalyst in a temperature range of 80 to 140°C. A preferred method is to then add polybasic acid anhydride (C) and react in a temperature range of 80 to 140°C.

Moreover, the reaction of the epoxy resin (A), the unsaturated monobasic acid (B), and the polybasic acid anhydride (C) can also be carried out in an organic solvent, if necessary. Moreover, a polymerization inhibitor and an antioxidant can also be used as necessary.

Examples of the basic catalyst include N-methylmorpholine, pyridine, 1,8-diazabicyclo[5.4.0]undecene-7 (DBU), and 1,5-diazabicyclo[4.3.0]nonene- 5 (DBN), 1,4-diazabicyclo[2.2.2]octane (DABCO), tri-n-butylamine or dimethylbenzylamine, butylamine, octylamine, monoethanolamine, diethanolamine, triethanolamine, imidazole, 1 -Methylimidazole, 2,4-dimethylimidazole, 1,4-diethylimidazole, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-(N-phenyl)aminopropyltrimethoxysilane, 3-( Amine compounds such as 2-aminoethyl)aminopropyltrimethoxysilane, 3-(2-aminoethyl)aminopropylmethyldimethoxysilane, and tetramethylammonium hydroxide; Quaternary compounds such as trioctylmethylammonium chloride and trioctylmethylammonium acetate Ammonium salts; phosphine compounds such as trimethylphosphine, tributylphosphine, triphenylphosphine; tetramethylphosphonium chloride, tetraethylphosphonium chloride, tetrapropylphosphonium chloride, tetrabutylphosphonium chloride, tetrabutylphosphonium bromide, trimethyl(2-hydroxylpropyl)phosphonium chloride , triphenylphosphonium chloride, benzylphosphonium chloride and other phosphonium salts; dibutyltin dilaurate, octyltin trilaurate, octyltin diacetate, dioctyltin diacetate, dioctyltin dineodecanoate, dibutyltin diacetate, tin octylate, 1 , 1,3,3-tetrabutyl-1,3-dodecanoyl distanoxane; organometallic compounds such as zinc octylate, bismuth octylate; inorganic tin compounds such as tin octoate; inorganic metal compounds, etc. can be mentioned. Furthermore, alkaline earth metal hydroxides, alkali metal carbonates, alkali metal hydroxides, and the like can also be used. These basic catalysts can be used alone or in combination of two or more. When used, these basic catalysts may be used in the form of an aqueous solution of about 10 to 55% by mass, or in the form of a solid.

The amount of the basic catalyst used is determined so that a curable resin composition that has excellent alkali developability and can form a cured product with excellent heat resistance and high elastic modulus can be obtained. , the unsaturated monobasic acid (B), and the polybasic acid anhydride (C), preferably in a range of 0.01 to 1 part by mass, and 0.05 to 0.8 parts by mass. range is more preferred.

As the organic solvent, the same ones as those exemplified above can be used, and the organic solvents can be used alone or in combination of two or more kinds. Further, in the present embodiment, 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 improved.

Further, the organic solvent and water may be used together. At this time, the proportion of water used in the mixed solvent is preferably in the range of 5 to 60 parts by weight, more preferably 10 to 50 parts by weight, based on 100 parts by weight of the mixed solvent.

Examples of the polymerization inhibitor include p-methoxyphenol, p-methoxycresol, 4-methoxy-1-naphthol, 4,4'-dialkoxy-2,2'-bi-1-naphthol, 3-(N -Salicyloyl)amino-1,2,4-triazole, N'1,N'12-bis(2-hydroxybenzoyl)dodecane dihydrazide, styrenated phenol, N-isopropyl-N'-phenylbenzene-1,4-diamine , phenolic compounds such as 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline, hydroquinone, methylhydroquinone, p-benzoquinone, methyl-p-benzoquinone, 2,5-diphenylbenzoquinone, 2-hydroxy- Quinone compounds such as 1,4-naphthoquinone, anthraquinone, and diphenoquinone, melamine, p-phenylenediamine, 4-aminodiphenylamine, N. N'-diphenyl-p-phenylenediamine, N-i-propyl-N'-phenyl-p-phenylenediamine, N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine, diphenylamine, 4 , 4'-dicumyl-diphenylamine, 4,4'-dioctyl-diphenylamine, poly(2,2,4-trimethyl-1,2-dihydroquinoline), styrenated diphenylamine, styrenated diphenylamine and 2,4,4-trimethyl Amine compounds such as reaction products of pentene, reaction products of diphenylamine and 2,4,4-trimethylpentene, phenothiazine, distearylthiodipropionate, 2,2-bis({[3-(dodecylthio)propionyl]oxy) }Thioether compounds such as methyl)-1,3-propanediyl bis[3-(dodecylthio)propionate], ditridecane-1-yl 3,3'-sulfanediyl dipropanoate, N-nitrosodiphenylamine, N- Nitrosophenylnaphthylamine, p-nitrosophenol, nitrosobenzene, p-nitrosodiphenylamine, α-nitroso-β-naphthol, etc., N,N-dimethyl p-nitrosoaniline, p-nitrosodiphenylamine, p-nitrone dimethylamine, p-nitrone -N,N-diethylamine, N-nitrosoethanolamine, N-nitrosodi-n-butylamine, N-nitroso-Nn-butyl-4-butanolamine, N-nitroso-diisopropanolamine, N-nitroso-N- Ethyl-4-butanolamine, 5-nitroso-8-hydroxyquinoline, N-nitrosomorpholine, N-nitroso-N-phenylhydroxylamine ammonium salt, nitrosobenzene, N-nitroso-N-methyl-p-toluenesulfonamide , N-nitroso-N-ethylurethane, N-nitroso-Nn-propylurethane, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 1-nitroso-2-naphthol-3,6-sulfone Nitroso compounds such as sodium acid, sodium 2-nitroso-1-naphthol-4-sulfonate, 2-nitroso-5-methylaminophenol hydrochloride, 2-nitroso-5-methylaminophenol hydrochloride, phosphoric acid and octadecane- 1-ol ester, triphenylphosphite, 3,9-dioctadecan-1-yl-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, trisnonylphenylphosphite, Phosphite-(1-methylethylidene)-di-4,1-phenylenetetra-C12-15-alkyl ester, 2-ethylhexyl diphenyl phosphite, diphenylisodecyl phosphite, triisodecyl phosphite, tris(2 , 4-di-tert-butylphenyl) phosphite, zinc compounds such as bis(dimethyldithiocarbamato-κ(2)S,S')zinc, zinc diethyldithiocarbamate, zinc dibutyl dithiocarbamate, etc. , nickel compounds such as bis(N,N-dibutylcarbamodithioato-S,S')nickel, 1,3-dihydro-2H-benzimidazole-2-thione, 4,6-bis(octylthiomethyl)- Sulfur compounds such as o-cresol, 2-methyl-4,6-bis[(octan-1-ylsulfanyl)methyl]phenol, dilaurylthiodipropionate, distearyl 3,3'-thiodipropionate, etc. can be mentioned. These polymerization inhibitors can be used alone or in combination of two or more.

As the antioxidant, the same compounds as those exemplified as the polymerization inhibitor can be used, and the antioxidants can be used alone or in combination of two or more kinds.

In addition, commercially available products of the polymerization inhibitor and the antioxidant include, for example, "Q-1300" and "Q-1301" manufactured by Wako Pure Chemical Industries, Ltd., and "Sumilizer BBM-S" manufactured by Sumitomo Chemical Co., Ltd. , "Sumilizer GA-80 ga", etc.

The resin having an acid group and a polymerizable unsaturated group of the present invention can be used as a curable resin composition by adding a photopolymerization initiator.

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

Examples of commercially available photopolymerization initiators include "Omnirad 1173", "Omnirad 184", "Omnirad 127", "Omnirad 2959", "Omnirad 369", "Omnirad 379", "Omnirad 907", “Omnirad 4265”, “Omnirad 1000”, “Omnirad 651”, “Omnirad TPO”, “Omnirad 819”, “Omnirad 2022”, “Omnirad 2100”, “Omnirad 754”, “Omnirad ad 784”, “Omnirad 500”, "Omnirad 81" (manufactured by IGM Resins); "KAYACURE DETX", "KAYACURE MBP", "KAYACURE DMBI", "KAYACURE EPA", "KAYACURE OA" (manufactured by Nippon Kayaku Co., Ltd.); "Vicure 10", " "Vicure 55" (manufactured by Stoffa Chemical); "Trigonal P1" (manufactured by Akzo Nobel), "SANDORAY 1000" (manufactured by SANDOZ); "DEAP" (manufactured by Upjohn Chemical), "Quan tacure PDO”, “Quantacure ITX” , "Quantacure EPD" (manufactured by Ward Blenkinsop); "Runtecure 1104" (manufactured by Runtec), and the like. These photopolymerization initiators can be used alone or in combination of two or more.

The amount of the photopolymerization initiator added to the curable resin composition is preferably in the range of 0.5 to 20% by mass, for example.

<Other resin components: resin (D) having acid groups and polymerizable unsaturated groups, etc.>
The curable resin composition of the present invention contains resin components other than the resin having acid groups and polymerizable unsaturated groups of the present invention (hereinafter sometimes referred to as "other resin components"). Also good. Examples of the other resin components include a resin (D) having an acid group and a polymerizable unsaturated group, various (meth)acrylate monomers, and the like.

The resin (D) having an acid group and a polymerizable unsaturated group may be any resin as long as it has an acid group and a polymerizable unsaturated group in the resin. Epoxy resins having polymerizable unsaturated groups, urethane resins having acid groups and polymerizable unsaturated groups, acrylic resins having acid groups and polymerizable unsaturated groups, amide-imide resins having acid groups and polymerizable unsaturated groups, acids Examples include acrylamide resins having a group and a polymerizable unsaturated group, and ester resins having an acid group and a polymerizable unsaturated group.

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

As the epoxy resin having an acid group and a polymerizable unsaturated group, for example, an epoxy (meth)acrylate resin having an acid group whose essential raw materials are an epoxy resin, an unsaturated monobasic acid, and a polybasic acid anhydride; Examples include epoxy resins, unsaturated monobasic acids, polybasic acid anhydrides, polyisocyanate compounds, and epoxy (meth)acrylate resins having acid groups and urethane groups that use (meth)acrylate compounds having hydroxyl groups as reaction raw materials. .

Examples of the epoxy resin include bisphenol type epoxy resin, phenylene ether type epoxy resin, naphthylene ether type epoxy resin, biphenyl type epoxy resin, triphenylmethane type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, Bisphenol novolac type epoxy resin, naphthol novolac type epoxy resin, naphthol-phenol cocondensed novolac type epoxy resin, naphthol-cresol cocondensed novolac type epoxy resin, phenol aralkyl type epoxy resin, naphthol aralkyl type epoxy resin, dicyclopentadiene-phenol addition Examples include reactive epoxy resins, biphenylaralkyl epoxy resins, fluorene epoxy resins, xanthene epoxy resins, dihydroxybenzene epoxy resins, trihydroxybenzene epoxy resins, oxazolidone epoxy resins, and the like. These epoxy resins can be used alone or in combination of two or more.

Examples of the bisphenol type epoxy resin include bisphenol A type epoxy resin, bisphenol AP type epoxy resin, bisphenol B type epoxy resin, bisphenol BP type epoxy resin, bisphenol E type epoxy resin, bisphenol F type epoxy resin, and bisphenol S type epoxy resin. Examples include resin.

Examples of the hydrogenated bisphenol epoxy resin include hydrogenated bisphenol A epoxy resin, hydrogenated bisphenol B epoxy resin, hydrogenated bisphenol E epoxy resin, hydrogenated bisphenol F epoxy resin, and hydrogenated bisphenol S epoxy. Examples include resin.

Examples of the biphenol epoxy resin include 4,4'-biphenol epoxy resin, 2,2'-biphenol epoxy resin, tetramethyl-4,4'-biphenol epoxy resin, and tetramethyl-2,2' -Biphenol type epoxy resins, etc.

Examples of the hydrogenated biphenol epoxy resin include hydrogenated 4,4'-biphenol epoxy resin, hydrogenated 2,2'-biphenol epoxy resin, and hydrogenated tetramethyl-4,4'-biphenol epoxy resin. , hydrogenated tetramethyl-2,2'-biphenol type epoxy resin, and the like.

As the unsaturated monobasic acid, those similar to those exemplified as the above-mentioned unsaturated monobasic acid (B) can be used, and the unsaturated monobasic acid may be used alone or in combination of two or more. They can also be used together.

As the polybasic acid anhydride, those similar to those exemplified as the above-mentioned polybasic acid anhydride (C) can be used, and the polybasic acid anhydride may be used alone or in combination of two or more types. They can also be used together.

Examples of the polyisocyanate compound include aliphatic diisocyanate compounds such as butane diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and 2,4,4-trimethylhexamethylene diisocyanate; norbornane diisocyanate, isophorone diisocyanate, Alicyclic diisocyanate compounds such as hydrogenated xylylene diisocyanate and hydrogenated diphenylmethane diisocyanate; tolylene diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, 4,4'-diisocyanate-3 , 3'-dimethylbiphenyl, o-tolidine diisocyanate and other aromatic diisocyanate compounds; polymethylene polyphenyl polyisocyanate having a repeating structure represented by the following general formula (9); isocyanurate modified products, biuret modified products thereof, Examples include modified allophanate. Moreover, these polyisocyanate compounds can be used alone or in combination of two or more types.

[In general formula (14), each R ¹ is independently a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. R ² is each independently an alkyl group having 1 to 4 carbon atoms, l is 0 or an integer of 1 to 3, and m is an integer of 1 to 15. ]

Examples of the (meth)acrylate compound having a hydroxyl group include hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, trimethylolpropane (meth)acrylate, trimethylolpropane di(meth)acrylate, and pentaerythritol (meth)acrylate. acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol(meth)acrylate, dipentaerythritol di(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate ) acrylate, dipentaerythritol penta(meth)acrylate, ditrimethylolpropane(meth)acrylate, ditrimethylolpropane di(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, and the like. In addition, (poly)oxyalkylene chains such as (poly)oxyethylene chains, (poly)oxypropylene chains, (poly)oxytetramethylene chains, etc. are introduced into the molecular structures of the (meth)acrylate compounds having various hydroxyl groups. (Poly)oxyalkylene modified products and lactone modified products in which a (poly)lactone structure is introduced into the molecular structure of the (meth)acrylate compounds having various hydroxyl groups can also be used. These (meth)acrylate compounds having a hydroxyl group can be used alone or in combination of two or more.

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

As the organic solvent, the same ones as those exemplified above can be used, and the organic solvents can be used alone or in combination of two or more kinds.

As the basic catalyst, the same ones as those exemplified above can be used, and the basic catalysts can be used alone or in combination of two or more types.

The urethane resin having an acid group and a polymerizable unsaturated group includes, for example, a polyisocyanate compound, a (meth)acrylate compound having a hydroxyl group, a polyol compound having a carboxyl group, and optionally a polybasic acid anhydride; Those obtained by reacting with polyol compounds other than polyol compounds having carboxyl groups, polyisocyanate compounds, (meth)acrylate compounds having hydroxyl groups, polybasic acid anhydrides, and polyols other than polyol compounds having carboxyl groups. Examples include those obtained by reacting with a compound.

As the polyisocyanate compound, those similar to those exemplified as the above-mentioned polyisocyanate compound can be used, and the polyisocyanate compound can be used alone or in combination of two or more types.

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

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

As the polybasic acid anhydride, those similar to those exemplified as the above-mentioned polybasic acid anhydride (C) can be used, and the polybasic acid anhydride may be used alone or in combination of two or more types. They can also be used together.

Examples of polyol compounds other than the polyol compound having a carboxyl group 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 chains, (poly)oxypropylene chains, and (poly)oxytetramethylene chains in the molecular structures of the various polyol compounds mentioned above; Examples include (poly)oxyalkylene modified products in which a (poly)oxyalkylene modified product is introduced; and lactone modified products in which a (poly)lactone structure is introduced into the molecular structure of the various polyol compounds described above. Polyol compounds other than the polyol compound having a carboxyl group can be used alone or in combination of two or more.

The method for producing the urethane resin having an acid group and a polymerizable unsaturated group is not particularly limited, and any method may be used. The production of the urethane resin having an acid group and a polymerizable unsaturated group 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 ones as those exemplified above can be used, and the organic solvents can be used alone or in combination of two or more kinds.

As the basic catalyst, the same ones as those exemplified above can be used, and the basic catalysts can be used alone or in combination of two or more types.

As the acrylic resin having an acid group and a polymerizable unsaturated group, 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 the resulting acrylic resin intermediate with a (meth)acrylate compound (β) having a reactive functional group that can react with these functional groups. Examples include products obtained by reacting polybasic acid anhydrides with hydroxyl groups in the reaction products.

In addition to the (meth)acrylate compound (α), the acrylic resin intermediate may be one obtained by copolymerizing other compounds having polymerizable unsaturated groups as necessary. Examples of the other compounds having polymerizable unsaturated groups include (meth)acrylate, 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)acrylates such as cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate; phenyl (meth)acrylate, benzyl (meth)acrylate, Examples include aromatic ring-containing (meth)acrylates such as phenoxyethyl acrylate; (meth)acrylates having a silyl group such as 3-methacryloxypropyltrimethoxysilane; and styrene derivatives such as styrene, α-methylstyrene, and chlorostyrene. 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 possessed by the (meth)acrylate compound (α), but from the viewpoint of reactivity it should be the following combination: is preferred. That is, when a (meth)acrylate having a hydroxyl group is used as the (meth)acrylate compound (α), it is preferable to use a (meth)acrylate having an isocyanate group as the (meth)acrylate compound (β). When a (meth)acrylate having a carboxyl group is used as the (meth)acrylate compound (α), it is preferable to use a (meth)acrylate having a glycidyl group as the (meth)acrylate compound (β). When a (meth)acrylate having an isocyanate group is used as the (meth)acrylate compound (α), it is preferable to use a (meth)acrylate having a hydroxyl group as the (meth)acrylate compound (β). When a (meth)acrylate having a glycidyl group is used as the (meth)acrylate compound (α), it is preferable to use a (meth)acrylate having a carboxyl group 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 similar to those exemplified as the above-mentioned polybasic acid anhydride (C) can be used, and the polybasic acid anhydride may be used alone or in combination of two or more types. You can also.

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

As the organic solvent, the same ones as those exemplified above can be used, and the organic solvents can be used alone or in combination of two or more kinds.

As the basic catalyst, the same ones as those exemplified above can be used, and the basic catalysts can be used alone or in combination of two or more types.

Examples of the amide-imide resin having an acid group and a polymerizable unsaturated group include an amide-imide resin having an acid group and/or an acid anhydride group, and a (meth)acrylate compound having a hydroxyl group and/or a (meth)acrylate compound having an epoxy group. ) Those obtained by reacting an acrylate compound with a compound having one or more reactive functional groups selected from the group consisting of a hydroxyl group, a carboxyl group, an isocyanate group, a glycidyl group, and an acid anhydride group, if necessary. can be mentioned. Note that the compound having a reactive functional group may or may not have a (meth)acryloyl group.

The amide-imide resin may have only either an acid group or an acid anhydride group, or may have both. From the viewpoint of reactivity and reaction control with a (meth)acrylate compound having a hydroxyl group or an epoxy compound having a (meth)acryloyl group, it is preferable that the compound has an acid anhydride group. It is more preferable that it has both. The solid content acid value of the amide-imide resin is preferably in the range of 60 to 350 mgKOH/g as measured under neutral conditions, ie, under conditions where the acid anhydride group is not ring-opened. On the other hand, it is preferable that the value measured under conditions where the acid anhydride group is ring-opened, such as in the presence of water, is in the range of 61 to 360 mgKOH/g.

Examples of the amide-imide resin include those obtained by using a polyisocyanate compound and a polybasic acid anhydride as reaction raw materials.

As the polyisocyanate compound, those similar to those exemplified as the above-mentioned polyisocyanate compound can be used, and the polyisocyanate compound can be used alone or in combination of two or more types.

As the polybasic acid anhydride, those similar to those exemplified as the above-mentioned polybasic acid anhydride (C) can be used, and the polybasic acid anhydride may be used alone or in combination of two or more types. They can also be used together.

Further, in addition to the polyisocyanate compound and polybasic acid anhydride, polybasic acid can be used in combination with the amide-imide resin as a reaction raw material, if necessary.

Any compound having two or more carboxyl groups in one molecule can be used as the polybasic acid. For example, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, hexahydro Phthalic acid, methylhexahydrophthalic acid, citraconic acid, itaconic acid, glutaconic acid, 1,2,3,4-butanetetracarboxylic acid, cyclohexanetricarboxylic acid, cyclohexanetetracarboxylic acid, bicyclo[2.2.1]heptane- 2,3-dicarboxylic acid, methylbicyclo[2.2.1]heptane-2,3-dicarboxylic acid, 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydro Examples include naphthalene-1,2-dicarboxylic acid, trimellitic acid, pyromellitic acid, naphthalenedicarboxylic acid, naphthalenetricarboxylic acid, naphthalenetetracarboxylic acid, biphenyldicarboxylic acid, biphenyltricarboxylic acid, biphenyltetracarboxylic acid, benzophenonetetracarboxylic acid, etc. It will 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 the (meth)acrylate compound having a hydroxyl group, those similar to those exemplified as the above-mentioned (meth)acrylate compound having a hydroxyl group can be used, and the (meth)acrylate compound having a hydroxyl group can be used alone. It is also possible to use two or more types together.

As the (meth)acrylate compound having an epoxy group, the same compounds as those exemplified above as the (meth)acrylate compound having an epoxy group can be used, and the (meth)acrylate compound having an epoxy group is They can be used alone or in combination of two or more.

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

As the organic solvent, the same ones as those exemplified above can be used, and the organic solvents can be used alone or in combination of two or more kinds.

As the basic catalyst, the same ones as those exemplified above can be used, and the basic catalysts can be used alone or in combination of two or more types.

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

The compound having a phenolic hydroxyl group refers to a compound having at least one phenolic hydroxyl group in the molecule. Examples of the compound having at least one phenolic hydroxyl group in the molecule include compounds represented by the following structural formulas (4-1) to (4-5).

In the above structural formulas (4-1) to (4-5), 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, or a halogen atom. , R ² are each independently a hydrogen atom or a methyl group. Further, p is 0 or an integer of 1 or more, preferably 0 or an integer of 1 to 3, more preferably 0 or 1, and even more preferably 0. q is an integer of 1 or more, preferably 2 or 3. Note that the position of the substituent on the aromatic ring in the above structural formula is arbitrary; for example, in the naphthalene ring of structural formula (4-2), it may be substituted on any ring; In 4-3), it may be substituted on any of the benzene rings present in one molecule, and in structural formula (4-4), it may be substituted on any of the benzene rings present in one molecule. In structural formula (4-5), substitution may be made on any of the benzene rings present in one molecule, and the number of substituents in one molecule is p and q. It shows that.

Further, as the compound having a phenolic hydroxyl group, for example, a compound having at least one phenolic hydroxyl group in the molecule, a compound represented by any of the following structural formulas (5-1) to (5-5), and A reaction product containing/or formaldehyde as an essential reaction raw material can also be used. Further, a novolac type phenol resin, etc., which uses one or more kinds of compounds having at least one phenolic hydroxyl group in the molecule as a reaction raw material can also be used.

[In structural formula (5-1), h is 0 or 1. In structural formulas (5-2) to (5-5), 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, or a halogen atom, i is 0 or an integer from 1 to 4. In structural formulas (5-2), (5-3), and (5-5), W is each independently a vinyl group, a halomethyl group, a hydroxymethyl group, or an alkyloxymethyl group. In formula (5-5), V is any one of an alkylene group having 1 to 4 carbon atoms, an oxygen atom, a sulfur atom, or a carbonyl group, and j is an integer of 1 to 4. ]

Specific examples of the compounds represented by the above general formulas (5-1) to (5-5) and the reaction products include phenol, cresol, xylenol; dialkylphenols such as dimethylphenol and diethylphenol; trimethylphenol, Trialkylphenols such as triethylphenol; diphenylphenol, triphenylphenol, catechol, resorcinol, hydroquinone, 3-methylcatechol, 4-methylcatechol, 4-allylpyrocatechol, tetramethylbisphenol A, 1,2,3-trihydroxybenzene , 1,2,4-trihydroxybenzene, 1-naphthol, 2-naphthol, 1,3-naphthalene diol, 1,5-naphthalene diol, 2,6-naphthalene diol, 2,7-naphthalene diol, polyphenylene ether type Examples include diol, polynaphthylene ether type diol, phenol novolak resin, cresol novolak resin, bisphenol novolak type resin, naphthol novolak type resin, phenol aralkyl type resin, naphthol aralkyl type resin, and phenol resin having a cyclo ring structure.

These compounds having a phenolic hydroxyl group 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 is preferred because it provides a curable resin composition that has excellent alkali developability and can form a cured product with excellent heat resistance and high elastic modulus. The alkylene oxides 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 is preferred because it provides a curable resin composition that has excellent alkali developability and can form a cured product with excellent heat resistance and high elastic modulus. The alkylene carbonates can be used alone or in combination of two or more.

Examples of the N-alkoxyalkyl (meth)acrylamide compounds 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 compounds can be used alone or in combination of two or more.

As the polybasic acid anhydride, those similar to those exemplified as the above-mentioned polybasic acid anhydride (C) can be used, and the polybasic acid anhydride may be used alone or in combination of two or more types. They can also be used together.

As the unsaturated monobasic acid, the same as those exemplified as the above-mentioned unsaturated monobasic acid (B) can be used, and the unsaturated monobasic acid may be used alone or in combination of two or more types. You can also do that.

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

As the organic solvent, the same ones as those exemplified above can be used, and the organic solvents can be used alone or in combination of two or more kinds.

As the basic catalyst, the same ones as those exemplified above can be used, and the basic catalysts can be used alone or in combination of two or more types.

Examples of the acidic catalyst include inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid; organic acids such as methanesulfonic acid, p-toluenesulfonic acid, and oxalic acid; and Lewis acids such as boron trifluoride, anhydrous aluminum chloride, and zinc chloride. Examples include. Furthermore, a solid acid catalyst having a strong acid such as a sulfonyl group can also be used. These acidic catalysts can be used alone or in combination of two or more.

As the ester resin having an acid group and a polymerizable unsaturated group, for example, a compound having a phenolic hydroxyl group, an alkylene oxide or an alkylene carbonate, an unsaturated monobasic acid, and a polybasic acid anhydride are reacted. Here are the results obtained.

As the compound having a phenolic hydroxyl group, the same compounds as those exemplified above as the compound having a phenolic hydroxyl group can be used, and the compound having a phenolic hydroxyl group may be used alone or in combination of two or more. They can also be used together.

As the alkylene oxide, those similar to those exemplified above as the alkylene oxide can be used. Among these, ethylene oxide or propylene oxide is preferred because it provides a curable resin composition that has excellent alkali developability and can form a cured product with excellent elongation, adhesion, and dielectric properties. The alkylene oxides can be used alone or in combination of two or more.

As the alkylene carbonate, those similar to those exemplified above as the alkylene carbonate can be used. Among these, ethylene carbonate or propylene carbonate is preferred because it provides a curable resin composition that has excellent alkali developability and can form a cured product with excellent elongation, adhesion, and dielectric properties. The alkylene carbonates can be used alone or in combination of two or more.

As the unsaturated monobasic acid, the same as those exemplified as the above-mentioned unsaturated monobasic acid (B) can be used, and the unsaturated monobasic acid may be used alone or in combination of two or more types. You can also do that.

As the polybasic acid anhydride, those similar to those exemplified as the above-mentioned polybasic acid anhydride (C) can be used, and the polybasic acid anhydride may be used alone or in combination of two or more types. They can also be used together.

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

As the organic solvent, the same ones as those exemplified above can be used, and the organic solvents can be used alone or in combination of two or more kinds.

As the basic catalyst, the same ones as those exemplified above can be used, and the basic catalysts can be used alone or in combination of two or more types.

As the acidic catalyst, the same ones as those exemplified above can be used, and the acidic catalysts can be used alone or in combination of two or more types.

The amount of the resin (D) having an acid group and a polymerizable unsaturated group used is preferably in the range of 10 to 900 parts by mass based on 100 parts by mass of the resin having an acid group and a polymerizable unsaturated group of the present invention. .

Examples of the various (meth)acrylate monomers include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, 2 - Aliphatic mono(meth)acrylate compounds such as ethylhexyl(meth)acrylate and octyl(meth)acrylate; alicyclic mono(meth)acrylates 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, Aromatic mono(meth)acrylate such as phenoxyethyl(meth)acrylate, phenoxyethoxyethyl(meth)acrylate, 2-hydroxy-3-phenoxypropyl(meth)acrylate, phenoxybenzyl(meth)acrylate, phenylphenoxyethyl(meth)acrylate Mono(meth)acrylate compounds such as acrylate compounds: The molecular structures of the various mono(meth)acrylate monomers include polyoxy(poly)oxyethylene chains, (poly)oxypropylene chains, (poly)oxytetramethylene chains, etc. A (poly)oxyalkylene-modified mono(meth)acrylate compound with an alkylene chain introduced; a lactone-modified mono(meth)acrylate compound with a (poly)lactone structure introduced into the molecular structure of the various mono(meth)acrylate compounds mentioned above; ethylene Aliphatic di(meth)acrylate compounds such as glycol di(meth)acrylate, propylene glycol di(meth)acrylate, butanediol di(meth)acrylate, hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate; 1,4-Cyclohexane dimethanol di(meth)acrylate, norbornane di(meth)acrylate, norbornane dimethanol di(meth)acrylate, dicyclopentanyl di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, etc. alicyclic di(meth)acrylate compounds; aromatic di(meth)acrylate compounds such as biphenol di(meth)acrylate and bisphenol di(meth)acrylate; Polyoxyalkylene-modified di(meth)acrylate compounds into which (poly)oxyalkylene chains such as poly)oxyethylene chains, (poly)oxypropylene chains, and (poly)oxytetramethylene chains are introduced; the various di(meth)acrylates mentioned above. Lactone-modified di(meth)acrylate compounds with a (poly)lactone structure introduced into the molecular structure of the compound; aliphatic tri(meth)acrylate compounds such as trimethylolpropane tri(meth)acrylate and glycerin tri(meth)acrylate; (Poly)oxyalkylene in which a (poly)oxyalkylene chain such as a (poly)oxyethylene chain, (poly)oxypropylene chain, or (poly)oxytetramethylene chain is introduced into the molecular structure of an aliphatic tri(meth)acrylate compound. Modified tri(meth)acrylate compound; lactone-modified tri(meth)acrylate compound in which a (poly)lactone structure is introduced into the molecular structure of the aliphatic tri(meth)acrylate compound; pentaerythritol tetra(meth)acrylate, ditrimethylolpropane Tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate and other tetrafunctional or higher functional aliphatic poly(meth)acrylate compounds; the molecular structure of the aliphatic poly(meth)acrylate compound includes (poly)oxyethylene chains, Tetrafunctional or higher (poly)oxyalkylene-modified poly(meth)acrylate compound into which a (poly)oxyalkylene chain such as a (poly)oxypropylene chain or a (poly)oxytetramethylene chain is introduced; the aliphatic poly(meth)acrylate Examples include lactone-modified poly(meth)acrylate compounds having four or more functional groups in which a (poly)lactone structure is introduced into the molecular structure of the compound.

In addition to those mentioned above, the other (meth)acrylate monomers include (meth)acrylate monomers that use a phenol compound, a cyclic carbonate compound or a cyclic ether compound, and an unsaturated monocarboxylic acid as essential reaction raw materials. can be used.

Examples of the phenolic compound include cresol, xylenol, catechol, resorcinol, hydroquinone, 3-methylcatechol, 4-methylcatechol, 4-allylpyrocatechol, 1,2,3-trihydroxybenzene, 1,2,4- Trihydroxybenzene, 1-naphthol, 2-naphthol, 1,3-naphthalene diol, 1,5-naphthalene diol, 2,6-naphthalene diol, 2,7-naphthalene diol, hydrogenated bisphenol, hydrogenated biphenol, polyphenylene ether Type diols, polynaphthylene ether type diols, phenol novolak resins, cresol novolak resins, bisphenol novolak type resins, naphthol novolak type resins, phenol aralkyl type resins, naphthol aralkyl type resins, phenol resins containing a cyclocyclic structure, and the like.

Examples of the cyclic carbonate compound include ethylene carbonate, propylene carbonate, butylene carbonate, pentylene carbonate, and the like. These cyclic carbonate compounds can be used alone or in combination of two or more.

Examples of the cyclic ether compound include ethylene oxide, propylene oxide, and tetrahydrofuran. These cyclic ether compounds can be used alone or in combination of two or more.

As the unsaturated monocarboxylic acid, those similar to those exemplified as the above-mentioned unsaturated monobasic acid (B) can be used.

The content of the other (meth)acrylate monomers in the curable resin composition of the present invention is preferably 90% by mass or less.

In addition, the curable resin composition of the present invention may optionally contain a curing accelerator, an ultraviolet absorber, a polymerization inhibitor, an antioxidant, an organic solvent, an inorganic filler, fine polymer particles, a pigment, an antifoaming agent, It may also contain various additives such as viscosity modifiers, leveling agents, flame retardants, and storage stabilizers.

The curing accelerator accelerates the curing reaction, and includes, for example, phosphorus compounds, amine compounds, imidazole, organic acid metal salts, Lewis acids, amine complex salts, and the like. These curing accelerators can be used alone or in combination of two or more. Further, the amount of the curing accelerator added is preferably in the range of 0.01 to 10% by mass based on the solid content of the curable resin composition.

Examples of the ultraviolet absorber include 2-[4-{(2-hydroxy-3-dodecyloxypropyl)oxy}-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1 , 3,5-triazine, 2-[4-{(2-hydroxy-3-tridecyloxypropyl)oxy}-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1, Triazine derivatives such as 3,5-triazine, 2-(2'-xanthenecarboxy-5'-methylphenyl)benzotriazole, 2-(2'-o-nitrobenzyloxy-5'-methylphenyl)benzotriazole, 2 -xanthenecarboxy-4-dodecyloxybenzophenone, 2-o-nitrobenzyloxy-4-dodecyloxybenzophenone, and the like. These ultraviolet absorbers can be used alone or in combination of two or more.

As the polymerization inhibitor, the same ones as those exemplified above can be used, and the polymerization inhibitors can be used alone or in combination of two or more kinds.

As the antioxidant, the same antioxidants as those exemplified above can be used, and the antioxidants can be used alone or in combination of two or more.

As the organic solvent, the same ones as those exemplified above can be used, and the organic solvents can be used alone or in combination of two or more kinds.

Examples of the inorganic filler include fused silica, crystalline silica, alumina, silicon nitride, and aluminum hydroxide.

As the pigment, known and commonly used inorganic pigments and organic pigments can be used.

Examples of the inorganic pigment include white pigment, antimony red, red red, cadmium red, cadmium yellow, cobalt blue, deep blue, ultramarine blue, carbon black, and graphite. These inorganic pigments can be used alone or in combination of two or more.

Examples of the white pigment include titanium oxide, zinc oxide, magnesium oxide, zirconium oxide, aluminum oxide, barium sulfate, silica, talc, mica, aluminum hydroxide, calcium silicate, aluminum silicate, hollow resin particles, and zinc sulfide. etc.

Examples of the organic pigments include quinacridone pigments, quinacridonequinone pigments, dioxazine pigments, phthalocyanine pigments, anthrapyrimidine pigments, anthanthrone pigments, indanthrone pigments, flavanthrone pigments, perylene pigments, diketopyrrolopyrrole pigments, perinone pigments, Examples include quinophthalone pigments, anthraquinone pigments, thioindigo pigments, benzimidazolone pigments, and azo pigments. These organic pigments can be used alone or in combination of two or more.

Examples of the flame retardant include red phosphorus, ammonium phosphates such as monoammonium phosphate, diammonium phosphate, triammonium phosphate, and ammonium polyphosphate; inorganic phosphorus compounds such as phosphoric acid amide; phosphate ester compounds, and phosphones. acid compounds, phosphinic acid compounds, phosphine oxide compounds, phosphorane compounds, organic nitrogen-containing phosphorus compounds, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(2,5-dihydroxy Cyclic organic compounds such as phenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(2,7-dihydroxynaphthyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide, etc. Organic phosphorus compounds such as phosphorus compounds and derivatives obtained by reacting them with compounds such as epoxy resins and phenol resins; nitrogen-based flame retardants such as triazine compounds, cyanuric acid compounds, isocyanuric acid compounds, and phenothiazines; silicone oils, silicone rubber, Examples include silicone flame retardants such as silicone resins; inorganic flame retardants such as metal hydroxides, metal oxides, metal carbonate compounds, metal powders, boron compounds, and low-melting glass. These flame retardants can be used alone or in combination of two or more. Furthermore, when these flame retardants are used, they are preferably in the range of 0.1 to 20% by mass based on the total resin composition.

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. Further, when ultraviolet rays are used as the active energy rays, in order to efficiently perform the curing reaction by ultraviolet rays, the irradiation may be performed in an inert gas atmosphere such as nitrogen gas, or in an air atmosphere.

As a source of ultraviolet light, an ultraviolet lamp is generally used from the viewpoint of practicality and economy. Specifically, low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, xenon lamps, gallium lamps, metal halide lamps, sunlight, LEDs, etc. can be mentioned.

The cumulative amount of active energy rays is not particularly limited, but is preferably 0.1 to 50 kJ/m ² , more preferably 0.5 to 10 kJ/m ² . It is preferable that the cumulative light amount is within the above range because it is possible to prevent or suppress the occurrence of uncured portions.

Note that the irradiation with the active energy rays may be performed in one step, or may be performed in two or more steps.

In addition, the cured product of the present invention has excellent alkali developability, heat resistance, and high elastic modulus, so that it can be used, for example, in solder resists, interlayer insulation materials, packaging materials, underfill materials, etc. in semiconductor device applications. It can be suitably used as a package adhesive layer for circuit elements and the like, or as an adhesive layer between integrated circuit elements and circuit boards. Further, it can be suitably used for thin film transistor protective films, liquid crystal color filter protective films, pigment resists for color filters, black matrix resists, spacers, etc. in thin display applications such as LCDs and OELDs. Among these, it can be particularly suitably used for solder resist applications.

The resist member of the present invention can be prepared, for example, by coating the resin material for solder resist on a base material, drying it by evaporating the organic solvent at a temperature range of about 60 to 100°C, and then forming a photomask on which a desired pattern is formed. It can be obtained by exposing the film to active energy rays through the film, developing the unexposed areas 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-clad laminates made of copper, aluminum, and the like.

Hereinafter, the present invention will be specifically explained with reference to Examples and Comparative Examples. Note that the present invention is not limited to the examples listed below.
<Evaluation of GPC measurement)>
Measurements were made using the following measuring device and measurement conditions, and the synthesis of a phenol resin obtained by the synthesis method shown below and an epoxy resin obtained using the phenol resin was confirmed based on GPC measurement.
Measuring device: “HLC-8320 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 G3000HXL" manufactured by Tosoh Corporation "TSK-GEL G4000HXL"
Detector: RI (differential refractometer)
Data processing: “GPC Workstation EcoSEC-WorkStation” manufactured by Tosoh Corporation
Measurement conditions: Column temperature 40℃
Developing solvent Tetrahydrofuran
Flow rate: 1.0 ml/min Standard: The following monodisperse polystyrene with a known molecular weight was used in accordance with the measurement manual of the above-mentioned "GPC Workstation EcoSEC-WorkStation".
(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 1.0% by mass tetrahydrofuran solution in terms of epoxy resin solid content was filtered through a microfilter (50 μl).
Regarding the content ratio (area %) of residual (unreacted) catechol compounds in the phenol resin, from the viewpoint of reducing volatile matter during curing, the content ratio of residual catechol compounds is 5.0 area %. It is preferable that it is below.

<Softening point>
Measurement method: Based on JIS K7234 (ring and ball method), the softening point (°C) of the phenol resin obtained in the synthesis example shown below was measured.

[Synthesis Example 1] Synthesis of phenolic resin (a-1) 330.3 parts by mass (3.00 mol) of catechol, 328.3 parts by mass of toluene, and para-toluenesulfonic acid were placed in a 2L flask equipped with a thermometer, cooling tube, and stirrer. 0.95 parts by mass (0.05 mol) was charged, and the temperature was raised to 100° C. while dissolving. While maintaining the temperature, 106.1 parts by mass (1.00 mol) of benzaldehyde was added dropwise over 1 hour, and the reaction was further continued for 3 hours. After the reaction, 616.2 parts by mass of methyl isobutyl ketone was charged, washed with water until neutral, concentrated under reduced pressure at 150°C, and unreacted catechol was distilled off while blowing in steam to obtain the desired product. 261 parts by mass of phenol resin (a-1) was obtained. The hydroxyl equivalent of the obtained phenol resin (a-1) was 86 g/eq, the softening point was 96°C, and the melt viscosity at 150°C was 3.6 dPa·s. A GPC chart of the obtained phenolic resin (a-1) is shown in FIG. Production was confirmed by the main peak at peak top 34.1 min.
In addition, the "principal component" mentioned here means that it contains 50 area% or more in terms of GPC area%, and the GPC area% of each component is the sum of the GPC peak area value of each component and the GPC peak area value of all components. refers to the value divided by

[Synthesis Example 2] Synthesis of phenolic resin (a-2) Synthesis was carried out in the same manner as in Synthesis Example 1 except that the amount of catechol charged was changed to 440.4 parts by mass (4.00 mol). ) was obtained in an amount of 275 parts by mass. The hydroxyl equivalent of the obtained phenol resin (a-2) was 82 g/eq, the softening point was 89°C, and the melt viscosity at 150°C was 1.9 dPa·s.

[Synthesis Example 3] Synthesis of phenolic resin (a-3) Synthesis was performed in the same manner as in Synthesis Example 1 except that the amount of catechol charged was changed to 550.6 parts by mass (5.00 mol). ) was obtained in an amount of 260 parts by mass. The hydroxyl equivalent of the obtained phenol resin (a-3) was 80 g/eq, the softening point was 92°C, and the melt viscosity at 150°C was 2.6 dPa·s.

[Synthesis Example 4] Synthesis of phenolic resin (a-4) Synthesis was performed in the same manner as in Synthesis Example 1 except that the amount of catechol charged was changed to 660.7 parts by mass (6.00 mol). ) was obtained in an amount of 260 parts by mass. The hydroxyl equivalent of the obtained phenol resin (a-4) was 82 g/eq, the softening point was 91°C, and the melt viscosity at 150°C was 2.3 dPa·s.

[Synthesis Example 5] Synthesis of phenolic resin (a-5) 495.5 parts by mass (4.50 mol) of catechol and 4.9 parts by mass of 3-mercaptopropionic acid ( 0.046 mol), 247.8 parts by mass of 1,4-dioxane, and 52.5 parts by mass (0.54 mol) of 98% sulfuric acid were charged, and the temperature was raised to 40° C. under nitrogen flow. While maintaining the temperature, 87.0 parts by mass (1.55 mol) of acetone was added dropwise over 1 hour, and the mixture was reacted for an additional 3 hours. After the reaction, 520.0 parts by mass of methyl isobutyl ketone was added and washed with water until the mixture became neutral. Next, the system was dehydrated by azeotropy, passed through microfiltration, and then concentrated under reduced pressure at 150°C. Further, unreacted catechol was distilled off while blowing water vapor, thereby obtaining 236 parts by mass of phenol resin (a-5). The hydroxyl equivalent of the obtained phenol resin (a-5) was 72 g/eq, and the melt viscosity (150° C.) was 0.7 dPa·s.

[Synthesis Example 6] Synthesis of phenolic resin (a-6) In a 2L flask equipped with a thermometer, cooling tube, and stirrer, 200.0 parts by mass (1.82 mol) of catechol, 220.0 parts by mass of 1,4-dioxane, 35.0 parts by mass (0.36 mol) of 98% sulfuric acid was charged, and the temperature was raised to 40° C. under nitrogen flow. While maintaining the temperature, 60.0 parts by mass (1.07 mol) of acetone was added dropwise over 1 hour, and the reaction was further continued for 3 hours. After the reaction, 300.0 parts by mass of methyl isobutyl ketone was added and washed with water until the mixture became neutral. Next, the system was dehydrated by azeotropy, passed through microfiltration, and then concentrated under reduced pressure at 150°C to obtain 160 parts by mass of phenol resin (a-6). The hydroxyl equivalent of the obtained phenol resin (a-6) was 71 g/eq, and the melt viscosity (150°C) was 0.6 dPa·s.

[Synthesis Example 7] Synthesis of Epoxy Resin (A-1) 180.0 parts by mass of the phenolic resin (a-1) obtained in Synthesis Example 1 and 774.0 parts by mass of epichlorohydrin were placed in a 2L flask equipped with a thermometer, a cooling tube, and a stirrer. 4 parts by mass (8.37 mol) was charged, and the temperature was raised to 50° C. while stirring and dissolving. Next, 9.74 parts by mass of a 50% aqueous benzyltrimethylammonium chloride solution was added, and the mixture was reacted for 24 hours at a temperature of 50°C. Furthermore, 199.2 parts by mass of a 49% aqueous sodium hydroxide solution (1.10 equivalents to the hydroxyl group) was added dropwise over 3 hours, and the mixture was further reacted at 50° C. for 1 hour. After the reaction was completed, 246.7 parts by mass of isopropyl alcohol was added, stirring was stopped, the aqueous layer accumulated in the lower layer was removed, stirring was restarted, and unreacted epichlorohydrin was distilled off at 150° C. under reduced pressure. 517.6 parts by mass of methyl isobutyl ketone was added to and dissolved in the obtained crude epoxy resin, and washing was repeated with 152.2 parts by mass of water until the pH of the washing liquid became neutral. Next, the system was dehydrated by azeotropy, and after passing through microfiltration, the solvent was distilled off under reduced pressure to obtain 273.0 parts by mass of the desired epoxy resin (A-1). The epoxy equivalent of the obtained epoxy resin (A-1) was 159 g/eq, and the melt viscosity at 150° C. was 0.52 dPa·s. A GPC chart of the epoxy resin (A-1) is shown in FIG. Production was confirmed by the main peak at peak top 32.4 min.

[Synthesis Example 8] Synthesis of epoxy resin (A-2) Except that the charged amount of the phenol resin (a-2) obtained in Synthesis Example 2 was 175 parts by mass and 793.4 parts by mass (8.58 mol) of epichlorohydrin. was synthesized in the same manner as in Synthesis Example 7 to obtain 255 parts by mass of epoxy resin (A-2). The epoxy equivalent was 163 g/eq, and the melt viscosity at 150°C was 0.50 dPa·s.

[Synthesis Example 9] Synthesis of epoxy resin (A-3) Synthesis except that the amount of phenol resin (a-3) obtained in Synthesis Example 3 was 180 parts by mass and 832.5 parts by mass (9 mol) of epichlorohydrin. Synthesis was carried out in the same manner as in Example 7 to obtain 271 parts by mass of epoxy resin (A-3). The epoxy equivalent was 154 g/eq, and the melt viscosity at 150°C was 0.48 dPa·s.

[Synthesis Example 10] Synthesis of epoxy resin (A-4) Except that the amount of phenol resin (a-4) obtained in Synthesis Example 4 was 180 parts by mass and 794.5 parts by mass (8.59 mol) of epichlorohydrin. was synthesized in the same manner as in Synthesis Example 7 to obtain 266 parts by mass of epoxy resin (A-4). The epoxy equivalent was 161 g/eq, and the melt viscosity at 150°C was 0.48 dPa·s.

[Synthesis Example 11] Synthesis of epoxy resin (A-5) 170.0 parts by mass of the phenol resin (a-5) obtained in Synthesis Example 5 (2 parts by mass as hydroxyl groups) was placed in a 2L flask equipped with a thermometer, a cooling tube, and a stirrer. .36 mol) and 873.6 parts by mass (9.44 mol) of epichlorohydrin were charged, and the temperature was raised to 50° C. while stirring and dissolving. Next, 10.35 parts by mass of a 50% aqueous tetramethylammonium solution was added and reacted for 24 hours. Furthermore, 211.6 parts by mass of a 49% aqueous sodium hydroxide solution (1.10 equivalents to the hydroxyl group) was added dropwise over 3 hours, and the mixture was further reacted at 50° C. for 1 hour. After the reaction was completed, 262.1 parts by mass of isopropyl alcohol was added, stirring was stopped, the aqueous layer accumulated in the lower layer was removed, stirring was restarted, and unreacted epichlorohydrin was distilled off at 150° C. under reduced pressure. 517.8 parts by mass of methyl isobutyl ketone was added to and dissolved in the obtained crude epoxy resin, and washing was repeated with 152.3 parts by mass of water until the pH of the washing solution became neutral. Next, the system was dehydrated by azeotropy, and after passing through microfiltration, the solvent was distilled off under reduced pressure to obtain 270.0 parts by mass of the target epoxy resin (A-5). The obtained epoxy resin (A-5) was a viscous semi-solid at room temperature, had an epoxy equivalent of 152 g/eq, and a melt viscosity (150° C.) of 0.2 dPa·s.

[Synthesis Example 12] Synthesis of epoxy resin (A-6) 100.0 parts by mass of the phenolic resin (a-6) obtained in Synthesis Example 6 (1 part by mass as hydroxyl group) was placed in a 2L flask equipped with a thermometer, a cooling tube, and a stirrer. .41 mol) and 513.9 parts by mass (5.56 mol) of epichlorohydrin were charged, and the temperature was raised to 50° C. while stirring and dissolving. Next, 6.09 parts by mass of a 50% aqueous tetramethylammonium solution was added and reacted for 24 hours. Furthermore, 124.7 parts by mass of a 49% aqueous sodium hydroxide solution (1.10 equivalents to the hydroxyl group) was added dropwise over 3 hours, and the mixture was further reacted at 50° C. for 1 hour. After the reaction was completed, 154.2 parts by mass of isopropyl alcohol was added, stirring was stopped, the aqueous layer accumulated in the lower layer was removed, stirring was restarted, and unreacted epichlorohydrin was distilled off at 150° C. under reduced pressure. 614.1 parts by mass of methyl isobutyl ketone was added to and dissolved in the obtained crude epoxy resin, and washing was repeated with 180.6 parts by mass of water until the pH of the washing liquid became neutral. Next, the system was dehydrated by azeotropy, and after passing through microfiltration, the solvent was distilled off under reduced pressure to obtain 160.0 parts by mass of the desired epoxy resin (A-6). The epoxy equivalent of the obtained epoxy resin (A-6) was 158 g/eq, and the melt viscosity (150° C.) was 0.1 dPa·s.

[Synthesis Example 13] Resin having acid group and polymerizable unsaturated group (C-1)
123 parts by mass of diethylene glycol monoethyl ether acetate was placed in a flask equipped with a thermometer, a stirrer, and a reflux condenser, and an orthocresol novolac type epoxy resin "EPICLON N-680" (manufactured by DIC Corporation, softening point 86°C, Epoxy equivalent: 214 g/eq) (hereinafter abbreviated as "epoxy resin (1)") 214 parts by mass was dissolved, 0.9 parts by mass of dibutylhydroxytoluene and 0.2 parts by mass of methoquinone were added, and then acrylic acid 72 parts by mass and 1.4 parts by mass of triphenylphosphine were added, and the reaction was carried out at 120° C. for 10 hours while blowing air. Next, 72 parts by mass of diethylene glycol monoethyl ether acetate and 76 parts by mass of tetrahydrophthalic anhydride were added and reacted at 110°C for 3 hours to obtain a resin (C-1) having an acid group and a polymerizable unsaturated group. The nonvolatile content of this resin (C-1) having an acid group and a polymerizable unsaturated group was 65% by mass, and the solid content acid value was 80 mgKOH/g.

(Example 1 Resin having acid group and polymerizable unsaturated group (B-1))
Put 57.8 parts by mass of diethylene glycol monoethyl ether acetate into a flask equipped with a thermometer, a stirrer, and a reflux condenser, and dissolve 159 parts by mass of the epoxy resin (A-1) obtained in Synthesis Example 7. After adding 0.6 parts by mass of dibutylhydroxytoluene and 0.1 parts by mass of methoquinone, 72 parts by mass of acrylic acid and 1.2 parts by mass of triphenylphosphine were added, and the reaction was carried out at 120°C for 10 hours while blowing air. . Next, 100.2 parts by mass of diethylene glycol monoethyl ether acetate and 62.3 parts by mass of tetrahydrophthalic anhydride were added and reacted at 110°C for 3 hours to obtain a resin (B-1) having an acid group and a polymerizable unsaturated group. Ta. The nonvolatile content of this resin (B-1) having an acid group and a polymerizable unsaturated group was 65% by mass, and the solid content acid value was 81 mgKOH/g.

(Example 2 Resin having acid group and polymerizable unsaturated group (B-2))
Put 58.8 parts by mass of diethylene glycol monoethyl ether acetate into a flask equipped with a thermometer, a stirrer, and a reflux condenser, and dissolve 163 parts by mass of the epoxy resin (A-2) obtained in Synthesis Example 8. After adding 0.6 parts by mass of dibutylhydroxytoluene and 0.1 parts by mass of methoquinone, 72 parts by mass of acrylic acid and 1.2 parts by mass of triphenylphosphine were added, and the reaction was carried out at 120°C for 10 hours while blowing air. . Next, 101.3 parts by mass of diethylene glycol monoethyl ether acetate and 62.3 parts by mass of tetrahydrophthalic anhydride were added and reacted at 110°C for 3 hours to obtain a resin (B-2) having an acid group and a polymerizable unsaturated group. Ta. The nonvolatile content of this resin (B-2) having acid groups and polymerizable unsaturated groups was 65% by mass, and the solid content acid value was 80 mgKOH/g.

(Example 3 Resin having acid group and polymerizable unsaturated group (B-3))
Put 56.5 parts by mass of diethylene glycol monoethyl ether acetate into a flask equipped with a thermometer, a stirrer, and a reflux condenser, and dissolve 154 parts by mass of the epoxy resin (A-3) obtained in Synthesis Example 9. After adding 0.6 parts by mass of dibutylhydroxytoluene and 0.1 parts by mass of methoquinone, 72 parts by mass of acrylic acid and 1.1 parts by mass of triphenylphosphine were added, and the reaction was carried out at 120°C for 10 hours while blowing air. . Next, 97.9 parts by mass of diethylene glycol monoethyl ether acetate and 60.8 parts by mass of tetrahydrophthalic anhydride were added and reacted at 110°C for 3 hours to obtain a resin (B-3) having an acid group and a polymerizable unsaturated group. Ta. The nonvolatile content of this resin (B-3) having an acid group and a polymerizable unsaturated group was 65% by mass, and the solid content acid value was 80 mgKOH/g.

(Example 4 Resin having acid group and polymerizable unsaturated group (B-4))
Put 58.3 parts by mass of diethylene glycol monoethyl ether acetate into a flask equipped with a thermometer, a stirrer, and a reflux condenser, and dissolve 161 parts by mass of the epoxy resin (A-4) obtained in Synthesis Example 10. After adding 0.6 parts by mass of dibutylhydroxytoluene and 0.1 parts by mass of methoquinone, 72 parts by mass of acrylic acid and 1.2 parts by mass of triphenylphosphine were added, and the reaction was carried out at 120°C for 10 hours while blowing air. . Next, 100.8 parts by mass of diethylene glycol monoethyl ether acetate and 62.3 parts by mass of tetrahydrophthalic anhydride were added and reacted at 110°C for 3 hours to obtain a resin (B-4) having an acid group and a polymerizable unsaturated group. Ta. The nonvolatile content of this resin (B-4) having acid groups and polymerizable unsaturated groups was 65% by mass, and the solid content acid value was 81 mgKOH/g.

(Example 5 Resin having acid group and polymerizable unsaturated group (B-5))
56 parts by mass of diethylene glycol monoethyl ether acetate was put into a flask equipped with a thermometer, a stirrer, and a reflux condenser, and 152 parts by mass of the epoxy resin (A-5) obtained in Synthesis Example 11 was dissolved therein. After adding 0.6 parts by mass of toluene and 0.1 parts by mass of methoquinone, 72 parts by mass of acrylic acid and 1.1 parts by mass of triphenylphosphine were added, and reaction was carried out at 120° C. for 10 hours while blowing air. Next, 97.4 parts by mass of diethylene glycol monoethyl ether acetate and 60.8 parts by mass of tetrahydrophthalic anhydride were added and reacted at 110°C for 3 hours to obtain a resin (B-5) having an acid group and a polymerizable unsaturated group. Ta. The nonvolatile content of this resin (B-5) having an acid group and a polymerizable unsaturated group was 65% by mass, and the solid content acid value was 82 mgKOH/g.

(Example 6 Resin having acid group and polymerizable unsaturated group (B-6))
Put 57.5 parts by mass of diethylene glycol monoethyl ether acetate into a flask equipped with a thermometer, a stirrer, and a reflux condenser, and dissolve 158 parts by mass of the epoxy resin (A-6) obtained in Synthesis Example 12. After adding 0.6 parts by mass of dibutylhydroxytoluene and 0.1 parts by mass of methoquinone, 72 parts by mass of acrylic acid and 1.2 parts by mass of triphenylphosphine were added, and the reaction was carried out at 120°C for 10 hours while blowing air. . Next, 99.1 parts by mass of diethylene glycol monoethyl ether acetate and 60.8 parts by mass of tetrahydrophthalic anhydride were added and reacted at 110°C for 3 hours to obtain a resin (B-6) having an acid group and a polymerizable unsaturated group. Ta. The nonvolatile content of this resin (B-6) having an acid group and a polymerizable unsaturated group was 65% by mass, and the solid content acid value was 80 mgKOH/g.

(Example 7 Resin having acid group and polymerizable unsaturated group (B-7))
Put 57.4 parts by mass of diethylene glycol monoethyl ether acetate into a flask equipped with a thermometer, a stirrer, and a reflux condenser, and dissolve 159 parts by mass of the epoxy resin (A-1) obtained in Synthesis Example 7. After adding 0.6 parts by mass of dibutylhydroxytoluene and 0.1 parts by mass of methoquinone, 70.6 parts by mass of acrylic acid and 1.2 parts by mass of triphenylphosphine were added, and the reaction was carried out at 120°C for 8 hours while blowing air. I did it. Next, 100.6 parts by mass of diethylene glycol monoethyl ether acetate and 63.8 parts by mass of tetrahydrophthalic anhydride were added and reacted at 110°C for 3 hours to obtain a resin (B-7) having an acid group and a polymerizable unsaturated group. Ta. The nonvolatile content of this resin (B-7) having an acid group and a polymerizable unsaturated group was 65% by mass, and the solid content acid value was 80 mgKOH/g.

(Example 8 Resin having acid group and polymerizable unsaturated group (B-8))
Put 58.7 parts by mass of diethylene glycol monoethyl ether acetate into a flask equipped with a thermometer, a stirrer, and a reflux condenser, and dissolve 159 parts by mass of the epoxy resin (A-1) obtained in Synthesis Example 7. After adding 0.6 parts by mass of dibutylhydroxytoluene and 0.1 parts by mass of methoquinone, 75.6 parts by mass of acrylic acid and 1.2 parts by mass of triphenylphosphine were added, and the reaction was carried out at 120°C for 8 hours while blowing air. I did it. Next, 99.6 parts by mass of diethylene glycol monoethyl ether acetate and 59.3 parts by mass of tetrahydrophthalic anhydride were added and reacted at 110°C for 3 hours to obtain a resin (B-8) having an acid group and a polymerizable unsaturated group. Ta. The nonvolatile content of this resin (B-8) having an acid group and a polymerizable unsaturated group was 65% by mass, and the solid content acid value was 82 mgKOH/g.

(Example 9 Resin having acid group and polymerizable unsaturated group (B-9))
Put 57.8 parts by mass of diethylene glycol monoethyl ether acetate into a flask equipped with a thermometer, a stirrer, and a reflux condenser, and dissolve 159 parts by mass of the epoxy resin (A-1) obtained in Synthesis Example 7. After adding 0.6 parts by mass of dibutylhydroxytoluene and 0.1 parts by mass of methoquinone, 72 parts by mass of acrylic acid and 1.2 parts by mass of triphenylphosphine were added, and the reaction was carried out at 120°C for 10 hours while blowing air. . Next, 86 parts by mass of diethylene glycol monoethyl ether acetate and 36 parts by mass of succinic anhydride were added and reacted at 110°C for 3 hours to obtain a resin (B-9) having an acid group and a polymerizable unsaturated group. The nonvolatile content of this resin (B-9) having acid groups and polymerizable unsaturated groups was 65% by mass, and the solid content acid value was 79 mgKOH/g.

(Example 10 Resin having acid group and polymerizable unsaturated group (B-10))
Put 57.8 parts by mass of diethylene glycol monoethyl ether acetate into a flask equipped with a thermometer, a stirrer, and a reflux condenser, and dissolve 159 parts by mass of the epoxy resin (A-1) obtained in Synthesis Example 7. After adding 0.6 parts by mass of dibutylhydroxytoluene and 0.1 parts by mass of methoquinone, 72 parts by mass of acrylic acid and 1.2 parts by mass of triphenylphosphine were added, and the reaction was carried out at 120°C for 10 hours while blowing air. . Next, 99.8 parts by mass of diethylene glycol monoethyl ether acetate and 61.6 parts by mass of hexahydrophthalic anhydride were added and reacted at 110°C for 3 hours to obtain a resin having an acid group and a polymerizable unsaturated group (B-10). I got it. The nonvolatile content of this resin (B-10) having an acid group and a polymerizable unsaturated group was 65% by mass, and the solid content acid value was 80 mgKOH/g.

(Example 11 Resin having acid group and polymerizable unsaturated group (B-11))
Put 57.8 parts by mass of diethylene glycol monoethyl ether acetate into a flask equipped with a thermometer, a stirrer, and a reflux condenser, and dissolve 159 parts by mass of the epoxy resin (A-1) obtained in Synthesis Example 7. After adding 0.6 parts by mass of dibutylhydroxytoluene and 0.1 parts by mass of methoquinone, 72 parts by mass of acrylic acid and 1.2 parts by mass of triphenylphosphine were added, and the reaction was carried out at 120°C for 10 hours while blowing air. . Next, 86.3 parts by mass of diethylene glycol monoethyl ether acetate and 36.5 parts by mass of tetrahydrophthalic anhydride were added and reacted at 110°C for 3 hours to obtain a resin (B-11) having an acid group and a polymerizable unsaturated group. Ta. The nonvolatile content of this resin (B-11) having an acid group and a polymerizable unsaturated group was 65% by mass, and the solid content acid value was 52 mgKOH/g.

(Example 12 Resin having acid group and polymerizable unsaturated group (B-12))
Put 57.8 parts by mass of diethylene glycol monoethyl ether acetate into a flask equipped with a thermometer, a stirrer, and a reflux condenser, and dissolve 159 parts by mass of the epoxy resin (A-1) obtained in Synthesis Example 7. After adding 0.6 parts by mass of dibutylhydroxytoluene and 0.1 parts by mass of methoquinone, 72 parts by mass of acrylic acid and 1.2 parts by mass of triphenylphosphine were added, and the reaction was carried out at 120°C for 10 hours while blowing air. . Next, 126.4 parts by mass of diethylene glycol monoethyl ether acetate and 111 parts by mass of tetrahydrophthalic anhydride were added and reacted at 110°C for 3 hours to obtain a resin (B-12) having an acid group and a polymerizable unsaturated group. The nonvolatile content of this resin (B-12) having acid groups and polymerizable unsaturated groups was 65% by mass, and the solid content acid value was 122 mgKOH/g.

(Example 13 Resin having acid group and polymerizable unsaturated group (B-13))
56 parts by mass of diethylene glycol monoethyl ether acetate was put into a flask equipped with a thermometer, a stirrer, and a reflux condenser, and 152 parts by mass of the epoxy resin (A-5) obtained in Synthesis Example 11 was dissolved therein. After adding 0.6 parts by mass of toluene and 0.1 parts by mass of methoquinone, 70.6 parts by mass of acrylic acid and 1.1 parts by mass of triphenylphosphine were added, and the reaction was carried out at 120°C for 10 hours while blowing air. . Next, 96.9 parts by mass of diethylene glycol monoethyl ether acetate and 60.8 parts by mass of tetrahydrophthalic anhydride were added and reacted at 110°C for 3 hours to obtain a resin (B-13) having an acid group and a polymerizable unsaturated group. Ta. The nonvolatile content of this resin (B-13) having an acid group and a polymerizable unsaturated group was 65% by mass, and the solid content acid value was 78 mgKOH/g.

(Example 14 Resin having acid group and polymerizable unsaturated group (B-14))
Put 56.9 parts by mass of diethylene glycol monoethyl ether acetate into a flask equipped with a thermometer, a stirrer, and a reflux condenser, and dissolve 152 parts by mass of the epoxy resin (A-5) obtained in Synthesis Example 11. After adding 0.6 parts by mass of dibutylhydroxytoluene and 0.1 parts by mass of methoquinone, 75.6 parts by mass of acrylic acid and 1.1 parts by mass of triphenylphosphine were added, and the reaction was carried out at 120°C for 10 hours while blowing air. I did it. Next, 96.8 parts by mass of diethylene glycol monoethyl ether acetate and 57.8 parts by mass of tetrahydrophthalic anhydride were added and reacted at 110°C for 3 hours to obtain a resin (B-14) having an acid group and a polymerizable unsaturated group. Ta. The nonvolatile content of this resin (B-14) having an acid group and a polymerizable unsaturated group was 65% by mass, and the solid content acid value was 81 mgKOH/g.

(Example 15 Resin having acid group and polymerizable unsaturated group (B-15))
56 parts by mass of diethylene glycol monoethyl ether acetate was put into a flask equipped with a thermometer, a stirrer, and a reflux condenser, and 152 parts by mass of the epoxy resin (A-5) obtained in Synthesis Example 11 was dissolved therein. After adding 0.6 parts by mass of toluene and 0.1 parts by mass of methoquinone, 72 parts by mass of acrylic acid and 1.1 parts by mass of triphenylphosphine were added, and reaction was carried out at 120° C. for 10 hours while blowing air. Next, 83.5 parts by mass of diethylene glycol monoethyl ether acetate and 35 parts by mass of succinic anhydride were added and reacted at 110°C for 3 hours to obtain a resin (B-15) having an acid group and a polymerizable unsaturated group. The nonvolatile content of this resin (B-15) having an acid group and a polymerizable unsaturated group was 65% by mass, and the solid content acid value was 80 mgKOH/g.

(Example 16 Resin having acid group and polymerizable unsaturated group (B-16))
56 parts by mass of diethylene glycol monoethyl ether acetate was put into a flask equipped with a thermometer, a stirrer, and a reflux condenser, and 152 parts by mass of the epoxy resin (A-5) obtained in Synthesis Example 11 was dissolved therein. After adding 0.6 parts by mass of toluene and 0.1 parts by mass of methoquinone, 72 parts by mass of acrylic acid and 1.1 parts by mass of triphenylphosphine were added, and reaction was carried out at 120° C. for 10 hours while blowing air. Next, 97 parts by mass of diethylene glycol monoethyl ether acetate and 60.1 parts by mass of hexahydrophthalic anhydride were added and reacted at 110°C for 3 hours to obtain a resin (B-16) having an acid group and a polymerizable unsaturated group. Ta. The nonvolatile content of this resin (B-16) having an acid group and a polymerizable unsaturated group was 65% by mass, and the solid content acid value was 81 mgKOH/g.

(Example 17 Resin having acid group and polymerizable unsaturated group (B-17))
56 parts by mass of diethylene glycol monoethyl ether acetate was put into a flask equipped with a thermometer, a stirrer, and a reflux condenser, and 152 parts by mass of the epoxy resin (A-5) obtained in Synthesis Example 11 was dissolved therein. After adding 0.6 parts by mass of toluene and 0.1 parts by mass of methoquinone, 72 parts by mass of acrylic acid and 1.1 parts by mass of triphenylphosphine were added, and reaction was carried out at 120° C. for 10 hours while blowing air. Next, 83.4 parts by mass of diethylene glycol monoethyl ether acetate and 35 parts by mass of tetrahydrophthalic anhydride were added and reacted at 110°C for 3 hours to obtain a resin (B-17) having an acid group and a polymerizable unsaturated group. The nonvolatile content of this resin (B-17) having an acid group and a polymerizable unsaturated group was 65% by mass, and the solid content acid value was 51 mgKOH/g.

(Example 18 Resin having acid group and polymerizable unsaturated group (B-18))
56 parts by mass of diethylene glycol monoethyl ether acetate was put into a flask equipped with a thermometer, a stirrer, and a reflux condenser, and 152 parts by mass of the epoxy resin (A-5) obtained in Synthesis Example 11 was dissolved therein. After adding 0.6 parts by mass of toluene and 0.1 parts by mass of methoquinone, 72 parts by mass of acrylic acid and 1.1 parts by mass of triphenylphosphine were added, and reaction was carried out at 120° C. for 10 hours while blowing air. Next, 122.7 parts by mass of diethylene glycol monoethyl ether acetate and 107.9 parts by mass of tetrahydrophthalic anhydride were added and reacted at 110°C for 3 hours to obtain a resin (B-18) having an acid group and a polymerizable unsaturated group. Ta. The nonvolatile content of this resin (B-18) having acid groups and polymerizable unsaturated groups was 65% by mass, and the solid content acid value was 122 mgKOH/g.

(Example 19: Preparation of curable resin composition (1))
100 parts by mass (65 parts by mass as solid content) of the resin (B-1) having an acid group and a polymerizable unsaturated group with a nonvolatile content of 65% by mass obtained in Example 1, and an orthocresol novolak type epoxy resin as a curing agent. ("EPICLON N-680" manufactured by DIC Corporation, epoxy equivalent: 214) 19.9 parts by mass, 10.7 parts by mass of diethylene glycol monoethyl ether acetate, and a photopolymerization initiator ("Omnirad 907" manufactured by IGM Resins) ), 6.5 parts by mass of dipentaerythritol hexaacrylate, 0.4 parts by mass of 2-ethyl-4-methyl-imidazole, and 0.5 parts by mass of phthalocyanine green, and curable A resin composition (1) was obtained.

(Examples 20 to 37: Preparation of curable resin compositions (2) to (19))
Instead of the resin (B-1) having an acid group and a polymerizable unsaturated group used in Example 1, the resin (B-1) having an acid group and a polymerizable unsaturated group obtained in Examples 2 to 18 and Synthesis Example 13 was used. Curable resin compositions (2) and (19) was obtained.

(Comparative Example 1: Preparation of curable resin composition (C2))
100 parts by mass (65 parts by mass as solid content) of the resin (C-1) having acid groups and polymerizable unsaturated groups with a nonvolatile content of 65% by mass obtained in Synthesis Example 13, and an ortho-cresol novolak type epoxy resin as a curing agent. ("EPICLON N-680" manufactured by DIC Corporation, epoxy equivalent: 214) 19.7 parts by mass, 10.6 parts by mass of diethylene glycol monoethyl ether acetate, and a photopolymerization initiator ("Omnirad 907" manufactured by IGM Resins) ), 6.5 parts by mass of dipentaerythritol hexaacrylate, 0.4 parts by mass of 2-ethyl-4-methyl-imidazole, and 0.5 parts by mass of phthalocyanine green, and curable A resin composition (C2) was obtained.

The following evaluations were performed using the curable resin compositions (1) to (19) and (C2) obtained in the above Examples and Comparative Examples.

[Evaluation method of alkaline developability]
The curable resin compositions obtained in each example and comparative example were applied onto a glass substrate using an applicator to a film thickness of 50 μm, and then heated at 80°C for 60 minutes, 70 minutes, and 80 minutes, respectively. , 90 minutes, 100 minutes, 110 minutes, 120 minutes, 130 minutes, and 140 minutes to create samples with different drying times. These were developed with a 1% by mass aqueous sodium carbonate solution at 30° C. for 180 seconds, and the drying time at 80° C. of the sample that left no residue on the substrate was evaluated as the drying control width. Note that the longer the drying control range, the better the alkali developability.

The compositions and evaluation results of the curable resin compositions (1) to (19) prepared in Examples 19 to 37 and the curable resin composition (C2) prepared in Comparative Example 1 are shown in Tables 1 to 2.

(Example 38: Preparation of curable resin composition (20))
100 parts by mass (65 parts by mass as solid content) of the resin (B-1) having an acid group and a polymerizable unsaturated group with a nonvolatile content of 65% by mass obtained in Example 1, and an orthocresol novolak type epoxy resin as a curing agent. ("EPICLON N-680" manufactured by DIC Corporation, epoxy equivalent: 214) 19.9 parts by mass, 10.7 parts by mass of diethylene glycol monoethyl ether acetate, and a photopolymerization initiator ("Omnirad 907" manufactured by IGM Resins) ) was mixed with 3.25 parts by mass to obtain a curable resin composition (20).

(Examples 39 to 56: Preparation of curable resin compositions (21) to (38))
Instead of the resin (B-1) having an acid group and a polymerizable unsaturated group used in Example 38, the resin (B-1) having an acid group and a polymerizable unsaturated group obtained in Examples 2 to 18 and Synthesis Example 13 was used. Curable resin compositions (21) to (38) was obtained.

(Comparative Example 2: Preparation of curable resin composition (C3))
100 parts by mass (65 parts by mass as solid content) of the resin (C-1) having acid groups and polymerizable unsaturated groups with a nonvolatile content of 65% by mass obtained in Synthesis Example 13, and an ortho-cresol novolak type epoxy resin as a curing agent. ("EPICLON N-680" manufactured by DIC Corporation, epoxy equivalent: 214) 19.7 parts by mass, 10.6 parts by mass of diethylene glycol monoethyl ether acetate, and a photopolymerization initiator ("Omnirad 907" manufactured by IGM Resins) ) was mixed with 3.25 parts by mass to obtain a curable resin composition (C3).

The following evaluations were performed using the curable resin compositions (20) to (38) and (C3) obtained in the above Examples and Comparative Examples.

[Heat resistance evaluation method]
The curable resin composition obtained in each Example and Comparative Example was applied to a film thickness of 50 μm on copper foil (manufactured by Furukawa Sangyo Co., Ltd., electrolytic copper foil “F2-WS” 18 μm) using an applicator. and dried at 80°C for 30 minutes. Next, after irradiating with ultraviolet rays at 10 kJ/m ² using a metal halide lamp, the film was heated at 160° C. for 1 hour to obtain a cured coating film. Next, the cured coating film was peeled off from the copper foil to obtain a cured product. A test piece of 6 mm x 35 mm was cut out from the cured product, and measured using a viscoelasticity measuring device (DMA: solid viscoelasticity measuring device "RSAII" manufactured by Rheometric Co., Ltd., tensile method: frequency 1 Hz, heating rate 3 ° C./min). The temperature at which the change in elastic modulus was maximum was evaluated as the glass transition temperature. Note that the higher the glass transition temperature, the better the heat resistance.

[Evaluation method of elasticity]
The elasticity was evaluated by measuring the elastic modulus using a tensile test.

<Tensile test>
The test piece 1 was cut into a size of 10 mm x 80 mm, and the test piece was subjected to a tensile test under the following measurement conditions using a precision universal testing machine "AG-IS" manufactured by Shimadzu Corporation. The elastic modulus (MPa) until the test piece broke was measured and evaluated according to the following criteria.

Measurement conditions: temperature 23°C, humidity 50%, distance between gauge lines 20mm, distance between fulcrums 20mm, tensile speed 10mm/min

The compositions and evaluation results of the curable resin compositions (20) to (38) produced in Examples 38 to 56 and the curable resin composition (C3) produced in Comparative Example 3 are shown in Tables 3 and 4.

The parts by mass of resins having acid groups and polymerizable unsaturated groups in Tables 1 to 4 are solid content values.

"Curing agent" in Tables 1 to 4 indicates an orthocresol novolac type epoxy resin ("EPICLON N-680" manufactured by DIC Corporation).

"Organic solvent" in Tables 1 to 4 indicates diethylene glycol monoethyl ether acetate.

"Photopolymerization initiator" in Tables 1 to 4 refers to "Omnirad-907" manufactured by IGM Resins.

Examples 19 to 37 shown in Tables 1 and 2 are examples of curable resin compositions using the resins having acid groups and polymerizable unsaturated groups of the present invention. It was confirmed that these curable resin compositions had excellent alkali developability.

Further, Examples 38 to 56 shown in Tables 3 to 4 are examples of curable resin compositions using the resins having acid groups and polymerizable unsaturated groups of the present invention. It was confirmed that the cured products of these curable resin compositions had excellent heat resistance and high elastic modulus.

On the other hand, Comparative Examples 2 and 3 shown in Tables 3 and 4 are glycidyl obtained by reacting a phenol resin having at least two catechol skeletons and epihalohydrin as raw materials for resins having acid groups and polymerizable unsaturated groups. This is an example of a curable resin composition that does not use an epoxy resin containing an ether group-containing compound. It was confirmed that the cured product of the curable resin composition obtained in Comparative Example 3 had insufficient heat resistance and elastic modulus.

Claims (9)

A phenol resin having at least two catechol skeletons derived from a catechol compound, and an epoxy resin (A) containing a glycidyl ether group-containing compound obtained by reacting epihalohydrin;
an unsaturated monobasic acid (B),
A resin having an acid group and a polymerizable unsaturated group, which contains a polybasic acid anhydride (C) as an essential reaction raw material. The resin having an acid group and a polymerizable unsaturated group according to claim 1, wherein the phenol resin is a reaction product of a catechol compound and a ketone group-containing compound. The amount of the unsaturated monobasic acid (B) used is such that the number of moles of acid groups contained in the unsaturated monobasic acid (B) is 0.9 with respect to 1 mole of epoxy groups contained in the epoxy resin (A). The resin having an acid group and a polymerizable unsaturated group according to claim 1 or 2, wherein the amount is in the range of 1.1 mol. Claim 1 or Claim 2, wherein the amount of the polybasic acid anhydride (C) used is in the range of 0.2 to 1.05 mol per 1 mol of the epoxy group possessed by the epoxy resin (A). A resin having the acid group and polymerizable unsaturated group described above. A curable resin composition comprising the resin having an acid group and a polymerizable unsaturated group according to claim 4 and a photopolymerization initiator. The curable resin composition according to claim 5, further comprising a resin (D) having an acid group and a polymerizable unsaturated group other than the resin having an acid group and a polymerizable unsaturated group. A cured product of the curable resin composition according to claim 6. An insulating material comprising the cured product according to claim 7. A resist member comprising the cured product according to claim 7.

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