JP2022174730A - Resin composition, curable resin composition, cured product, and electric/electronic component - Google Patents

Abstract

To provide a resin composition which is excellent in moldability and solvent solubility and gives a cured product excellent in heat resistance.SOLUTION: The resin composition contains a phenolic resin having a structure represented by the following formula (1). (R1 and R2 each represent a hydrogen atom, a linear aliphatic hydrocarbon group or the like; and R3-R10 each represent a hydrogen atom, a halogen atom, a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group or the like.)SELECTED DRAWING: None

Description

TECHNICAL FIELD The present invention relates to resin compositions, curable resin compositions, cured products, and electric/electronic parts.

A thermosetting resin composition is used in various fields as a thermosetting molding material or the like by utilizing its curability. Among them, phenolic resin is suitably used as a curing agent for epoxy resin, and thermosetting resin compositions that combine phenolic resin and epoxy resin are excellent in various properties such as heat resistance and adhesiveness, so they are widely used in printing. It is widely used in the fields of semiconductors and electronic parts as a wiring board material, an interlayer insulating material for built-up boards, a semiconductor sealing material, a conductive adhesive material, and the like.

Phenolic resins are known to have various skeletons and structures. For example, Patent Documents 1 and 2 disclose polyhydric phenol compounds having flavan skeletons obtained by polycondensation of resorcinols and carbonyl compounds. Proposed.
Patent Document 3 discloses a phenolic resin having a propenyl group, and a resin composition having excellent heat resistance containing the propenyl group-containing phenolic resin and a maleimide compound having two or more maleimide groups in one molecule is provided. disclosed.

JP-A-4-241353 JP-A-8-169937 JP 2019-019149 A

In the past, most semiconductors were used with relatively small currents and power, such as LSIs, but in recent years, the development of power semiconductors, which use semiconductors to control motors, lighting, etc. and to convert power, has been rapid. progressing to Along with this, semiconductors and semiconductor encapsulation materials that can be used with higher power and current than ever before are desired, and semiconductor encapsulation materials are required to have higher heat resistance than ever before. In addition, printed wiring boards used in electrical and electronic equipment are increasingly being used in harsh environments such as high-temperature environments, and high heat resistance is required.
Further, among printed wiring boards, multilayer printed wiring boards in particular are required to have higher multilayers, higher densities, thinner and lighter weight, improved reliability and moldability, and the like.
In addition, as the wiring becomes finer and finer, higher heat resistance and moldability are required for the characteristics of the resin used as the substrate material.
Furthermore, in printed wiring board applications, the curable resin composition may be dissolved in a solvent and used as a varnish, so the resin used is required to have high solvent solubility.

The polyhydric phenol compounds having flavan skeletons described in Patent Documents 1 and 2 are not satisfactory in terms of heat resistance in response to such demands.
In addition, many phenolic resins with flavan skeletons have a large number of OH groups directly substituted on the flavan skeleton, and many hydrogen bonds are formed. There was a possibility that the moldability in substrate applications would be insufficient.

On the other hand, the resin composition containing a propenyl group-containing phenolic resin and a maleimide compound described in Patent Document 3 has heat resistance for use in the applications described above, or low viscosity and solvent solubility for molding. was not satisfactory in terms of

The present invention is to provide a resin composition that gives a cured product having excellent moldability and solvent solubility and excellent heat resistance, a curable resin composition using the same, its cured product, and electric and electronic parts. aim.

As a result of intensive studies aimed at solving the above problems, the inventors of the present invention found that there is a correlation between the structure of a phenolic resin having a flavan skeleton and the viscosity, Tg, and heat resistance of the resulting resin composition. A flavan skeleton-containing phenolic resin having a structure of, specifically, a structure having at least one phenyl group having a propenyl group and having a controlled position and number of OH groups substituted on the flavan skeleton We have found that the above problems can be solved, and have completed the present invention.
That is, the gist of the present invention resides in the following [1] to [7].

[1] A resin composition containing a phenol resin having a structure represented by the following formula (1).

(In formula (1) above, R ¹ and R ² are each independently a hydrogen atom, a linear aliphatic hydrocarbon group having 1 to 6 carbon atoms, a substituted or unsubstituted aryl group, or a substituted or unsubstituted represents a substituted heteroaryl group, except when both R ¹ and R ² are hydrogen atoms, and R ³ to R ¹⁰ each independently represent a hydrogen atom, a halogen atom, or a substituted or unsubstituted aliphatic hydrocarbon; group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group, and at least one of R ³ to R ¹⁰ is a substituent represented by the following formula ( ² ). Adjacent groups of R ¹⁰ may combine to form a ring.)

(In formula (2) above, Y is a direct bond, —SO ₂ —, —O—, —CO—, —C(CF ₃ ) ₂ —, —S— and an aliphatic hydrocarbon having 1 to 20 carbon atoms) and R ²¹ is a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, or a halogen atom.)

[2] The resin composition according to [1], which contains 0.1 to 100,000 parts by mass of the compound represented by the following formula (3) with respect to 100 parts by mass of the phenolic resin having the structure represented by the formula (1). thing.

(In formula (3) above, X is a direct bond, —SO ₂ —, —O—, —CO—, —C(CF ₃ ) ₂ —, —S— and an aliphatic hydrocarbon having 1 to 20 carbon atoms) and R ¹¹ and R ¹² are a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms or a halogen atom, and may be the same or different.)

[3] For 100 parts by mass of the resin composition described in [1] or [2], an epoxy resin, a maleimide resin, a phenolic resin other than the phenolic resin having the structure represented by the formula (1), a benzoxazine resin, A curable resin composition containing 0.01 to 10,000 parts by mass of at least one selected from the group consisting of cyanate ester resins, active ester resins, resins having radically polymerizable functional groups, isocyanate resins, acid anhydride resins and carbodiimide resins. thing.

[4] A cured product obtained by curing the curable resin composition according to [3].

[5] An electric/electronic component comprising a cured product of the curable resin composition according to [4].

[6] A cured product containing a structure derived from the structure represented by the following formula (1).

(In formula (1) above, R ¹ and R ² are each independently a hydrogen atom, a linear aliphatic hydrocarbon group having 1 to 6 carbon atoms, a substituted or unsubstituted aryl group, or a substituted or unsubstituted represents a substituted heteroaryl group, except when both R ¹ and R ² are hydrogen atoms, and R ³ to R ¹⁰ each independently represent a hydrogen atom, a halogen atom, or a substituted or unsubstituted aliphatic hydrocarbon; group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group, and at least one of R ³ to R ¹⁰ is a substituent represented by the following formula ( ² ). Adjacent groups of R ¹⁰ may combine to form a ring.)

(In formula (2) above, Y is a direct bond, —SO ₂ —, —O—, —CO—, —C(CF ₃ ) ₂ —, —S— and an aliphatic hydrocarbon having 1 to 20 carbon atoms) and R ²¹ is a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, or a halogen atom.)

[7] An electric/electronic component containing the cured product of [6].

The resin composition of the present invention is a resin composition that is excellent in moldability and solvent solubility and gives a cured product with excellent heat resistance. Therefore, the resin composition and curable resin composition of the present invention can be particularly effectively applied to electrical and electronic parts such as semiconductor sealing materials and laminates.

Embodiments of the present invention will be described in detail below, but the following description is an example of the embodiments of the present invention, and the present invention is not limited to the following description unless it exceeds the gist of the present invention. do not have. In addition, when the expression "~" is used in this specification, it is used as an expression including numerical values or physical property values before and after it.

[Resin composition]
The resin composition of the present invention is characterized by containing a phenol resin having a structure represented by the following formula (1) (hereinafter sometimes referred to as "phenol resin (1)"). Although the structure represented by the following formula (1) does not contain a repeating structure and is a monomolecular structure, it is referred to as a "phenol resin" in the industry and is sold as a "phenol resin." Sometimes it is done. In addition, since "phenolic compounds (uncured ones)" are also called "phenolic resins" in the industry, the compounds represented by the following formula (1) are also called "phenolic resins". Phenolic resin (1) is generally called "phenolic resin".

(In formula (1) above, R ¹ and R ² are each independently a hydrogen atom, a linear aliphatic hydrocarbon group having 1 to 6 carbon atoms, a substituted or unsubstituted aryl group, or a substituted or unsubstituted represents a substituted heteroaryl group, except when both R ¹ and R ² are hydrogen atoms, and R ³ to R ¹⁰ each independently represent a hydrogen atom, a halogen atom, or a substituted or unsubstituted aliphatic hydrocarbon; group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group, and at least one of R ³ to R ¹⁰ is a substituent represented by the following formula ( ² ). Adjacent groups of R ¹⁰ may combine to form a ring.)

(In formula (2) above, Y is a direct bond, —SO ₂ —, —O—, —CO—, —C(CF ₃ ) ₂ —, —S— and an aliphatic hydrocarbon having 1 to 20 carbon atoms) and R ²¹ is a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, or a halogen atom.)

<Phenolic resin (1)>
Linear aliphatic hydrocarbon groups having 1 to 6 carbon atoms for R ¹ and R ² in the above formula (1) are preferably alkyl groups having 1 to 6 carbon atoms and alkenyl groups having 2 to 6 carbon atoms. , an alkynyl group having 2 to 6 carbon atoms, and the like.
Examples of alkyl groups having 1 to 6 carbon atoms include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group and n-hexyl group.
Examples of the alkenyl group having 2 to 6 carbon atoms include vinyl group, 1-propenyl group, 2-propenyl group, 1-methylvinyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group and the like. .
Examples of alkynyl groups having 2 to 6 carbon atoms include ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl and 3-butynyl groups.

Examples of substituted or unsubstituted aryl groups for R ¹ and R ² include phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, ethylphenyl group, styryl group, xylyl group, n-propylphenyl group, isopropylphenyl group, mesityl group, ethynylphenyl group, naphthyl group, vinylnaphthyl group and the like. Substituents which the aryl group may have include alkyl groups, alkoxy groups, aryl groups, alkenyl groups, alkynyl groups and the like, and the molecular weight of the substituents is usually 500 or less.

Examples of substituted or unsubstituted heteroaryl groups for R ¹ and R ² include furan ring, benzofuran ring, dibenzofuran ring, thiophene ring, benzothiophene ring, dibenzothiophene ring, pyrrole ring, and pyrazole having a monovalent free valence. ring, imidazole ring, carbazole ring, thienothiophene ring, benzimidazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, cinnoline ring, quinoxaline ring, perimidine ring and the like. The substituent which the heteroaryl group may have includes an alkyl group, an alkoxy group, an aryl group, an alkenyl group, an alkynyl group and the like, and the molecular weight of the substituent is usually 500 or less.

Among these, R ¹ and R ² are preferably a hydrogen atom or a linear aliphatic hydrocarbon group having 1 to 6 carbon atoms, and from the viewpoint that heat resistance can be improved, more preferably, Both R ¹ and R ² are preferably linear aliphatic hydrocarbon groups having 1 to 6 carbon atoms, more preferably alkyl groups having 1 to 6 carbon atoms, and most preferably methyl groups. is. If both R ¹ and R ² are hydrogen atoms, the solvent solubility is poor, so the case where both R ¹ and R ² are hydrogen atoms is excluded.

R ³ to R ¹⁰ in formula (1) each independently represent a hydrogen atom, a halogen atom, a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted It represents a heteroaryl group, and at least one of R ³ to R ¹⁰ is a substituent represented by the formula (2).

Halogen atoms of R ³ to R ¹⁰ include fluorine, chlorine, bromine and iodine atoms.

Aliphatic hydrocarbon groups for R ³ to R ¹⁰ are not particularly limited, but include alkyl groups, alkenyl groups, alkynyl groups, alkoxy groups and the like. Examples of substituents that the aliphatic hydrocarbon group may have include alkyl groups, aryl groups, alkoxy groups, aryloxy groups, amino groups, alkylthio groups, and arylthio groups. The molecular weight of the substituent is preferably 400 or less.
Examples of substituted or unsubstituted alkyl groups include the following. For example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, tert-pentyl group, cyclopentyl group, n-hexyl group, isohexyl group, cyclohexyl group, n-heptyl group, cycloheptyl group, methylcyclohexyl group, n-octyl group, cyclooctyl group, n-nonyl group, 3,3,5-trimethylcyclohexyl group, n- decyl group, cyclodecyl group, n-undecyl group, n-dodecyl group, cyclododecyl group, benzyl group, methylbenzyl group, dimethylbenzyl group, trimethylbenzyl group, naphthylmethyl group, phenethyl group, 2-phenylisopropyl group and the like. .
Substituted or unsubstituted alkoxy groups include the following. For example, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, tert-butoxy, n-pentoxy, isopentoxy, neopentoxy, tert-pentoxy, cyclopentyl thoxy group, n-hexyloxy group, isohexyloxy group, cyclohexyloxy group, n-heptoxy group, cycloheptoxy group, methylcyclohexyloxy group, n-octyloxy group, cyclooctyloxy group, n-nonyloxy group, 3,3,5-trimethyl cyclohexyloxy group, n-decyloxy group, cyclodecyloxy group, n-undecyloxy group, n-dodecyloxy group, cyclododecyloxy group, benzyloxy group, methylbenzyloxy group, dimethylbenzyloxy group, trimethylbenzyloxy group, naphthylmethoxy group, phenethyloxy group, 2-phenylisopropoxy group, and the like.
Examples of substituted or unsubstituted alkenyl groups include the following. For example, vinyl group, 1-propenyl group, 2-propenyl group, 1-methylvinyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 1,3-butadienyl group, cyclohexenyl group, cyclohexadienyl group groups, cinnamyl groups, naphthylvinyl groups, and the like.
Examples of substituted or unsubstituted alkynyl groups include the following. Examples include ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1,3-butandienyl, phenylethynyl, naphthylethynyl and the like.

Examples of substituted or unsubstituted aryl groups for R ³ to R ¹⁰ include phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, ethylphenyl group, styryl group, xylyl group, n-propylphenyl group, isopropylphenyl group, mesityl group, ethynylphenyl group, naphthyl group, vinylnaphthyl group and the like. Examples of the substituent which the aryl group may have include an alkyl group, an alkoxy group, an alkenyl group, an alkynyl group and the like, and the molecular weight of the substituent is usually 200 or less.

The substituted or unsubstituted heteroaryl group represented by R ³ to R ¹⁰ includes furan ring, benzofuran ring, dibenzofuran ring, thiophene ring, benzothiophene ring, dibenzothiophene ring, pyrrole ring and pyrazole having a monovalent free valence. ring, imidazole ring, carbazole ring, thienothiophene ring, benzimidazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, cinnoline ring, quinoxaline ring, perimidine ring and the like. The substituent which the heteroaryl group may have includes an alkyl group, an alkoxy group, an aryl group, an alkenyl group, an alkynyl group and the like, and the molecular weight of the substituent is usually 500 or less.

At least one of R ³ to R ¹⁰ is a substituent represented by formula (2) (hereinafter sometimes referred to as "substituent (2)").

In the above formula (2), the aliphatic hydrocarbon group having 1 to 20 carbon atoms for Y is preferably an aliphatic hydrocarbon group having 1 to 10 carbon atoms, particularly preferably having a branch having 1 to 10 carbon atoms. alkylene groups that may be present. Y is preferably a direct bond or an aliphatic hydrocarbon group having 1 to 10 carbon atoms, more preferably a direct bond, a methylene group or an isopropylidene group, still more preferably a direct bond or an isopropylidene group. , and most preferably Y is a direct bond.

A halogen atom for R ²¹ includes a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. The hydrocarbon group having 1 to 10 carbon atoms for R ²¹ includes an alkyl group having 1 to 10 carbon atoms. Preferably R ²¹ is a hydrogen atom or a methyl group, most preferably a hydrogen atom.

Since the substituent (2) has a propenyl group, it has an effect of contributing to heat resistance, and the softening point or melting point does not become too high, and the fluidity and moldability tend to be excellent.
In the above formula (2), the propenyl group is preferably present at the meta-position with respect to the carbon atom to which Y is bonded, from the viewpoint of reactivity. From the viewpoint of reactivity, the hydroxyl group is preferably present at the para-position or ortho-position with respect to the carbon atom to which Y is bonded. From the viewpoint of reactivity, R ²¹ is preferably present at the meta-position with respect to the carbon atom to which Y is bonded.

When there are multiple substituents (2) in formula (1), each Y and R ²¹ may be the same or different.

Adjacent groups of R ³ to R ¹⁰ may combine to form a ring. In that case, the ring formed may be either an aromatic ring or a non-aromatic ring, but is preferably an aromatic ring. When adjacent groups of R ³ to R ¹⁰ are combined to form a ring, the ring generally has a molecular weight of 300 or less.

The phenolic resin (1) preferred in the present invention has the formula (1) wherein one of R ³ to R ⁶ is the substituent (2), and the remaining three are each independently a hydrogen atom, a halogen atom, or a substituted or an unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group, and one of R ⁷ to R ¹⁰ is a substituent (2), and the rest 3 are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group, more preferably Phenolic resin (1) is represented by formula (1), wherein R ⁵ and R ⁹ are substituents (2), and R ³ , R ⁴ , R ⁶ , R ⁷ , R ⁸ and R ¹⁰ are hydrogen atoms or carbon atoms. An aliphatic hydrocarbon group having 1 to 12 carbon atoms, particularly preferably an unsaturated aliphatic hydrocarbon group having 2 to 3 carbon atoms.

Phenolic resin (1) is most preferably a phenolic resin having a structure represented by the following formula (1A) from the viewpoint of heat resistance and moldability (low viscosity).

(In formula (1A) above, Y and R ²¹ have the same meanings as Y and R ²¹ in formula (2), and the preferred ones are also the same. R ³ and R ⁷ are R ³ and R in formula (1) ⁷ , and the preferred ones are also the same.)

The phenolic resin having the structure represented by formula (1A) tends to exhibit higher heat resistance because it has both a flavan skeleton and a phenyl group. Moreover, since it has a propenyl group, a curable resin composition prepared by mixing with a maleimide resin exhibits excellent thermosetting properties and can give a cured product having high heat resistance.

R ³ , R ⁷ and R ²¹ in formula (1A) are preferably each independently a hydrogen atom or a methyl group, and most preferably all are hydrogen atoms.

<Compound (3)>
The resin composition of the present invention contains a compound represented by the following formula (3) (hereinafter sometimes referred to as "compound (3)") in an amount of 0.1 to 100 parts by mass of phenol resin (1). It is preferable to include 100000 parts by mass.

(In formula (3) above, X is a direct bond, —SO ₂ —, —O—, —CO—, —C(CF ₃ ) ₂ —, —S— and an aliphatic hydrocarbon having 1 to 20 carbon atoms) and R ¹¹ and R ¹² are a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms or a halogen atom, and may be the same or different.)

In the above formula (3), the aliphatic hydrocarbon group having 1 to 20 carbon atoms for X is preferably an aliphatic hydrocarbon group having 1 to 10 carbon atoms, particularly preferably having a branch having 1 to 10 carbon atoms. alkylene groups that may be present. X is preferably a direct bond or an aliphatic hydrocarbon group having 1 to 10 carbon atoms, more preferably a direct bond, a methylene group or an isopropylidene group, still more preferably a direct bond or an isopropylidene group. , most preferably X is a direct bond.

Halogen atoms for R ¹¹ and R ¹² include fluorine, chlorine, bromine and iodine atoms. Examples of the hydrocarbon group having 1 to 10 carbon atoms for R ¹¹ and R ¹² include alkyl groups having 1 to 10 carbon atoms. Preferably, R ¹¹ and R ¹² are each independently a hydrogen atom or a methyl group, and most preferably both are hydrogen atoms.

The resin composition of the present invention tends to have a lower melt viscosity when the content of the compound (3) is higher than that of the phenol resin (1), and tends to have a higher solvent solubility when the content is lower. From such a viewpoint, the resin composition of the present invention more preferably contains 1 to 1000 parts by mass of the compound (3) with respect to 100 parts by mass of the phenolic resin (1), more preferably 2 to 800 parts by mass. be.

<Melt viscosity>
The resin composition of the present invention preferably has a melt viscosity at 150°C of 0.01 to 100.0P, more preferably 0.05 to 90P, still more preferably 0.1 to 80P. When the melt viscosity is equal to or less than the above upper limit, the viscosity is low, and mixing with a maleimide resin, an epoxy resin, or the like, which will be described later, is facilitated. When the melt viscosity is at least the above lower limit, bleeding out is less likely to occur during molding into a mold or the like.
The melt viscosity of the resin composition is measured by the method described in the Examples section below.

<Softening point or melting point>
The softening point or melting point of the resin composition of the present invention is preferably 40 to 150°C, more preferably 50 to 140°C, still more preferably 55 to 120°C. If the softening point or melting point is at least the above lower limit, blocking is unlikely to occur, and if it is at most the above upper limit, the polymer will flow in a short time upon heating.
The softening point or melting point of the resin composition is measured by the method described in Examples below.

<Production of phenolic resin (1)>
The method for producing the phenolic resin (1) is not particularly limited. ", "Phenol compound (5)", and these are sometimes collectively referred to as "Phenol compounds (4) and (5)") are heated to form flavans. Phenolic compounds (4) and (5) may be used alone or in combination. When heating, the phenol compounds (4) and (5) may be dissolved in a solvent, or a catalyst may be added.

(In formulas (4) and (5) above, R ¹ to R ¹⁰ have the same definitions as R ¹ to R ¹⁰ in formula (1) above. Preferably, in formula (4), R ⁵ is substituted In group (2), R ³ , R ⁴ and R ⁶ are hydrogen atoms, and in formula (5) R ⁹ is substituent (2) and R ⁷ , R ⁸ and R ¹⁰ are hydrogen atoms .)

Any solvent that dissolves the phenol compounds (4) and (5) may be used for the flavanation reaction. For example, toluene, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, N,N-dimethylformamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, methanol, ethanol, butanol, ethylene glycol, ethyl acetate, butyl acetate, methyl cellosolve, Ethyl diglycol acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, tetrahydrofuran. A solvent may be used individually by 1 type, and may use 2 or more types together.

When a solvent is used, it is preferably used in an amount of 10 to 1,000 parts by weight, particularly 50 to 500 parts by weight, per 100 parts by weight of the phenol compounds (4) and (5).

When a catalyst is added to the flavanation reaction, examples of the catalyst include acidic catalysts such as sulfuric acid, hydrochloric acid, p-toluenesulfonic acid, and acetic acid. A catalyst may be used individually by 1 type, and may use 2 or more types together.

When a catalyst is used, the amount used is preferably 0.001 to 5.0 times the molar amount of the hydroxyl groups of the phenol compounds (4) and (5), preferably 0.002 to 2.0 times the molar amount. Mole is more preferred.

The reaction temperature of the flavanation reaction is preferably 50 to 200°C, more preferably 80 to 160°C. When the reaction temperature is at least the above lower limit, the flavanation reaction proceeds easily. If the reaction temperature is equal to or lower than the above upper limit, side reactions are less likely to occur.

After the flavanation reaction, if necessary, the reaction product may be subjected to treatments such as removal of unreacted raw materials by distillation or the like, concentration, purification (washing, column chromatography, etc.).

<Production of compound (3)>
The method for producing compound (3) is not particularly limited. ) to obtain an allyloxy group-containing compound represented by the following formula (7) (hereinafter sometimes abbreviated as "allyloxy group-containing compound (7)"), and then, allyloxy group-containing compound (7) to obtain a 2-propenyl group-containing phenol compound (8) represented by the following formula (8) by transferring the allyl group of the 2-propenyl group of the 2-propenyl group-containing phenol compound (8) to a 1-propenyl group is changed to the compound (3).

(In formulas (6), (7) and (8) above, X, R ¹¹ and R ¹² have the same meanings as in formula (3) above.)

As a method for allylating the dihydric phenol compound (6), for example, the dihydric phenol compound (6) is reacted with an allyl halide, and at least part of the hydroxyl groups are allyl-etherified to form —O—CH ₂ —CH. = _CH2 .

In this reaction, the allyl halide should be used in an amount of 2.0 to 8.0 times the moles of the dihydric phenol compound (6), particularly 3.0 to 6.0 times the moles of the dihydric phenol compound (6) while the reaction proceeds efficiently. , is preferable from the viewpoint of suppressing the production cost.

The allyl etherification reaction between the dihydric phenol compound (6) and allyl halide is preferably carried out in the presence of a catalyst.

Examples of catalysts for the allyl etherification reaction include alkali metals such as sodium hydroxide, potassium hydroxide and potassium carbonate; amines such as diazabicyclononene, diazabicycloundecene and triethylamine; sodium tert-butoxide; tert-butoxide, lithium diisopropylamide, silicon-basic amines, lithium tetramethylpiperidine and the like. Among these, alkali metals, diazabicyclononene, and diazabicycloundecene are preferable because they are relatively inexpensive and less likely to cause side reactions. A catalyst may be used individually by 1 type, and may use 2 or more types together.

The amount of the catalyst used in the allyl etherification reaction is preferably 0.7 to 2.0 times the molar amount of the allyl halide used, and more preferably 0.8 to 1.5 times the molar amount. If the amount of catalyst used is too small, the reaction rate will be slow.

Moreover, the allyl etherification reaction is preferably carried out in the presence of a solvent, and examples of the solvent for the allyl etherification reaction include polar solvents used in the propenylation reaction described later.

The reaction temperature for the allyl etherification reaction is not particularly limited as long as it is a temperature at which the hydroxyl group of the dihydric phenol compound (6) reacts with the allyl halide.

After the allyl etherification reaction, if necessary, the reaction product may be subjected to treatments such as removal of unreacted raw materials by distillation or the like, concentration, purification (washing, column chromatography, etc.).

The allyl group transfer of the allyloxy group-containing compound (7) obtained by allylation of the dihydric phenol compound (6) is performed by, for example, Claisen rearrangement reaction by heating the allyloxy group-containing compound (7) after the allylation reaction. can be implemented in Due to the Claisen rearrangement reaction, the allyl group of the allyloxy group (—O—CH ₂ —CH=CH ₂ ) bonded to the benzene ring of the allyloxy group-containing compound (7) is rearranged to the ortho position where the allyloxy group was present.

Claisen rearrangement reaction may be carried out according to a conventional method, for example, allyloxy group-containing compound (7) in the presence of a high boiling point solvent such as carbitol, paraffin oil, N,N'-dimethylaniline, N,N'-diethylaniline or Heat in the absence of solvent. 10 to 200 parts by mass of the solvent is used as necessary with respect to 100 parts by mass of the allyloxy group-containing compound (7). After completion of the reaction, the solvent used can be removed if necessary to obtain the 2-propenyl group-containing phenol compound (8). After the reaction, the 2-propenyl group-containing phenol compound (8) can be recovered by dropping the reaction solution into an aqueous sodium hydroxide solution, dropping the separated aqueous layer into an acid solution, and stirring.

The heating temperature for this Claisen rearrangement reaction is preferably 150 to 220° C., more preferably 170 to 200° C., and the rearrangement reaction in the presence of an inert gas such as nitrogen is even more preferable. If the heating temperature is equal to or higher than the above lower limit, rearrangement reaction of allyl groups easily occurs. When the heating temperature is equal to or lower than the above upper limit, polymerization of allyl groups is less likely to occur.

After the reaction, if necessary, the reaction product may be subjected to a treatment such as washing with water.

The time for dropping into the aqueous sodium hydroxide solution after the reaction is preferably 10 to 30 minutes. If the dropping time is at least the above lower limit, heat generation due to mixing can be suppressed and production can be carried out safely. If the dropping time is equal to or less than the above upper limit, productivity will improve. The stirring time after dropping into the acid solution is preferably 15 to 60 minutes. If the stirring time is at least the above lower limit, the neutralization reaction proceeds and the yield in the subsequent separation step is improved. If the stirring time is equal to or less than the above upper limit, productivity will improve.

As a method for converting the 2-propenyl group of the 2-propenyl group-containing phenol compound (8) to a 1-propenyl group, the 2-propenyl group-containing phenol compound (8) is dissolved in a solvent and heated under the propenylation reaction catalyst. method.

The solvent used for the propenylation reaction may be any solvent as long as it dissolves the 2-propenyl group-containing phenol compound (8), and typically includes polar solvents.
Polar solvents include, for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, N,N-dimethylformamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, methanol, ethanol, butanol, ethylene glycol, ethyl acetate, butyl acetate, Methyl cellosolve, ethyl diglycol acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, tetrahydrofuran. As the solvent, one type may be used alone, or two or more types may be used in combination.

The solvent is preferably used in an amount of 20 to 900 parts by weight, particularly 50 to 600 parts by weight, per 100 parts by weight of the 2-propenyl group-containing phenol compound (8).

Catalysts for the propenylation reaction include, for example, alkali metals such as sodium hydroxide and potassium hydroxide, amines such as diazabicyclononene, diazabicycloundecene and triethylamine, sodium tert-butoxide, potassium tert-butoxide, Lithium diisopropylamide, silicon-basic amines, lithium tetramethylpiperidine and the like. Among them, potassium hydroxide and sodium hydroxide are preferable because they are relatively inexpensive and less likely to cause side reactions. A catalyst may be used individually by 1 type, and may use 2 or more types together.

The amount of propenylation reaction catalyst used is preferably 0.4 to 6.0 times the molar amount of hydroxyl groups in the 2-propenyl group-containing phenol compound (8), preferably 1.0 to 4.0 times the molar amount. Mole is more preferred. If the amount of the catalyst used is too small, the propenylation reaction will be difficult to proceed.

The reaction temperature for the propenylation reaction is preferably 40 to 140°C, more preferably 70 to 120°C. When the reaction temperature is at least the above lower limit, the propenylation reaction proceeds easily. When the reaction temperature is equal to or lower than the above upper limit, polymerization of propenyl groups is less likely to occur.

After the propenylation reaction, if necessary, the reaction product may be subjected to treatments such as removal of unreacted raw materials by distillation or the like, concentration, purification (washing, column chromatography, etc.).

<Method for producing resin composition>
As a method for producing the resin composition of the present invention, phenol resin (1) obtained by heating phenol compounds (4) and (5) to form flavans and compound (3) are prepared and mixed. However, as described above, the dihydric phenol compound (6) is allylated to obtain the allyloxy group-containing compound (7), and then the allyloxy group-containing compound (7) is produced. A 2-propenyl group-containing phenol compound (8) was obtained by transferring an allyl group, and the 2-propenyl group of this 2-propenyl group-containing phenol compound (8) was changed to a 1-propenyl group to obtain a compound (3). It is also possible to prepare the resin composition of the present invention by performing a flavanation reaction to produce the phenol resin (1) and leaving the compound (3).

The resin composition of the present invention contains phenol resin (1), preferably phenol resin (1) and compound (3). The content of the phenol resin (1) in 100% by mass of the resin composition of the present invention or the total content of the phenol resin (1) and the compound (3) is not particularly limited, but is preferably 30% by mass or more, In particular, it is preferably 40% by mass or more, particularly preferably 50 to 100% by mass.

In the resin composition of the present invention, the dihydric phenol compound (6) is allylated to obtain an allyloxy group-containing compound (7), and then the allyl group of the allyloxy group-containing compound (7) is transferred to contain a 2-propenyl group. A phenol compound (8) is obtained, and the 2-propenyl group of the 2-propenyl group-containing phenol compound (8) is changed to a 1-propenyl group to obtain a compound (3), which is subjected to a flavanation reaction to obtain a phenol resin (1 ) and leave the compound (3), the content of the phenol resin (1) and the compound (3) in the resulting resin composition depends on the reaction temperature and reaction time of flavan formation, Usually, the content of phenol resin (1) is 1 to 99% by mass, the content of compound (3) is 1 to 99% by mass, and other by-products are produced in a series of reactions, although it varies depending on the addition of a catalyst. A resin composition containing about 1 to 60% by mass of by-products such as high molecular weight substances is obtained.
Such a resin composition may be used as it is for the production of the curable resin composition of the present invention or the production of the cured product (1) of the present invention to be described later, or the phenol resin (1) may be obtained by chromatographic separation, crystallization, or the like. ) and other reaction by-products other than compound (3) may be removed before use in these applications.

[Curable resin composition]
The curable resin composition of the present invention is the resin composition of the present invention described above and an epoxy resin, a maleimide resin, and a phenolic resin other than the phenolic resin (1) (hereinafter sometimes referred to as "other phenolic resin". ), one or more resins selected from the group consisting of benzoxazine resins, cyanate ester resins, active ester resins, resins having radically polymerizable functional groups, isocyanate resins, acid anhydride resins and carbodiimide resins (hereinafter referred to as The curing component is preferably one or more resins selected from the group consisting of epoxy resins, maleimide resins and other phenolic resins.

In the curable resin composition of the present invention, the propenyl group in the phenolic resin (1) of the resin composition of the present invention and the maleimide group of the maleimide resin react under predetermined conditions to proceed curing. . Thus, the resin composition of the present invention functions as a curing agent for maleimide resins.
In the case of an epoxy resin, the curing reaction proceeds by reacting the hydroxyl groups in the phenolic resin (1) of the resin composition of the present invention with the epoxy groups of the epoxy resin. Also in this case, the resin composition of the present invention functions as a curing agent for epoxy resins.
Other phenolic resins can also be used in combination with epoxy resins.
The curable resin composition of the present invention has excellent adhesion of the cured product, and the curing reaction proceeds easily and the molecular weight of the cured product tends to increase. It preferably contains an epoxy resin.

In the curable resin composition of the present invention, the content of the curing component is 0.01 to 10000 parts by mass, preferably 0.1 to 1000 parts by mass, with respect to 100 parts by mass of the resin composition of the present invention. 1.0 to 500 parts by mass is more preferable. When the content of the curing component is at least the above lower limit, a cured product having excellent heat resistance and good adhesion can be obtained. If the content of the curing component is equal to or less than the above upper limit, a cured product that is uniform and excellent in curability can be produced.

<Hardening component>
Each curing component contained in the curable resin composition of the present invention is described below.

<Maleimide resin>
A maleimide resin is a maleimide compound having an average of one or more maleimide groups in one molecule. Examples of maleimide resins include bismaleimides having two maleimide groups in one molecule, polyphenylmethane maleimide, and the like.

Examples of bismaleimides include alkylbismaleimide, diphenylmethanebismaleimide, phenylenebismaleimide, bisphenol A diphenylether bismaleimide, 3,3′-dimethyl-5,5′-diethyl-4,4′-diphenylmethanebismaleimide, and the like. 4,4′-diphenylmethanebismaleimide, 4-methyl-1,3-phenylenebismaleimide, 1,6′-bismaleimide-(2,2,4-trimethyl)hexane, 4,4′-diphenyletherbismaleimide, 4 ,4'-diphenylsulfonebismaleimide, 1,3-bis(3-maleimidophenoxy)benzene, and 1,3-bis(4-maleimidophenoxy)benzene.
Polyphenylmethane maleimide is a polymer in which three or more benzene rings substituted with maleimide groups are linked via methylene groups.

Among the maleimide resins described above, 4,4′-diphenylmethanebismaleimide and polyphenylmethanemaleimide are preferred as the maleimide resin because of their excellent compatibility with the propenyl group-containing composition of the present invention and their relatively low cost. preferable.

A commercially available product may be used as the maleimide resin. Examples of commercially available maleimide resins include product name "BMI-1100" (4,4'-diphenylmethane bismaleimide) and product name "BMI-2300" (polyphenylmethane maleimide) manufactured by Daiwa Kasei Kogyo Co., Ltd. .

The maleimide resin may be used alone or in combination of two or more.

<Epoxy resin>
The epoxy resin is not particularly limited, and examples thereof include phenol novolak type epoxy resin, orthocresol novolak type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, biphenol type epoxy resin, naphthalene type epoxy resin, and anthracene type epoxy resin. resins, naphthol-type epoxy resins, xylylene-type epoxy resins, biphenyl-type epoxy resins, triphenylmethane-type epoxy resins, dicyclopentadiene-type epoxy resins, stilbene-type epoxy resins, sulfur atom-containing epoxy resins, phosphorus atom-containing epoxy resins, and the like. be done.

As the epoxy resin, an epoxy resin obtained by epoxidizing at least part of the hydroxyl groups of the propenyl group-containing composition may be used. Epoxidation of hydroxyl groups can be carried out by known methods. For example, by reacting a propenyl group-containing composition with epichlorohydrin, some or all of the hydroxyl groups of the propenyl group-containing composition are -OZ (where Z is a glycidyl group). Epoxy resin can be obtained.

An epoxy resin may be used individually by 1 type, and may use 2 or more types together.

<Other phenolic resins>
Other phenolic resins other than phenolic resin (1) contained in the resin composition of the present invention include, for example, phenols such as phenol, cresol, resorcinol, catechol, bisphenol A, bisphenol F, phenylphenol, aminophenol, and / Or a novolak-type phenolic resin obtained by condensation or co-condensation of naphthols such as α-naphthol, β-naphthol and dihydroxynaphthalene and compounds having aldehyde groups such as formaldehyde, benzaldehyde and salicylaldehyde in the presence of an acidic catalyst. Phenol-aralkyl resins synthesized from phenols and/or naphthols and dimethoxyparaxylene or bis(methoxymethyl)biphenyl; Aralkyl-type phenol resins such as biphenylene-type phenol-aralkyl resins and naphthol-aralkyl resins; Phenols and / Or dicyclopentadiene-type phenolic resins such as dicyclopentadiene-type phenolic novolak resins and dicyclopentadiene-type naphthol novolak resins synthesized by copolymerization of naphthols and dicyclopentadiene; triphenylmethane-type phenolic resins; terpene-modified phenol resin; para-xylylene and/or meta-xylylene-modified phenol resin; melamine-modified phenol resin; cyclopentadiene-modified phenol resin; and phenol resin obtained by copolymerizing two or more of these.

These other phenol resins may be used individually by 1 type, and may use 2 or more types together.

<Benzoxazine resin>
Benzoxazine resins include, for example, 6,6-(1-methylethylidene)bis(3,4-dihydro-3-phenyl-2H-1,3-benzoxazine), 6,6-(1-methylethylidene) bis(3,4-dihydro-3-methyl-2H-1,3-benzoxazine) and the like. The benzoxazine resin may contain a structure in which the oxazine ring is ring-opening polymerized.
The benzoxazine resins may be used singly or in combination of two or more.

<Cyanate ester resin>
Examples of cyanate ester resins include bisphenol A dicyanate, polyphenolcyanate (oligo(3-methylene-1,5-phenylenecyanate)), 4,4'-methylenebis(2,6-dimethylphenylcyanate), 4,4' -ethylidene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis(4-cyanate)phenylpropane, 1,1-bis(4-cyanatophenylmethane), bis(4-cyanate-3,5-dimethylphenyl ) bifunctional cyanate resins such as methane, 1,3-bis(4-cyanatophenyl-1-(methylethylidene))benzene, bis(4-cyanatophenyl)thioether, and bis(4-cyanatophenyl)ether, phenol novolak and polyfunctional cyanate resins derived from cresol novolak and the like, and prepolymers in which these cyanate resins are partially triazined.

A cyanate ester resin may be used individually by 1 type, and may use 2 or more types together.

<Active ester resin>
The active ester resin is not particularly limited, but generally contains two highly reactive ester groups in one molecule, such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds. A compound having one or more is preferably used. The active ester resin is preferably obtained by a condensation reaction between a carboxylic acid compound and/or a thiocarboxylic acid compound and a hydroxy compound and/or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester resin obtained from a carboxylic acid compound and a hydroxy compound is preferred, and an active ester resin obtained from a carboxylic acid compound and a phenol compound and/or a naphthol compound is more preferred.
Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid and pyromellitic acid.
Examples of the phenol compound or naphthol compound include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalin, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m - cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucine , benzenetriol, dicyclopentadiene-type diphenol compound, phenol novolac, and the like. Here, the term "dicyclopentadiene-type diphenol compound" refers to a diphenol compound obtained by condensing one molecule of dicyclopentadiene with two molecules of phenol.

Specifically, an active ester resin containing a dicyclopentadiene type diphenol structure, an active ester resin containing a naphthalene structure, an active ester resin containing an acetylated phenol novolac, and an active ester resin containing a benzoylated phenol novolac are preferred. Among them, an active ester resin containing a naphthalene structure and an active ester resin containing a dicyclopentadiene-type diphenol structure are more preferable. Here, the "dicyclopentadiene-type diphenol structure" represents a divalent structural unit composed of phenylene-dicyclopentalene-phenylene.

Active ester resin may be used individually by 1 type, and may use 2 or more types together.

<Resin having a radically polymerizable functional group>
Resins having a radically polymerizable functional group include resins having one or more ethylenically unsaturated groups having a carbon-carbon double bond in the molecule. The ethylenically unsaturated group is preferably one or more groups selected from the group consisting of acryl groups, methacryl groups, styryl groups, olefin groups and maleimide groups. Preferred examples of olefinic groups include allyl, vinyl and propenyl groups. Thus, in one preferred embodiment, the radically polymerizable functional group is one or more selected from the group consisting of acrylic groups, methacrylic groups, styryl groups, allyl groups, vinyl groups, propenyl groups and maleimide groups.
A resin having a radically polymerizable functional group may have one or more radically polymerizable functional groups.

A resin having a radically polymerizable functional group may be used alone or in combination of two or more.

<Isocyanate resin>
Examples of isocyanate resins include resins having one or more isocyanate groups in the molecule. The isocyanate resin preferably has two or more isocyanate groups in its molecule. Examples of isocyanate resins include 4,4′-diphenylmethane diisocyanate, polymethylene polyphenyl polyisocyanate, tolylene diisocyanate, hexamethylene diisocyanate and the like.

The isocyanate resin may be used singly or in combination of two or more.

<Acid anhydride resin>
Acid anhydride resins include resins having one or more acid anhydride groups in the molecule. Examples of acid anhydride resins include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, hydrogenated methylnadic anhydride, trialkyltetrahydrophthalic anhydride, dodecenylsuccinic anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, naphthalenetetracarboxylic dianhydride, oxydiphthalic dianhydride, 3,3'-4,4'-diphenylsulfone tetra Carboxylic dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1,2-C]furan-1,3- Examples include polymer-type acid anhydrides such as dione, ethylene glycol bis(anhydrotrimellitate), and styrene-maleic acid resin obtained by copolymerizing styrene and maleic acid.

The acid anhydride resin may be used alone or in combination of two or more.

<Carbodiimide resin>
Carbodiimide resins include resins having one or more carbodiimide groups (-N=C=N-) in the molecule. The carbodiimide resin preferably has two or more carbodiimide groups in its molecule. Specific examples of carbodiimide resins include “V-03” and “V-07” manufactured by Nisshinbo Chemical Co., Ltd.

Carbodiimide resin may be used individually by 1 type, and may use 2 or more types together.

<Other ingredients>
The curable resin composition of the present invention may contain one or more other components in addition to the resin composition of the present invention and the above curing component. Other components include curing accelerators, inorganic fillers, solvents, release agents, surface treatment agents, colorants, thermoplastic polymers, organic fillers, flame retardants, and the like.

The curing accelerator is not particularly limited, but specific examples include imidazoles, organic peroxides, phosphorus compounds, tertiary amines, organic acid metal salts, Lewis acids, amine complex salts and the like.

Examples of imidazoles include 2-ethyl-4-methylimidazole, 2-methylimidazole, 2-ethylimidazole, 2,4-dimethylimidazole, 2-unde__cylimidazole, 2-heptadecylimidazole, and 2-phenylimidazole. , 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 1-vinyl-2 -methylimidazole, 1-propyl-2-methylimidazole, 2-isopropylimidazole, 1-cyanomethyl-2-methyl-imidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole , 1-cyanoethyl-2-phenylimidazole.

Examples of organic peroxides include ketone peroxides, peroxyketals, hydroperoxides, dialkyl peroxides, diacyl peroxides, peroxydicarbonates, and peroxyesters.

Phosphorus compounds include triphenylphosphine, tris-2,6-dimethoxyphenylphosphine, tri-p-tolylphosphine, triphenyl phosphite and the like.
Tertiary amines include 2-dimethylaminomethylphenol, benzyldimethylamine, α-methylbenzyldimethylamine, 1,8-diazabicyclo[5.4.0]undecene-7 and the like.

As the curing accelerator, those that are relatively stable at high temperatures, have good solvent solubility, and are easy to handle are preferable. is preferably dicumyl peroxide, and triphenylphosphine, which is a phosphorus-based compound.

These curing accelerators may be used alone or in combination of two or more.

When the curable resin composition of the present invention contains a curing accelerator, its content is preferably 0.1 to 5.0% by mass based on the curing component such as maleimide resin.

Examples of inorganic fillers include crystalline silica powder, fusible silica powder, quartz glass powder, talc, calcium silicate powder, zirconium silicate powder, alumina powder, and calcium carbonate powder. Among these, crystalline silica powder and fusible silica powder are preferred. An inorganic filler may be used individually by 1 type, and may use 2 or more types together.

When the curable resin composition of the present invention contains an inorganic filler, the content thereof is preferably 30 to 90% by mass with respect to the entire curable resin composition.

When the curable resin composition of the present invention is used as a thermosetting molding material for forming a sealing material, the curable resin composition of the present invention preferably contains a curing accelerator and an inorganic filler.

The curable resin composition of the present invention can be made into a resin varnish by blending a solvent and dissolving a curing component such as a maleimide resin or an epoxy resin in the solvent. The solvent is not particularly limited as long as it dissolves the phenolic resin composition, the curing component, etc., and includes the same solvents as those mentioned in the description of the flavanation reaction. A solvent may be used individually by 1 type, and may use 2 or more types together.

The resin varnish contains the resin composition of the present invention, a curing component such as a maleimide resin or an epoxy resin, and a solvent as essential components. Laminates can be produced.

The content of the solvent in the resin varnish is appropriately set according to the solid content concentration of the resin varnish. The solid content concentration of the resin varnish varies depending on the application, but is preferably 20 to 80% by mass, more preferably 30 to 70% by mass.
The solid content concentration of the resin varnish is the ratio of the mass of the resin varnish excluding the solvent to the total mass of the resin varnish.

The resin varnish can be produced by mixing a curing component such as a maleimide resin or an epoxy resin, the resin composition of the present invention, other components blended as necessary, and a solvent. Mixing of each component can be performed by the method described above.

In producing the resin varnish, a curing component such as a maleimide resin, the resin composition of the present invention, and a solvent may be mixed, and then the maleimide resin and the like may be pre-reacted with the resin composition of the present invention. By performing the pre-reaction in the varnish state, it is possible to suppress precipitation of highly crystalline maleimide resin or the like from the resin varnish.

The reaction temperature for the pre-reaction is preferably 50 to 150°C, more preferably 70 to 130°C, even more preferably 80 to 120°C. If the reaction temperature is too low, the reaction will be difficult to proceed. If the reaction temperature is excessively high, it becomes difficult to control the reaction, making it difficult to stably obtain a resin varnish.

Examples of release agents include various waxes such as carnauba wax.
Examples of the surface treatment agent include known silane coupling agents.
Carbon black etc. are mentioned as a coloring agent.

Thermoplastic polymers include polyethylene, polypropylene, polystyrene, polyphenylene ether resin, phenoxy resin, polycarbonate resin, polyester resin, polyamide resin, polyamideimide resin, polyimide resin, xylene resin, polyphenylene sulfide resin, polyetherimide resin, poly Ether ether ketone resins, polyether imide resins, silicone resins, tetrafluoroethylene resins and the like can be mentioned.

Organic fillers include, for example, polyethylene, polypropylene, polystyrene, polyphenylene ether resins, silicone resins, tetrafluoroethylene resin fillers having a uniform structure, acrylic acid ester resins, methacrylic acid ester resins, and conjugated diene resins. A resin filler having a core-shell structure having a rubber-like core layer made of, etc., and a glass-like shell layer made of an acrylic acid ester-based resin, a methacrylic acid ester-based resin, an aromatic vinyl-based resin, a vinyl cyanide-based resin, etc. is mentioned.

Flame retardants include, for example, halogen-containing flame retardants containing bromine and chlorine; triphenyl phosphate, tricresyl phosphate, trisdichloropropyl phosphate, phosphoric acid ester compounds, red phosphorus and other phosphorus-based flame retardants; sulfamic acid Nitrogen flame retardants such as guanidine, melamine sulfate, melamine polyphosphate, and melamine cyanurate; phosphazene flame retardants such as cyclophosphazene and polyphosphazene; inorganic flame retardants such as antimony trioxide;

Curing of the curable resin composition of the present invention is preferably carried out by controlling the curing temperature to 150 to 250°C. An example of the curing operation includes a method of once curing at the suitable curing temperature for 30 seconds or more and 3 hours or less, and then post-curing at the suitable curing temperature for 1 to 20 hours. .

Applications of the curable resin composition of the present invention will be further described later. Coating agents, adhesives, build-up laminate materials, fiber reinforced plastics (FRP), and the like.

The curable resin composition of the present invention may be used after being cured for these uses, or may be used after being cured in the manufacturing process for these uses.

[Cured product]
<Cured product made from the curable resin composition of the present invention>
The cured product of the present invention can be obtained by curing the curable resin composition of the present invention. The cured product of the present invention obtained by curing the curable resin composition of the present invention has excellent heat resistance and adhesive properties.

The method for curing the curable resin composition of the present invention is not particularly limited, but usually a cured product can be obtained by a thermosetting reaction by heating. During the thermosetting reaction, it is preferable to appropriately select the curing temperature depending on the type of curing component used. For example, when using a maleimide resin, the curing temperature is usually 80-250°C, and when using an epoxy resin it is usually 100-200°C. By adding a curing accelerator to these curing components, it is also possible to lower the curing temperature. The curing reaction time is preferably 1 to 20 hours, more preferably 2 to 18 hours, still more preferably 3 to 15 hours. When the reaction time is at least the above lower limit, the curing reaction tends to proceed sufficiently, which is preferable. On the other hand, when the reaction time is equal to or less than the above upper limit, deterioration due to heating and energy loss during heating are easily reduced, which is preferable.

<Cured product (1)>
The cured product of another aspect of the present invention is a cured product containing a structure derived from the structure represented by the following formula (1) (hereinafter sometimes referred to as "cured product (1)"), It can be obtained by curing the resin composition of the present invention or the curable resin composition of the present invention.

(In formula (1) above, R ¹ and R ² are each independently a hydrogen atom, a linear aliphatic hydrocarbon group having 1 to 6 carbon atoms, a substituted or unsubstituted aryl group, or a substituted or unsubstituted represents a substituted heteroaryl group, except when both R ¹ and R ² are hydrogen atoms, and R ³ to R ¹⁰ each independently represent a hydrogen atom, a halogen atom, or a substituted or unsubstituted aliphatic hydrocarbon; group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group, and at least one of R ³ to R ¹⁰ is a substituent represented by the following formula ( ² ). Adjacent groups of R ¹⁰ may combine to form a ring.)

(In formula (2) above, Y is a direct bond, —SO ₂ —, —O—, —CO—, —C(CF ₃ ) ₂ —, —S— and an aliphatic hydrocarbon having 1 to 20 carbon atoms) and R ²¹ is a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, or a halogen atom.)

For the above formulas (1) and (2), the description of the above formulas (1) and (2) in the phenol resin (1) is applied.

The cured product (1) also has excellent heat resistance and adhesive properties due to having a structure derived from the structure represented by formula (1).

[Use]
The curable resin composition of the present invention is excellent in solvent solubility, moldability and heat resistance, and the cured product and cured product (1) using the curable resin composition of the present invention are excellent in heat resistance and adhesiveness.

Therefore, the resin composition, the curable resin composition, the cured product thereof, and the cured product (1) of the present invention can be effectively used in any application as long as these physical properties are required. For example, coating fields such as optical materials, automotive coatings such as automotive electrodeposition coatings, heavy anticorrosion coatings for ships and bridges, and coatings for the inner surface of beverage cans; composite materials, laminates, semiconductor sealing materials, liquid insulation Electrical and electronic fields such as sealing materials, insulating powder coatings, coil impregnation; seismic reinforcement of bridges, concrete reinforcement, building floor materials, linings of water supply facilities, drainage and permeable pavement, adhesives for structures, vehicles and aircraft It can be suitably used for any application in the fields of civil engineering, construction, adhesives, and the like. Among these, it is particularly useful for electrical and electronic parts.

[Laminate]
As a method for producing a laminate using the curable resin composition of the present invention, a laminate containing a prepreg in which a fibrous base material is impregnated with the resin varnish made of the curable resin composition of the present invention is heated and pressurized. a method of producing a laminate by curing with a heat.

More specifically, a fibrous base material is impregnated with a resin varnish, dried, and the solvent is removed to obtain a prepreg. This prepreg is laminated with another base material to be used as necessary to form a laminate, and the laminate is cured by heating and pressurization to obtain a laminate.

The number of prepreg layers in the laminate may be one, or two or more. In the laminate, other base material than prepreg may be laminated. Other substrates include, for example, metal foils such as copper foils.

Examples of fibers constituting the fibrous base material include inorganic fibers such as glass fiber, carbon fiber, ceramic fiber and stainless steel fiber; natural fibers such as cotton, hemp and paper; synthetic organic fibers such as polyester resin and polyamide resin. mentioned. Any one of these fibers may be used alone, or two or more thereof may be used in combination.

The shape of the fibrous base material is not particularly limited, and examples thereof include staple fiber, yarn, mat and sheet.

The amount of the resin varnish with which the fibrous base material is impregnated is not particularly limited, and for example, the solid content of the resin varnish to be impregnated is about 30 to 50% by mass with respect to the fibrous base material (100% by mass). make it
The heating temperature for heating and pressurizing the laminate is preferably the curing temperature described above. The pressurization conditions are preferably 2 to 20 kN/m ² .

A laminate manufactured in this manner comprises a fiber-reinforced resin layer containing a fibrous base material and a cured resin varnish. The number of fiber-reinforced resin layers included in the laminate may be one or two or more. As mentioned above, the laminate may have a metal foil layer, such as a copper foil.

[Sealant]
When the curable resin composition of the present invention is used as a sealing material, the shape of the sealing material to which the curable resin composition of the present invention is applied is not particularly limited. A shape similar to the shape can be adopted.
Examples of the method of forming a sealing material using the curable resin composition of the present invention include a method of sealing a semiconductor using a transfer molding method, a compression molding method, or the like.

EXAMPLES The content of the present invention will be described in more detail below using examples, but the present invention is not limited by the following examples as long as the gist thereof is not exceeded. Various production conditions and values of evaluation results in the following examples have meanings as preferred values of the upper limit or lower limit in the embodiments of the present invention, and the preferred range is the above-mentioned upper limit or lower limit value, and the following It may be a range defined by the value of the example or a combination of the values of the examples.

[Materials used]
The compounds and resins used in the following examples and comparative examples are as follows.

- Maleimide resin: polyphenylmethane maleimide represented by the following structural formula ("BMI-2300" manufactured by Daiwa Kasei Kogyo Co., Ltd.)

- Other phenolic resins: phenolic novolac represented by the following structural formula ("PSM4261" manufactured by Gun Ei Chemical Industry Co., Ltd.)

- Other flavan structure-containing phenolic resins: 4',7-isoflavanediol represented by the following structural formula (manufactured by Tokyo Kasei Kogyo Co., Ltd.).

-Other propenyl resins: Propenyl forms of phenol biphenylene resins represented by the following structural formulas ("BPN-01S" manufactured by Gunei Chemical Industry Co., Ltd.)

Epoxy resin: tetramethylbiphenyl type epoxy resin represented by the following structural formula (“YX4000” manufactured by Mitsubishi Chemical Corporation)

・Curing accelerator: Triphenylphosphine

[Example 1: Production of resin composition A containing phenolic resin (1)]
<Allylation>
840 mL of N,N-dimethylformamide, 575 g (7.51 mol) of allyl chloride, 1245 g (9.01 mol) of potassium carbonate, and 280 g (1.50 mol) of biphenol were added to a 10 L autoclave, sealed, and heated to 40°C. The temperature was raised to 65° C. over 1 hour. After aging at 65° C. for 5 hours, it was cooled to room temperature and the autoclave was opened. 1678 g of water and 1600 g of methyl isobutyl ketone were added thereto to dissolve the inorganic salt and crystals, and the aqueous layer was removed by liquid separation. After repeating the operation of adding 1678 g of water to the remaining methyl isobutyl ketone layer and washing with water at 60° C. three times, methyl isobutyl ketone is distilled off to give a compound represented by the following formula (7-1) (hereinafter referred to as “compound (7-1)”) was obtained.

<Claisen rearrangement reaction>
165 g (620 mmol) of compound (7-1) and 825 mL of N,N-diethylaniline were placed in a 2 L four-necked flask, heated at 200° C. for 6 hours, and then cooled to room temperature. Subsequently, 495 mL of water and 149 mL (1.86 mol) of a 50% by mass sodium hydroxide aqueous solution were placed in a 2 L separable flask and cooled to 10° C., then the above N,N-diethylaniline solution was added dropwise and stirred for 30 minutes. After that, the mixture was allowed to stand, and the upper layer and the lower layer were extracted. Next, 495 mL of water and 93.1 g (1.86 mol) of concentrated sulfuric acid were placed in a 2 L separable flask and cooled to 10° C., and the lower layer extracted in the previous operation was added dropwise and stirred for 1 hour. The precipitated solid was collected by filtration, washed with water, and dried under reduced pressure. As a gray solid, a compound represented by the following formula (8-1), which is a 2-propenyl group-containing phenol compound (8) (hereinafter referred to as "compound ( 8-1)”) was obtained (1.19 mol, two-step yield 80.4%).

<Propenylation>
100 parts by mass of compound (8-1) and 100 parts by mass of methanol were charged in a reaction vessel, stirred and dissolved, and then 79 parts by mass of granular potassium hydroxide (purity 85%) were added. After the addition, methanol was distilled off while heating, and the reaction was carried out for 4 hours while maintaining the internal temperature at 100°C. Then, 203 parts by mass of methyl isobutyl ketone was added, neutralized with sulfuric acid, and washed with water repeatedly. Then, methyl isobutyl ketone is distilled off from the oil layer under heating at 120° C. under reduced pressure to obtain a propenyl group-containing phenol compound (3) represented by the following formula (3-1) (hereinafter referred to as “compound (3- 1)” was obtained.

<flavanization>
The resin composition containing the compound (3-1) obtained by the above propenylation is charged into a reaction vessel, and the reaction is performed for 2.5 hours while stirring and heating while maintaining the internal temperature at 120 ° C. to obtain a phenol resin. 100 parts by mass of a resin composition A containing a phenolic resin (1) having a structure represented by the following formula (1-1) (hereinafter referred to as “compound (1-1)”) was obtained.

This resin composition A contains compound (1-1) and compound (3-1), as is apparent from the following compositional analysis.

<Identification of resin composition containing phenolic resin (1) by NMR analysis>
The resulting resin composition A was dissolved in deuterated chloroform, and ¹ H-NMR, DOSY, COSY, ¹ H- ¹³ C HSQC, and ¹ H- ¹³ C HMBC analyzes were performed using an AVANCE NEO spectrometer manufactured by BRUKER. By doing so, the molecular structure was identified. As a result of analysis and assignment of resin composition A, the structure of compound (1-1) could be confirmed.

The obtained resin composition A was subjected to composition analysis by the following method. Moreover, a solvent solubility test was conducted by the following method. Table 1 shows the results.

<Composition analysis of resin composition>
Resin composition A was dissolved in tetrahydrofuran to a concentration of 0.1% by mass, and analyzed using Tosoh Corporation's "HLC-8320GPCEcoSEC (registered trademark)" under the following conditions.
Apparatus: Agilent 1100 series Column: "TSKGELSuperHM-H+H5000+" manufactured by Tosoh Corporation
H4000 + H3000 + H2000"
Eluent: Tetrahydrofuran Flow rate: 0.5 mL/min
Detection: RI
Temperature: 40°C
Injection: 10 μl

<Solvent solubility test>
Using toluene as a test solvent, resin composition A was added to toluene so that the concentration of resin composition A was 75% by mass to prepare a test solution, which was weighed into a 50 mL vial bottle. After that, after heating to completely dissolve the resin composition A, it was stored at 23 ° C. and no crystals precipitated within 1 day, and then stored at -5 ° C. and no crystals precipitated within 1 week. Good solvent solubility is "○", storage at 23 ° C does not precipitate within 1 day, then storage at -5 ° C and crystal precipitates within 1 day, good solvent solubility "△ ”, and one day after storage at 23° C., crystals precipitated were evaluated as poor solvent solubility “×”.

[Example 2: Production of resin composition B containing phenolic resin (1)]
In Example 1, except that the reaction time in <flavanization> was changed from 2.5 hours to 10 minutes, a resin composition B containing phenolic resin (1) was obtained in the same manner as in Example 1. Compositional analysis and solvent solubility tests were performed. Table 1 shows the results.

[Example 3: Production of resin composition C containing phenolic resin (1)]
In Example 1, except that the reaction time in <flavanization> was changed from 2.5 hours to 10 hours, a resin composition C containing phenol resin (1) was obtained, and the same composition analysis and solvent A solubility test was performed. Table 1 shows the results.

[Example 4: Production of resin composition D containing phenolic resin (1)]
<Propenylation>
Propenyl in the same manner as in Example 1 except that a 2-propenyl group-containing phenol compound represented by the following formula (8-2) (“DABPA” manufactured by Daiwa Kasei Co., Ltd.) was used instead of the compound (8-1). A resin composition containing a propenyl group-containing phenol compound (3) represented by the following formula (3-2) (hereinafter referred to as “compound (3-2)”) was obtained. .

<flavanization>
A resin composition containing the compound (3-2) obtained by the above propenylation was charged into a reaction vessel and flavanated in the same manner as in Example 1 to produce a phenol resin (1) of the following formula (1-2). ) (hereinafter referred to as “compound (1-2)”) was obtained.
For this resin composition D, the same composition analysis and solvent solubility test as in Example 1 were performed. Table 1 shows the results.

[Comparative Example 1: Other Phenolic Resin]
Phenol novolac resin (“PSM4261” manufactured by Gun Ei Chemical Industry Co., Ltd.) is used.

[Comparative Example 2: Other Flavan Structure-Containing Phenolic Resins]
4',7-Isoflavanediol (manufactured by Tokyo Kasei Kogyo Co., Ltd.) is used.

The resin compositions A, B and D of Examples 1, 2 and 4 and the phenolic resins of Comparative Examples 1 and 2 were evaluated as follows, and the results are shown in Table 2.

<Measurement of softening point of resin composition>
The softening point of the resin composition was measured according to JIS K7234.

<Measurement of Melting Point of Resin Composition>
Using a differential scanning calorimeter (DSC: EXSTAR7020 manufactured by Seiko Instruments Inc.), the temperature was raised from 30° C. to 250° C. at a rate of 1° C./min to measure the melting point of the resin composition.

<Measurement of melt viscosity of resin composition>
The resin composition was melted on a hot plate of a cone-plate viscometer (manufactured by Tokai Yagami Co., Ltd.) adjusted to 150° C., and the melt viscosity was measured at a rotational speed of 750 rpm.

<Measurement of 5% Weight Loss Temperature of Resin Composition>
Thermal analysis was performed using a thermal analysis device (TG/DTA: EXSTAR7200 manufactured by Seiko Instruments Inc.) (heating rate: 10 ° C./min, measurement temperature range: 30 ° C. to 600 ° C., air: flow rate 200 mL / minutes). The temperature at which the weight of the resin composition decreased by 5% was measured and defined as the 5% weight loss temperature.

[Examples 5 to 7, Comparative Example 3]
A curable resin composition was obtained by mixing resin compositions A, B, and D or another propenyl resin (BPN-01S), a maleimide resin (BMI-2300), and a curing accelerator in the proportions shown in Table 3. After that, a curing reaction was performed at 120° C. for 2 hours and then at 200° C. for 6 hours to prepare a cured product.
Tg (tan δ) of the obtained cured product was measured by the following method. Moreover, using the produced curable resin composition, the shear adhesive strength to metal (Cu) was measured by the following method. Table 3 shows the results.

<Cured product: Tg (tan δ) and storage elastic modulus E' (40°C), E'(250°C)>
Using a test piece obtained by cutting the cured product into a length of 5 cm, a width of 1 cm, and a thickness of 4 mm, dynamic viscoelasticity measurement (DMA: Dynamic Mechanical Analysis) was performed under the following conditions, Tg (tan δ) and 40 ° C. and storage modulus (E') at 250°C.
Analyzer: EXSTAR6100 manufactured by Seiko Instruments Inc.
Measurement mode: 3-point bending mode Measurement temperature range: 30°C to 300°C
Heating rate: 5°C/min
Temperature drop rate: 5°C/min
* The temperature at the peak top of tan δ was defined as Tg (tan δ).

<Shear adhesive strength to metal>
It was carried out according to JIS-K6850. That is, a 25 mm wide × 100 mm long × 1.6 mm thick metal piece (copper plate (double-sided mirror type manufactured by Yutaka Panel Service Co., Ltd.)) is placed between two curable resin compositions. I applied it so that it would be. After coating, the coating was placed in a constant temperature bath and cured at 120° C. for 2 hours and at 200° C. for 6 hours to prepare peel test pieces.
The prepared peel test piece was subjected to a tensile shear test using a tensile tester "Instron 5582" (manufactured by Instron) at a speed of 5 mm / min and the number of tests n = 3, and the tensile shear strength was measured, and the average sought the value.

[Example 8, Comparative Example 4]
Resin composition A or compound (8-1), a maleimide resin (BMI-2300), and a curing accelerator are mixed in the proportions shown in Table 4 to obtain a curable resin composition, which is then heated at 120°C for 2 hours. Then, a curing reaction was performed at 200° C. for 6 hours to prepare a cured product.
The storage modulus E' (40°C), E' (250°C) and Tg (tan δ) of the obtained cured product were measured by the methods described above. Also, the coefficient of linear expansion was obtained by the following method. Table 4 shows the results.
In Comparative Example 4, the storage elastic modulus E′ (40° C.), storage elastic modulus E′ (250° C.) and Tg (tan δ) tests were brittle, and test pieces could not be prepared, and evaluation could not be performed. rice field.

<Linear expansion coefficient>
The cured product was cut into a cylindrical test piece with a diameter of about 7 mm and a thickness of 4 mm, and thermomechanical analysis was performed in compression mode using a thermomechanical analyzer (TMA: EXSTAR6000 manufactured by Seiko Instruments Inc.) under the following conditions. Measurement weight: 30mN
Heating rate: Twice at 5°C/min Measurement temperature range: 30°C to 300°C
From the results of the second measurement, the coefficient of linear expansion in the temperature range shown in Table 4 was determined.

[Evaluation of results]
Table 1 shows that the resin compositions of the present invention (Examples 1 to 4) are excellent in solvent solubility.
From Table 2, the resin compositions of the present invention (Examples 1, 2, and 4) have low melt viscosities, and their softening points or melting points are , the melting point of Comparative Example 2) is lower than that of Comparative Example 2), and the moldability is excellent. With respect to heat resistance, the phenol novolak resin (PSM4261, Comparative Example 1) and other flavan structure-containing phenolic resins (4′,7-isoflavanediol, Comparative Example 2) have a 5% weight loss temperature. It can be seen that it is high and has excellent heat resistance.
From Table 3, the cured products using the resin composition of the present invention (Examples 5 to 7) are superior in heat resistance compared to the cured products using other propenyl resins (Comparative Example 3), and are resistant to metals. It can be seen that high adhesiveness is exhibited.
From Table 4, the cured product using the resin composition of the present invention (Example 8) has a higher strength and a lower coefficient of linear expansion than the cured product using the compound (8-1) (Comparative Example 4). It can be seen that

Claims (7)

A resin composition containing a phenolic resin having a structure represented by the following formula (1).

(In formula (1) above, R ¹ and R ² are each independently a hydrogen atom, a linear aliphatic hydrocarbon group having 1 to 6 carbon atoms, a substituted or unsubstituted aryl group, or a substituted or unsubstituted represents a substituted heteroaryl group, except when both R ¹ and R ² are hydrogen atoms, and R ³ to R ¹⁰ each independently represent a hydrogen atom, a halogen atom, or a substituted or unsubstituted aliphatic hydrocarbon; group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group, and at least one of R ³ to R ¹⁰ is a substituent represented by the following formula ( ² ). Adjacent groups of R ¹⁰ may combine to form a ring.)

(In formula (2) above, Y is a direct bond, —SO ₂ —, —O—, —CO—, —C(CF ₃ ) ₂ —, —S— and an aliphatic hydrocarbon having 1 to 20 carbon atoms) and R ²¹ is a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, or a halogen atom.) The resin composition according to claim 1, comprising 0.1 to 100,000 parts by mass of a compound represented by the following formula (3) with respect to 100 parts by mass of the phenolic resin having the structure represented by the formula (1).

(In formula (3) above, X is a direct bond, —SO ₂ —, —O—, —CO—, —C(CF ₃ ) ₂ —, —S— and an aliphatic hydrocarbon having 1 to 20 carbon atoms) and R ¹¹ and R ¹² are a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms or a halogen atom, and may be the same or different.) 100 parts by mass of the resin composition according to claim 1 or 2, an epoxy resin, a maleimide resin, a phenolic resin other than the phenolic resin having the structure represented by the formula (1), a benzoxazine resin, a cyanate ester resin, an active A curable resin composition containing 0.01 to 10,000 parts by mass of at least one selected from the group consisting of an ester resin, a resin having a radically polymerizable functional group, an isocyanate resin, an acid anhydride resin and a carbodiimide resin. A cured product obtained by curing the curable resin composition according to claim 3 . An electric/electronic component comprising a cured product of the curable resin composition according to claim 4. A cured product containing a structure derived from the structure represented by the following formula (1).

(In formula (1) above, R ¹ and R ² are each independently a hydrogen atom, a linear aliphatic hydrocarbon group having 1 to 6 carbon atoms, a substituted or unsubstituted aryl group, or a substituted or unsubstituted represents a substituted heteroaryl group, except when both R ¹ and R ² are hydrogen atoms, and R ³ to R ¹⁰ each independently represent a hydrogen atom, a halogen atom, or a substituted or unsubstituted aliphatic hydrocarbon; group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group, and at least one of R ³ to R ¹⁰ is a substituent represented by the following formula ( ² ). Adjacent groups of R ¹⁰ may combine to form a ring.)

(In formula (2) above, Y is a direct bond, —SO ₂ —, —O—, —CO—, —C(CF ₃ ) ₂ —, —S— and an aliphatic hydrocarbon having 1 to 20 carbon atoms) and R ²¹ is a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, or a halogen atom.) An electric/electronic component comprising the cured product according to claim 6 .