JP2024040962A - Curable resin composition, cured product, insulating material, and resist member - Google Patents

Abstract

[Problem] To provide a curable resin composition that has high developability, and furthermore is capable of producing a cured product having a low elastic modulus, high adhesion to adjacent members, and excellent dielectric properties. [Solution] The curable resin composition contains an active ester resin (A) and a resin (B) having an acid group and a polymerizable unsaturated group, characterized in that the active ester resin (A) contains, as essential reaction raw materials, a compound (a1) having one phenolic hydroxyl group in its molecular structure, a phenolic hydroxyl group-containing resin (a2) whose essential reaction raw materials are a phenolic hydroxyl group-containing compound (a2-1) and a divinyl compound (a2-2), and an aromatic polycarboxylic acid or an acid halide thereof (a3). [Selected Figures] None

Description

The present invention relates to a curable resin composition, a cured product, an insulating material, and a resist member.

Conventionally, when electronic components are mounted and soldered onto a printed wiring board, a film is formed to prevent solder from adhering to areas other than the mounting area, and to semi-permanently prevent oxidation and corrosion of wiring. Solder resist is widely used as a material. Technologies for forming such solder resist patterns include photoresist methods that can accurately form fine patterns; among these, alkaline-developed liquid photoresist methods are mainstream due to environmental considerations. It becomes.

For example, as an alkali-soluble photosensitive resin used in an alkaline-developable liquid photoresist method, a reaction product (acid Pendant type epoxy acrylate) is widely used, and a solder resist film is formed from a curable resin composition containing the alkali-soluble photosensitive resin (for example, see Patent Document 1).

Special Publication No. 1-54390

On the other hand, printed wiring boards are becoming increasingly finer, more multi-layered, and more integrated into one board in order to achieve higher density, and the mounting method is also shifting to surface mount technology (SMT). . Therefore, there is an increasing demand for solder resist films to be finer, have high Tg (high heat resistance), high resolution, high precision, and high reliability.
In addition, in order to achieve high reliability, the solder resist film must have excellent adhesion to adjacent components (copper foil, etc.), and must also have low elasticity so that it can follow the adjacent components. It is also important that
Furthermore, as transmission signals become faster, a solder resist film exhibiting a low dielectric constant and a low dielectric loss tangent is required from the viewpoint of reducing time delay due to the use of high frequencies (gigahertz band).

In response to these demands, conventional curable resin compositions containing alkali-soluble photosensitive resins have insufficient developability, and the cured products obtained by curing the curable resin compositions have It has a high elastic modulus, and has poor adhesion with adjacent members and dielectric properties, so there is room for improvement.

Therefore, the present invention solves the problems of the prior art described above, and has high developability, low elastic modulus, high adhesion to adjacent members (copper foil, etc.), and excellent dielectric properties (dielectric constant and An object of the present invention is to provide a curable resin composition from which a cured product (having a low dielectric loss tangent) can be obtained.
A further object of the present invention is to provide a cured product, an insulating material, and a resist member that have a low elastic modulus, high adhesion to adjacent members, and excellent dielectric properties.

As a result of intensive studies to solve the above problems, the present inventors have found that a specific active ester resin (A) and a resin (B) having an acid group and a polymerizable unsaturated group are combined into a curable resin composition. By blending, the developability of the curable resin composition is improved, and the cured product obtained by curing such a curable resin composition has a low elastic modulus, high adhesion to adjacent members, and a dielectric It was discovered that this material has excellent properties, and the present invention was completed.
That is, the gist of the present invention for solving the above problems is as follows.

[1] Contains an active ester resin (A) and a resin (B) having an acid group and a polymerizable unsaturated group,
The active ester resin (A) contains a compound (a1) having one phenolic hydroxyl group in its molecular structure, a phenolic hydroxyl group-containing compound (a2-1), and a divinyl compound (a2-2) as essential reaction raw materials. A curable resin composition comprising a phenolic hydroxyl group-containing resin (a2) and an aromatic polycarboxylic acid or its acid halide (a3) as essential reaction raw materials.

[2] The number of moles of hydroxyl groups possessed by the compound (a1) having one phenolic hydroxyl group in the molecular structure (a1 _OH ) and the number of moles of hydroxyl groups possessed by the phenolic hydroxyl group-containing resin (a2) (a2 _OH ). The curable resin composition according to [1], wherein the ratio [(a1 _OH )/(a2 _OH )] is 10/90 to 75/25.

[3] The number of moles of hydroxyl groups possessed by the compound (a1) having one phenolic hydroxyl group in the molecular structure (a1 _OH ) and the number of moles of hydroxyl groups possessed by the phenolic hydroxyl group-containing resin (a2) (a2 _OH ). is 0.95 to 1.05 mol per 1 mol of the carboxyl groups or acid halide groups of the aromatic polycarboxylic acid or its acid halide (a3), [1] or [ 2].

[4] The curable resin composition according to any one of [1] to [3], wherein the active ester resin (A) has a weight average molecular weight (Mw) of 600 to 5,000.

[5] The solid content mass ratio [(A)/(B)] of the active ester resin (A) and the resin (B) having an acid group and a polymerizable unsaturated group is 5/95 to 50/ 50, the curable resin composition according to any one of [1] to [4].

[6] The curable resin composition according to any one of [1] to [5], further containing a photopolymerization initiator.

[7] The curable resin composition according to any one of [1] to [6], further containing a curing agent.

[8] A cured product obtained by curing the curable resin composition according to any one of [1] to [7].

[9] An insulating material comprising the curable resin composition according to any one of [1] to [7].

[10] A resist member comprising the curable resin composition according to any one of [1] to [7].

According to the present invention, a cured product with high developability, low elastic modulus, high adhesion to adjacent members (such as copper foil), and excellent dielectric properties (low dielectric constant and dielectric loss tangent) is obtained. A curable resin composition can be provided.
Further, according to the present invention, it is possible to provide a cured product, an insulating material, and a resist member that have a low elastic modulus, high adhesion to adjacent members, and excellent dielectric properties.

Below, the curable resin composition, cured product, insulating material, and resist member of the present invention will be illustrated in detail based on the embodiments thereof.

(Explanation of terms)
Unless otherwise specified in this specification, the following terminology is applicable.

In this specification, "alkyl group" includes, for example, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, group, tert-pentyl group, neopentyl group, 1,2-dimethylpropyl group, n-hexyl group, isohexyl group, (n-)heptyl group, (n-)octyl group, (n-)nonyl group, (n- ) decyl group, (n-) undecyl group, (n-) dodecyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, or cyclononyl group.

In this specification, examples of the "aryl group" include a phenyl group, a naphthyl group, a phenalenyl group, a phenanthrenyl group, an anthryl group, an azulenyl group, an indenyl group, an indanyl group, a tetralinyl group, and the like. In addition, the "aryl group" means that the hydrogen atom of the aromatic ring in the aryl group is substituted with, for example, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a halogen atom. Good too.

In this specification, examples of the "aralkyl group" include a benzyl group, a diphenylmethyl group, a biphenyl group, a naphthylmethyl group, and the like.

In this specification, "alkoxy group (alkyloxy group)" includes, for example, methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, pentyloxy group, hexyloxy group, 2-ethylhexyloxy group, octyl group, etc. Examples include oxy group and nonyloxy group.

In this specification, examples of the "halogen atom" include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like.

In this specification, "alkylene group" includes, for example, methylene group, ethylene group, propylene group, 1-methylmethylene group, 1,1-dimethylmethylene group, 1-methylethylene group, 1,1-dimethylethylene group. , 1,2-dimethylethylene group, propylene group, butylene group, 1-methylpropylene group, 2-methylpropylene group, pentylene group, hexylene group, heptylene group, octylene group, nonylene group, decylene group, undecylene group, dodecylene group etc.

In this specification, the "monovalent hydrocarbon group" includes, for example, the above alkyl group, and one or more -CH ₂ -s in the alkyl group are arranged so that -O- or It may be substituted with -S-, or one or more -CH ₂ -CH ₂ - in the alkyl group may be substituted with -CH=CH- so that they are not adjacent to each other.

In this specification, the "divalent hydrocarbon group" includes, for example, the above-mentioned alkylene group, and _-O- or It may be substituted with -S-, or one or more -CH ₂ -CH ₂ - in the alkylene group may be substituted with -CH=CH- so that they are not adjacent to each other.

As used herein, "(meth)acrylate" means acrylate and/or methacrylate. Moreover, in this specification, "(meth)acryloyl" means acryloyl and/or methacryloyl. Furthermore, in this specification, "(meth)acrylic" means acrylic and/or methacryl.

<Curable resin composition>
The curable resin composition of this embodiment contains an active ester resin (A) and a resin (B) having an acid group and a polymerizable unsaturated group. In the curable resin composition of the present embodiment, the active ester resin (A) contains a compound (a1) having one phenolic hydroxyl group in its molecular structure, a phenolic hydroxyl group-containing compound (a2-1), and a divinyl A phenolic hydroxyl group-containing resin (a2) containing the compound (a2-2) as an essential reaction raw material, and an aromatic polycarboxylic acid or its acid halide (a3) as an essential reaction raw material.

Since the curable resin composition of this embodiment contains the resin (B) having an acid group and a polymerizable unsaturated group, it exhibits high photosensitivity and high developability.
Note that the developability relates to the contrast between exposed areas and unexposed areas, and "high developability" refers to the contrast being sufficiently high. One of the causes of low developability is that when the curable resin composition applied to the base material is dried and then exposed, unexposed areas remain after (alkali) development due to heating accompanying drying, etc. One example of this is that the contrast deteriorates. Therefore, in this specification, the developability is evaluated by the drying control width (minutes), as described in Examples below. The drying control width defines a range of drying conditions (drying time) in which developing defects are unlikely to occur due to drying of the coating film, etc. Therefore, even if the drying time is prolonged, if development residues are not likely to occur (that is, if the drying control range is wide), it is considered that high developability will be exhibited.

In addition, in the curable resin composition of the present embodiment, by using an active ester resin (A) whose reaction raw material is a phenolic hydroxyl group-containing resin (a2) whose reaction raw material is a divinyl compound (a2-2), By reducing the polarity of the cured product obtained by curing the curable resin composition, the dielectric constant and dielectric loss tangent are reduced, and the dielectric properties are improved.
Furthermore, the active ester resin (A), which uses the divinyl compound (a2-2) as the reaction raw material and the phenolic hydroxyl group-containing resin (a2) as the reaction raw material, has a low curing shrinkage rate. A cured product obtained by curing a material has high adhesion to adjacent members (copper foil, etc.).
Furthermore, the cured product obtained by curing the curable resin composition containing the active ester resin (A) and the resin (B) having an acid group and a polymerizable unsaturated group does not become too hard and has an elastic modulus of is low.

(Active ester resin (A))
The curable resin composition of this embodiment contains an active ester resin (A). The active ester resin (A) is
・Compound (a1) having one phenolic hydroxyl group in its molecular structure,
・A phenolic hydroxyl group-containing resin (a2) containing a phenolic hydroxyl group-containing compound (a2-1) and a divinyl compound (a2-2) as essential reaction raw materials, and ・Aromatic polycarboxylic acid or its acid halide (a3 )
is an essential reaction raw material.

--Compound (a1) having one phenolic hydroxyl group in its molecular structure--
The compound (a1) having one phenolic hydroxyl group in the molecular structure may be any aromatic compound having one hydroxyl group on the aromatic ring, and other specific structures are not particularly limited. The compound (a1) having one phenolic hydroxyl group in its molecular structure may be used singly or in combination of two or more. Specifically, the compound (a1) having one phenolic hydroxyl group in the molecular structure is a phenol compound having one or more substituents on phenol or the aromatic nucleus of phenol, naphthol, or a phenolic compound having one or more substituents on the aromatic nucleus of naphthol. Examples include naphthol compounds having one or more substituents, anthracenol or anthracenol compounds having one or more substituents on the aromatic nucleus of anthracenol. Substituents on the aromatic nucleus include, for example, aliphatic carbonization groups such as methyl group, ethyl group, vinyl group, propyl group, butyl group, pentyl group, hexyl group, cyclohexyl group, heptyl group, octyl group, nonyl group, etc. Hydrogen groups; alkoxy groups such as methoxy, ethoxy, propyloxy and butoxy groups; halogen atoms such as fluorine, chlorine and bromine; phenyl, naphthyl and anthryl groups; Aliphatic hydrocarbon groups, alkoxy groups, aryl groups substituted with halogen atoms, etc.; phenylmethyl groups, phenylethyl groups, naphthylmethyl groups, naphthylethyl groups, and the above aliphatic hydrocarbon groups or alkoxy groups on these aromatic nuclei. , an aralkyl group substituted with a halogen atom, etc. Among these, naphthol compounds are preferred, and 1-naphthol or 2-naphthol is particularly preferred, since they provide active ester resins with low curing shrinkage and excellent dielectric properties in the cured product.

--Phenolic hydroxyl group-containing resin (a2)--
Regarding the phenolic hydroxyl group-containing resin (a2), the phenolic hydroxyl group-containing compound (a2-1) may be any aromatic compound having a hydroxyl group on an aromatic ring, and other specific structures are not particularly limited. . Specifically, compounds similar to the various compounds exemplified as the compound (a1) having one phenolic hydroxyl group in the molecular structure may be mentioned, and compounds having multiple phenolic hydroxyl groups in the molecular structure (multiple) may be mentioned. Functional phenols) can also be used. Here, examples of compounds having multiple phenolic hydroxyl groups in the molecular structure include hydroquinone, resorcinol, catechol, bisphenol A, bisphenol F, bisphenol S, bisphenol B, bisphenol AD, bisphenol Z, tetrabromobisphenol A, dihydroxydiphenyl ether, and phenol. Phthalein, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, polyhydroxynaphthylene ether, dihydroxybenzophenone, trihydroxy Examples include benzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol, and the like. Further, the phenolic hydroxyl group-containing compound (a2-1) may be used alone or in combination of two or more. Among these, naphthol compounds are preferred, and 1-naphthol or 2-naphthol is particularly preferred, since they provide active ester resins with low curing shrinkage and excellent dielectric properties in the cured product.

（式中、Ｒ^１は、それぞれ独立して脂肪族炭化水素基、アルコキシ基、ハロゲン原子、アリール基、アラルキル基の何れかであり、ｉは、０又は１～４の整数である。Ｙは、炭素原子数１～４のアルキレン基、酸素原子、硫黄原子、カルボニル基の何れかである。ｊは、１～４の整数である。）の何れかで表される化合物等が挙げられる。 The divinyl compound (a2-2) has at least two vinyl groups (-CH=CH ₂ ), and reacts with the phenolic hydroxyl group-containing compound (a2-1) to form the phenolic hydroxyl group-containing compound (a2). -1) Any compound may be used as long as it can bind the two together, and other specific structures are not particularly limited. Further, the divinyl compound (a2-2) may be used alone or in combination of two or more. Among these, compounds having an aromatic ring or cyclo ring in their molecular structure are preferred because they provide an active ester resin with a low curing shrinkage rate and excellent dielectric properties in the cured product. More preferable specific structures of the divinyl compound (a2-2) include, for example, the following structural formulas (1-1) to (1-4):

(In the formula, R ¹ is each independently an aliphatic hydrocarbon group, an alkoxy group, a halogen atom, an aryl group, or an aralkyl group, and i is 0 or an integer from 1 to 4. Y is , an alkylene group having 1 to 4 carbon atoms, an oxygen atom, a sulfur atom, or a carbonyl group (j is an integer of 1 to 4).

R ¹ in the structural formulas (1-1) to (1-4) are each independently an aliphatic hydrocarbon group, an alkoxy group, a halogen atom, an aryl group, or an aralkyl group, and specifically, is an aliphatic hydrocarbon group such as methyl group, ethyl group, vinyl group, propyl group, butyl group, pentyl group, hexyl group, cyclohexyl group, heptyl group, octyl group, nonyl group; methoxy group, ethoxy group , propyloxy group, butoxy group; halogen atoms such as fluorine atom, chlorine atom, bromine atom; phenyl group, naphthyl group, anthryl group; , an aryl group substituted with a halogen atom, etc.; a phenylmethyl group, a phenylethyl group, a naphthylmethyl group, a naphthylethyl group, and an aralkyl group substituted with the above-mentioned aliphatic hydrocarbon group, alkoxy group, halogen atom, etc. on the aromatic nucleus thereof. Examples include groups.

Among the compounds represented by any of the structural formulas (1-1) to (1-4), the active ester resin has a low curing shrinkage rate and has excellent dielectric properties in the cured product. A compound represented by formula (1-1) is preferred.

［式中、Ｘは、下記構造式（Ｘ－１）～（Ｘ－４）：

（式中、Ｒ^１は、それぞれ独立して脂肪族炭化水素基、アルコキシ基、ハロゲン原子、アリール基、アラルキル基の何れかであり、ｉは、０又は１～４の整数である。Ｙは、炭素原子数１～４のアルキレン基、酸素原子、硫黄原子、カルボニル基の何れかである。ｊは、１～４の整数である。）の何れかで表される構造部位である。］で表される構造部位（α）で結節された分子構造を有するものとなる。 When a compound represented by any of the structural formulas (1-1) to (1-4) is used as the divinyl compound (a2-2), the phenolic hydroxyl group-containing resin (a2) has a phenolic hydroxyl group. The containing compound (a2-1) has the following structural formula (2):

[Wherein, X is the following structural formulas (X-1) to (X-4):

(In the formula, R ¹ is each independently an aliphatic hydrocarbon group, an alkoxy group, a halogen atom, an aryl group, or an aralkyl group, and i is 0 or an integer from 1 to 4. Y is , an alkylene group having 1 to 4 carbon atoms, an oxygen atom, a sulfur atom, or a carbonyl group; j is an integer of 1 to 4). ] It has a molecular structure that is knotted at the structural site (α).

In addition to the phenolic hydroxyl group-containing compound (a2-1) and the divinyl compound (a2-2), other compounds may be used as reaction raw materials for the phenolic hydroxyl group-containing resin (a2). Other compounds include, for example, a compound (a2-2') which is a compound other than the divinyl compound (a2-2) and can bind the phenolic hydroxyl group-containing compound (a2-1), such as various aldehyde compounds; Substituent introduction agent (a2-3) for introducing an aliphatic hydrocarbon group, alkoxy group, halogen atom, aryl group, or aralkyl group as a substituent on the aromatic ring in the phenolic hydroxyl group-containing resin (a2-1) etc.

When the compound (a2-2') is used, the effects of low curing shrinkage and low dielectric loss tangent in the cured product are fully exhibited. The divinyl compound (a2-2) preferably accounts for 50% by mass or more, more preferably 80% by mass or more, based on the total amount of the divinyl compound (a2-2').

Examples of the substituent-introducing agent (a2-3) include aralkyl group-introducing agents such as phenylmethanol compounds, phenylmethyl halide compounds, naphthylmethanol compounds, naphthylmethyl halide compounds, and styrene compounds.

The method for producing the phenolic hydroxyl group-containing resin (a2) is not particularly limited, but it is preferable to adjust the ratio of reaction raw materials so that the number of phenolic hydroxyl groups per molecule is 2 or more. For example, the phenolic hydroxyl group-containing compound (a2-1) is used in an amount of 2 to 10 mol per 1 mol of the divinyl compound (a2-2), under acid catalytic conditions and at a temperature of about 80 to 180°C. It can be produced by a method of heating and stirring. The reaction may be carried out in an organic solvent if necessary. After the reaction is completed, an excess amount of the phenolic hydroxyl group-containing compound (a2-1) may be distilled off, if desired. Further, the unreacted phenolic hydroxyl group-containing compound (a2-1) in the reaction product may be used as it is as the compound (a1) having one phenolic hydroxyl group in its molecular structure.

Examples of the acid catalyst include para-toluenesulfonic acid, dimethyl sulfuric acid, diethyl sulfuric acid, sulfuric acid, hydrochloric acid, and oxalic acid. Each of these may be used alone or in combination of two or more. The amount of the acid catalyst added is preferably in the range of 0.01 to 10% by mass based on the phenolic hydroxyl group-containing compound (a2-1).

Examples of the organic solvent include ketone solvents such as acetone, methyl ethyl ketone, and cyclohexanone, acetate ester solvents such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and carbitol acetate, and carbitols such as cellosolve and butyl carbitol. Solvents include aromatic hydrocarbon solvents such as toluene and xylene, dimethylformamide, dimethylacetamide, and N-methylpyrrolidone. Each of these may be used alone or as a mixed solvent of two or more.

As an example of the specific structure of the phenolic hydroxyl group-containing resin (a2), for example, when naphthol is used as the phenolic hydroxyl group-containing compound (a2-1) and divinylbenzene is used as the divinyl compound (a2-2), A structural example is shown in the following structural formula (2-1). Note that the following structural formula (2-1) is only an example of a specific structure of the phenolic hydroxyl group-containing resin (a2), and does not exclude other resin structures.

［式（２－１）中、ｎは、１～１０の整数である。Ｒは、それぞれ独立に水素原子又は下記構造式（Ｒ－１）：

で表される構造部位である。また、式（Ｒ－１）中、Ｒは、上記式（２－１）中のＲと同義であり、ｍは、１～１０の整数である。］

[In formula (2-1), n is an integer from 1 to 10. R is each independently a hydrogen atom or the following structural formula (R-1):

It is a structural part represented by . Further, in formula (R-1), R has the same meaning as R in the above formula (2-1), and m is an integer of 1 to 10. ]

Furthermore, commercially available divinylbenzene may contain a portion of ethylstyrene. In this case, a structure represented by the following structural formula (R-2) may be partially introduced as R in the above structural formula (2-1).

The hydroxyl equivalent of the phenolic hydroxyl group-containing resin (a2) is preferably in the range of 130 to 300 g/equivalent, since the active ester resin has high solvent solubility and is easy to use for various purposes.

--Aromatic polycarboxylic acid or its acid halide (a3)--
The aromatic polycarboxylic acid or its acid halide (a3) reacts with the phenolic hydroxyl group of the compound (a1) having one phenolic hydroxyl group in its molecular structure and the phenolic hydroxyl group-containing resin (a2). The specific structure is not particularly limited, and any compound may be used as long as it is an aromatic compound that can form an ester bond. Specific examples include benzenedicarboxylic acids such as isophthalic acid and terephthalic acid, benzenetricarboxylic acids such as trimellitic acid, naphthalene-1,4-dicarboxylic acid, naphthalene-2,3-dicarboxylic acid, and naphthalene-2,6-dicarboxylic acid. - dicarboxylic acid, naphthalene dicarboxylic acid such as naphthalene-2,7-dicarboxylic acid, acid halides thereof, and compounds in which the above-mentioned aliphatic hydrocarbon group, alkoxy group, halogen atom, etc. are substituted on the aromatic nucleus thereof, etc. Can be mentioned. Examples of acid halides include acid chlorides, acid bromides, acid fluorides, and acid iodides. Each of these may be used alone or in combination of two or more. Among these, benzene dicarboxylic acids such as isophthalic acid and terephthalic acid or their acid halides are preferred because they provide active ester resins with high reaction activity and excellent curability.

--Production method--
The active ester resin (A) is, for example, a compound (a1) having one phenolic hydroxyl group in the molecular structure, the phenolic hydroxyl group-containing resin (a2), and the aromatic polycarboxylic acid or its acid halide. It can be produced by a method in which a reaction raw material that requires (a3) is heated and stirred in the presence of an alkali catalyst at a temperature of about 40 to 65°C. The reaction may be carried out in an organic solvent if necessary. Further, after the reaction is completed, the reaction product may be purified by washing with water, reprecipitation, etc., as desired.

Examples of the alkali catalyst include sodium hydroxide, potassium hydroxide, triethylamine, and pyridine. Each of these may be used alone or in combination of two or more. It may also be used as an aqueous solution of about 3.0 to 30%. Among these, sodium hydroxide or potassium hydroxide, which has high catalytic ability, is preferred.

Examples of the organic solvent include ketone solvents such as acetone, methyl ethyl ketone, and cyclohexanone, acetate ester solvents such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and carbitol acetate, and carboxylic acids such as cellosolve and butyl carbitol. Examples include toll solvents, aromatic hydrocarbon solvents such as toluene and xylene, dimethylformamide, dimethylacetamide, and N-methylpyrrolidone. Each of these may be used alone or as a mixed solvent of two or more.

The reaction ratio of the compound (a1) having one phenolic hydroxyl group in the molecular structure, the phenolic hydroxyl group-containing resin (a2), and the aromatic polycarboxylic acid or its acid halide (a3) is determined according to the desired molecular structure. It can be changed as appropriate depending on the design. Among these, since the active ester resin has high solvent solubility and is easy to use for various purposes, the number of moles of hydroxyl group (a1 _OH ) of the compound (a1) having one phenolic hydroxyl group in the molecular structure The ratio of the number of moles of hydroxyl groups (a2 _OH ) possessed by the phenolic hydroxyl group-containing resin (a2) [(a1 _OH )/(a2 _OH )] is preferably a ratio of 10/90 to 75/25. , a ratio of 25/75 to 50/50 is more preferable.

Furthermore, the number of moles of hydroxyl groups (a1 _OH ) possessed by the compound (a1) having one phenolic hydroxyl group in the molecular structure and the number of moles of hydroxyl groups possessed by the phenolic hydroxyl group-containing resin (a2) (a2 _OH ). The total amount is preferably 0.95 to 1.05 mol per 1 mol of the carboxyl groups or acid halide groups possessed by the aromatic polycarboxylic acid or its acid halide (a3).

--Ester compound (a1-a3)--
The active ester resin (A) is an ester compound (a1-a3) of the compound (a1) having one phenolic hydroxyl group in the molecular structure and the aromatic polycarboxylic acid or its acid halide (a3). may partially contain. The ester compounds (a1-a3) include, for example, the compound (a1) having one phenolic hydroxyl group in the molecular structure, the phenolic hydroxyl group-containing resin (a2), and the aromatic polycarboxylic acid or its acid halogen. By adjusting the reaction ratio of compound (a3), it can be produced as one component of the active ester resin.

As an example of the specific structure of the ester compound (a1-a3), for example, a naphthol compound is used as the compound (a1) having one phenolic hydroxyl group in the molecular structure, and the aromatic polycarboxylic acid or its acid halide is used. A structural example when benzenedicarboxylic acid or its acid halide is used as (a3) is shown in the following structural formula (3). Note that the following structural formula (3) is only an example of a specific structure of the ester compounds (a1-a3), and does not exclude diester compounds having other molecular structures.

（式中、Ｒ^２は、それぞれ独立して脂肪族炭化水素基、アルコキシ基、ハロゲン原子、アリール基、アラルキル基の何れかであり、ナフタレン環を形成するどの炭素原子に結合していても良い。ｐは０又は１～３の整数である。）

(In the formula, ^R2 is independently any one of an aliphatic hydrocarbon group, an alkoxy group, a halogen atom, an aryl group, and an aralkyl group, and may be bonded to any carbon atom forming a naphthalene ring. p is 0 or an integer of 1 to 3.)

When the active ester resin (A) contains the ester compounds (a1-a3), the content is such that the active ester resin has a low curing shrinkage rate and has excellent curability. It is preferably less than 40%, particularly preferably 10% or more and less than 35%.

The content of the ester compounds (a1-a3) in the active ester resin (A) is a value calculated from the area ratio of the GPC chart measured under the following conditions.

Measuring device: “HLC-8320 GPC” manufactured by Tosoh Corporation,
Column: Guard column “HXL-L” manufactured by Tosoh Corporation
+ “TSK-GEL G4000HXL” manufactured by Tosoh Corporation
+ “TSK-GEL G3000HXL” manufactured by Tosoh Corporation
+ “TSK-GEL G2000HXL” manufactured by Tosoh Corporation
+ “TSK-GEL G2000HXL” manufactured by Tosoh Corporation
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: In accordance with the measurement manual for "GPC-8320", the following monodisperse polystyrene with a known molecular weight was used.
(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 (calculated as resin solid content) filtered through a microfilter (50μL)

--Physical properties--
The weight average molecular weight (Mw) of the active ester resin (A) is preferably in the range of 600 to 5,000, and preferably in the range of 800 to 3,000, since the active ester resin has a low curing shrinkage rate. It is particularly preferable that there be. Here, the weight average molecular weight (Mw) of the active ester resin (A) is a polystyrene equivalent value measured by GPC under the same conditions as when determining the content of the ester compounds (a1-a3).

The softening point of the active ester resin (A) is preferably in the range of 80 to 180°C, more preferably in the range of 85 to 160°C, as measured based on JIS K7234.

The functional group equivalent of the active ester resin (A) is preferably in the range of 100 to 500 g/equivalent, and 100 to 400 g, since the active ester resin has a low curing shrinkage rate and has excellent curability. /equivalent, and particularly preferably from 200 to 300 g/equivalent. Further, the ester group equivalent of the active ester resin (A) is preferably in the range of 200 to 500 g/equivalent, and 200 It is more preferably in the range of ~400 g/equivalent, particularly preferably in the range of 200 ~ 300 g/equivalent. Here, the functional group in the active ester resin (A) refers to the ester bond site and the phenolic hydroxyl group in the active ester resin (A). Moreover, the functional group equivalent and ester group equivalent of the active ester resin (A) are values calculated from the charged amount of the reaction raw material.

--Content--
The content of the active ester resin (A) in the total amount (100% by mass) of the curable resin composition of the present embodiment is determined from the viewpoint of improving developability, adhesion, and dielectric properties in a well-balanced manner while lowering the elastic modulus. Therefore, the solid content (non-volatile content) is preferably 1% by mass or more, more preferably 5% by mass or more, even more preferably 10% by mass or more, and preferably 80% by mass or less, more preferably 50% by mass or less, More preferably, it is 30% by mass or less.

(Resin (B) having an acid group and a polymerizable unsaturated group)
The curable resin composition of this embodiment contains a resin (B) having an acid group and a polymerizable unsaturated group. The resin (B) only needs to have an acid group and a polymerizable unsaturated group, and other specific structures or molecular weights are not particularly limited, and a wide variety of resins can be used.

Examples of the acid group that the resin (B) has include a carboxyl group, a sulfonic acid group, and a phosphoric acid group. Among these, carboxyl groups are preferred as acid groups because they exhibit excellent alkali developability.

Further, examples of the polymerizable unsaturated group that the resin (B) has include a (meth)acryloyl group, an allyl group, an isopropenyl group, a 1-propenyl group, a styryl group, a styrylmethyl group, a maleimide group, and a vinyl ether group. can be mentioned.

Examples of the resin (B) having an acid group and a polymerizable unsaturated group include the following [1] to [6]:
[1] Epoxy resin (B1) having an acid group and a polymerizable unsaturated group,
[2] Urethane resin having acid group and polymerizable unsaturated group (B2)
[3] Acrylic resin (B3) having an acid group and a polymerizable unsaturated group,
[4] Amide-imide resin (B4) having an acid group and a polymerizable unsaturated group,
[5] Acrylamide resin (B5) having an acid group and a polymerizable unsaturated group,
[6] Ester resin (B6) having an acid group and a polymerizable unsaturated group,
etc.
Among these, the epoxy resin (B1) having an acid group and a polymerizable unsaturated group and the amide-imide resin (B4) having an acid group and a polymerizable unsaturated group are preferred; A combination with an epoxy resin (B1) having a sexually unsaturated group and/or an amide-imide resin (B4) having an acid group and a polymerizable unsaturated group is particularly preferable in terms of achieving the effects of the present invention.

--Epoxy resin having acid group and polymerizable unsaturated group (B1) --
Examples of the epoxy resin (B1) having an acid group and a polymerizable unsaturated group include an epoxy resin (b1-1), an unsaturated monobasic acid (b1-2), and a polybasic acid anhydride (b1-3). ) as an essential reaction raw material, epoxy (meth)acrylate resins having acid groups, epoxy resins (b1-1), unsaturated monobasic acids (b1-2), polybasic acid anhydrides (b1-3), Examples include epoxy (meth)acrylate resins having an acid group and a urethane bond, which are made using a polyisocyanate compound (b1-4) and a (meth)acrylate compound (b1-5) having a hydroxyl group as reaction raw materials.

The specific structure of the epoxy resin (b1-1) is not particularly limited as long as it has a plurality of epoxy groups in the resin. Examples of the epoxy resin (b1-1) include bisphenol type epoxy resin, hydrogenated bisphenol type epoxy resin, biphenol type epoxy resin, hydrogenated biphenol type epoxy resin, phenylene ether type epoxy resin, naphthylene ether type epoxy resin, Biphenyl type epoxy resin, triphenylmethane type epoxy resin, phenol novolak type epoxy resin, cresol novolac type epoxy resin, bisphenol novolac type epoxy resin, naphthol novolac type epoxy resin, naphthol-phenol co-condensed novolac type epoxy resin, naphthol-cresol co-condensed epoxy resin Condensed novolac type epoxy resin, phenol aralkyl type epoxy resin, naphthol aralkyl type epoxy resin, dicyclopentadiene-phenol addition reaction type epoxy resin, biphenylaralkyl type epoxy resin, fluorene type epoxy resin, xanthene type epoxy resin, dihydroxybenzene type epoxy resin , trihydroxybenzene type epoxy resin, oxazolidone type epoxy resin and the like. The epoxy resin (b1-1) may 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.

［上記一般式（４）中、Ｘ^４１は、炭素数１～１０のアルキレン鎖、ポリオキシアルキレン鎖、（ポリ）エステル鎖、芳香族炭化水素鎖、又は（ポリ）カーボネート鎖を表し、Ｘ^４１の構造中の水素原子がハロゲン原子又はアルコキシ基に置換されてもよく、Ｙ^４１は、水素原子又はメチル基である。］で表される化合物等を用いることもできる。上記一般式（４）で表される化合物の分子量は、１００～５００の範囲が好ましく、１５０～４００の範囲がより好ましい。前記不飽和一塩基酸（ｂ１－２）は、１種単独で用いてもよく、２種以上を組み合わせて用いてもよい。 Examples of the unsaturated monobasic acid (b1-2) include acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, α-cyanocinnamic acid, β-styrylacrylic acid, β-furfurylacrylic acid, etc. . Furthermore, acid halides and esters of the unsaturated monobasic acids can also be used. Furthermore, as the unsaturated monobasic acid (b1-2), the following general formula (4):

[In the above general formula (4), X ⁴¹ represents an alkylene chain, polyoxyalkylene chain, (poly)ester chain, aromatic hydrocarbon chain, or (poly)carbonate chain having 1 ^to 10 carbon atoms, The hydrogen atom in the structure may be substituted with a halogen atom or an alkoxy group, and Y ⁴¹ is a hydrogen atom or a methyl group. ] Compounds represented by the following can also be used. The molecular weight of the compound represented by the above general formula (4) is preferably in the range of 100 to 500, more preferably in the range of 150 to 400. The unsaturated monobasic acids (b1-2) may be used alone or in combination of two or more.

［上記一般式（５）中、Ｒ^５１及びＲ^５２は、炭素原子数１～１０のアルキレン基を表し、ｎ^５１は１～５の整数を表す。］で表される（ポリ）エステル鎖が挙げられる。
前記芳香族炭化水素鎖としては、例えば、フェニレン鎖、ナフチレン鎖、ビフェニレン鎖、フェニルナフチレン鎖又はビナフチレン鎖等が挙げられる。また、部分構造として、ベンゼン環、ナフタレン環、アントラセン環、フェナントレン環等の芳香環を有する炭化水素鎖も用いることができる。
前記（ポリ）カーボネート鎖としては、例えば、下記一般式（６）：

［上記一般式（６）中、Ｒ^６１は、炭素原子数１～１０のアルキレン基を表し、ｎ^６１は１～５の整数を表す。］で表される（ポリ）カーボネート鎖が挙げられる。 Examples of the polyoxyalkylene chain include a polyoxyethylene chain and a polyoxypropylene chain.
As the (poly)ester chain, for example, the following general formula (5):

[In the above general formula (5), R ⁵¹ and R ⁵² represent an alkylene group having 1 to 10 carbon atoms, and n ⁵¹ represents an integer of 1 to 5. ] Examples include (poly)ester chains represented by the following.
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.
As the (poly)carbonate chain, for example, the following general formula (6):

[In the above general formula (6), R ⁶¹ represents an alkylene group having 1 to 10 carbon atoms, and n ⁶¹ represents an integer of 1 to 5. ] Examples include (poly)carbonate chains represented by the following.

Examples of the polybasic acid anhydride (b1-3) include aliphatic polybasic acid anhydrides, alicyclic polybasic acid anhydrides, aromatic polybasic acid anhydrides, and aliphatic polybasic acid anhydrides. Examples include halides, acid halides of alicyclic polybasic acid anhydrides, and acid halides of aromatic polybasic acid anhydrides.

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 this specification, as the alicyclic polybasic acid anhydride, those in which an acid anhydride group is bonded to an alicyclic structure are referred to as alicyclic polybasic acid anhydrides; It does not matter whether or not there is. 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.

The polybasic acid anhydride (b1-3) may be used alone or in combination of two or more. Among these, tetrahydrophthalic anhydride, succinic anhydride, and cyclohexanedicarboxylic anhydride are preferred from the viewpoint of more effectively improving photosensitivity, developability, and adhesion.

［上記一般式（７）中、Ｒ^７２及びＲ^７３はそれぞれ独立して、水素原子又は炭素原子数１～６の一価の炭化水素基のいずれかを表し、Ｒ^７１はそれぞれ独立して、炭素原子数１～４のアルキル基を表し、ｋ^７１は０又は１～３の整数であり、ｎ^７１は１以上の整数である。］で表される繰返し構造を有するポリメチレンポリフェニルポリイソシアネート；これらのイソシアヌレート変性体、ビウレット変性体、アロファネート変性体等が挙げられる。前記ポリイソシアネート化合物（ｂ１－４）は、１種単独で用いてもよく、２種以上を組み合わせて用いてもよい。 Examples of the polyisocyanate compound (b1-4) include aliphatic diisocyanate compounds such as butane diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and 2,4,4-trimethylhexamethylene diisocyanate; norbornane; Alicyclic diisocyanate compounds such as diisocyanate, isophorone diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated diphenylmethane diisocyanate; tolylene diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, 4,4 Aromatic diisocyanate compounds such as '-diisocyanato-3,3'-dimethylbiphenyl and o-tolidine diisocyanate; general formula (7) below:

[In the above general formula (7), R ⁷² and R ⁷³ each independently represent either a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms, and R ⁷¹ each independently, It represents an alkyl group having 1 to 4 carbon atoms, k ⁷¹ is 0 or an integer of 1 to 3, and n ⁷¹ is an integer of 1 or more. ] A polymethylene polyphenyl polyisocyanate having a repeating structure represented by the following: Isocyanurate-modified products, biuret-modified products, allophanate-modified products of these, and the like. The polyisocyanate compound (b1-4) may be used alone or in combination of two or more.

Examples of the (meth)acrylate compound (b1-5) having a hydroxyl group include hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, trimethylolpropane (meth)acrylate, trimethylolpropane di(meth)acrylate, Pentaerythritol (meth)acrylate, Pentaerythritol di(meth)acrylate, Pentaerythritol tri(meth)acrylate, Dipentaerythritol (meth)acrylate, Dipentaerythritol di(meth)acrylate, Dipentaerythritol tri(meth)acrylate, Di Examples include pentaerythritol tetra(meth)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. Among these, those having a molecular weight of 1,000 or less are preferred from the viewpoint of more effectively improving photosensitivity, developability, and adhesion. Further, when the (meth)acrylate compound (b1-5) having a hydroxyl group is an oxyalkylene modified product or a lactone modified product, it is preferable that the weight average molecular weight (Mw) is 1,000 or less. The (meth)acrylate compound (b1-5) having a hydroxyl group may be used alone or in combination of two or more.

The method for producing the epoxy resin (B1) having an acid group and a polymerizable unsaturated group is not particularly limited and may be produced by any method. A basic acid (b1-2) and a polybasic acid anhydride (b1-3) are used as essential reaction raw materials, or an epoxy resin (b1-1), an unsaturated monobasic acid (b1-2), and a polybasic acid anhydride (b1-3) are used as essential reaction raw materials. It is preferable to use a basic acid anhydride (b1-3), a polyisocyanate compound (b1-4), and a (meth)acrylate compound having a hydroxyl group (b1-5) as reaction raw materials. Here, the epoxy resin (B1) may be produced by a method in which all of the reaction raw materials are reacted at once, or may be produced by a method in which reaction raw materials are reacted one after another. Among these, since the reaction can be easily controlled, the epoxy resin (b1-1) and the unsaturated monobasic acid (b1-2) are first reacted, and then the polybasic acid anhydride (b1-3) is reacted. A method of reacting is preferred. The reaction is carried out, for example, by reacting the epoxy resin (b1-1) and the unsaturated monobasic acid (b1-2) in the presence of a basic catalyst at a temperature range of 100 to 150°C, and then adding This can be carried out by adding a polybasic acid anhydride (b1-3) and reacting in a temperature range of 80 to 140°C. The production of the epoxy resin (B1) 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.

The reaction ratio of the epoxy resin (b1-1) and the unsaturated monobasic acid (b1-2) is 1 mole of the epoxy group in the epoxy resin (b1-1). 2) is preferably used in a range of 0.9 to 1.1 mol. Further, the reaction ratio of the polybasic acid anhydride (b1-3) is preferably used in a range of 0.2 to 1.0 mol per 1 mol of epoxy groups in the epoxy resin (b1-1).

Examples of the organic solvent include hydrocarbon solvents such as toluene, xylene, heptane, hexane, and mineral spirits; ketone solvents such as methyl ethyl ketone, acetone, dimethyl formamide, methyl isobutyl ketone, cyclohexanone, and dimethyl acetamide; and tetrahydrofuran and dioxolane. Cyclic ether solvents; 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, cellosolve, methanol, ethanol, and 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 monoalkyl ether, di- Glycol ether solvents such as alkylene 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 monomethyl ether acetate, etc. It will be done. These organic solvents may be used alone or in combination of two or more.
Further, as the organic solvent, commercially available products can 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 amount of the organic solvent to be used is preferably in the range of about 0.1 to 5 times the total mass of the reaction raw materials, since the reaction efficiency is improved.

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; class ammonium salts; phosphines such as trimethylphosphine, tributylphosphine, triphenylphosphine; tetramethylphosphonium chloride, tetraethylphosphonium chloride, tetrapropylphosphonium chloride, tetrabutylphosphonium chloride, tetrabutylphosphonium bromide, trimethyl(2-hydroxylpropyl)phosphonium Phosphonium salts such as chloride, triphenylphosphonium chloride, benzylphosphonium chloride; dibutyltin dilaurate, octyltin trilaurate, octyltin diacetate, dioctyltin diacetate, dioctyltin dineodecanoate, dibutyltin diacetate, tin octylate, Organotin compounds such as 1,1,3,3-tetrabutyl-1,3-dodecanoyldistanoxane; Organometallic compounds such as zinc octylate and bismuth octylate; Inorganic tin compounds such as tin octoate; Inorganic metal compounds Examples include. Furthermore, alkaline earth metal hydroxides, alkali metal carbonates, alkali metal hydroxides, and the like can also be used. The basic catalysts may be used alone or in combination of two or more.
The amount of the basic catalyst added is preferably in the range of 0.001 to 5 parts by weight based on a total of 100 parts by weight of the reaction raw materials.

The acid value of the epoxy resin (B1) having an acid group and a polymerizable unsaturated group is preferably in the range of 30 to 150 mgKOH/g from the viewpoint of more effectively improving photosensitivity, developability, and adhesion. The range of 40 to 120 mgKOH/g is more preferable. In this specification, the acid value of the resin (B) having an acid group and a polymerizable unsaturated group is a value measured by the neutralization titration method of JIS 0070 (1992).

--Urethane resin (B2) having acid group and polymerizable unsaturated group--
Examples of the urethane resin (B2) having an acid group and a polymerizable unsaturated group include a polyisocyanate compound (b1-4), a hydroxyl group-containing (meth)acrylate compound (b1-5), and a carboxyl group-containing polyol compound (b2). -1) and, if necessary, a polybasic acid anhydride (b1-3) and a polyol compound (b2-2) other than the carboxyl group-containing polyol compound (b2-1); Isocyanate compound (b1-4), hydroxyl group-containing (meth)acrylate compound (b1-5), polybasic acid anhydride (b1-3), and optionally carboxyl group-containing polyol compound (b2-1) A resin obtained by reacting a polyol compound (b2-2) other than; or an epoxy resin (b1-1), an unsaturated monobasic acid (b1-2), and a polybasic acid anhydride (b1- 3), a polyisocyanate compound (b1-4), and a hydroxyl group-containing (meth)acrylate compound (b1-5).

Examples of the carboxyl group-containing polyol compound (b2-1) include 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, and 2,2-dimethylolvaleric acid. The carboxyl group-containing polyol compounds can be used alone or in combination of two or more.

Examples of the polyol compound (b2-2) other than the carboxyl group-containing polyol compound (b2-1) include ethylene glycol, propylene glycol, butanediol, hexanediol, glycerin, trimethylolpropane, ditrimethylolpropane, pentaerythritol, Aliphatic polyol compounds such as dipentaerythritol; aromatic polyol compounds such as biphenol and bisphenol; (poly)oxyethylene chains, (poly)oxypropylene chains, and (poly)oxytetramethylene in the molecular structure of the various polyol compounds. Examples include (poly)oxyalkylene modified products in which a (poly)oxyalkylene chain such as a chain is introduced; lactone modified products in which a (poly)lactone structure is introduced into the molecular structure of the various polyol compounds described above. The polyol compounds other than the carboxyl group-containing polyol compound may be used alone or in combination of two or more.

The method for producing the urethane resin (B2) 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 acid groups and polymerizable unsaturated bonds 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 organic solvents as those described in the column of "Epoxy resin having an acid group and a polymerizable unsaturated group (B1)" above can be used, and the organic solvent may be one type alone. It can also be used in combination of two or more types.
Further, as the basic catalyst, the same basic catalyst as described in the above-mentioned "Epoxy resin having an acid group and a polymerizable unsaturated group (B1)" can be used, and the basic catalyst These can be used alone or in combination of two or more.

--Acrylic resin having acid group and polymerizable unsaturated group (B3)--
As the acrylic resin (B3) 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 essential. A (meth)acryloyl group is introduced into the acrylic resin intermediate obtained by polymerization as a component by further reacting a (meth)acrylate compound (β) having a reactive functional group that can react with these functional groups. Examples include the resulting reaction product, or a resin obtained by reacting a polybasic acid anhydride (b1-3) with a hydroxyl group in the reaction product.

In addition to the (meth)acrylate compound (α), the acrylic resin intermediate may be one obtained by copolymerizing other polymerizable unsaturated group-containing compounds as necessary. The other polymerizable unsaturated group-containing compounds 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 esters; (meth)acrylates containing alicyclic structures such as cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, and dicyclopentanyl (meth)acrylate; phenyl (meth)acrylate, benzyl (meth)acrylate, phenoxy Examples include aromatic ring-containing (meth)acrylates such as ethyl acrylate; silyl group-containing (meth)acrylates such as 3-methacryloxypropyltrimethoxysilane; styrene derivatives such as styrene, α-methylstyrene, and chlorostyrene. The other polymerizable unsaturated group-containing compounds may be used alone or in combination of two or more.

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

The method for producing the acrylic resin (B3) 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 (B3) 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 organic solvents as those described in the column of "Epoxy resin having an acid group and a polymerizable unsaturated group (B1)" above can be used, and the organic solvent may be one type alone. It can also be used in combination of two or more types.
Further, as the basic catalyst, the same basic catalyst as described in the above-mentioned "Epoxy resin having an acid group and a polymerizable unsaturated group (B1)" can be used, and the basic catalyst These can be used alone or in combination of two or more.

The acid value of the acrylic resin (B3) having an acid group and a polymerizable unsaturated group is preferably in the range of 30 to 150 mgKOH/g from the viewpoint of more effectively improving photosensitivity, developability, and adhesion. The range of 40 to 120 mgKOH/g is more preferable.

--Amidimide resin (B4) having an acid group and a polymerizable unsaturated group--
Examples of the amide-imide resin (B4) having an acid group and a polymerizable unsaturated group include an amide-imide resin (b4-1) having an acid group and/or an acid anhydride group, and a (meth)acrylate compound having a hydroxyl group ( b1-5) and/or a (meth)acrylate compound (b4-2) having an epoxy group, and optionally selected from the group consisting of a hydroxyl group, a carboxyl group, an isocyanate group, a glycidyl group, and an acid anhydride group. Examples include those obtained by reacting compounds having one or more reactive functional groups. Note that the compound having a reactive functional group may or may not have a (meth)acryloyl group.

The amide-imide resin (b4-1) having an acid group and/or an acid anhydride group may have only 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 (b1-5) having a hydroxyl group or an epoxy compound having a (meth)acryloyl group, the amide-imide resin (b4-1) preferably has an acid anhydride group, and more preferably has both an acid group and an acid anhydride group. The solid content acid value of the amide-imide resin (b4-1) is preferably in the range of 60 to 350 mg KOH/g measured under neutral conditions, i.e., conditions in which the acid anhydride group is not ring-opened. On the other hand, it is preferably in the range of 61 to 360 mg KOH/g measured under conditions in which the acid anhydride group is ring-opened, such as in the presence of water.

Examples of the amide-imide resin (b4-1) include those obtained by using a polyisocyanate compound (b1-4) and a polybasic acid anhydride (b1-3) as reaction raw materials. In addition, in addition to the polyisocyanate compound (b1-4) and the polybasic acid anhydride (b1-3), the amide-imide resin (b4-1) may be used in combination with a polybasic acid as a reaction raw material, if necessary. can.

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. The polybasic acids can be used alone or in combination of two or more.

The (meth)acrylate compound (b4-2) having an epoxy group is not particularly limited in other specific structures as long as it has a (meth)acryloyl group and an epoxy group in its molecular structure, and a wide variety of compounds can be used. Compounds can be used. For example, glycidyl group-containing (meth)acrylate monomers such as glycidyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate glycidyl ether, and epoxycyclohexylmethyl (meth)acrylate, hydroxybenzene diglycidyl ether, and dihydroxynaphthalene diglycidyl ether. , biphenol diglycidyl ether, mono(meth)acrylates of diglycidyl ether compounds of bisphenol diglycidyl ether, and the like. The (meth)acrylate compound having an epoxy group can be used alone or in combination of two or more.

Further, the specific structure or manufacturing method of the amide-imide resin (b4-1) having an acid group and/or an acid anhydride group is not particularly limited, and a wide variety of general amide-imide resins can be used. The amide-imide resin (b4-1) having an acid group and/or an acid anhydride group can be obtained, for example, by using a polyisocyanate compound (b1-4) and a polybasic acid anhydride (b1-3) as reaction raw materials. Preferably.

In addition, as the polyisocyanate compound (b1-4), an alicyclic diisocyanate compound or a modified product thereof, an aliphatic diisocyanate compound or a modified product thereof are used, since a curable resin composition having high solvent solubility is obtained. Preferred are alicyclic diisocyanates or modified isocyanurates thereof, and more preferred are aliphatic diisocyanates or modified isocyanurates thereof.
The proportion of the total mass of the alicyclic diisocyanate compound or its modified product and the aliphatic diisocyanate compound or its modified product in the total mass of the polyisocyanate compound (b1-4) is preferably 70% by mass or more. , preferably 90% by mass or more.
In addition, when using an alicyclic diisocyanate compound or a modified product thereof together with an aliphatic diisocyanate compound or a modified product thereof, the mass ratio of both (alicyclic diisocyanate compound or a modified product thereof/aliphatic diisocyanate compound or a modified product thereof) It is preferable that the ratio of modified product) is in the range of 30/70 to 70/30.

The amide-imide resin (B4) having an acid group and a polymerizable unsaturated group may be amide-imide resin (b4-1) having an acid group and/or an acid anhydride group, hydroxyl group-containing (meth) ) In addition to the reaction raw materials for the acrylate compound (b1-5) and/or the (meth)acrylate compound having an epoxy group (b4-2), other reaction raw materials can also be used in combination. In this case, the proportion of the total mass of the components (b4-1) to (b4-2) in the total mass of the reaction raw materials for the resin (B4) having an acid group and a polymerizable unsaturated group is 80% by mass or more. It is preferably 90% by mass or more, and more preferably 90% by mass or more.

The method for producing the amide-imide resin (B4) having an acid group and a polymerizable unsaturated group is not particularly limited, and any method may be used. For example, an amide-imide resin (b4-1) having an acid group and/or an acid anhydride group, and a (meth)acrylate compound (b1-5) having a hydroxyl group and/or a (meth)acrylate compound (b4-2) having an epoxy group. ) may be produced by reacting all the reaction raw materials at once, or may be produced by reacting the reaction raw materials sequentially. Further, for example, the reaction between the amide-imide resin (b4-1) having an acid group and/or an acid anhydride group and the hydroxyl group-containing (meth)acrylate compound (b1-5) can be carried out in the presence of an appropriate basic catalyst. This can be carried out by heating and stirring at a temperature of about 140°C. In the production of the amide-imide resin (B4) having an acid group and a polymerizable unsaturated group, it may be carried out in an organic solvent as necessary, and a basic catalyst or an acidic catalyst may be used as necessary. .

As the organic solvent, the same organic solvents as described in the column of "Epoxy resin having an acid group and a polymerizable unsaturated group (B1)" above can be used, and the organic solvent may be one type alone. It can also be used in combination of two or more types.
Further, as the basic catalyst, the same basic catalyst as described in the above-mentioned "Epoxy resin having an acid group and a polymerizable unsaturated group (B1)" can be used, and the basic catalyst These can be used alone or in combination of two or more.
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.

The acid value of the amide-imide resin (B4) having an acid group and a polymerizable unsaturated group is preferably in the range of 30 to 150 mgKOH/g from the viewpoint of more effectively improving photosensitivity, developability, and adhesion. The range of 40 to 120 mgKOH/g is more preferable.

--Acrylamide resin (B5) having acid group and polymerizable unsaturated group--
As the acrylamide resin (B5) having an acid group and a polymerizable unsaturated group, for example, a phenolic hydroxyl group-containing compound (b5-1), an alkylene carbonate (b5-2a) or an alkylene oxide (b5-2b), Using N-alkoxyalkyl (meth)acrylamide compound (b5-3), polybasic acid anhydride (b1-3), and optionally unsaturated monobasic acid (b1-2) as reaction raw materials, the reaction is carried out. Examples include resins obtained by reacting raw materials.

The phenolic hydroxyl group-containing compound (b5-1) refers to a compound having at least one phenolic hydroxyl group in the molecule. Examples of the phenolic hydroxyl group-containing compound (b5-1) include compounds represented by any of the following general formulas (8.1) to (8.5), aromatic polyhydroxy compounds (b5-4), and the following compounds: A reaction product using a compound represented by any of the general formulas (9.1) to (9.5) as an essential reaction raw material, or an aromatic polyhydroxy compound (b5-4) or other phenol in the molecule. It is also possible to use a novolak type phenol resin in which one or more compounds having one hydroxyl group (b5-5) are used as a reaction raw material.

［上記一般式（８．１）～（８．５）中、Ｒ^８１～Ｒ^８４及びＲ^８７はそれぞれ独立して、炭素原子数１～２０のアルキル基、炭素原子数１～２０のアルコキシ基、アリール基又はハロゲン原子のいずれかを表し、Ｒ^８５及びＲ^８６はそれぞれ独立して、水素原子又はメチル基を表し、ｊ^８１～ｊ^８４及びｊ^８７はそれぞれ独立して、０又は１以上の整数を表し、好ましくは０又は１～３の整数であり、より好ましくは０又は１である。ｋ^８１～ｋ^８４及びｋ^８７はそれぞれ独立して、１以上の整数を表し、好ましくは、２又は３である。］
なお、上記一般式（８．１）～（８．５）における芳香環上の置換基の位置については、任意であり、例えば、一般式（８．２）のナフタレン環においてはいずれの環上の水素原子と置換してもよく、一般式（８．３）では、ビフェニル１分子中に存在するベンゼン環のいずれの水素原子に置換してもよく、一般式（８．４）では、アラルキル１分子中に存在するベンゼン環のいずれかの水素原子と置換してもよく、一般式（８．５）では、１分子中に存在するベンゼン環のいずれの水素原子と置換していてもよいことを示し、１分子中における置換基の個数がｊ^８１～ｊ^８４、ｊ^８７及びｋ^８１～ｋ^８４、ｋ^８７であることを示している。

[In the above general formulas (8.1) to (8.5), R ⁸¹ to R ⁸⁴ and R ⁸⁷ are each independently an alkyl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms. , represents either an aryl group or a halogen atom, R ⁸⁵ and R ⁸⁶ each independently represent a hydrogen atom or a methyl group, j ⁸¹ to j ⁸⁴ and j ⁸⁷ each independently represent 0 or one or more It represents an integer, preferably 0 or an integer from 1 to 3, more preferably 0 or 1. k ⁸¹ to k ⁸⁴ and k ⁸⁷ each independently represent an integer of 1 or more, preferably 2 or 3. ]
In addition, the position of the substituent on the aromatic ring in the above general formulas (8.1) to (8.5) is arbitrary. For example, in the naphthalene ring of the general formula (8.2), the position of the substituent on any ring In general formula (8.3), any hydrogen atom in the benzene ring present in one biphenyl molecule may be substituted, and in general formula (8.4), aralkyl It may be substituted with any hydrogen atom of the benzene ring present in one molecule, and in general formula (8.5), it may be substituted with any hydrogen atom of the benzene ring present in one molecule. This shows that the number of substituents in one molecule is j ⁸¹ to j ⁸⁴ , j ⁸⁷ and k ⁸¹ to k ⁸⁴ , k ⁸⁷ .

［上記一般式（９．１）～（９．５）中、ｈ^９１は、０又は１を表し、Ｒ^９１～Ｒ^９６はそれぞれ独立して、一価の脂肪族炭化水素基、アルコキシ基、ハロゲン原子、アリール基、アリールオキシ基又はアラルキル基のいずれかを表し、ｋ^９１～ｋ^９６はそれぞれ独立して、０又は１～４の整数を表し、Ｚ^９１～Ｚ^９６はそれぞれ独立して、ビニル基、ハロメチル基、ヒドロキシメチル基又はアルキルオキシメチル基のいずれかを表し、Ｙ^９１は、炭素原子数１～４のアルキレン基、酸素原子、硫黄原子又はカルボニル基のいずれかを表し、ｎ^９１は１～４の整数を表す。］
上記一般式（９．１）～（９．５）で表される化合物は、１種単独で用いることも、２種以上を併用することもできる。

[In the above general formulas (9.1) to (9.5), h ⁹¹ represents 0 or 1, and R ⁹¹ to R ⁹⁶ each independently represent a monovalent aliphatic hydrocarbon group, an alkoxy group, represents either a halogen atom, an aryl group, an aryloxy group or an aralkyl group, k ⁹¹ to k ⁹⁶ each independently represent 0 or an integer of 1 to 4, Z ⁹¹ to Z ⁹⁶ each independently, represents a vinyl group, a halomethyl group, a hydroxymethyl group, or an alkyloxymethyl group; Y ⁹¹ represents an alkylene group having 1 to 4 carbon atoms, an oxygen atom, a sulfur atom, or a carbonyl group; n ⁹¹ represents an integer from 1 to 4. ]
The compounds represented by the above general formulas (9.1) to (9.5) can be used alone or in combination of two or more.

Examples of the aromatic polyhydroxy compound (b5-4) include dihydroxybenzene, trihydroxybenzene, tetrahydroxybenzene, dihydroxynaphthalene, trihydroxynaphthalene, tetrahydroxynaphthalene, dihydroxyanthracene, trihydroxyanthracene, tetrahydroxyanthracene, and biphenol. , tetrahydroxybiphenyl, bisphenol, etc., as well as compounds having one or more substituents on these aromatic nuclei. Further, examples of the substituent on the aromatic nucleus include methyl group, ethyl group, vinyl group, propyl group, butyl group, pentyl group, hexyl group, cyclohexyl group, heptyl group, octyl group, nonyl group, etc. Monovalent aliphatic hydrocarbon groups; alkoxy groups such as methoxy, ethoxy, propyloxy, and butoxy; halogen atoms such as fluorine, chlorine, and bromine; phenyl, naphthyl, anthryl, and Aryl groups substituted with the aliphatic hydrocarbon group, alkoxy group, halogen atom, etc. on these aromatic nuclei; phenyloxy group, naphthyloxy group; Alkoxy group, aryloxy group substituted with the above halogen atom, etc.; phenylmethyl group, phenylethyl group, naphthylmethyl group, naphthylethyl group, and on these aromatic nuclei, the above aliphatic hydrocarbon group, the above alkoxy group, the above halogen Examples include aralkyl groups substituted with atoms and the like. These aromatic polyhydroxy compounds can be used alone or in combination of two or more. Among these, compounds that do not contain halogen are preferred because they yield resins that have acid groups and polymerizable unsaturated groups that have high insulation reliability.

The compound (b5-5) having one phenolic hydroxyl group in the molecule may be any aromatic compound having one hydroxyl group on the aromatic nucleus, for example, phenol or the aromatic nucleus of phenol. Phenolic compounds having one or more substituents on naphthol or naphthol compounds having one or more substituents on the aromatic nucleus of naphthol, anthracenol or one or more on the aromatic nucleus of anthracenol Examples include anthracenol compounds having a substituent. In addition, examples of substituents on the aromatic nucleus include monovalent aliphatic hydrocarbon groups, alkoxy groups, halogen atoms, aryl groups, aryloxy groups, aralkyl groups, etc. Specific examples of each are as described above. It is. These compounds having one phenolic hydroxyl group can be used alone or in combination of two or more.

Examples of the novolac type phenolic resin include resins obtained by reacting one or more compounds having one phenolic hydroxyl group in the molecule with an aldehyde compound under an acidic catalyst.
Examples of the aldehyde compounds include formaldehyde; alkyl aldehydes such as acetaldehyde, propylaldehyde, butyraldehyde, isobutyraldehyde, pentylaldehyde, and hexylaldehyde; salicylaldehyde, 3-hydroxybenzaldehyde, 4-hydroxybenzaldehyde, and 2-hydroxy-4 - Hydroxybenzaldehyde such as methylbenzaldehyde, 2,4-dihydroxybenzaldehyde, 3,4-dihydroxybenzaldehyde; 2-hydroxy-3-methoxybenzaldehyde, 3-hydroxy-4-methoxybenzaldehyde, 4-hydroxy-3-methoxybenzaldehyde, 3 - Benzaldehydes having both hydroxy and alkoxy groups such as ethoxy-4-hydroxybenzaldehyde and 4-hydroxy-3,5-dimethoxybenzaldehyde; alkoxybenzaldehydes such as methoxybenzaldehyde and ethoxybenzaldehyde; 1-hydroxy-2-naphthaldehyde; Examples include hydroxynaphthaldehydes such as 2-hydroxy-1-naphthaldehyde and 6-hydroxy-2-naphthaldehyde; and halogenated benzaldehydes such as brombenzaldehyde. The aldehyde compounds can be used alone or in combination of two or more.

Examples of the alkylene carbonate (b5-2a) include ethylene carbonate, propylene carbonate, butylene carbonate, pentylene carbonate, and the like. Among these, ethylene carbonate or propylene carbonate is preferred from the viewpoint that the curable resin composition exhibits higher photosensitivity and developability, and the resulting cured product (cured coating film) exhibits better adhesion. The alkylene carbonate (b5-2a) can be used alone or in combination of two or more.

Examples of the alkylene oxide (b5-2b) include ethylene oxide, propylene oxide, butylene oxide, and pentylene oxide. Among these, ethylene oxide or propylene oxide is preferable from the viewpoint that the curable resin composition exhibits higher photosensitivity and developability, and the resulting cured product (cured coating film) exhibits better adhesion. The alkylene oxide (b5-2b) can be used alone or in combination of two or more.

Examples of the N-alkoxyalkyl (meth)acrylamide compound (b5-3) include N-methoxymethyl (meth)acrylamide, N-ethoxymethyl (meth)acrylamide, N-butoxymethyl (meth)acrylamide, and N-methoxymethyl (meth)acrylamide. Examples include ethyl (meth)acrylamide, N-ethoxyethyl (meth)acrylamide, and N-butoxyethyl (meth)acrylamide. Among these, N-methoxymethyl (meth)acrylamide is used from the viewpoint of making the curable resin composition exhibit higher photosensitivity and developability, and exhibiting better adhesion in the resulting cured product (cured coating film). is preferred. The N-alkoxyalkyl (meth)acrylamide compound (b5-3) can be used alone or in combination of two or more.

When the N-alkoxyalkyl (meth)acrylamide compound (b5-3) is used as a reaction raw material for the acrylamide resin (B5) having an acid group and a polymerizable unsaturated group, the N-alkoxyalkyl (meth)acrylamide compound (b5- 3) and the polybasic acid anhydride (b1-3) [(b5-3)/(b1-3)] is such that the curable resin composition exhibits higher photosensitivity and developability, and From the viewpoint of developing better adhesion in the cured product (cured coating film), the range is preferably from 0.2 to 7, more preferably from 0.25 to 6.7.

The method for producing the acrylamide resin (B5) having an acid group and a polymerizable unsaturated group is not particularly limited, and may be produced by any method. For example, it may be produced by reacting all of the reaction raw materials at once, or by reacting the reaction raw materials one after another. Among these, since the reaction can be easily controlled, the phenolic hydroxyl group-containing compound (b5-1) and the alkylene carbonate (b5-2a) or alkylene oxide (b5-2b) are first reacted (for example, reaction in the presence of a basic catalyst in a temperature range of 100 to 200°C), then react with an unsaturated monobasic acid (b1-2) and/or an N-alkoxyalkyl (meth)acrylamide compound (b5-3) (e.g., reaction in the presence of an acidic catalyst in a temperature range of 80 to 140°C), and then reacting the polybasic acid anhydride (b1-3) (e.g., reaction in a temperature range of 80 to 140°C) The method is preferred.

The acrylamide resin (B5) having an acid group and a polymerizable unsaturated group is a resin obtained from the above reaction raw materials. For example, the acrylamide resin (B5) has a structure in which a structural part (I) represented by the following general formula (10.1) and a structural part (II) represented by the following general formula (10.2) are repeated. A resin having a resin structure as a unit, or a structural unit consisting of a structural part (III) represented by the following formula (10.3) and a structural part (IV) represented by the following formula (10.4) as a repeating structural unit. Examples include resins having a resin structure.

［上記式（１０．１）又は（１０．２）中、Ｒ^ｂ２及びＲ^ｂ８はそれぞれ独立して、水素原子又は炭素原子数１～４の一価の炭化水素基を表し、Ｒ^ｂ３及びＲ^ｂ９はそれぞれ独立して、水素原子、炭素原子数１～４の炭化水素基、炭素原子数１～４のアルコキシ基又はハロゲン原子のいずれかを表し、ｎ^１及びｎ^２はそれぞれ独立して、１又は２を表し、Ｒ^ｂ４及びＲ^ｂ１０はそれぞれ独立して、メチレン基又は下記一般式（１１．１）～（１１．５）のいずれかで表される構造部位を表し、Ｒ^ｂ５及びＲ^ｂ６はそれぞれ独立して、水素原子又は炭素原子数１～２０の炭化水素基を表し、但し、Ｒ^ｂ５とＲ^ｂ６とが、連結して飽和又は不飽和の環を形成してもよく、Ｒ^ｂ１１は、炭素原子数１～１２の二価の炭化水素基を表し、Ｒ^ｂ１２は、水素原子又はメチル基を表し、Ｒ^ｂ１及びＲ^ｂ７はそれぞれ独立して、前記Ｒ^ｂ３及び前記Ｒ^ｂ９で表される基、あるいは、式（１０．１）で表される構造部位（Ｉ）又は式（１０．２）で表される構造部位（ＩＩ）が、＊印が付されたＲ^ｂ４又はＲ^ｂ１０を介して連結する結合点である。］

[In the above formula (10.1) or (10.2), R ^b2 and R ^b8 each independently represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 4 carbon atoms, and R ^b3 and R ^b9 each independently represents 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 n ¹ and n ² each independently, 1 or 2, R ^b4 and R ^b10 each independently represent a methylene group or a structural moiety represented by any of the following general formulas (11.1) to (11.5), and R ^b5 and R ^b6 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, provided that R ^b5 and R ^b6 may be connected to form a saturated or unsaturated ring, and R ^b11 represents a divalent hydrocarbon group having 1 to 12 carbon atoms, R ^b12 represents a hydrogen atom or a methyl group, and R ^b1 and R ^b7 each independently represent the above R ^b3 and the above R ^b9 . The group represented by the formula (10.1) or the structural moiety (II) represented by the formula (10.2) is R ^b4 or R This is a connection point that connects via ^b10 . ]

［上記一般式（１０．３）又は（１０．４）中、Ｒ^ｂ２及びＲ^ｂ８はそれぞれ独立して、水素原子又は炭素原子数１～４の炭化水素基を表し、Ｒ^ｂ３及びＲ^ｂ９はそれぞれ独立して、水素原子、炭素原子数１～４の炭化水素基、炭素原子数１～４のアルコキシ基又はハロゲン原子のいずれかを表し、ｎ^３及びｎ^４はそれぞれ独立して、１又は２を表し、Ｒ^ｂ４及びＲ^ｂ１０はそれぞれ独立して、メチレン基又は下記式（１１．１）～（１１．５）のいずれかで表される構造部位を表し、Ｒ^ｂ５及びＲ^ｂ６はそれぞれ独立して、水素原子又は炭素原子数１～２０の炭化水素基を表し、但し、Ｒ^ｂ５とＲ^ｂ６とが、連結して飽和又は不飽和の環を形成してもよく、Ｒ^ｂ１１は、炭素原子数１～１２の二価の炭化水素基を表し、Ｒ^ｂ１２は、水素原子又はメチル基を表し、Ｒ^ｂ１及びＲ^ｂ７はそれぞれ独立して、前記Ｒ^ｂ３及び前記Ｒ^ｂ９で表される基、あるいは、一般式（１０．３）で表される構造部位（ＩＩＩ）又は一般式（１０．４）で表される構造部位（ＩＶ）が、＊印が付されたＲ^ｂ４又はＲ^ｂ１０を介して連結する結合点である。］

[In the above general formula (10.3) or (10.4), R ^b2 and R ^b8 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms, and R ^b3 and R ^b9 are Each independently represents 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 n ³ and n ⁴ each independently represent 1 or 2, R ^b4 and R ^b10 each independently represent a methylene group or a structural moiety represented by any of the following formulas (11.1) to (11.5), and R ^b5 and R ^b6 each represent Each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, provided that R ^b5 and R ^b6 may be linked to form a saturated or unsaturated ring, and R ^b11 is represents a divalent hydrocarbon group having 1 to 12 carbon atoms, R ^b12 represents a hydrogen atom or a methyl group, R ^b1 and R ^b7 are each independently represented by the above R ^b3 and the above R ^b9 group, or the structural moiety (III) represented by general formula (10.3) or the structural moiety (IV) represented by general formula (10.4) is R ^b4 or R ^b10 marked with * It is a connection point that connects via. ]

［上記一般式（１１．１）～（１１．５）中、ｈ^９１は、０又は１を表し、Ｒ^９１～Ｒ^９６はそれぞれ独立して、一価の脂肪族炭化水素基、アルコキシ基、ハロゲン原子、アリール基又はアラルキル基のいずれかを表し、ｋ^９１～ｋ^９６はそれぞれ独立して、０又は１～４の整数を表し、Ｙ^９１は、炭素原子数１～４のアルキレン基、酸素原子、硫黄原子又はカルボニル基のいずれかを表し、ｎ^９１は１～４の整数を表し、Ｒ^１１１～Ｒ^１１５はそれぞれ独立して、水素原子又はメチル基を表し、Ｗは、下記式（１２．１）又は（１２．２）を表す。］

[In the above general formulas (11.1) to (11.5), h ⁹¹ represents 0 or 1, and R ⁹¹ to R ⁹⁶ each independently represent a monovalent aliphatic hydrocarbon group, an alkoxy group, represents either a halogen atom, an aryl group or an aralkyl group, k ⁹¹ to k ⁹⁶ each independently represents 0 or an integer of 1 to 4, Y ⁹¹ represents an alkylene group having 1 to 4 carbon atoms, oxygen atom, a sulfur atom, or a carbonyl group, n ⁹¹ represents an integer of 1 to 4, R ¹¹¹ to R ¹¹⁵ each independently represent a hydrogen atom or a methyl group, and W represents the following formula (12 .1) or (12.2). ]

［上記式（１２．１）又は（１２．２）中、Ｒ^１２１及びＲ^１２４はそれぞれ独立して、水素原子又は炭素原子数１～４の炭化水素基を表し、Ｒ^１２２及びＲ^１２３はそれぞれ独立して、水素原子又は炭素原子数１～２０の炭化水素基を表し、但し、Ｒ^１２２とＲ^１２３とが、連結して飽和又は不飽和の環を形成してもよく、Ｒ^１２５は、炭素原子数１～１２の二価の炭化水素基を表し、Ｒ^１２６は、水素原子又はメチル基を表す。］

[In the above formula (12.1) or (12.2), R ¹²¹ and R ¹²⁴ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms, and R ¹²² and R ¹²³ each Each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, provided that R ¹²² and R ¹²³ may be linked to form a saturated or unsaturated ring, and R ¹²⁵ is It represents a divalent hydrocarbon group having 1 to 12 carbon atoms, and R ¹²⁶ represents a hydrogen atom or a methyl group. ]

The acid value of the acrylamide resin (B5) having an acid group and a polymerizable unsaturated group is such that the curable resin composition exhibits higher photosensitivity and developability, and the resulting cured product (cured coating film) is superior. From the viewpoint of developing good adhesion, the range is preferably from 30 to 150 mgKOH/g, and more preferably from 40 to 120 mgKOH/g.

--Ester resin (B6) having an acid group and a polymerizable unsaturated group --
As the ester resin (B6) having an acid group and a polymerizable unsaturated group, for example, a phenolic hydroxyl group-containing compound (b5-1), an alkylene oxide (b5-2b) or an alkylene carbonate (b5-2a), Examples include resins obtained by reacting an unsaturated monobasic acid (b1-2) with a polybasic acid anhydride (b1-3).

As the alkylene oxide (b5-2b), the same alkylene oxides as described in the above-mentioned "acrylamide resin having an acid group and a polymerizable unsaturated group (B5)" can be used. Among these, ethylene oxide or propylene oxide is preferred from the viewpoint of more effectively improving photosensitivity, developability, and adhesion. The alkylene oxide (b5-2b) can be used alone or in combination of two or more.

As the alkylene carbonate (b5-2a), the same alkylene carbonate as described in the above-mentioned "acrylamide resin having an acid group and a polymerizable unsaturated group (B5)" can be used. Among these, ethylene carbonate or propylene carbonate is preferred from the viewpoint of more effectively improving photosensitivity, developability, and adhesion. The alkylene carbonate (b5-2a) can be used alone or in combination of two or more.

The method for producing the ester resin (B6) 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 organic solvents as described in the column of "Epoxy resin having an acid group and a polymerizable unsaturated group (B1)" above can be used, and the organic solvent may be one type alone. It can also be used in combination of two or more types.
Further, as the basic catalyst, the same one as the basic catalyst described in the column "Epoxy resin having an acid group and a polymerizable unsaturated group (B1)" can be used, and the basic catalyst is , can be used alone or in combination of two or more.
Further, as the acidic catalyst, the same acidic catalyst as described in the above-mentioned "Amidoimide resin having an acid group and a polymerizable unsaturated group (B4)" can be used, and the acidic catalyst is 1 A single species can be used alone, or two or more species can be used in combination.

--Content--
The content of the resin (B) having an acid group and a polymerizable unsaturated group in the total amount (100% by mass) of the curable resin composition of this embodiment is determined to improve developability, adhesion and dielectric properties while lowering the elastic modulus. From the viewpoint of improving the properties in a well-balanced manner, the solid content (nonvolatile content) is preferably 20% by mass or more, more preferably 40% by mass or more, even more preferably 50% by mass or more, and preferably 99% by mass or less, and 90% by mass or more. It is more preferably at most 80% by mass, even more preferably at most 80% by mass.

Furthermore, in the curable resin composition of the present embodiment, the solid content (nonvolatile content) mass ratio [(A )/(B)] is preferably 5/95 to 50/50, and 10/90 to 30/50, from the viewpoint of improving developability, adhesion, and dielectric properties in a well-balanced manner while lowering the elastic modulus. More preferably, it is 70.

The curable resin composition of this embodiment may be composed only of the active ester resin (A) and the resin (B) having an acid group and a polymerizable unsaturated group, but the photopolymerization initiator described below, It may further contain a curing agent and the like.
Total content of solid content (nonvolatile content) of the active ester resin (A) and the resin (B) having an acid group and a polymerizable unsaturated group in the total amount (100% by mass) of the curable resin composition of the present embodiment The amount is preferably 40% by mass or more, more preferably 50% by mass or more, and preferably 95% by mass or less, from the viewpoint of improving developability, adhesion, and dielectric properties in a well-balanced manner while lowering the elastic modulus. It is more preferably 90% by mass or less, and even more preferably 85% by mass or less.

(Photopolymerization initiator)
It is preferable that the curable resin composition of this embodiment further contains a photopolymerization initiator. When the curable resin composition contains a photopolymerization initiator, the curing reaction (polymerization) by light is easily initiated. The photopolymerization initiators may be used alone or in combination of two or more.

The photopolymerization initiator can be appropriately selected and used depending on the type of active energy ray to be irradiated. Further, it may be used in combination with a photosensitizer such as an amine compound, a urea compound, a sulfur-containing compound, a phosphorus-containing compound, a chlorine-containing compound, or a nitrile compound. Further, the photopolymerization initiator is preferably a radical polymerization initiator.

Specific examples of the photopolymerization initiator include 1-hydroxycyclohexyl-phenyl-ketone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone, and 1,2-(dimethylamino). Alkylphenone photopolymerization initiator such as -2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone; 2,4,6-trimethylbenzoyl-diphenyl- Examples include acylphosphine oxide photopolymerization initiators such as phosphine oxide; and intramolecular hydrogen abstraction type photopolymerization initiators such as benzophenone compounds. Further, specific examples of the photopolymerization initiator include 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, bis( Also included are 2,4,6-trimethylbenzoyl)phenylphosphine oxide, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, and the like.
Commercially available photopolymerization initiators include, for example, "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-784'', ``Omnirad-500'', ``Omnirad-81'' (manufactured by IGM), ``Kayacure-DETX'', ``Kayacure-MBP'', ``Kayacure-DMBI'', ``Kayacure-EPA'', “Kayacure-OA” (manufactured by Nippon Kayaku Co., Ltd.), “Bicure-10”, “Bicure-55” (manufactured by Stouffer Chemical Co., Ltd.), “Trigonal P1” (manufactured by Akzo Co., Ltd.), “Sandray 1000” (manufactured by Sandoz Co., Ltd.) ), "Deep" (manufactured by Upjohn), "Quantacure-PDO", "Quantacure-ITX", "Quantacure-EPD" (manufactured by Ward Blenkinsop), "Runtecure-1104" (manufactured by Runtec) ) etc.

When using the photopolymerization initiator, the content of the photopolymerization initiator in the curable resin composition of the present embodiment is determined based on the content of the photopolymerization initiator in the curable resin composition of the present embodiment. ) is preferably 0.1 parts by mass or more and 10 parts by mass or less, based on a total of 100 parts by mass of solid content (non-volatile content).

(hardening agent)
It is preferable that the curable resin composition of this embodiment further contains a curing agent. When the curable resin composition contains a curing agent, the curability of the curable resin composition is improved.
Examples of the curing agent include epoxy resins and other curing agents (amine curing agents, acid anhydride curing agents, phenolic resin curing agents, etc.), and among these, epoxy resins are preferred.

The epoxy resin is not particularly limited, but is preferably a curable resin that contains two or more epoxy groups in its molecule and can be cured by forming a crosslinked network with the epoxy groups. Examples of epoxy resins include, but are not limited to, phenol novolak epoxy resins, cresol novolac epoxy resins, α-naphthol novolac epoxy resins, β-naphthol novolac epoxy resins, bisphenol A novolak epoxy resins, biphenyl novolac epoxy resins. Novolac type epoxy resins such as; aralkyl type epoxy resins such as phenol aralkyl type epoxy resins, naphthol aralkyl type epoxy resins, phenol biphenylaralkyl type epoxy resins; bisphenol A type epoxy resins, bisphenol AP type epoxy resins, bisphenol AF type epoxy resins, Bisphenol type epoxy resins such as bisphenol B type epoxy resin, bisphenol BP type epoxy resin, bisphenol C type epoxy resin, bisphenol E type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, tetrabromobisphenol A type epoxy resin; Biphenyl-type epoxy resins such as biphenyl-type epoxy resins, tetramethylbiphenyl-type epoxy resins, epoxy resins having a biphenyl skeleton and diglycidyloxybenzene skeleton; naphthalene-type epoxy resins; binaphthol-type epoxy resins; binaphthyl-type epoxy resins; dicyclopentadiene phenol dicyclopentadiene type epoxy resin such as type epoxy resin; glycidylamine type epoxy resin such as tetraglycidyldiaminodiphenylmethane type epoxy resin, triglycidyl-p-aminophenol type epoxy resin, glycidylamine type epoxy resin of diaminodiphenylsulfone; 2, Diglycidyl ester type epoxy resins such as 6-naphthalene dicarboxylic acid diglycidyl ester type epoxy resins and glycidyl ester type epoxy resins of hexahydrophthalic anhydride; benzopyran types such as dibenzopyran, hexamethyldibenzopyran, and 7-phenylhexamethyldibenzopyran Examples include epoxy resin. Among these epoxy resins, so-called glycidyl ether type epoxy resins obtained by epoxidizing a phenol compound are preferred, and among these, novolac type epoxy resins, aralkyl type epoxy resins, and dicyclopentadiene type epoxy resins are preferred because of their dielectric properties. It is more preferable from the viewpoint of The above-mentioned epoxy resins may be used alone or in combination of two or more.

The epoxy equivalent of the epoxy resin is preferably 120 to 400 g/eq, more preferably 150 to 300 g/eq. When the epoxy equivalent of the epoxy resin is 120 g/eq or more, it is preferable because the dielectric properties of the obtained cured product are better. On the other hand, when the epoxy equivalent of the epoxy resin is 400 g/eq or less, the heat resistance of the obtained cured product improves. This is preferable because it has an excellent balance between properties and dielectric loss tangent.
The softening point of the epoxy resin is preferably 20 to 200°C, more preferably 40 to 150°C, from the viewpoint of improving photosensitivity, developability, dielectric properties, and adhesion in a well-balanced manner.

The amine curing agent is not particularly limited, but includes diethylenetriamine (DTA), triethylenetetramine (TTA), tetraethylenepentamine (TEPA), dipropylene diamine (DPDA), diethylaminopropylamine (DEAPA), and N-aminoethyl. Aliphatic amines such as piperazine, menzendiamine (MDA), isophoronediamine (IPDA), 1,3-bisaminomethylcyclohexane (1,3-BAC), piperidine, N,N,-dimethylpiperazine, triethylenediamine; m-xylene diamine (XDA), methanephenylene diamine (MPDA), diaminodiphenylmethane (DDM), diaminodiphenylsulfone (DDS), benzylmethylamine, 2-(dimethylaminomethyl)phenol, 2,4,6-tris(dimethyl) Examples include aromatic amines such as (aminomethyl) phenol.
Examples of the acid anhydride curing agent include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, ethylene glycol bis trimellitate, glycerol tris trimellitate, maleic anhydride, tetrahydrophthalic anhydride, Methyltetrahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, methylbutenyltetrahydrophthalic anhydride, dodecenylsuccinic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, succinic anhydride, Examples include methylcyclohexenedicarboxylic anhydride.
Examples of the phenolic resin curing agent include phenol novolak resin, cresol novolak resin, naphthol novolak resin, bisphenol novolak resin, biphenyl novolak resin, dicyclopentadiene-phenol addition type resin, phenol aralkyl resin, naphthol aralkyl resin, and triphenol methane type resin. , tetraphenolethane type resin, aminotriazine modified phenol resin, and the like.
Any of the other curing agents mentioned above may be used alone or in combination of two or more.

When the curing agent is used, the content of the curing agent in the curable resin composition of this embodiment is the solid content of the active ester resin (A) and the resin (B) having an acid group and a polymerizable unsaturated group. It is preferably 10 to 40 parts by mass based on 100 parts by mass of the total amount of nonvolatile components. When the amount is 10 parts by mass or more, heat resistance and curability can be further improved, and when it is 40 parts by mass or less, a lower dielectric loss tangent and higher flexibility can be obtained.

(Optional addition ingredient)
The curable resin composition of this embodiment may further contain optional additive components within a range that does not deviate from the purpose. Optional additive components include, for example, compounds with polymerizable unsaturated groups, curing accelerators, other resins, organic solvents, polymerization inhibitors, antioxidants, flame retardants, fillers, pigments, antifoaming agents, and viscosity adjusters. Various additives may be mentioned, such as additives, leveling agents, ultraviolet light stabilizers, and storage stabilizers.

--Compound having a polymerizable unsaturated group--
Examples of the compound having a polymerizable unsaturated group include (meth)acrylate compounds, specifically, for example, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, and butyl (meth)acrylate. Aliphatic mono(meth)acrylate compounds such as acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate; cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, Alicyclic mono(meth)acrylate compounds such as adamantyl mono(meth)acrylate; heterocyclic mono(meth)acrylate compounds such as glycidyl(meth)acrylate and tetrahydrofurfuryl acrylate; benzyl(meth)acrylate, phenyl(meth)acrylate Acrylate, phenylbenzyl (meth)acrylate, phenoxy (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxyethoxyethyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, phenoxybenzyl (meth)acrylate, Mono(meth)acrylate compounds such as aromatic mono(meth)acrylate compounds such as benzylbenzyl(meth)acrylate and phenylphenoxyethyl(meth)acrylate: (poly) in the molecular structure of the various mono(meth)acrylate monomers mentioned above. (Poly)oxyalkylene-modified mono(meth)acrylate compounds into which polyoxyalkylene chains such as oxyethylene chains, (poly)oxypropylene chains, and (poly)oxytetramethylene chains have been introduced; A lactone-modified mono(meth)acrylate compound with a (poly)lactone structure introduced into its molecular structure;
Aliphatic di(meth)acrylate compounds such as ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, butanediol di(meth)acrylate, hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, etc. ;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 Alicyclic di(meth)acrylate compounds such as; aromatic di(meth)acrylate compounds such as biphenol di(meth)acrylate and bisphenol di(meth)acrylate; Polyoxyalkylene-modified di(meth)acrylate compounds into which a (poly)oxyalkylene chain such as a (poly)oxyethylene chain, (poly)oxypropylene chain, or (poly)oxytetramethylene chain is introduced; the various di(meth)acrylate compounds mentioned above A lactone-modified di(meth)acrylate compound with a (poly)lactone structure introduced into the molecular structure of the acrylate compound;
Aliphatic tri(meth)acrylate compounds such as trimethylolpropane tri(meth)acrylate and glycerin tri(meth)acrylate; (poly)oxyethylene chain, (poly) in the molecular structure of the aliphatic tri(meth)acrylate compound; A (poly)oxyalkylene-modified tri(meth)acrylate compound into which a (poly)oxyalkylene chain such as an oxypropylene chain or a (poly)oxytetramethylene chain is introduced; A lactone-modified tri(meth)acrylate compound with a poly)lactone structure;
Tetrafunctional or higher functional aliphatic poly(meth)acrylate compounds such as pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate; Tetrafunctional or higher (poly)oxyalkylene-modified poly(meth) with (poly)oxyalkylene chains such as (poly)oxyethylene chains, (poly)oxypropylene chains, (poly)oxytetramethylene chains introduced into the molecular structure Acrylate compound; a tetrafunctional or higher-functional lactone-modified poly(meth)acrylate compound in which a (poly)lactone structure is introduced into the molecular structure of the aliphatic poly(meth)acrylate compound;
Hydroxyethyl (meth)acrylate, Hydroxypropyl (meth)acrylate, Trimethylolpropane (meth)acrylate, Trimethylolpropane di(meth)acrylate, Pentaerythritol (meth)acrylate, Pentaerythritol di(meth)acrylate, Pentaerythritol tri( meth)acrylate, dipentaerythritol (meth)acrylate, dipentaerythritol di(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, ditrimethylol (Meth)acrylate compounds having a hydroxyl group such as propane (meth)acrylate, ditrimethylolpropane di(meth)acrylate, and ditrimethylolpropane tri(meth)acrylate; ) A (poly)oxyalkylene modified product into which a (poly)oxyalkylene chain such as an oxyethylene chain, a (poly)oxypropylene chain, or a (poly)oxytetramethylene chain is introduced; the molecular structure of the (meth)acrylate compound having the hydroxyl group. Lactone modified product with (poly)lactone structure introduced inside;
(meth)acrylate compounds having an isocyanate group such as 2-acryloyloxyethyl isocyanate, 2-methacryloyloxyethyl isocyanate, 1,1-bis(acryloyloxymethyl)ethyl isocyanate;
(meth)acrylate monomers having a glycidyl group such as glycidyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate glycidyl ether, epoxycyclohexylmethyl (meth)acrylate, droxybenzene diglycidyl ether, dihydroxynaphthalene diglycidyl ether , biphenol diglycidyl ether, and mono(meth)acrylate compounds of diglycidyl ether compounds of bisphenol diglycidyl ether.
The compounds having a polymerizable unsaturated group may be used alone or in combination of two or more.

--Curing accelerator--
Examples of the curing accelerator include, but are not particularly limited to, phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, guanidine-based curing accelerators, urea-based curing accelerators, and the like. The curing accelerator may be used alone or in combination of two or more.

Examples of the phosphorus curing accelerator include organic phosphine compounds such as triphenylphosphine, tributylphosphine, triparatolylphosphine, diphenylcyclohexylphosphine, and tricyclohexylphosphine; organic phosphite compounds such as trimethylphosphite and triethylphosphite; ethyltriphenyl; Phosphonium bromide, benzyltriphenylphosphonium chloride, butylphosphonium tetraphenylborate, tetraphenylphosphonium tetraphenylborate, tetraphenylphosphonium tetra-p-tolylborate, triphenylphosphine triphenylborane, tetraphenylphosphonium thiocyanate, tetraphenylphosphonium dicyanamide, Examples include phosphonium salts such as butylphenylphosphonium dicyanamide and tetrabutylphosphonium decanoate.
Examples of the amine curing accelerator include triethylamine, tributylamine, N,N-dimethyl-4-aminopyridine (DMAP), 2,4,6-tris(dimethylaminomethyl)phenol, 1,8-diazabicyclo[5, Examples thereof include 4,0]-undecene-7 (DBU) and 1,5-diazabicyclo[4,3,0]-nonene-5 (DBN).
Examples of the imidazole curing accelerator include 2-methylimidazole, 2-undecylimidazole, 2-heptadecyl imidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, and 2-phenyl. -4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl -4-Methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2-phenylimidazole isocyanuric acid adduct , 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, 1-dodecyl-2 -Methyl-3-benzylimidazolium chloride, 2-methylimidazoline and the like.
Examples of the guanidine-based curing accelerator include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1, 5,7-triazabicyclo[4.4.0]dec-5-ene, 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, 1-methylbiguanide , 1-ethylbiguanide, 1-butylbiguanide, 1-cyclohexylbiguanide, 1-allylbiguanide, 1-phenylbiguanide, and the like.
Examples of the urea-based curing accelerator include 3-phenyl-1,1-dimethylurea, 3-(4-methylphenyl)-1,1-dimethylurea, chlorophenylurea, 3-(4-chlorophenyl)-1,1 -dimethylurea, 3-(3,4-dichlorophenyl)-1,1-dimethylurea, and the like.
Among the above-mentioned curing accelerators, it is preferable to use 2-ethyl-4-methylimidazole and N,N-dimethyl-4-aminopyridine (DMAP).

When the curing accelerator is used, the content of the curing accelerator in the curable resin composition of this embodiment is the same as that of the active ester resin (A) and the resin (B) having an acid group and a polymerizable unsaturated group. The amount is preferably 0.01 to 5 parts by weight based on 100 parts by weight of the total solid content (nonvolatile content). When the content of the curing accelerator is 0.01 part by mass or more, curability can be more reliably improved. On the other hand, when the content of the curing accelerator is 5 parts by mass or less, insulation reliability can be maintained sufficiently well. From the same viewpoint, the content of the curing accelerator is 100 parts by mass of the total solid content (nonvolatile content) of the active ester resin (A) and the resin (B) having an acid group and a polymerizable unsaturated group. On the other hand, it is more preferably 0.1 parts by mass or more, and more preferably 5 parts by mass or less.

--Other resins--
Examples of the other resins include, but are not limited to, maleimide resins, polyphenylene ether resins, polyimide resins, cyanate ester resins, benzoxazine resins, triazine-containing cresol novolak resins, cyanate ester resins, styrene-maleic anhydride resins, diallyl bisphenol. Examples include allyl group-containing resins such as and triallyl isocyanurate, polyphosphoric acid esters, and phosphoric acid ester-carbonate copolymers. These other resins may be used alone or in combination of two or more.
When using the other resin, the content of the other resin in the curable resin composition of this embodiment is preferably 50% by mass or less of the total.

--Organic solvent--
The organic solvent can have a function of adjusting the viscosity of the curable resin composition. Specific examples of organic solvents include, but are not limited to, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ether solvents such as diethyl ether and tetrahydrofuran; ethyl acetate, butyl acetate, cellosolve acetate, and propylene glycol monomethyl. Ester solvents such as ether acetate and carbitol acetate; carbitols such as cellosolve and butyl carbitol; toluene, xylene, ethylbenzene, mesitylene, 1,2,3-trimethylbenzene, 1,2,4-trimethylbenzene, etc. Examples include aromatic hydrocarbons, amide solvents such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone. The organic solvents may be used alone or in combination of two or more.
When using the organic solvent, the content of the organic solvent in the curable resin composition of the present embodiment is preferably 90% by mass or less based on the total amount (100% by mass) of the curable resin composition, and 10 to 10% by mass. It is more preferably 90% by mass, and even more preferably from 20 to 80% by mass. It is preferable that the content of the organic solvent is 10% by mass or more because it provides excellent handling properties. On the other hand, it is preferable from the viewpoint of economy that the content of the organic solvent is 90% by mass or less.

--Polymerization inhibitor--
The polymerization inhibitor is not particularly limited, but includes p-methoxyphenol (methoquinone), 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, 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline and other phenolic compounds; hydroquinone, methylhydroquinone, p-benzoquinone, methyl-p-benzoquinone, 2,5-diphenyl Quinone compounds such as benzoquinone, 2-hydroxy-1,4-naphthoquinone, anthraquinone, and diphenoquinone;
Melamine, p-phenylenediamine, 4-aminodiphenylamine, N,N'-diphenyl-p-phenylenediamine, Ni-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), styrene amine compounds such as styrenated diphenylamine, reaction products of styrenated diphenylamine and 2,4,4-trimethylpentene, and reaction products of diphenylamine and 2,4,4-trimethylpentene;
Phenothiazine, distearylthiodipropionate, 2,2-bis({[3-(dodecylthio)propionyl]oxy}methyl)-1,3-propanediylbis[3-(dodecylthio)propionate], ditridecane-1- yl=3,3'-sulfanediyl dipropanoate and other thioether compounds;
N-nitrosodiphenylamine, N-nitrosophenylnaphthylamine, p-nitrosophenol, nitrosobenzene, p-nitrosodiphenylamine, α-nitroso-β-naphthol, 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- Nitroso compounds such as sodium 3,6-sulfonate, sodium 2-nitroso-1-naphthol-4-sulfonate, 2-nitroso-5-methylaminophenol hydrochloride, 2-nitroso-5-methylaminophenol hydrochloride;
Ester of phosphoric acid and octadecane-1-ol, triphenylphosphite, 3,9-dioctadecan-1-yl-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, tris Nonylphenyl phosphite, phosphorous acid-(1-methylethylidene)-di-4,1-phenylenetetra-C12-15-alkyl ester, 2-ethylhexyl diphenyl phosphite, diphenylisodecyl phosphite, triisodecyl phosphite phosphite compounds such as phyto, tris(2,4-di-tert-butylphenyl) phosphite;
Zinc compounds such as bis(dimethyldithiocarbamato-κ(2)S,S')zinc, zinc diethyldithiocarbamate, zinc dibutyldithiocarbamate;
Nickel compounds such as bis(N,N-dibutylcarbamodithioato-S,S')nickel;
1,3-dihydro-2H-benzimidazole-2-thione, 4,6-bis(octylthiomethyl)-o-cresol, 2-methyl-4,6-bis[(octan-1-ylsulfanyl)methyl] Examples include sulfur compounds such as phenol, dilaurylthiodipropionate, and distearyl 3,3'-thiodipropionate.
The polymerization inhibitors may be used alone or in combination of two or more.

--Antioxidant--
The antioxidant is not particularly limited, but compounds similar to those exemplified as polymerization inhibitors can be used. The antioxidants may be used alone or in combination of two or more.

Examples of commercially available polymerization inhibitors and antioxidants include "Q-1300" and "Q-1301" manufactured by Wako Pure Chemical Industries, Ltd., "Sumilizer BBM-S" and "Sumilizer GA" manufactured by Sumitomo Chemical Co., Ltd. -80ga'', etc.

--Flame retardants--
Examples of the flame retardant include, but are not particularly limited to, inorganic phosphorus flame retardants, organic phosphorus flame retardants, halogen flame retardants, and the like. The flame retardants may be used alone or in combination of two or more.

Examples of the inorganic phosphorus flame retardant include, but are not limited to, red phosphorus; ammonium phosphates such as monoammonium phosphate, diammonium phosphate, triammonium phosphate, and ammonium polyphosphate; and phosphoric acid amides.
The organic phosphorus flame retardant is not particularly limited, but includes methyl acid phosphate, ethyl acid phosphate, isopropyl acid phosphate, dibutyl phosphate, monobutyl phosphate, butoxyethyl acid phosphate, 2-ethylhexyl acid phosphate, and bis(2-ethylhexyl). Phosphate, monoisodecyl acid phosphate, lauryl acid phosphate, tridecyl acid phosphate, stearyl acid phosphate, isostearyl acid phosphate, oleyl acid phosphate, butyl pyrophosphate, tetracosyl acid phosphate, ethylene glycol acid phosphate, (2-hydroxyethyl ) Phosphoric acid esters such as methacrylate acid phosphate; 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, diphenylphosphine such as diphenylphosphine oxide; 10-(2,5-dihydroxyphenyl)-10H- 9-Oxa-10-phosphaphenanthrene-10-oxide, 10-(1,4-dioxynaphthalene)-10H-9-oxa-10-phosphaphenanthrene-10-oxide, diphenylphosphinylhydroquinone, diphenylphos Phosphorus-containing phenols such as phenyl-1,4-dioxynaphthalene, 1,4-cyclooctylenephosphinyl-1,4-phenyldiol, and 1,5-cyclooctylenephosphinyl-1,4-phenyldiol ;9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide, 10 -(2,7-dihydroxynaphthyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide and other cyclic phosphorus compounds; the phosphoric acid ester, the diphenylphosphine, the phosphorus-containing phenol, and an epoxy resin or Examples include compounds obtained by reacting with aldehyde compounds and phenol compounds.
The halogen flame retardant is not particularly limited, but includes brominated polystyrene, bis(pentabromophenyl)ethane, tetrabromobisphenol A bis(dibromopropyl ether), 1,2,-bis(tetrabromophthalimide), 2, Examples include 4,6-tris(2,4,6-tribromophenoxy)-1,3,5-triazine and tetrabromophthalic acid.

When using the flame retardant, the amount of the flame retardant to be used in the resin composition of the present embodiment is determined based on the solid content (non-volatile The amount is preferably from 0.1 to 50 parts by weight based on 100 parts by weight of the total amount of ingredients. When the content of the flame retardant is 0.1 part by mass or more, flame retardancy can be imparted more reliably. On the other hand, when the content of the flame retardant is 50 parts by mass or less, flame retardancy can be imparted while maintaining dielectric properties. From the same viewpoint, the content of the flame retardant is based on 100 parts by mass of the total solid content (nonvolatile content) of the active ester resin (A) and the resin (B) having an acid group and a polymerizable unsaturated group. It is more preferably 1 part by mass or more, and more preferably 30 parts by mass or less.

--filler--
Examples of the filler include organic fillers and inorganic fillers. The organic fillers have the function of improving elongation and mechanical strength. The inorganic fillers have the function of reducing the thermal expansion coefficient and imparting flame retardancy. The above-mentioned fillers may be used alone or in combination of two or more.

The organic filler is not particularly limited, but includes polyamide particles and the like.
The inorganic filler is not particularly limited, but includes silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, and nitride. Boron, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide, barium titanate, barium zirconate titanate, barium zirconate , calcium zirconate, zirconium phosphate, zirconium tungstate phosphate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, carbon black and the like. Among these, it is preferable to use silica. In this case, as the silica, amorphous silica, fused silica, crystalline silica, synthetic silica, hollow silica, etc. can be used.

Further, the filler may be surface-treated if necessary. At this time, surface treatment agents that can be used include, but are not particularly limited to, aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, silane coupling agents, organosilazane compounds, titanate coupling agents, etc. A ring agent or the like may be used. Specific examples of surface treatment agents include 3-glycidoxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, and hexamethyldimethoxysilane. Examples include silazane. In addition, the above-mentioned fillers may be used alone or in combination of two or more.

When using the filler, the amount of the filler used in the resin composition of the present embodiment is determined based on the solid content (non-volatile The amount is preferably 0.5 to 95 parts by weight based on 100 parts by weight of the total amount of the ingredients. When the content of the filler is 0.5 parts by mass or more, the effect of the filler can be sufficiently imparted. On the other hand, when the content of the filler is 95 parts by mass or less, deterioration of moldability due to the increase in the viscosity of the compound can be suppressed. From the same viewpoint, the content of the filler is based on 100 parts by mass of the total solid content (nonvolatile content) of the active ester resin (A) and the resin (B) having an acid group and a polymerizable unsaturated group. The amount is more preferably 5 parts by mass or more, and more preferably 80 parts by mass or less.

The method for producing the curable resin composition of this embodiment is not particularly limited, and can be produced by kneading the various components described above using a kneader such as a roll.

<Cured product>
The cured product of this embodiment is characterized by being formed by curing the above-mentioned curable resin composition. The cured product of this embodiment has a low elastic modulus, high adhesion to adjacent members, excellent dielectric properties, and can suitably function as an insulating material or a resist member.
The cured product of this embodiment is preferably obtained by curing a curable resin composition by irradiating it 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. Furthermore, 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.

Examples of sources of ultraviolet light include ultraviolet lamps such as low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, xenon lamps, gallium lamps, and metal halide lamps, sunlight, and LEDs. Ultraviolet lamps are commonly used from the viewpoint of performance and economy.

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 . When the cumulative amount of light is within the above range, the occurrence of uncured portions can be sufficiently prevented or suppressed. Note that the irradiation with active energy rays may be performed in one step, or may be performed in two or more steps.

Further, as another method for obtaining a cured product by subjecting the curable resin composition to a curing reaction, for example, heat curing can be mentioned. The heating temperature during heat curing is not particularly limited, but it is preferably 100 to 300°C, and the heating time is preferably 1 to 24 hours.

The curable resin composition or cured product of this embodiment is used for circuit boards such as printed wiring board materials, resin compositions for flexible wiring boards, interlayer insulation materials for build-up boards, and adhesive films for build-up. Insulating materials, resin casting materials, adhesives, semiconductor encapsulation materials, semiconductor devices, prepregs, conductive pastes, build-up films, build-up substrates, fiber-reinforced composite materials, molded products made by curing the above composite materials, etc. Can be mentioned. Among these various applications, printed wiring board materials, insulating materials for circuit boards, and build-up adhesive films are used for so-called electronic component embedded substrates in which passive components such as capacitors and active components such as IC chips are embedded within the substrate. It can be used as an insulating material. Furthermore, among the above, the curable resin composition or cured product of this embodiment can be used as a semiconductor encapsulation material, semiconductor device, prepreg, flexible material, etc. by taking advantage of the characteristics that the cured product has excellent heat resistance and coating film appearance. It can be suitably applied to rubble wiring boards, circuit boards, build-up films, build-up boards, multilayer printed wiring boards, fiber-reinforced composite materials, and molded products obtained by curing the composite materials.

<Insulating material>
The insulating material of this embodiment is characterized by being made of the above-mentioned curable resin composition. Moreover, it is preferable that the insulating material of this embodiment is obtained by curing the above-mentioned curable resin composition by irradiation with active energy rays. The insulating material of this embodiment has a low elastic modulus, high adhesion to adjacent members, and excellent dielectric properties.

Examples of the insulating material include the above-mentioned interlayer insulating material for build-up boards, insulating materials for circuit boards such as adhesive films for build-up, insulating materials for circuit boards, and insulating materials for electronic component built-in boards. For example, a method for manufacturing a build-up board from the above-mentioned curable resin composition includes a method comprising the following three steps. The first step is a step of applying the above-mentioned curable resin composition containing appropriate blends of rubber, filler, etc. to the circuit board on which the circuit has been formed using a spray coating method, curtain coating method, etc., and then curing the composition. In the second step, after drilling predetermined through-holes as necessary, the surface is treated with a roughening agent, and the surface is washed with hot water to form unevenness. This is a process of plating metal, and the third process is a process of sequentially repeating such operations as desired to alternately build up and form a resin insulating layer and a conductor layer with a predetermined circuit pattern. . Note that it is preferable that the through-hole portion be formed after the outermost resin insulating layer is formed. The first step can be carried out not only by solution coating as described above, but also by laminating a build-up film that has been coated to a desired thickness and dried. In addition, the build-up board of the present invention can be produced by heat-pressing a resin-coated copper foil obtained by semi-curing the resin composition on the copper foil at 170 to 250°C onto a wiring board on which a circuit has been formed. It is also possible to manufacture a build-up board by omitting the steps of forming a chemically coated surface and plating.

<Resist material>
The resist member of this embodiment is characterized by being made of the above-mentioned curable resin composition. The resist member is prepared, for example, by applying the above-mentioned curable resin composition onto a base material, drying it at a temperature range of about 60 to 100°C, and then exposing it to active energy rays through a photomask on which a desired pattern is formed. It can be obtained by exposing the film to light, developing the unexposed areas with an alkaline aqueous solution, and further curing by heating at a temperature range of about 140 to 180°C. The resist member (resist film) of this embodiment has a low elastic modulus, high adhesion to adjacent members, and excellent dielectric properties.

EXAMPLES The present invention will be described in more detail below with reference to Examples, but the present invention is not limited to the Examples below. The descriptions of "parts" and "%" in the examples are based on mass unless otherwise specified. Note that the GPC measurement conditions in this example are as follows.

[GPC measurement conditions]
Measuring device: “HLC-8320 GPC” manufactured by Tosoh Corporation,
Column: Guard column “HXL-L” manufactured by Tosoh Corporation
+ “TSK-GEL G4000HXL” manufactured by Tosoh Corporation
+ “TSK-GEL G3000HXL” manufactured by Tosoh Corporation
+ “TSK-GEL G2000HXL” manufactured by Tosoh Corporation
+ “TSK-GEL G2000HXL” manufactured by Tosoh Corporation
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: In accordance with the measurement manual for "GPC-8320", the following monodisperse polystyrene with a known molecular weight was used.
(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 (calculated as resin solid content) filtered through a microfilter (50μL)

(Synthesis Example 1: Synthesis of active ester resin (A-1))
In a flask equipped with a thermometer, dropping funnel, cooling tube, fractionating tube, and stirrer, 209 parts by mass of 1-naphthol, 350 parts by mass of toluene, divinylbenzene ("DVB-810" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., divinylbenzene purity) 81% (containing 19% ethylstyrene)) and 1 part by mass of p-toluenesulfonic acid monohydrate were charged. The contents of the flask were heated to 115° C. while stirring, and the mixture was stirred at 115° C. for 1 hour to react. After the reaction was completed, 0.6 parts by mass of a 49% aqueous sodium hydroxide solution was added to neutralize the mixture, 400 parts by mass of toluene was added, and the mixture was washed three times with 200 parts by mass of water. Toluene and the like were distilled off under heating and reduced pressure conditions to obtain 250 parts by mass of a mixture (M-1) containing unreacted 1-naphthol and a phenolic hydroxyl group-containing resin. The hydroxyl equivalent of the obtained mixture (M-1) was 177 g/equivalent, and the number of moles of hydroxyl groups in unreacted 1-naphthol (a1 _OH ) and the number of moles of hydroxyl groups in the phenolic hydroxyl group-containing resin (a2 _OH ) [(a1 _OH )/(a2 _OH )] was 1.45/1.41.
Next, 147 parts by mass of isophthalic acid chloride and 1000 parts by mass of toluene were charged into a flask equipped with a thermometer, a dropping funnel, a condenser tube, a fractionator tube, and a stirrer, and the mixture was dissolved while purging the system with nitrogen under reduced pressure. Next, 250 parts by mass of the mixture (M-1) obtained above was charged and dissolved while purging the system with nitrogen under reduced pressure. Here, the number of moles of hydroxyl groups in the mixture (M-1) is 0.98 moles per mole of acid halide groups that isophthalic acid chloride has. 0.5 g of tetrabutylammonium bromide was added, and 299 parts by mass of a 20% aqueous sodium hydroxide solution was added dropwise over 3 hours while controlling the inside of the reaction system to 60° C. or lower while purging with nitrogen gas. After the dropwise addition was completed, stirring was continued for 1 hour to allow reaction. After the reaction was completed, the reaction mixture was allowed to stand still for liquid separation, and the aqueous layer was removed. After adding water to the remaining organic layer and stirring and mixing for about 15 minutes, the mixture was allowed to stand to separate the layers, and the aqueous layer was removed. After repeating this operation until the pH of the aqueous layer became 7, toluene and the like were distilled off under heating and reduced pressure conditions to obtain 320 parts by mass of active ester resin (A-1). The functional group equivalent of the active ester resin (A-1) was 241 g/equivalent, and the softening point measured based on JIS K7234 was 130°C. The weight average molecular weight (Mw) of the active ester resin (A-1) calculated from the area ratio of the GPC chart was 1236.

(Synthesis Example 2: Synthesis of active ester resin (A-2))
In a flask equipped with a thermometer, dropping funnel, cooling tube, fractionating tube, and stirrer, 200 parts by mass of 1-naphthol, 350 parts by mass of toluene, divinylbenzene ("DVB-960" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., divinylbenzene purity) 96% (containing 4% ethylstyrene) and 1 part by mass of para-toluenesulfonic acid monohydrate were charged. The contents of the flask were heated to 115° C. while stirring, and the mixture was stirred at 115° C. for 1 hour to react. After the reaction was completed, 0.6 parts by mass of a 49% aqueous sodium hydroxide solution was added to neutralize the mixture, 400 parts by mass of toluene was added, and the mixture was washed three times with 200 parts by mass of water. Toluene and the like were distilled off under heating and reduced pressure conditions to obtain 254 parts by mass of a mixture (M-2) containing unreacted 1-naphthol and a phenolic hydroxyl group-containing resin. The hydroxyl equivalent of the obtained mixture (M-2) was 187 g/equivalent, and the number of moles of hydroxyl groups in unreacted 1-naphthol (a1 _OH ) and the number of moles of hydroxyl groups in the phenolic hydroxyl group-containing resin (a2 _OH ) [(a1 _OH )/(a2 _OH )] was 1.39/1.36.
Next, 140 parts by mass of isophthalic acid chloride and 1000 parts by mass of toluene were charged into a flask equipped with a thermometer, dropping funnel, condenser tube, fractionator tube, and stirrer, and dissolved while purging the system with nitrogen under reduced pressure. Next, 254 parts by mass of the mixture (M-2) obtained above was charged and dissolved while purging the system with nitrogen under reduced pressure. Here, the number of moles of hydroxyl groups in the mixture (M-2) is 0.98 moles per mole of acid halide groups that isophthalic acid chloride has. 0.5 g of tetrabutylammonium bromide was added, and 286 parts by mass of a 20% aqueous sodium hydroxide solution was added dropwise over 3 hours while controlling the inside of the reaction system to 60° C. or lower while purging with nitrogen gas. After the dropwise addition was completed, stirring was continued for 1 hour to allow reaction. After the reaction was completed, the reaction mixture was allowed to stand still for liquid separation, and the aqueous layer was removed. After adding water to the remaining organic layer and stirring and mixing for about 15 minutes, the mixture was allowed to stand to separate the layers, and the aqueous layer was removed. After repeating this operation until the pH of the aqueous layer reached 7, toluene and the like were distilled off under heating and reduced pressure conditions to obtain 320 parts by mass of active ester resin (A-2). The functional group equivalent of the active ester resin (A-2) was 252 g/equivalent, and the softening point measured based on JIS K7234 was 165°C. The weight average molecular weight (Mw) of the active ester resin (A-2) calculated from the area ratio of the GPC chart was 2,772.

(Synthesis Example 3: Synthesis of active ester resin (A-3))
In a flask equipped with a thermometer, dropping funnel, cooling tube, fractionating tube, and stirrer, 200 parts by mass of 1-naphthol, 350 parts by mass of toluene, divinylbenzene ("DVB-960" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., divinylbenzene purity) 96% (containing 4% ethylstyrene)) and 1 part by mass of para-toluenesulfonic acid monohydrate were charged. The contents of the flask were heated to 115° C. while stirring, and the mixture was stirred at 115° C. for 1 hour to react. After the reaction was completed, 0.6 parts by mass of a 49% aqueous sodium hydroxide solution was added to neutralize the mixture, 400 parts by mass of toluene was added, and the mixture was washed three times with 200 parts by mass of water. Toluene and the like were distilled off under heating and reduced pressure conditions to obtain 245 parts by mass of a mixture (M-3) containing unreacted 1-naphthol and a phenolic hydroxyl group-containing resin. The hydroxyl equivalent of the obtained mixture (M-3) was 181 g/equivalent, and the number of moles of hydroxyl groups in unreacted 1-naphthol (a1 _OH ) and the number of moles of hydroxyl groups in the phenolic hydroxyl group-containing resin (a2 _OH ) [(a1 _OH )/(a2 _OH )] was 1.39/1.35.
Next, 140 parts by mass of isophthalic acid chloride and 1000 parts by mass of toluene were charged into a flask equipped with a thermometer, dropping funnel, condenser tube, fractionator tube, and stirrer, and dissolved while purging the system with nitrogen under reduced pressure. Next, 245 parts by mass of the mixture (M-3) obtained above was charged and dissolved while purging the system with nitrogen under reduced pressure. Here, the number of moles of hydroxyl groups in the mixture (M-3) is 0.98 moles per mole of acid halide groups that isophthalic acid chloride has. 0.5 g of tetrabutylammonium bromide was added, and 286 parts by mass of a 20% aqueous sodium hydroxide solution was added dropwise over 3 hours while controlling the inside of the reaction system to 60° C. or lower while purging with nitrogen gas. After the dropwise addition was completed, stirring was continued for 1 hour to allow reaction. After the reaction was completed, the reaction mixture was allowed to stand still for liquid separation, and the aqueous layer was removed. After adding water to the remaining organic layer and stirring and mixing for about 15 minutes, the mixture was allowed to stand to separate the layers, and the aqueous layer was removed. After repeating this operation until the pH of the aqueous layer became 7, toluene and the like were distilled off under heating and reduced pressure conditions to obtain 312 parts by mass of active ester resin (A-3). The functional group equivalent of the active ester resin (A-3) was 245 g/equivalent, and the softening point measured based on JIS K7234 was 150°C. The weight average molecular weight (Mw) of the active ester resin (A-3) calculated from the area ratio of the GPC chart was 1377.

(Synthesis Example 4: Synthesis of active ester resin (A-4))
In a flask equipped with a thermometer, dropping funnel, cooling tube, fractionating tube, and stirrer, 255 parts by mass of orthophenylphenol, 400 parts by mass of toluene, divinylbenzene ("DVB-810" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., divinylbenzene purity) 81% (containing 19% ethylstyrene) and 1 part by mass of para-toluenesulfonic acid monohydrate were charged. The contents of the flask were heated to 115° C. while stirring, and the mixture was stirred at 115° C. for 1 hour to react. After the reaction was completed, 0.6 parts by mass of a 49% aqueous sodium hydroxide solution was added to neutralize the mixture, 400 parts by mass of toluene was added, and the mixture was washed three times with 200 parts by mass of water. Toluene and the like were distilled off under heating and reduced pressure conditions to obtain 295 parts by mass of a mixture (M-4) containing unreacted orthophenylphenol and a phenolic hydroxyl group-containing resin. The hydroxyl equivalent of the obtained mixture (M-4) was 203 g/equivalent, and the number of moles of hydroxyl groups possessed by unreacted orthophenylphenol (a1 _OH ) and the number of moles of hydroxyl groups possessed by the phenolic hydroxyl group-containing resin (a2 _OH ) [(a1 _OH )/(a2 _OH )] was 1.50/1.45.
Next, 151 parts by mass of isophthalic acid chloride and 800 parts by mass of toluene were charged into a flask equipped with a thermometer, a dropping funnel, a cooling tube, a fractionating tube, and a stirrer, and the mixture was dissolved while purging the system with nitrogen under reduced pressure. Next, 295 parts by mass of the mixture (M-4) obtained above was charged and dissolved while purging the system with nitrogen under reduced pressure. Here, the number of moles of hydroxyl groups in the mixture (M-4) is 0.98 moles per mole of acid halide groups that isophthalic acid chloride has. 0.5 g of tetrabutylammonium bromide was added, and 308 parts by mass of a 20% aqueous sodium hydroxide solution was added dropwise over 3 hours while controlling the inside of the reaction system to 60° C. or lower while purging with nitrogen gas. After the dropwise addition was completed, stirring was continued for 1 hour to allow reaction. After the reaction was completed, the reaction mixture was allowed to stand still for liquid separation, and the aqueous layer was removed. After adding water to the remaining organic layer and stirring and mixing for about 15 minutes, the mixture was allowed to stand to separate the layers, and the aqueous layer was removed. After repeating this operation until the pH of the aqueous layer reached 7, toluene and the like were distilled off under heating and reduced pressure conditions to obtain 365 parts by mass of active ester resin (A-4). The functional group equivalent of the active ester resin (A-4) was 267 g/equivalent, and the softening point measured based on JIS K7234 was 94°C. The weight average molecular weight (Mw) of the active ester resin (A-4) calculated from the area ratio of the GPC chart was 1181.

(Synthesis Example 5: Synthesis of active ester resin (A-5))
In a flask equipped with a thermometer, dropping funnel, cooling tube, fractionating tube, and stirrer, 245 parts by mass of orthophenylphenol, 400 parts by mass of toluene, divinylbenzene ("DVB-810" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., divinylbenzene purity) 81% (containing 19% ethylstyrene) and 1 part by mass of para-toluenesulfonic acid monohydrate were charged. The contents of the flask were heated to 115° C. while stirring, and the mixture was stirred at 115° C. for 1 hour to react. After the reaction was completed, 0.6 parts by mass of a 49% aqueous sodium hydroxide solution was added to neutralize the mixture, 400 parts by mass of toluene was added, and the mixture was washed three times with 200 parts by mass of water. Toluene and the like were distilled off under heating and reduced pressure conditions to obtain 300 parts by mass of a mixture (M-5) containing unreacted orthophenylphenol and a phenolic hydroxyl group-containing resin. The hydroxyl equivalent of the obtained mixture (M-5) was 213 g/equivalent, and the number of moles of hydroxyl groups possessed by unreacted orthophenylphenol (a1 _OH ) and the number of moles of hydroxyl groups possessed by the phenolic hydroxyl group-containing resin (a2 _OH ) [(a1 _OH )/(a2 _OH )] was 1.44/1.41.
Next, 145 parts by mass of isophthalic acid chloride and 800 parts by mass of toluene were charged into a flask equipped with a thermometer, a dropping funnel, a cooling tube, a fractionating tube, and a stirrer, and the mixture was dissolved while purging the system with nitrogen under reduced pressure. Next, 300 parts by mass of the mixture (M-5) obtained above was charged and dissolved while purging the system with nitrogen under reduced pressure. Here, the number of moles of hydroxyl groups in the mixture (M-5) is 0.99 moles per 1 mole of acid halide groups that isophthalic acid chloride has. 0.5 g of tetrabutylammonium bromide was added, and 297 parts by mass of a 20% aqueous sodium hydroxide solution was added dropwise over 3 hours while controlling the inside of the reaction system to 60° C. or lower while purging with nitrogen gas. After the dropwise addition was completed, stirring was continued for 1 hour to allow reaction. After the reaction was completed, the reaction mixture was allowed to stand still for liquid separation, and the aqueous layer was removed. After adding water to the remaining organic layer and stirring and mixing for about 15 minutes, the mixture was allowed to stand to separate the layers, and the aqueous layer was removed. After repeating this operation until the pH of the aqueous layer became 7, toluene and the like were distilled off under heating and reduced pressure conditions to obtain 365 parts by mass of active ester resin (A-5). The functional group equivalent of the active ester resin (A-5) was 278 g/equivalent, and the softening point measured based on JIS K7234 was 102°C. The weight average molecular weight (Mw) of the active ester resin (A-5) calculated from the area ratio of the GPC chart was 1795.

(Synthesis Example 6: Production of active ester resin (C-1))
In a flask equipped with a thermometer, dropping funnel, cooling tube, fractionating tube, and stirrer, 165 parts by mass of an addition reaction product of dicyclopentadiene and phenol (hydroxyl equivalent: 165 g/equivalent, softening point: 85°C), 1-naphthol. 72 parts by mass and 630 parts by mass of toluene were charged and dissolved while purging the system with nitrogen under reduced pressure. Next, 152 parts by mass of isophthaloyl chloride was charged and dissolved while purging the system with nitrogen under reduced pressure. While purging with nitrogen gas, the inside of the system was controlled at 60° C. or lower, and 300 parts by mass of a 20% aqueous sodium hydroxide solution was added dropwise over 3 hours. After the dropwise addition was completed, stirring was continued for 1 hour to allow reaction. After the reaction was completed, the reaction mixture was allowed to stand still for liquid separation, and the aqueous layer was removed. After adding water to the remaining organic layer and stirring and mixing for about 15 minutes, the mixture was allowed to stand to separate the layers, and the aqueous layer was removed. After repeating this operation until the pH of the aqueous layer reached 7, toluene and the like were distilled off under heating and reduced pressure conditions to obtain active ester resin (C-1). The functional group equivalent of the active ester resin (C-1) was 223 g/equivalent, and the softening point measured based on JIS K7234 was 150°C.

(Synthesis Example 7: Synthesis of resin (B-1) having an acid group and a polymerizable unsaturated group)
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, ) 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 72 parts by mass of acrylic acid and 1.4 parts by mass of triphenylphosphine were added. 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 (B-1) having an acid group and a polymerizable unsaturated group. 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 80 mgKOH/g. Note that the acid value is a value measured based on the neutralization titration method of JIS K 0070 (1992).

(Synthesis Example 8: Synthesis of resin (B-2) having an acid group and a polymerizable unsaturated group)
499.7 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 an isocyanurate modified product of isophorone diisocyanate ("VESTANAT T-1890/100" manufactured by EVONIK, NCO) was added. %=17.2%) and 192.0 parts by mass of trimellitic anhydride were dissolved, and 1.0 parts by mass of dibutylhydroxytoluene was added. The reaction was carried out at 160° C. for 6 hours in a nitrogen atmosphere, and it was confirmed that the NCO% was 0.1 or less. Next, after adding 0.4 parts by mass of methquinone as a thermal polymerization inhibitor, 147.6 parts by mass of a pentaerythritol polyacrylate mixture ("Aronix M-306" manufactured by Toagosei Co., Ltd., hydroxyl value: 159.7 mgKOH/g) and 3.5 parts by mass of triphenylphosphine were added, and the reaction was carried out at 110° C. for 5 hours while blowing air. Thereafter, 165.0 parts by mass of glycidyl methacrylate was added and reacted at 110°C for 6 hours. Next, 110.4 parts by mass of succinic anhydride was added and reacted at 110°C for 5 hours to obtain a resin (B-2) having an acid group and a polymerizable unsaturated group. The nonvolatile content of this resin (B-2) having an acid group and a polymerizable unsaturated group was 62% by mass, and the solid content acid value was 80 mgKOH/g.

(Examples 1 to 20, Comparative Examples 1 to 2)
Each component was mixed in the proportions shown in Tables 1 and 2 below to obtain curable resin compositions (1) to (20) and (C1) to (C2). In addition, in Tables 1 and 2, the blending amounts of resins (B-1) and (B-2) having acid groups and polymerizable unsaturated groups are the blending amounts as non-volatile content (solid content).
The following tests were conducted on the obtained curable resin composition.

[Evaluation of alkaline developability]
The curable resin composition obtained in each example and comparative example was applied onto a glass substrate using an applicator to a film thickness of 50 μm, and then heated at 80° C. for 50 minutes, 60 minutes, 70 minutes, and 80 minutes. Samples with different drying times were prepared by drying for 90 minutes and 90 minutes, respectively. These were developed with a 1% by mass sodium carbonate aqueous solution (alkaline aqueous 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 (minutes). The longer the drying control width (minutes), the higher the developability.

[Method of measuring elastic modulus]
The curable resin compositions obtained in Examples and Comparative Examples were applied onto copper foil (manufactured by Furukawa Sangyo Co., Ltd., electrolytic copper foil "F2-WS" 18 μm) using a 50 μm applicator, and then heated at 10 kJ/cm using a metal halide lamp. After irradiating with m ² of ultraviolet light, it was heated at 160° C. for 1 hour. The cured product was peeled off from the copper foil to obtain test piece 1 (cured product). Using this test piece 1, the elastic modulus (MPa) was measured under the condition of 2 mm/min in accordance with JIS K7181. The smaller the value, the lower the elasticity.

[Adhesion evaluation method]
Adhesion was evaluated by measuring peel strength. Specifically, the curable resin compositions obtained in Examples and Comparative Examples were applied onto copper foil (manufactured by Furukawa Sangyo Co., Ltd., electrolytic copper foil "F2-WS" 18 μm) using a 50 μm applicator, and a metal halide lamp was applied. After irradiating with 10 kJ/m ² of ultraviolet rays using a 10 kJ/m 2 ultraviolet ray, the sample was heated at 160° C. for 1 hour to obtain a test piece 2 (cured product). This test piece 2 was cut into a size of 1 cm wide and 12 cm long, and the 90° peel strength (N/cm) was measured using a peel tester (“A&D Tensilon” manufactured by A&D Co., Ltd., peeling speed 50 mm/min). It was measured. The larger the value, the better the adhesion.

[Measurement method of dielectric constant]
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 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 glass substrate to obtain a cured product. Next, the test piece was stored in a room at a temperature of 23°C and a humidity of 50% for 24 hours, and the permittivity of the test piece at 1 GHz was measured using the cavity resonance method using "Network Analyzer E8362C" manufactured by Agilent Technologies. It was measured.

[Measurement method of dielectric loss tangent]
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 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 glass substrate to obtain a cured product. Next, the test piece was stored in a room at a temperature of 23°C and a humidity of 50% for 24 hours, and the dielectric loss tangent of the test piece at 1 GHz was measured by the cavity resonance method using "Network Analyzer E8362C" manufactured by Agilent Technologies. It was measured.

*1 Active ester resin (A-1): Active ester resin obtained in Synthesis Example 1, active ester resin using divinyl compound (a2-2) as a reaction raw material and phenolic hydroxyl group-containing resin (a2) as a reaction raw material, Nonvolatile content (solid content) = 100% by mass
*2 Active ester resin (A-2): Active ester resin obtained in Synthesis Example 2, active ester resin using divinyl compound (a2-2) as a reaction raw material and phenolic hydroxyl group-containing resin (a2) as a reaction raw material, Nonvolatile content (solid content) = 100% by mass
*3 Active ester resin (A-3): Active ester resin obtained in Synthesis Example 3, active ester resin using divinyl compound (a2-2) as a reaction raw material and phenolic hydroxyl group-containing resin (a2) as a reaction raw material, Nonvolatile content (solid content) = 100% by mass
*4 Active ester resin (A-4): Active ester resin obtained in Synthesis Example 4, active ester resin using divinyl compound (a2-2) as a reaction raw material and phenolic hydroxyl group-containing resin (a2) as a reaction raw material, Nonvolatile content (solid content) = 100% by mass
*5 Active ester resin (A-5): Active ester resin obtained in Synthesis Example 5, active ester resin using divinyl compound (a2-2) as a reaction raw material and phenolic hydroxyl group-containing resin (a2) as a reaction raw material, Nonvolatile content (solid content) = 100% by mass
*6 Active ester resin (C-1): Active ester resin obtained in Synthesis Example 6, active ester resin that uses divinyl compound (a2-2) as a reaction raw material but does not use phenolic hydroxyl group-containing resin (a2) as a reaction raw material, Nonvolatile content (solid content) = 100% by mass
*7 Resin having an acid group and a polymerizable unsaturated group (B-1): Resin having an acid group and a polymerizable unsaturated group obtained in Synthesis Example 7, epoxy resin having an acid group and a polymerizable unsaturated group, Nonvolatile content (solid content) = 65% by mass
*8 Resin having an acid group and a polymerizable unsaturated group (B-2): Resin having an acid group and a polymerizable unsaturated group obtained in Synthesis Example 8, urethane resin having an acid group and a polymerizable unsaturated group, Nonvolatile content (solid content) = 62% by mass
*9 Curing agent: Orthocresol novolac type epoxy resin, manufactured by DIC, trade name "EPICLON N-680", epoxy equivalent: 214 g/eq
*10 Organic solvent: diethylene glycol monoethyl ether acetate *11 Photopolymerization initiator: Manufactured by IGM Resins, product name "Omnirad 907"

From Table 1, it can be seen that the curable resin compositions of Examples 1 to 10 according to the present invention used active ester resins that did not use the phenolic hydroxyl group-containing resin (a2) as the reaction raw material but did use the divinyl compound (a2-2) as the reaction raw material. It can be seen that the developability is higher than that of the curable resin composition of Comparative Example 1.

Furthermore, from Table 2, the cured products obtained by curing the curable resin compositions of Examples 11 to 20 according to the present invention are the phenolic hydroxyl group-containing resin (a2) using the divinyl compound (a2-2) as a reaction raw material. It can be seen that the cured product of Comparative Example 2 using an active ester resin that does not use as a reaction raw material has a lower elastic modulus, higher adhesion, and excellent dielectric properties (lower dielectric constant and lower dielectric loss tangent).

The curable resin composition and cured product of the present invention can be used for insulating materials, resist members, and the like.

Claims (10)

Contains an active ester resin (A) and a resin (B) having an acid group and a polymerizable unsaturated group,
The active ester resin (A) contains a compound (a1) having one phenolic hydroxyl group in its molecular structure, a phenolic hydroxyl group-containing compound (a2-1), and a divinyl compound (a2-2) as essential reaction raw materials. A curable resin composition comprising a phenolic hydroxyl group-containing resin (a2) and an aromatic polycarboxylic acid or its acid halide (a3) as essential reaction raw materials. The ratio between the number of moles of hydroxyl groups (a1 _OH ) possessed by the compound (a1) having one phenolic hydroxyl group in the molecular structure and the number of moles (a2 OH ) of hydroxyl groups possessed by the phenolic hydroxyl group-containing resin ( _a2 ) [ The curable resin composition according to claim 1, wherein (a1 _OH )/(a2 _OH )] is 10/90 to 75/25. The total number of moles of hydroxyl groups (a1 _OH ) possessed by the compound (a1) having one phenolic hydroxyl group in the molecular structure and the number of moles (a2 _OH ) of hydroxyl groups possessed by the phenolic hydroxyl group-containing resin (a2) is , the curability according to claim 1, which is 0.95 to 1.05 mol per 1 mol of the carboxyl group or acid halide group in the aromatic polycarboxylic acid or its acid halide (a3). Resin composition. The curable resin composition according to claim 1, wherein the active ester resin (A) has a weight average molecular weight (Mw) of 600 to 5,000. The solid content mass ratio [(A)/(B)] of the active ester resin (A) and the resin (B) having an acid group and a polymerizable unsaturated group is 5/95 to 50/50. , the curable resin composition according to claim 1. The curable resin composition according to claim 1, further comprising a photopolymerization initiator. The curable resin composition according to claim 1, further comprising a curing agent. A cured product obtained by curing the curable resin composition according to any one of claims 1 to 7. An insulating material comprising the curable resin composition according to any one of claims 1 to 7. A resist member comprising the curable resin composition according to any one of claims 1 to 7.