CN116368122A - Composition, cured product, method for producing cured product, and additive - Google Patents

Abstract

。The main subject of the present application is to provide a composition having an excellent balance between curability and heat resistance of a cured product. This application solves the said subject by providing the composition containing the compound represented by following general formula (A1), a metal deactivator, and a curable component. It is preferable that the said metal deactivator contains at least 1 of a benzotriazole compound, a hydrazide compound, a salicylic acid compound, and a triazine compound. (In the formula, refer to the specification for R ¹⁰¹ , R ¹⁰² , R ¹⁰³ , R ¹⁰⁴ , n, a1 and X.)

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Description

Composition, cured product, method for producing cured product, and additive

Technical Field

The present application relates to a composition, a cured product, a method for producing the cured product, and an additive.

Background Art

An insulating film such as a solder resist is formed on the printed wiring board to protect wiring.

The solder resist film is required to have improved heat resistance due to the thermal history caused by contact with solder, light irradiation from a light source, and heat generation.

Patent Document 1 describes the use of a curable composition containing a compound having a phenol skeleton and an amide bond, such as N'1,N'12-bis(2-hydroxybenzoyl)dodecane dihydrazide, which is known as a metal deactivator. The document describes that the curable composition described in the document can form a solder resist film having excellent heat resistance.

Prior art literature

Patent Literature

Patent Document 1: Japanese Patent Application Publication No. 2019-191303

Summary of the invention

However, the curable composition containing a metal deactivator as described in Patent Document 1 has disadvantages such as a failure to obtain a cured product having sufficient heat resistance or a change in color of the cured product under high temperature conditions.

Furthermore, the present inventors have studied the use of a conventionally known antioxidant in combination with a metal deactivator in order to improve heat resistance, but have found disadvantages such as insufficient heat resistance and insufficient curability.

The present application has been made in view of the above-mentioned problems, and a main object of the present invention is to provide a composition having an excellent balance between curability and heat resistance of a cured product.

The present inventors have conducted intensive studies to solve the above problems and have found that a compound having a specific structure in which a phenolic hydroxyl group is protected by a protecting group as an antioxidant and a metal deactivator can be used together to exhibit excellent curability and obtain a cured product having excellent heat resistance.

The present inventors have completed the present invention based on these findings.

That is, the present application provides a composition comprising a compound represented by the following general formula (A1) (hereinafter sometimes referred to as compound A), a metal deactivator, and a curable component.

(wherein, R ¹⁰¹ represents an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 40 carbon atoms, an unsubstituted or substituted aromatic hydrocarbon group having 6 to 40 carbon atoms, an unsubstituted or substituted heterocyclic group having 2 to 40 carbon atoms, or an unsubstituted or substituted silyl group having 0 to 40 carbon atoms, or R ¹⁰¹ represents a group having 1 to 40 carbon atoms obtained by replacing one or more methylene groups in an unsubstituted or substituted aliphatic hydrocarbon group, an unsubstituted or substituted aromatic hydrocarbon group, an unsubstituted or substituted heterocyclic group, or an unsubstituted or substituted silyl group with a divalent group selected from the following Group I,

^R102 and ^R103 each independently represent a hydrogen atom or an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 40 carbon atoms,

^R104 represents a halogen atom, a cyano group, a hydroxyl group, a nitro group, a carboxyl group, an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 40 carbon atoms, an unsubstituted or substituted aromatic hydrocarbon group having 6 to 40 carbon atoms, or an unsubstituted or substituted heterocyclic group having 2 to 40 carbon atoms, or ^R104 represents a group having 1 to 40 carbon atoms obtained by replacing one or more methylene groups in an unsubstituted or substituted aliphatic hydrocarbon group, an unsubstituted or substituted aromatic hydrocarbon group, or an unsubstituted or substituted heterocyclic group with a divalent group selected from the following Group I,

When there are a plurality of R ¹⁰⁴ , the plurality of R ¹⁰⁴ may be bonded to each other to form a benzene ring or a naphthalene ring.

When there are a plurality of R ¹⁰⁴ , the plurality of R ¹⁰⁴ may be the same or different.

n represents an integer from 1 to 10,

a1 represents an integer from 0 to 2,

When n is 2 to 10, a plurality of R ¹⁰¹ , R ¹⁰² , R ¹⁰³ , R ¹⁰⁴ and a1 may be the same or different groups.

X represents an n-valent group. )

Group I: -O-, -COO-, -OCO-, -CO-, -CS-, -S-, -SO-, -SO ₂ -, -NR ²³⁰ -, -NR ²³⁰ -CO-, -CO-NR ²³⁰ -, -NR ²³⁰ -COO-, -OCO-NR ²³⁰ -, or -SiR ²³⁰ R ²³¹ -. ^{R 230} and R ²³¹ each independently represent a hydrogen atom or an unsubstituted aliphatic hydrocarbon group having 1 to 40 carbon atoms.

According to the present application, the composition has an excellent balance between curability and heat resistance of the cured product.

In the present application, ^R101 is preferably a group having 1 to 40 carbon atoms in which the terminal methylene group on the oxygen atom side of a group selected from an unsubstituted or substituted aliphatic hydrocarbon group, an unsubstituted or substituted aromatic hydrocarbon group and an unsubstituted or substituted heterocyclic group is substituted with a divalent group selected from -COO-, -CO-, -CS-, -S-, -SO-, _-SO2- , ^-NR230- , -NR230-CO-, -CO ^{-NR230- , -NR230} -COO- and ^-SiR230R231 in the above Group ^I , or an unsubstituted or substituted silyl group having 0 to 40 carbon atoms. This is because when ^R101 is the above group, the balance between curability and heat resistance of the cured product becomes excellent.

In the present application, the metal deactivator preferably includes at least one of a benzotriazole compound, a hydrazide compound, a salicylic acid compound, and a triazine compound. This is because the balance between the curability of the composition and the heat resistance of the cured product is further improved.

In the present application, the content of the metal deactivator is preferably 5 parts by mass or more and 90 parts by mass or less in a total of 100 parts by mass of the compound represented by the general formula (A1) and the metal deactivator. This is because: by setting the content of the metal deactivator to the above range, the balance of curability and heat resistance of the cured product becomes more excellent.

In the present application, the total content of the compound represented by the general formula (A1) and the metal deactivator is preferably 0.01 parts by mass or more and 10 parts by mass or less in a total of 100 parts by mass of the compound represented by the general formula (A1), the metal deactivator and the curable component. This is because: when the total content of the compound represented by the general formula (A1) and the metal deactivator is within the above range, the balance of curability and heat resistance of the cured product becomes more excellent.

In the present application, the curable component preferably includes a radical polymerizable compound and a thermosetting compound. This is because the curable component including both the radical polymerizable compound and the thermosetting compound can further improve the balance between curability and heat resistance of the cured product.

The composition of the present application is preferably used for solder resist, and this is because the effect of the present invention having excellent heat resistance and curability has particularly high technical significance.

The present application provides a cured product, which is obtained by curing the above-mentioned composition.

According to the present application, since the above-mentioned composition is used, heat resistance becomes excellent.

The present application provides a method for producing a cured product, which comprises a curing step of curing the above-mentioned composition.

According to the present application, since the above-mentioned composition is used, a cured product having excellent heat resistance can be easily obtained.

The present application provides an additive, which comprises a compound represented by the following general formula (A1) and a metal deactivator.

(wherein, R ¹⁰¹ represents an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 40 carbon atoms, an unsubstituted or substituted aromatic hydrocarbon group having 6 to 40 carbon atoms, an unsubstituted or substituted heterocyclic group having 2 to 40 carbon atoms, or an unsubstituted or substituted silyl group having 0 to 40 carbon atoms, or R ¹⁰¹ represents a group having 1 to 40 carbon atoms obtained by replacing one or more methylene groups in an unsubstituted or substituted aliphatic hydrocarbon group, an unsubstituted or substituted aromatic hydrocarbon group, an unsubstituted or substituted heterocyclic group, or an unsubstituted or substituted silyl group with a divalent group selected from the following Group I,

^R102 and ^R103 each independently represent a hydrogen atom or an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 40 carbon atoms,

^R104 represents a halogen atom, a cyano group, a hydroxyl group, a nitro group, a carboxyl group, an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 40 carbon atoms, an unsubstituted or substituted aromatic hydrocarbon group having 6 to 40 carbon atoms, or an unsubstituted or substituted heterocyclic group having 2 to 40 carbon atoms, or ^R104 represents a group having 1 to 40 carbon atoms obtained by replacing one or more methylene groups in an unsubstituted or substituted aliphatic hydrocarbon group, an unsubstituted or substituted aromatic hydrocarbon group, or an unsubstituted or substituted heterocyclic group with a divalent group selected from the following Group I,

When there are a plurality of R ¹⁰⁴ , the plurality of R ¹⁰⁴ may be bonded to each other to form a benzene ring or a naphthalene ring.

When there are a plurality of R ¹⁰⁴ , the plurality of R ¹⁰⁴ may be the same or different.

n represents an integer from 1 to 10,

a1 represents an integer from 0 to 2,

When n is 2 to 10, a plurality of R ¹⁰¹ , R ¹⁰² , R ¹⁰³ , R ¹⁰⁴ and a1 may be the same or different groups.

X represents an n-valent group. )

Group I: -O-, -COO-, -OCO-, -CO-, -CS-, -S-, -SO-, -SO ₂ -, -NR ²³⁰ -, -NR ²³⁰ -CO-, -CO-NR ²³⁰ -, -NR ²³⁰ -COO-, -OCO-NR ²³⁰ -, or -SiR ²³⁰ R ²³¹ -. ^{R 230} and R ²³¹ each independently represent a hydrogen atom or an unsubstituted aliphatic hydrocarbon group having 1 to 40 carbon atoms.

According to the present application, since the compound represented by the general formula (A1) and the metal deactivator are contained, by adding to a composition containing a curable component, a composition having an excellent balance between curability and heat resistance of a cured product can be easily formed.

DETAILED DESCRIPTION

The present application relates to a composition, a cured product thereof, a method for producing the cured product thereof, and an additive added to the composition.

Hereinafter, the composition, cured product, method for producing the cured product, and additives of the present application will be described in detail.

A. Composition

First, the composition of the present application will be described.

One of the characteristics of the composition of the present application is that it contains a compound represented by the following general formula (A1), a metal deactivator, and a curable component.

(wherein, R ¹⁰¹ represents an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 40 carbon atoms, an unsubstituted or substituted aromatic hydrocarbon group having 6 to 40 carbon atoms, an unsubstituted or substituted heterocyclic group having 2 to 40 carbon atoms, or an unsubstituted or substituted silyl group having 0 to 40 carbon atoms, or R ¹⁰¹ represents a group having 1 to 40 carbon atoms obtained by replacing one or more methylene groups in an unsubstituted or substituted aliphatic hydrocarbon group, an unsubstituted or substituted aromatic hydrocarbon group, an unsubstituted or substituted heterocyclic group, or an unsubstituted or substituted silyl group with a divalent group selected from the following Group I,

^R102 and ^R103 each independently represent a hydrogen atom or an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 40 carbon atoms,

^R104 represents a halogen atom, a cyano group, a hydroxyl group, a nitro group, a carboxyl group, an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 40 carbon atoms, an unsubstituted or substituted aromatic hydrocarbon group having 6 to 40 carbon atoms, or an unsubstituted or substituted heterocyclic group having 2 to 40 carbon atoms, or ^R104 represents a group having 1 to 40 carbon atoms obtained by replacing one or more methylene groups in an unsubstituted or substituted aliphatic hydrocarbon group, an unsubstituted or substituted aromatic hydrocarbon group, or an unsubstituted or substituted heterocyclic group with a divalent group selected from the following Group I,

When there are a plurality of R ¹⁰⁴ , the plurality of R ¹⁰⁴ may be bonded to each other to form a benzene ring or a naphthalene ring.

When there are a plurality of R ¹⁰⁴ , the plurality of R ¹⁰⁴ may be the same or different.

n represents an integer from 1 to 10,

a1 represents an integer from 0 to 2,

When n is 2 to 10, a plurality of R ¹⁰¹ , R ¹⁰² , R ¹⁰³ , R ¹⁰⁴ and a1 may be the same or different groups.

X represents an n-valent group. )

Group I: -O-, -COO-, -OCO-, -CO-, -CS-, -S-, -SO-, -SO ₂ -, -NR ²³⁰ -, -NR ²³⁰ -CO-, -CO-NR ²³⁰ -, -NR ²³⁰ -COO-, -OCO-NR ²³⁰ -, or -SiR ²³⁰ R ²³¹ -. ^{R 230} and R ²³¹ each independently represent a hydrogen atom or an unsubstituted aliphatic hydrocarbon group having 1 to 40 carbon atoms.

According to the present application, by using the compound A, which is the compound represented by the general formula (A1), and the metal deactivator in combination, the balance between the curability of the composition and the heat resistance of the cured product is excellent.

Here, the reason why the balance between the curability of the composition and the heat resistance of the cured product is excellent by using the compound A and the metal deactivator in combination is not clear, but is presumed as follows.

That is, compound A has a structure in which the phenolic hydroxyl group is protected, and the protecting group R ¹⁰¹ can be detached to generate a phenolic hydroxyl group. Compound A (hereinafter sometimes referred to as compound A') having generated a phenolic hydroxyl group can exert antioxidant ability by being able to capture peroxyl radicals, etc., thereby improving the heat resistance of the above-mentioned composition and its cured product.

In addition, compound A has a structure in which a phenolic hydroxyl group is protected by a protecting group R ¹⁰¹ , so for example, compared with a composition comprising an antioxidant having a phenolic hydroxyl group, the curing hindrance of the curable component can be suppressed. Therefore, the above-mentioned composition becomes a composition with excellent sensitivity of the curing reaction and few poorly cured products, and a cured product with a high cross-linking density can be obtained. The obtained cured product has a high cross-linking density, and can suppress the intrusion of oxygen into the cured product, and as a result, the oxidative degradation of the curable component and its polymer under a high temperature environment can be suppressed. As a result, the heat resistance of the above-mentioned cured product becomes excellent.

The metal deactivator can capture metal ions contained in or transferred to the composition, for example. Therefore, the generation of peroxy radicals from hydroperoxides generated by heat or light during processing or use due to the catalytic effect of the metal ions can be suppressed. In addition, the separation of the protecting group R ¹⁰¹ from compound A due to the catalytic effect of the metal ions can be effectively suppressed.

Thus, by using compound A and a metal deactivator in combination, prevention of oxygen intrusion, capture of peroxyl radicals, and suppression of peroxyl radical generation due to excellent curability can be effectively achieved, and the balance between the curability of the composition and the heat resistance of the cured product becomes excellent.

The composition of the present application comprises compound A, a metal deactivator and a curable component.

Hereinafter, each component of the composition of the present application will be described in detail.

1. Compound A

Compound A is a compound represented by the above-mentioned general formula (A1).

The aliphatic hydrocarbon group represented by R ¹⁰¹ , R ¹⁰² , R ¹⁰³ and R ¹⁰⁴ (hereinafter sometimes referred to as R ¹⁰¹ etc.) in the general formula (A1) (hereinafter also collectively referred to as "aliphatic hydrocarbon group represented by R ¹⁰¹ etc.") can be a group consisting of only hydrogen atoms and carbon atoms and not containing an aromatic hydrocarbon ring and a heterocyclic ring. The hydrocarbon group is a hydrocarbon group having 1 to 40 carbon atoms. The hydrocarbon group may be unsubstituted or may have a substituent. Examples of the aliphatic hydrocarbon group represented by R ¹⁰¹ etc. include alkyl groups having 1 to 40 carbon atoms, alkenyl groups having 2 to 40 carbon atoms, cycloalkyl groups having 3 to 40 carbon atoms, cycloalkylalkyl groups having 4 to 40 carbon atoms, and groups in which one or more hydrogen atoms of these groups are substituted by substituents described below.

As the alkyl group having 1 to 40 carbon atoms represented by ^R101 etc., a group consisting of only hydrogen atoms and carbon atoms can be used. The alkyl group having 1 to 40 carbon atoms may be a straight-chain alkyl group or a branched-chain alkyl group. Examples of the straight-chain alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl and heptyl. Examples of the branched alkyl group include isopropyl, sec-butyl, tert-butyl, isobutyl, isopentyl, tert-pentyl, 2-hexyl, 3-hexyl, 2-heptyl, 3-heptyl, isoheptyl, tert-heptyl, 1-octyl, isooctyl and tert-octyl.

As the alkenyl group having 2 to 40 carbon atoms represented by R ¹⁰¹ or the like, a group consisting only of hydrogen atoms and carbon atoms can be used. The alkenyl group having 2 to 40 carbon atoms can be a straight-chain alkenyl group or a branched alkenyl group. For example, vinyl, ethylene, 2-propenyl, 3-butenyl, 2-butenyl, 4-pentenyl, 3-pentenyl and 4-dodecenyl can be listed. As a branched alkenyl group, for example, 4,8,12-tetradecatrienylallyl can be listed.

As the cycloalkyl group having 3 to 40 carbon atoms represented by R ¹⁰¹ etc., a group consisting only of hydrogen atoms and carbon atoms can be used. The cycloalkyl group having 3 to 40 carbon atoms may be a saturated monocyclic alkyl group or a saturated polycyclic alkyl group. One or more hydrogen atoms in the cycloalkyl group having 3 to 40 carbon atoms may be substituted by an alkyl group.

Examples of the saturated monocyclic cycloalkyl group having 3 to 40 carbon atoms include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, and cyclodecyl. Examples of the saturated polycyclic alkyl group include adamantyl, decahydronaphthyl, octahydropentalene, and bicyclo[1.1.1]pentyl. Examples of the alkyl group substituting for hydrogen atoms in the ring of the saturated monocyclic alkyl group or the saturated polycyclic alkyl group include the same groups as those exemplified above as the alkyl group having 1 to 40 carbon atoms represented by ^R101 , etc.

Examples of the group in which one or two or more hydrogen atoms in the ring of the saturated polycyclic alkyl group are substituted with an alkyl group include bornyl and the like.

The cycloalkylalkyl group having 4 to 40 carbon atoms represented by R ¹⁰¹ and the like refers to a group having 4 to 40 carbon atoms obtained by replacing the hydrogen atoms of the alkyl group with a cycloalkyl group. The cycloalkyl group in the cycloalkylalkyl group having 4 to 40 carbon atoms may be a saturated monocyclic alkyl group or a saturated polycyclic alkyl group. Examples of the saturated monocyclic alkylalkyl group having 4 to 40 carbon atoms include cyclopropylmethyl, 2-cyclobutylethyl, and 3-cyclopentylpropyl. Examples of the saturated polycyclic alkylalkyl group having 4 to 40 carbon atoms include 3-3-adamantylpropyl and decahydronaphthylpropyl.

In the present application, the number of carbon atoms contained in a group refers to the number of carbon atoms contained in the group after the substitution when a hydrogen atom in the group is substituted by a substituent. For example, when a hydrogen atom of the above-mentioned alkyl group having 1 to 40 carbon atoms is substituted, the number of carbon atoms 1 to 40 refers to the number of carbon atoms after the hydrogen atom is substituted, and does not refer to the number of carbon atoms before the hydrogen atom is substituted.

In addition, when the definitions of symbols specified in the present application include both a group having a specified number of carbon atoms (e.g., an aliphatic hydrocarbon group) and a group obtained by replacing a methylene group in the same group (e.g., an aliphatic hydrocarbon group) with another divalent group, the range of the number of carbon atoms in the latter is set to be the same as the range of the number of carbon atoms in the former. Therefore, "a group having 1 to ⁴⁰ carbon atoms obtained by replacing one or more methylene groups in an unsubstituted or substituted aliphatic hydrocarbon group, an unsubstituted or substituted aromatic hydrocarbon group, an unsubstituted or substituted heterocyclic group, or an unsubstituted or substituted silyl group" as a candidate for "R 101 " means "a group having 1 to 40 carbon atoms obtained by replacing one or more methylene groups in an unsubstituted or substituted aliphatic hydrocarbon group with a divalent group selected from Group I, A group having 6 to 40 carbon atoms obtained by replacing one or more methylene groups in an unsubstituted or substituted aromatic hydrocarbon-containing group with a divalent group selected from Group I, a group having 2 to 40 carbon atoms obtained by replacing one or more methylene groups in an unsubstituted or substituted heterocyclic ring-containing group with a divalent group selected from Group I, or a group having 1 to 40 carbon atoms obtained by replacing one or more methylene groups in an unsubstituted or substituted silyl group with a divalent group selected from Group I. Similarly, "a group having 1 to ⁴⁰ carbon atoms in which one or more methylene groups in an unsubstituted or substituted aliphatic hydrocarbon group, an unsubstituted or substituted aromatic hydrocarbon group, or an unsubstituted or substituted heterocyclic ring-containing group are substituted with a divalent group selected from Group I" as a candidate for "R104" means "a group having 1 to 40 carbon atoms in which one or more methylene groups in an unsubstituted or substituted aliphatic hydrocarbon group are substituted with a divalent group selected from Group I, a group having 6 to 40 carbon atoms in which one or more methylene groups in an unsubstituted or substituted aromatic hydrocarbon group are substituted with a divalent group selected from Group I, or a group having 2 to 40 carbon atoms in which one or more methylene groups in an unsubstituted or substituted heterocyclic ring-containing group are substituted with a divalent group selected from Group I".

The aromatic hydrocarbon-containing group having 6 to 40 carbon atoms represented by the above-mentioned R ¹⁰¹ and R ¹⁰⁴ (hereinafter sometimes referred to as R ¹⁰⁴ , etc.) (hereinafter also collectively referred to as "aromatic hydrocarbon-containing group represented by R ¹⁰⁴ , etc.") can be set to a group containing an aromatic hydrocarbon ring composed only of hydrogen atoms and carbon atoms and not containing a heterocyclic ring. The aromatic hydrocarbon-containing group may be unsubstituted or may have a substituent. Examples of the aromatic hydrocarbon-containing group having 6 to 40 carbon atoms include aryl groups having 6 to 40 carbon atoms, arylalkyl groups having 7 to 40 carbon atoms, groups in which hydrogen atoms of an aliphatic hydrocarbon group are substituted by aryl groups, and groups in which one or more hydrogen atoms of these groups are substituted by substituents described below.

In addition, examples of the aliphatic hydrocarbon group in which a hydrogen atom is substituted with an aryl group include aliphatic hydrocarbon groups having a predetermined number of carbon atoms among the aliphatic hydrocarbon groups represented by R ¹⁰¹ and the like.

The aryl group having 6 to 40 carbon atoms represented by the above R ¹⁰⁴ and the like can be set to a group having aromaticity. The above aryl group can be an aryl group having a monocyclic structure or an aryl group having a condensed ring structure. Furthermore, the above aryl group can be an aryl group obtained by connecting an aryl group having a monocyclic structure to an aryl group having a monocyclic structure, an aryl group obtained by connecting an aryl group having a monocyclic structure to an aryl group having a condensed ring structure, or an aryl group obtained by connecting an aryl group having a condensed ring structure to an aryl group having a condensed ring structure. As a connecting group connecting two aryl groups, a single bond and a carbonyl group can be listed. The hydrogen atom in the above aryl group can also be substituted by an aliphatic hydrocarbon group which is unsubstituted or has a substituent. As an aryl group having a monocyclic structure, for example, phenyl, biphenyl and benzophenone (benzoylphenyl) can be listed. As an aryl group having a condensed ring structure, naphthyl, anthracenyl, phenanthrenyl and pyrenyl can be listed. Examples of the unsubstituted or substituted aliphatic hydrocarbon group that replaces the hydrogen atom in the above-mentioned aryl group include the same aliphatic hydrocarbon groups as exemplified above as the unsubstituted or substituted aliphatic hydrocarbon group having 1 to 40 carbon atoms represented by R ¹⁰¹ , etc. The unsubstituted or substituted aliphatic hydrocarbon group that replaces the hydrogen atom in the above-mentioned aryl group is preferably an unsubstituted alkyl group having 1 to 4 carbon atoms or a group in which all hydrogen atoms in an alkyl group having 1 to 4 carbon atoms are replaced by halogen atoms. In addition, examples of the halogen atom in this specification include those described below as the halogen atom represented by R ¹⁰⁴ .

Examples of the arylalkyl group having 7 to 40 carbon atoms represented by ^R104 and the like include groups in which one or two or more hydrogen atoms in the alkyl group represented by ^R101 and the like are substituted with aryl groups represented by ^R104 and the like. Examples of the arylalkyl group having 7 to 40 carbon atoms include benzyl, fluorenyl, indenyl, 9-fluorenylmethyl, α-methylbenzyl, α,α-dimethylbenzyl, phenylethyl and naphthylpropyl, and groups in which hydrogen atoms in these groups are substituted with unsubstituted or substituted aliphatic hydrocarbon groups. Examples of the unsubstituted or substituted aliphatic hydrocarbon group that replaces the hydrogen atoms in the alkyl group in the arylalkyl group and the arylalkyl group include the same aliphatic hydrocarbon groups as exemplified above as the unsubstituted or substituted aliphatic hydrocarbon group having 1 to 40 carbon atoms represented by ^R101 and the like.

As the heterocyclic group having 2 to 40 carbon atoms represented by R ¹⁰⁴ etc. (hereinafter also collectively referred to as "heterocyclic group represented by R ¹⁰⁴ etc."), a group containing a ring containing atoms other than hydrogen atoms and carbon atoms, i.e., a heterocyclic ring can be used. The heterocyclic group may be unsubstituted or have a substituent.

Examples of the heterocyclic group include tetrahydrofuranyl, dioxolanyl, tetrahydropyranyl, morpholinofuranyl, thienyl, methylthienyl, hexylthienyl, benzothienyl, pyrrolyl, pyrrolidinyl, imidazolyl, imidazolidinyl, imidazolinyl, pyrazolyl, pyrazolidinyl, piperidinyl, and piperazinyl; groups in which hydrogen atoms in these heterocyclic groups are replaced by unsubstituted or substituted aliphatic hydrocarbon groups; groups in which one or two or more hydrogen atoms of an aliphatic hydrocarbon group are replaced by the above heterocyclic group; groups in which one or two or more hydrogen atoms of these groups are replaced by substituents described below; and the like. Examples of the aliphatic hydrocarbon group include those listed as the unsubstituted or substituted aliphatic hydrocarbon group having 1 to 40 carbon atoms represented by R ^101, etc., which satisfy the carbon number of the heterocyclic group. It should be noted that, in the present specification, "2 to 40" in "a heterocyclic group having 2 to 40 carbon atoms" does not specify the number of carbon atoms in the "heterocyclic ring" but specifies the number of carbon atoms in the "heterocyclic group".

The silyl group having 0 to 40 carbon atoms represented by ^R101 may be unsubstituted or may have a substituent. Examples of the silyl group include a silyl group having unsubstituted hydrogen atoms, a substituted silyl group having hydrogen atoms substituted with other substituents, and groups having one or more hydrogen atoms of these groups substituted with substituents described below.

Examples of the substituted silyl group include monoalkylsilyl groups such as monomethylsilyl, monoarylsilyl groups such as monophenylsilyl, dialkylsilyl groups such as diethylsilyl, diarylsilyl groups such as diphenylsilyl, trialkylsilyl groups such as trimethylsilyl, triarylsilyl groups such as triphenylsilyl, monoalkyldiarylsilyl groups such as methyldiphenylsilyl, dialkylmonoarylsilyl groups such as dimethylphenylsilyl, trialkoxysilyl groups such as trimethoxysilyl and triethoxysilyl, and alkylalkoxysilyl groups having both an alkyl group and an alkoxy group.

Examples of the halogen atom represented by R ¹⁰⁴ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

In the group obtained by replacing two or more methylene groups of the above-mentioned aliphatic hydrocarbon group, aromatic hydrocarbon group-containing group or heterocyclic group-containing group with a divalent group selected from the above-mentioned group I, the multiple divalent groups may be the same as or different from each other, but the multiple divalent groups are set to be non-adjacent groups.

The “group having 1 ^{to 40} carbon atoms obtained by replacing one or more methylene groups in an unsubstituted or substituted aliphatic hydrocarbon group, an unsubstituted or substituted aromatic hydrocarbon group, an unsubstituted or substituted heterocyclic group, or an unsubstituted or substituted silyl group with a divalent group selected from Group I” represented by ^R101 and the “group having 1 to 40 carbon atoms obtained by replacing one or more methylene groups in an unsubstituted or substituted aliphatic hydrocarbon group, an unsubstituted or substituted aromatic hydrocarbon group, or an unsubstituted or substituted heterocyclic group with a divalent group selected from Group I” represented by R104 are described below. Examples of the unsubstituted or substituted aliphatic hydrocarbon group in the above-mentioned group having 1 to 40 carbon atoms include the same aliphatic hydrocarbon groups as those listed above as the unsubstituted or substituted aliphatic hydrocarbon group represented by ^R101 and the like, and groups suitable for replacing a methylene group in the group with a divalent group selected from Group I with the above-mentioned carbon number. Further, examples of the unsubstituted or substituted aromatic hydrocarbon-containing group, unsubstituted or substituted heterocyclic group and unsubstituted or substituted silyl group in the above-mentioned group having 1 to ⁴⁰ carbon atoms include the same aliphatic hydrocarbon groups as those listed above as the unsubstituted or substituted aromatic hydrocarbon-containing group, unsubstituted or substituted heterocyclic group and unsubstituted or substituted silyl group represented by R104 and the like, and groups suitable for replacing a methylene group in the group with a divalent group selected from Group I with the above-mentioned carbon number.

As a group obtained by replacing one or more methylene groups of the above-mentioned aliphatic hydrocarbon group with a divalent group selected from the above-mentioned group I, when the aliphatic hydrocarbon group is an alkyl group, for example, a group obtained by replacing the terminal methylene group on the benzene ring side of the alkyl group with -O-, i.e., an alkoxy group, etc. can be listed.

In addition, as the group represented by ^-OR101 bonded to the benzene ring, a group obtained by replacing the terminal methylene group on the -O- side of ^R101 with -CO-O-, that is, a group represented by -O-CO-OR (R represents a group other than the terminal methylene group on the oxygen atom side of ^R101 ) and the like can be used.

The divalent group is selected so that the oxygen atoms are not adjacent. For example, when the terminal methylene group on the -O- side of R ¹⁰¹ of "-OR ¹⁰¹ " is substituted with a divalent group selected from the above group I, -O- and -OCO- cannot be selected as the divalent group, and for example, -COO-, -CO-, -CS-, -S-, -SO-, -SO ₂ -, -NR ²³⁰ -, -NR ²³⁰ -CO-, -CO-NR ²³⁰ -, -NR ²³⁰ -COO- or -SiR ²³⁰ R ²³¹ - can be selected.

In the present application, the divalent group that usually replaces the methylene group is a group selected in a non-adjacent manner. That is, the methylene group substituted by the divalent group is a group selected in a non-adjacent manner.

As the unsubstituted aliphatic hydrocarbon group having 1 to 40 carbon atoms used for R ²³⁰ and R ²³¹ in the above Group I, a group in which the hydrogen atom in the aliphatic hydrocarbon group used for R ¹⁰¹ etc. is not replaced by a substituent can be used.

As a substituent for replacing a hydrogen atom in the aliphatic hydrocarbon group, aromatic hydrocarbon group, heterocyclic group, silyl group, and a group in which one or more methylene groups in these groups are replaced by a divalent group selected from the above Group I, more specifically, one or more of the above-mentioned alkyl, alkenyl, cycloalkyl, cycloalkylalkyl, aryl, arylalkyl, heterocyclic group, silyl group, and a group in which one or more methylene groups in these groups are replaced by a divalent group selected from the above Group I, The substituent group replacing the hydrogen atom includes, for example, ethylenically unsaturated groups such as vinyl, allyl, acryloyl, and methacryloyl; halogen atoms such as fluorine, chlorine, bromine, and iodine; acyl groups such as acetyl, 2-chloroacetyl, propionyl, octanoyl, acryloyl, methacryloyl, phenylcarbonyl (benzoyl), phthaloyl, 4-trifluoromethylbenzoyl, pivaloyl, salicyl, oxalyl, stearoyl, methoxycarbonyl, ethoxycarbonyl, tert-butoxycarbonyl, n-octadecyloxycarbonyl, and carbamoyl; acetoxy, benzoyloxy etc. acyloxy groups; amino, ethylamino, dimethylamino, diethylamino, butylamino, cyclopentylamino, 2-ethylhexylamino, dodecylamino, anilino, chlorophenylamino, toluidine, anisidine, N-methyl-anilino, diphenylamino, naphthylamino, 2-pyridylamino, methoxycarbonylamino, phenoxycarbonylamino, acetylamino, benzoylamino, formylamino, pivaloylamino, lauroylamino, carbamoylamino, N,N-dimethylaminocarbonylamino, N,N-diethylaminocarbonylamino , morpholinocarbonylamino, methoxycarbonylamino, ethoxycarbonylamino, tert-butoxycarbonylamino, n-octadecyloxycarbonylamino, N-methyl-methoxycarbonylamino, phenoxycarbonylamino, aminosulfonylamino, N,N-dimethylaminosulfonylamino, methylsulfonylamino, butylsulfonylamino, phenylsulfonylamino and the like substituted amino groups; sulfonyl, sulfonyl, carboxyl, cyano, sulfonyl, hydroxyl, nitro, mercapto, imide, carbamoyl, sulfonylamide, phosphonic acid, phosphate or salts of carboxyl, sulfonyl, phosphonic acid, phosphate and the like.

That is, examples of the substituents include an ethylenically unsaturated group, a halogen atom, an acyl group, an acyloxy group, a substituted amino group, a sulfonamide group, a sulfonyl group, a carboxyl group, a cyano group, a sulfo group, a hydroxyl group, a nitro group, a mercapto group, an imide group, a carbamoyl group, a sulfonamide group, a phosphonic acid group, a phosphoric acid group, or a salt of a carboxyl group, a salt of a sulfonic acid group, a salt of a phosphonic acid group, a salt of a phosphoric acid group, and the like.

From the viewpoint of being easily removed by heat treatment, ^R101 in the general formula (A1) is preferably a group having 1 to 40 carbon atoms in which the terminal methylene group on the oxygen atom side of an unsubstituted or substituted aliphatic hydrocarbon group, an unsubstituted or substituted aromatic hydrocarbon group, or an unsubstituted or substituted heterocyclic group is substituted with a divalent group selected from the above group I, or an unsubstituted or substituted silyl group having 0 to 40 carbon atoms. That is, R ¹⁰¹ is preferably a group having 1 to 40 carbon atoms obtained by replacing the methylene group at the oxygen atom terminal of an unsubstituted or substituted aliphatic hydrocarbon group with the above divalent group, a group having 6 to 40 carbon atoms obtained by replacing the methylene group at the oxygen atom terminal of an unsubstituted or substituted aromatic hydrocarbon group with the above divalent group (the oxygen atom terminal is bonded to the above divalent group), a group having 2 to 40 carbon atoms obtained by replacing the methylene group at the oxygen atom terminal of an unsubstituted or substituted heterocyclic group with the above divalent group (the oxygen atom terminal is bonded to the above divalent group), or an unsubstituted or substituted heterocyclic group having 0 to 40 carbon atoms. The silyl group having a substituent is preferably a group having 1 to 40 carbon atoms in which the methylene group at the terminal of the oxygen atom side of an unsubstituted or substituted aliphatic hydrocarbon group is replaced by -CO-O-, and is particularly preferably a group having 1 to 40 carbon atoms in which the methylene group at the terminal of the oxygen atom side of an unsubstituted or substituted alkyl group is replaced by -CO-O-, and is particularly preferably a group having 1 to 40 carbon atoms in which the methylene group at the terminal of the oxygen atom side of an unsubstituted or substituted alkyl group is bonded to -CO-O-, that is, a group represented by -CO-OR"(R" is an unsubstituted or substituted alkyl group having 1 to 39 carbon atoms).

In the present application, the above-mentioned R" is preferably an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms, among which an unsubstituted or substituted alkyl group having 1 to 8 carbon atoms is preferred, and an unsubstituted alkyl group having 1 to 8 carbon atoms is particularly preferred, among which an unsubstituted alkyl group having 3 to 6 carbon atoms is particularly preferred, among which isopropyl, n-butyl, sec-butyl, tert-butyl, isobutyl, n-pentyl, isopentyl, and tert-pentyl are particularly preferred, among which n-butyl, sec-butyl, tert-butyl, isobutyl, and tert-butyl are particularly preferred, that is, R ¹⁰¹ is a group represented by -CO-OC ₄ H ₉ , among which R" is tert-butyl, that is, R ¹⁰¹ is -CO-O-tert-butyl.

This is because when R ¹⁰¹ is the above group, it becomes easy to control the elimination of R ¹⁰² in the compound A by heat treatment.

The temperature at which the protecting group ^R101 contained in the compound A is removed by heat treatment can be appropriately set according to the use of the composition, and can be set to, for example, 80°C to 300°C, preferably 100°C to 290°C, particularly preferably 120°C to 280°C, particularly preferably 150°C to 250°C, and preferably 180°C to 240°C. This is because the balance between curability and heat resistance of the cured product is better.

The desorption temperature can be set to a temperature showing a thermal loss of 5% by mass by differential thermal analysis.

As a measurement method, for example, STA (differential thermal and thermogravimetric simultaneous measurement apparatus) is used to measure the thermal loss of a sample when the temperature is increased by about 5 mg, in a nitrogen atmosphere of 200 mL/min, at a heating start temperature of 30°C, a heating end temperature of 500°C, and a heating rate of 10°C/min. The temperature at which the weight of the sample is reduced by 5 mass% relative to the weight at 30°C can be set as the desorption temperature.

As a differential thermal and thermogravimetric simultaneous measuring apparatus, STA7000 (manufactured by Hitachi High-Tech Science Co., Ltd.) can be used.

From the viewpoint of facilitating removal by photoirradiation, a photo-detachable protecting group such as o-nitrobenzyl may be used as ^R101 in the general formula (A1).

It should be noted that, when the above-mentioned R ¹⁰¹ is a photodetachable protecting group, the wavelength of the light from which the protecting group R ¹⁰¹ is detached from compound A can be set, for example, to light having a wavelength of 365 nm, more specifically, to light having a wavelength of 250 nm to 450 nm, preferably to light having a wavelength of 280 nm to 380 nm.

The cumulative amount of light irradiated to remove ^R101 from the compound A can be set, for example, to 1,000 mJ/ ^cm2 or more and 10,000 mJ/ ^cm2 or less, preferably more than 1,000 mJ/ ^cm2 or less and 5,000 mJ/cm2 or ^less , and more preferably 2,000 mJ/ ^cm2 or more and 4,000 mJ/ ^cm2 or less. This is because the balance between curability and heat resistance of the cured product becomes better.

In the above general formula (A1), ^R102 and ^R103 are each independently preferably a hydrogen atom, an alkyl group having 1 to 40 carbon atoms, or a group in which one or more hydrogen atoms of the alkyl group are further substituted by the above-mentioned substituents, that is, each independently a hydrogen atom or an unsubstituted or substituted alkyl group having 1 to 40 carbon atoms, among which a hydrogen atom or an unsubstituted alkyl group having 1 to 40 carbon atoms is preferred.

Furthermore, it is preferred that at least one of ^R102 and ^R103 is an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 40 carbon atoms, wherein it is preferred that ^R102 and ^R103 are each independently an alkyl group having 1 to 40 carbon atoms or a group in which one or more hydrogen atoms of the alkyl group are further substituted with the above-mentioned substituent, that is, both ^R102 and ^R103 are unsubstituted or substituted alkyl groups having 1 to 40 carbon atoms, and particularly preferably an unsubstituted alkyl group having 1 to 40 carbon atoms.

It is preferred that R ¹⁰² and R ¹⁰³ are independently an alkyl group having 1 to 20 carbon atoms, preferably an alkyl group having 1 to 10 carbon atoms, particularly preferably an alkyl group having 2 to 6 carbon atoms, particularly preferably an alkyl group having 4 carbon atoms represented by -C ₄ H ₉ , and particularly preferably a tert-butyl group. This is because: when R ¹⁰² and R ¹⁰³ are the above-mentioned groups, the above-mentioned compound A becomes a compound with a large change in antioxidant ability before and after the removal of the protecting group R ^101. In addition, it is also because the above-mentioned compound A can suppress the generation of curing hindrance. Therefore, this is because the balance between curability and heat resistance of the cured product becomes better. Furthermore, it is also because the synthesis becomes easy.

As the above R ¹⁰⁴ , a halogen atom or an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 40 carbon atoms is preferred. This is because: when the above R ¹⁰⁴ is the above group, the above compound A becomes a compound with a large change in antioxidant ability before and after the removal of the protecting group R ^101. In addition, the above compound A can suppress the generation of curing hindrance. Therefore, this is because the balance between curability and heat resistance of the cured product becomes better. Furthermore, it is also because the synthesis becomes easy.

The above-mentioned a1 is an integer of 0 to 2, preferably 0 to 1, and preferably 0. This is because the balance between the curability of the above-mentioned composition and the heat resistance of the cured product becomes more excellent.

The above n is an integer of 1 to 10, preferably an integer of 1 to 6, preferably an integer of 1 to 4, and particularly preferably an integer of 2 to 4. This is because when the above n is within the above range, the balance between the curability of the above composition and the heat resistance of the cured product is further improved.

The above-mentioned X represents an n-valent atom or group.

As such X, any group that can obtain the desired curability and heat resistance of the cured product may be used, for example, the group represented by X and the substituent of the substituted alkoxy group described in International Publication No. 2014/021023, the group described as the group represented by X in the general formula (1) in Japanese Patent Application Laid-Open No. 2018-150301, etc. can also be used.

More specifically, X includes a direct bond; a hydrogen atom; a halogen atom; a cyano group; a hydroxyl group; a nitro group; a carboxyl group; a nitrogen atom; an oxygen atom; a sulfur atom; a phosphorus atom; a group represented by (II-a) below; a group represented by (II-b); >C=O;>NR⁵³; -OR ⁵³ ; -SR ⁵³ ; -NR ⁵³ R ⁵⁴ ; an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 40 carbon atoms and having the same valence as n; an unsubstituted or substituted aromatic hydrocarbon group having 6 to 40 carbon atoms and having the same valence as n; an unsubstituted or substituted heterocyclic group having 2 to 40 carbon atoms and having the same valence as n; or a group having 1 to 40 carbon atoms obtained by replacing one or more methylene groups in an unsubstituted or substituted aliphatic hydrocarbon group having the same valence as n with a divalent group selected from the following Group I, a group having 6 to 40 carbon atoms obtained by replacing one or more methylene groups in an unsubstituted or substituted aromatic hydrocarbon group having the same valence as n with a divalent group selected from the following Group I, or a group having 2 to 40 carbon atoms obtained by replacing one or more methylene groups in an unsubstituted or substituted heterocyclic group having the same valence as n with a divalent group selected from the following Group I, etc.

^R53 and ^R54 each independently represent a hydrogen atom, an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 40 carbon atoms, an unsubstituted or substituted aromatic hydrocarbon group having 6 to 40 carbon atoms, or an unsubstituted or substituted heterocyclic group having 2 to 40 carbon atoms, or a group having 1 to 40 carbon atoms obtained by replacing one or more methylene groups in the unsubstituted or substituted aliphatic hydrocarbon group with a divalent group selected from the following Group I, a group having 6 to 40 carbon atoms obtained by replacing one or more methylene groups in the unsubstituted or substituted aromatic hydrocarbon group with a divalent group selected from the following Group I, or a group having 2 to 40 carbon atoms obtained by replacing one or more methylene groups in the unsubstituted or substituted heterocyclic group with a divalent group selected from the following Group I.

When X is a nitrogen atom, a phosphorus atom, a group represented by (II-a) below, or a group represented by (II-b) below, n is 3. When X is a direct bond, an oxygen atom, a sulfur atom, >C=O, -NH-CO-, -CO-NH-, or >NR ⁵³ , n is 2. When X is a hydrogen atom, a halogen atom, a cyano group, a hydroxyl group, a nitro group, a carboxyl group, -OR ⁵³ , -SR ⁵³ , or -NR ⁵³ R ⁵⁴ , n is 1. X may form a ring together with a benzene ring to which X is bonded.

Group I: -O-, -COO-, -OCO-, -CO-, -CS-, -S-, -SO-, -SO ₂ -, -NR ²³⁰ -, -NR ²³⁰ -CO-, -CO-NR ²³⁰ -, -NR ²³⁰ -COO-, -OCO-NR ²³⁰ -, or -SiR ²³⁰ R ²³¹ -. ^{R 230} and R ²³¹ each independently represent a hydrogen atom or an unsubstituted aliphatic hydrocarbon group having 1 to 20 carbon atoms.

(Wherein, * indicates the bonding site.)

As the aliphatic hydrocarbon group having the same valence as n, the aromatic hydrocarbon group having the same valence as n, the heterocyclic group having the same valence as n, and the group obtained by replacing one or more methylene groups in the above-mentioned aliphatic hydrocarbon group, aromatic hydrocarbon group or heterocyclic group with a divalent group selected from Group I represented by X in the general formula (A1 ⁾ , for example, there can be mentioned groups satisfying the specified number of carbon atoms among the groups obtained by removing "n ^- 1" hydrogen atoms from the above-mentioned groups from the groups obtained by replacing one or more methylene groups in the aliphatic hydrocarbon group, aromatic hydrocarbon group or heterocyclic group represented by R 101 etc. or R 104 etc. with a divalent group selected from the following Group I.

Examples of the aliphatic hydrocarbon group, aromatic hydrocarbon group, heterocyclic group, and group obtained by replacing one or more methylene groups in the aliphatic hydrocarbon group, aromatic hydrocarbon group, or heterocyclic group represented by R ⁵³ and R ⁵⁴ include groups obtained by replacing one or more methylene groups in the aliphatic hydrocarbon group, aromatic hydrocarbon group, or heterocyclic group represented by R ¹⁰¹ or R ¹⁰⁴ , and groups satisfying the specified number of carbon atoms among the groups listed above.

The unsubstituted aliphatic hydrocarbon group having 1 to 20 carbon atoms represented by R ²³⁰ and R ²³¹ in Group I can be the same groups as R ²³⁰ and R ²³¹ in Group I used in R ¹⁰¹ and the like.

When n is 2 to 10, X in the general formula (A1) is preferably: an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 40 carbon atoms with the same valence as n; an unsubstituted or substituted aromatic hydrocarbon group having 6 to 40 carbon atoms with the same valence as n; an unsubstituted or substituted heterocyclic group having 2 to 40 carbon atoms with the same valence as n; or a group having 1 to 40 carbon atoms obtained by replacing one or more methylene groups in an unsubstituted or substituted aliphatic hydrocarbon group, aromatic hydrocarbon group or heterocyclic group having the same valence as n with a divalent group selected from the group consisting of the above-mentioned Group I (the carbon numbers of the groups replacing the methylene groups of each of the aliphatic hydrocarbon group, aromatic hydrocarbon group and heterocyclic group are 1 to 40, 6 to 40 and 2 to 40, respectively). Among them, X is preferably: an unsubstituted or substituted aliphatic hydrocarbon group having 2 to 30 carbon atoms with the same valence as n; an unsubstituted or substituted aromatic hydrocarbon group having 6 to 30 carbon atoms with the same valence as n; an unsubstituted or substituted heterocyclic group having 3 to 30 carbon atoms with the same valence as n; or a group having 2 to 30 carbon atoms obtained by replacing one or more methylene groups in an unsubstituted or substituted aliphatic hydrocarbon group, aromatic hydrocarbon group or heterocyclic group having the same valence as n with a divalent group selected from the group consisting of -O-, -COO-, -OCO- and -CO- (the carbon atoms of the groups replacing the methylene groups of each of the aliphatic hydrocarbon group, aromatic hydrocarbon group and heterocyclic group are 2 to 30, 6 to 30 and 2 to 30, respectively). In particular, X is preferably: an unsubstituted or substituted aliphatic hydrocarbon group having 10 to 25 carbon atoms and having the same valence as n; an unsubstituted or substituted heterocyclic group having 4 to 25 carbon atoms and having the same valence as n; or a group having 4 to 25 carbon atoms obtained by replacing one or more methylene groups in an unsubstituted or substituted aliphatic hydrocarbon group or heterocyclic group having the same valence as n with a divalent group selected from the group consisting of -O-, -COO-, -OCO- and -CO- (the carbon atoms of the groups replacing the methylene groups of the aliphatic hydrocarbon group and the heterocyclic group are 10 to 25 and 4 to 25, respectively). Particularly preferred are: an unsubstituted or substituted aliphatic hydrocarbon group with 14 to 22 carbon atoms having the same valence as n; an unsubstituted or substituted heterocyclic group with 5 to 22 carbon atoms having the same valence as n; or a group with 5 to 22 carbon atoms obtained by replacing one or more methylene groups in an unsubstituted or substituted aliphatic hydrocarbon group or heterocyclic group having the same valence as n with a divalent group selected from the group consisting of -O-, -COO-, -OCO- and -CO- (the carbon atoms of the group replacing the methylene groups of the aliphatic hydrocarbon group and the heterocyclic group are 14 to 22 and 5 to 22, respectively). This is because the balance between the curability of the above-mentioned composition and the heat resistance of the obtained cured product becomes more excellent.

In the present application, when (1) n is 2, X in the general formula (A1) is preferably a substituent represented by the following general formula (101) or a group selected from the following Group 1. When (2) n is 3, X in the general formula (A1) is preferably a group selected from the following Group 2. When (3) n is 4, X in the general formula (A1) is preferably a group selected from the following Group 3. When (4) n is 5, X in the general formula (A1) is preferably a group selected from the following Group 4. When (5) n is 6, X in the general formula (A1) is preferably a group selected from the following Group 5. When (6) n is 1, X in the general formula (A1) is preferably a hydrogen atom, an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 40 carbon atoms, or a group having 1 to 40 carbon atoms obtained by replacing one or more methylene groups in an unsubstituted or substituted aliphatic hydrocarbon group with a divalent group selected from the above Group I. This is because the balance between the curability of the composition and the heat resistance of the cured product is further improved.

*-Y ¹¹¹ -Y ¹¹² -Y ¹¹³ -Y ¹¹⁴ -Y ¹¹⁵ -* (101)

(wherein, Y ¹¹¹ and Y ¹¹⁵ each independently represent an unsubstituted or substituted divalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, or a group having 1 to 8 carbon atoms obtained by replacing one or more methylene groups in an unsubstituted or substituted aliphatic hydrocarbon group with a divalent group selected from the above Group I,

Y ¹¹² and Y ¹¹⁴ each independently represent a group represented by -O-, -CO-, -CO-O-, -O-CO-, -NR ²¹³ -, -CO-NR ²¹³ - or -NR ²¹³ -CO-,

R ²¹³ represents a hydrogen atom, an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 40 carbon atoms, or a group having 1 to 40 carbon atoms obtained by replacing one or more methylene groups in an unsubstituted or substituted aliphatic hydrocarbon group with a divalent group selected from Group I above,

Y ¹¹³ represents -CR ²¹⁴ R ²¹⁵ -, -NR ²¹⁶ -, a group represented by the following general formula (103), an unsubstituted or substituted divalent aliphatic hydrocarbon group having 1 to 40 carbon atoms, an unsubstituted or substituted divalent aromatic hydrocarbon group having 6 to 40 carbon atoms, or a group having 1 to 40 carbon atoms obtained by replacing one or two or more methylene groups in an unsubstituted or substituted aliphatic hydrocarbon group with a divalent group selected from the above Group I, or a group having 6 to 40 carbon atoms obtained by replacing one or two or more methylene groups in an unsubstituted or substituted aromatic hydrocarbon group with a divalent group selected from the above Group I,

R ²¹⁴ and R ²¹⁵ each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an arylalkyl group having 7 to 20 carbon atoms,

^R216 represents a hydrogen atom, an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 40 carbon atoms, an unsubstituted or substituted aromatic hydrocarbon group having 6 to 40 carbon atoms, an unsubstituted or substituted heterocyclic group having 2 to 40 carbon atoms, or a group having 1 to 40 carbon atoms obtained by replacing one or more methylene groups in an unsubstituted or substituted aliphatic hydrocarbon group with a divalent group selected from the above Group I, a group having 6 to 40 carbon atoms obtained by replacing one or more methylene groups in an unsubstituted or substituted aromatic hydrocarbon group with a divalent group selected from the above Group I, or a group having 2 to 40 carbon atoms obtained by replacing one or more methylene groups in an unsubstituted or substituted heterocyclic group with a divalent group selected from the above Group I,

*Indicates bonding location. )

(wherein, ^Y119 and ^Y120 each independently represent an unsubstituted or substituted divalent aliphatic hydrocarbon group having 1 to 40 carbon atoms, or a group having 1 to 40 carbon atoms obtained by replacing one or more methylene groups in the unsubstituted or substituted aliphatic hydrocarbon group with a divalent group selected from the above Group I,

*Indicates bonding location. )

<Group I>

(wherein, R ³¹ represents a hydrogen atom, an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 40 carbon atoms, an unsubstituted or substituted aromatic hydrocarbon group having 6 to 40 carbon atoms, or an unsubstituted or substituted heterocyclic group having 2 to 40 carbon atoms, or a group having 1 to 40 carbon atoms obtained by replacing one or more methylene groups in the unsubstituted or substituted aliphatic hydrocarbon group with a divalent group selected from the above Group I, a group having 6 to 40 carbon atoms obtained by replacing one or more methylene groups in the unsubstituted or substituted aromatic hydrocarbon group with a divalent group selected from the above Group I, or a group having 2 to 40 carbon atoms obtained by replacing one or more methylene groups in the unsubstituted or substituted heterocyclic group with a divalent group selected from the above Group I,

*Indicates bonding location. )

<Group 2>

(wherein, R ³² represents a hydrogen atom, an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 40 carbon atoms, an unsubstituted or substituted aromatic hydrocarbon group having 6 to 40 carbon atoms, an unsubstituted or substituted heterocyclic group having 2 to 40 carbon atoms, or a group having 1 to 40 carbon atoms obtained by replacing one or more methylene groups in an unsubstituted or substituted aliphatic hydrocarbon group with a divalent group selected from the above Group I, a group having 6 to 40 carbon atoms obtained by replacing one or more methylene groups in an unsubstituted or substituted aromatic hydrocarbon group with a divalent group selected from the above Group I, or a group having 2 to 40 carbon atoms obtained by replacing one or more methylene groups in an unsubstituted or substituted heterocyclic group with a divalent group selected from the above Group I. When there are two or more R ³² in the group, the two or more R ³² may be the same or different.

Z ¹¹ each independently represents a direct bond, -O-, -S-, >CO, -CO-O-, -O-CO-, -SO ₂ -, -SS-, -SO-, >NR ⁶³ , or -PR ⁶³ -, an unsubstituted or substituted divalent aliphatic hydrocarbon group having 1 to 40 carbon atoms, an unsubstituted or substituted divalent aromatic hydrocarbon group having 6 to 40 carbon atoms, an unsubstituted or substituted divalent heterocyclic group having 2 to 40 carbon atoms, or a group having 1 to 40 carbon atoms obtained by replacing one or more methylene groups in an unsubstituted or substituted aliphatic hydrocarbon group with a divalent group selected from the above Group I, a group having 6 to 40 carbon atoms obtained by replacing one or more methylene groups in an unsubstituted or substituted aromatic hydrocarbon group with a divalent group selected from the above Group I, or a group having 2 to 40 carbon atoms obtained by replacing one or more methylene groups in an unsubstituted or substituted heterocyclic group with a divalent group selected from the above Group I,

R ⁶³ represents a hydrogen atom, an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 40 carbon atoms, an unsubstituted or substituted aromatic hydrocarbon group having 6 to 40 carbon atoms, or an unsubstituted or substituted heterocyclic group having 2 to 40 carbon atoms, or a group having 1 to 40 carbon atoms obtained by replacing one or more methylene groups in the unsubstituted or substituted aliphatic hydrocarbon group with a divalent group selected from the above Group I, a group having 6 to 40 carbon atoms obtained by replacing one or more methylene groups in the unsubstituted or substituted aromatic hydrocarbon group with a divalent group selected from the above Group I, or a group having 2 to 40 carbon atoms obtained by replacing one or more methylene groups in the unsubstituted or substituted heterocyclic group with a divalent group selected from the above Group I,

*Indicates bonding location. )

<Group 3>

(wherein, R ³² represents the same group as R ³² in the above Group 2. When there are two or more R ³² in the group, the two or more R ³² may be the same or different.

^Z11 represents a group in the same range as the group represented by ^Z11 in the above Group 2,

*Indicates bonding location. )

<Group 4>

(wherein, the groups represented by Z ¹⁰ , Z ¹¹ , Z ¹² , Z ¹³ and Z ¹⁴ each independently represent a group in the same range as the group represented by Z ¹¹ in the above Group 2,

*Indicates bonding location. )

<Group 5>

(In the above formula, the groups represented by Z ¹⁰ , Z ¹¹ , Z ¹² , Z ¹³ , Z ¹⁴ and Z ¹⁵ each independently represent a group in the same range as the group represented by Z ¹¹ in the above Group 2,

*Indicates bonding location. )

It should be noted ^that , as the ^{unsubstituted} or ^substituted divalent aliphatic hydrocarbon group ^and the aliphatic hydrocarbon group in which a methylene group in the aliphatic hydrocarbon group is substituted with a ^divalent group selected from Group I ⁽ hereinafter also referred to as "divalent aliphatic hydrocarbon group, etc."), examples include aliphatic hydrocarbon groups satisfying the prescribed number of carbon atoms in the group obtained by removing one hydrogen atom from the unsubstituted or substituted aliphatic hydrocarbon group used in ^R101 , ^etc. As ^the unsubstituted or substituted divalent aromatic hydrocarbon group and the aromatic hydrocarbon group in which a methylene group in the aromatic hydrocarbon group is substituted with a divalent group selected from Group I, examples include aromatic hydrocarbon groups satisfying the prescribed number of carbon atoms in the group obtained by removing one hydrogen atom from the unsubstituted or substituted aromatic hydrocarbon group used in ^R104 , etc. Examples of the unsubstituted or substituted divalent heterocyclic group represented by ^Z11 and the heterocyclic group in which the methylene group in the heterocyclic group is substituted with a divalent group selected from Group I include heterocyclic groups satisfying the prescribed number of carbon atoms in the group obtained by removing one hydrogen atom from the unsubstituted or substituted heterocyclic group used in ^R104 and the like.

Examples of the unsubstituted or substituted divalent aliphatic hydrocarbon group represented by ^Y111 , ^Y113 , ^Y115 , ^Y119 and ^Y120 include an unsubstituted or substituted alkylene group obtained by removing one hydrogen atom from an unsubstituted or substituted alkyl group.

In the above formula (101), Y ¹¹¹ and Y ¹¹⁵ may be the same or different.

In the above formula (103), ^Y119 and ^Y120 may be the same or different.

The unsubstituted or substituted aliphatic hydrocarbon group and the aliphatic hydrocarbon group in which the methylene group in the aliphatic hydrocarbon group is substituted with a divalent group selected from Group I represented by R ²¹³ , R ²¹⁶ , R ²¹⁷ , R ³¹ , R ³² and ^R 63 can be the same as the unsubstituted or substituted aliphatic hydrocarbon group represented by R ¹⁰¹ etc.

The unsubstituted or substituted aromatic hydrocarbon-containing group and the aromatic hydrocarbon-containing group in ^which the methylene group in the aromatic hydrocarbon-containing group is substituted with a divalent group selected from Group I represented by ^{R 213} , R ²¹⁶ , R ²¹⁷ , ^R 31 , R 32 and R 63 can be the same as the unsubstituted or substituted aromatic hydrocarbon-containing group represented by R ¹⁰⁴ etc.

The unsubstituted or substituted heterocyclic group represented by R ²¹³ , R ²¹⁶ , R ²¹⁷ , R ³¹ , R ³² and R ⁶³ and the heterocyclic group in which the methylene group in the heterocyclic group is substituted with a divalent group selected from Group I can be the same as the unsubstituted or substituted heterocyclic group represented by R ¹⁰⁴ etc.

The alkyl group having ^{1 to 8 carbon atoms, the aryl group having 6 to 20 carbon atoms, and the arylalkyl group having 7 to 20 carbon atoms represented by R 214 and R 215 can be the} same as those satisfying the prescribed number of carbon atoms in the alkyl group, aryl group, and arylalkyl group used in R ¹⁰¹ or R ¹⁰⁴ .

A plurality of Z ¹¹ included in each formula of Group 2 and Group 3, Z ¹⁰ to Z ¹⁴ included in each formula of Group 4, and Z ¹⁰ to Z ¹⁵ included in each formula of Group 5 may be the same or different groups.

In the present application, when n is 2, X is preferably a group represented by the above general formula (101). This is because the balance between the curability of the above composition and the heat resistance of the obtained cured product becomes better.

In the general formula (101), ^Y111 and ^Y115 are each independently preferably an unsubstituted or substituted divalent aliphatic hydrocarbon group having 1 to 5 carbon atoms, and more preferably an unsubstituted or substituted divalent aliphatic hydrocarbon group having 1 to 3 carbon atoms, and particularly preferably an unsubstituted alkylene group having 1 to 3 carbon atoms. This is because the balance between the curability of the composition and the heat resistance of the obtained cured product is further improved.

In the general formula (101), ^Y112 and ^Y114 are each independently preferably -O-, -CO-, -CO-O- or -O-CO-, and -CO-O- or -O-CO- is preferred. This is because the balance between the curability of the composition and the heat resistance of the obtained cured product is further improved.

In the above general formula (101), Y ¹¹³ is preferably an unsubstituted or substituted divalent aliphatic hydrocarbon group having 1 to 40 carbon atoms, a group having 1 to 40 carbon atoms obtained by replacing one or more methylene groups in the unsubstituted or substituted divalent aliphatic hydrocarbon group with a divalent group selected from the above group I, or a group represented by the above general formula (103). Among them, it is preferably an unsubstituted or substituted divalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, a group having 1 to 20 carbon atoms obtained by replacing one or more methylene groups in the unsubstituted or substituted divalent aliphatic hydrocarbon group with a divalent group selected from the above group I, or a group represented by the above general formula (103). It is particularly preferred to be a group having 1 to 20 carbon atoms obtained by replacing one or more methylene groups in the unsubstituted or substituted divalent aliphatic hydrocarbon group with a divalent group selected from the above group I, or a group represented by the above general formula (103). Among them, the group represented by the above general formula (103) is particularly preferred. This is because the balance between the curability of the composition and the heat resistance of the obtained cured product becomes more excellent.

In the general formula (103), ^Y119 and ^Y120 are each independently preferably an unsubstituted or substituted divalent aliphatic hydrocarbon group having 1 to 40 carbon atoms, or a group having 1 to 40 carbon atoms obtained by replacing one or more methylene groups in the unsubstituted or substituted divalent aliphatic hydrocarbon group with a divalent group selected from the above group I, among which an unsubstituted or substituted divalent aliphatic hydrocarbon group having 1 to 20 carbon atoms is preferred, and an unsubstituted or substituted divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms is particularly preferred, and an unsubstituted or substituted divalent aliphatic hydrocarbon group having 1 to 5 carbon atoms is particularly preferred, and a linear or branched alkylene group having 2 to 5 carbon atoms is particularly preferred. This is because the balance between the curability of the composition and the heat resistance of the obtained cured product becomes more excellent.

In the present application, when n is 3, X is preferably a group represented by the general formula (II-2), a group represented by the general formula (II-3), or a group represented by the general formula (II-6) in Group 2, and preferably a group represented by the general formula (II-6). This is because the balance between the curability of the above-mentioned composition and the heat resistance of the obtained cured product becomes better.

^Z11 in the group represented by the general formula (II-2), the group represented by the general formula (II-3) and the general formula (II-6) is preferably a direct bond or an unsubstituted or substituted divalent aliphatic hydrocarbon group having 1 to 40 carbon atoms, and is preferably a direct bond or an unsubstituted or substituted divalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, and is particularly preferably a direct bond or an unsubstituted or substituted alkylene group having 1 to 10 carbon atoms, and is particularly preferably a direct bond or an unsubstituted alkylene group having 1 to 5 carbon atoms. This is because the balance between the curability of the above-mentioned composition and the heat resistance of the obtained cured product becomes better.

A plurality of Z ^11s contained in the group represented by the general formula (II-2), the group represented by the general formula (II-3), and the group represented by the general formula (II-6) may be the same or different.

In the present application, it is preferred that at least one of the three Z ¹¹ in the group represented by the general formula (II-2) is directly bonded, and at least one is a divalent aliphatic hydrocarbon group having 1 to 40 carbon atoms and being unsubstituted or having a substituent, and at least one is preferably directly bonded, and at least one is a divalent aliphatic hydrocarbon group having 1 to 20 carbon atoms and being unsubstituted or having a substituent, and at least one is preferably directly bonded, and at least one is an alkylene group having 1 to 10 carbon atoms and being unsubstituted or having a substituent, and at least one is preferably directly bonded, and at least one is an alkylene group having 1 to 5 carbon atoms and being unsubstituted. This is because the balance between the curability of the above-mentioned composition and the heat resistance of the obtained cured product becomes better.

In addition, all of ^Z11 in the group represented by the general formula (II-3) and the group represented by (II-6) are preferably unsubstituted or substituted divalent aliphatic hydrocarbon groups having 1 to 40 carbon atoms, among which unsubstituted or substituted divalent aliphatic hydrocarbon groups having 1 to 20 carbon atoms are preferred, unsubstituted or substituted alkylene groups having 1 to 10 carbon atoms are particularly preferred, and unsubstituted alkyl groups having 1 to 5 carbon atoms are particularly preferred. This is because the balance between the curability of the above-mentioned composition and the heat resistance of the obtained cured product becomes better.

R ³² in the group represented by the general formula (II-2) is preferably a hydrogen atom or an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 40 carbon atoms, and is preferably a hydrogen atom or an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 5 carbon atoms, and is particularly preferably a hydrogen atom. This is because the balance between the curability of the composition and the heat resistance of the obtained cured product becomes better.

In the present application, when n is 4, X is preferably a group represented by the general formula (III-1) in Group 3. In the general formula (III-1), Z ¹¹ is preferably an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 40 carbon atoms, or a group having 1 to 40 carbon atoms obtained by replacing one or more methylene groups in an unsubstituted or substituted aliphatic hydrocarbon group with a divalent group selected from the above Group I, and among them, it is preferably an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, or a group having 1 to 20 carbon atoms obtained by replacing one or more methylene groups in an unsubstituted or substituted aliphatic hydrocarbon group with a divalent group selected from the above Group I, Particularly preferred are groups having 1 to 10 carbon atoms in which one or more methylene groups in an unsubstituted or substituted alkylene group are replaced by a divalent group selected from the above group I, and particularly preferred are groups having 1 to 10 carbon atoms in which one or more methylene groups in an unsubstituted alkylene group are replaced by -O-, -COO-, -OCO-, or -CO-, and particularly preferred are groups having 2 to 5 carbon atoms in which one methylene group in an alkylene group having 2 to 5 carbon atoms is replaced by -O-CO- or -CO-O-. This is because the balance between the curability of the above composition and the heat resistance of the obtained cured product becomes more excellent.

This is because, when X in each n is the above group, the compound A becomes a compound with a large change in antioxidant ability before and after the removal of the protecting group R ^101. Also, as a result, the balance between the curability of the composition and the heat resistance of the cured product becomes excellent.

The bonding position of X to the benzene ring may be any bonding position in the benzene ring, but is preferably the para position relative to the bonding position of R ¹⁰¹ -O-, for example.

This is because the aforementioned bonding position makes the compound A a compound with a large change in antioxidant ability before and after the removal of the protecting group R ^101. Also, as a result, the balance between the curability of the composition and the heat resistance of the cured product becomes excellent.

Specific examples of the compound A include compounds specifically described in International Publication No. 2014/021023.

The method for producing the compound A is not particularly limited as long as it is a method that can obtain a desired structure, and for example, the method may be the same as the method described in International Publication No. 2014/021023.

As the type of the compound A, only one type may be present in the composition, or two or more types may be present.

The content of the compound A may be any content that can obtain desired curability and heat resistance of a cured product, and can be appropriately set according to the application of the composition and the like.

As the content of the above-mentioned compound A, for example, in 100 parts by mass of the solid content of the above-mentioned composition, it is preferably 0.01 parts by mass or more and 20 parts by mass or less, wherein it is preferably 0.05 parts by mass or more and 10 parts by mass or less, and particularly preferably 0.1 parts by mass or more and 5 parts by mass or less. This is because: by the above-mentioned content being within the above-mentioned range, the balance of the curability of the above-mentioned composition and the heat resistance of the cured product becomes more excellent.

In addition, the so-called solid content includes all components other than the solvent.

The content of the compound A varies depending on the content of the solvent, etc. For example, in 100 parts by mass of the composition, it is preferably 0.001 parts by mass or more and 20 parts by mass or less, wherein it is preferably 0.005 parts by mass or more and 10 parts by mass or less, and particularly preferably 0.01 parts by mass or more and 5 parts by mass or less. This is because: by the above content being within the above range, the balance of the curability of the composition and the heat resistance of the cured product becomes more excellent.

The content of the above-mentioned compound A is preferably 0.01 mass parts or more and 20 mass parts or less in a total of 100 mass parts of compound A, metal deactivator and curable component, wherein preferably 0.05 mass parts or more and 10 mass parts or less, particularly preferably 0.1 mass parts or more and 5 mass parts or less, particularly preferably 0.5 mass parts or more and 3 mass parts or less. This is because: by the content of compound A being within the above-mentioned range, the balance of the curability of the above-mentioned composition and the heat resistance of the cured product becomes more excellent.

The total content of the compound A and the metal deactivator is preferably 0.01 parts by mass or more and 10 parts by mass or less in a total of 100 parts by mass of the compound A, the metal deactivator and the curable component, wherein it is preferably 0.1 parts by mass or more and 5 parts by mass or less, and particularly preferably 0.5 parts by mass or more and 3 parts by mass or less. This is because: by the total content of the compound A and the metal deactivator being within the above range, the balance of the curability of the composition and the heat resistance of the cured product becomes more excellent.

The total content of the above-mentioned compound A, metal deactivator and curing component is preferably 10 parts by mass or more, preferably 30 parts by mass or more, and preferably 40 parts by mass or more in 100 parts by mass of solid content. This is because: by the above-mentioned range of the total content of the above-mentioned compound A, metal deactivator and curing component, the balance of the curability of the above-mentioned composition and the heat resistance of the cured product becomes more excellent. About the upper limit of the total content of the above-mentioned compound A, metal deactivator and curing component, it can be appropriately set according to the purpose of the composition of the present application, but it can be set to less than 99 parts by mass, preferably less than 90 parts by mass, particularly preferably less than 80 parts by mass, and particularly preferably less than 70 parts by mass. This is because: by the above-mentioned content being the above-mentioned range, the balance of the curability of the above-mentioned composition and the heat resistance of the cured product becomes more excellent.

The total content of the above-mentioned compound A, metal deactivator and curing component is preferably 50 parts by mass or more, preferably 70 parts by mass or more, and preferably 90 parts by mass or more in 100 parts by mass of the solid content other than the filler, when the above-mentioned composition includes a filler. This is because: by the above-mentioned compound A, the metal deactivator and the curing component The total content is within the above-mentioned range, the balance of the curability of the above-mentioned composition and the heat resistance of the cured product becomes more excellent. About the upper limit of the total content of the above-mentioned compound A, metal deactivator and curing component, it can be appropriately set according to the purpose of the composition of the present application, but it can be set to less than 99 parts by mass, wherein preferably less than 98 parts by mass, particularly preferably less than 96 parts by mass. This is because: by the above-mentioned content being within the above-mentioned range, the balance of the curability of the above-mentioned composition and the heat resistance of the cured product becomes more excellent.

2. Metal passivator

The metal deactivator is a substance that can capture metal ions by chelating metal ions and improve the heat resistance of the cured product.

Here, the captured metal ions may be any ions that can improve the curability and heat resistance of the composition by capturing the ions, and examples thereof include alkali metal ions such as sodium and potassium, copper ions, and iron ions.

As such a metal deactivator, a known metal deactivator can be used, and examples thereof include benzotriazole compounds, hydrazide compounds, salicylic acid compounds, triazine compounds, oxalic acid compounds, imidazole compounds, phosphite compounds, and guanidine compounds.

In the present application, the metal deactivator preferably includes at least one of a benzotriazole compound, a hydrazide compound, a salicylic acid compound, and a triazine compound. This is because the balance between the curability of the composition and the heat resistance of the cured product is further improved.

It should be noted that, in the present application, the metal deactivator is included as a component different from compound A, and generally, except for the hydrazide compound, a compound having no portion where the phenolic hydroxyl group is protected by a protecting group is used. More specifically, for the benzotriazole compound, salicylic acid compound, triazine compound, oxalic acid compound, imidazole compound, phosphite compound, and guanidine compound as the metal deactivator, a compound having no portion where the phenolic hydroxyl group is protected by a protecting group is generally used.

In the present application, the hydrazide compound as a metal deactivator is defined as a compound that may contain a site where a phenolic hydroxyl group is protected by a protecting group, and a compound having a hydrazine structure is defined as not belonging to the compound A.

Examples of the benzotriazole compound include compounds having a benzotriazole ring. For example, a compound having a benzotriazole ring and a hydrazine structure is also considered to be a benzotriazole compound.

In the present application, the benzotriazole compound is preferably a compound represented by the following general formula (B1). This is because the balance between the curability of the composition and the heat resistance of the cured product is further improved.

(wherein, ^R1 represents a hydrogen atom, a hydroxyl group, an unsubstituted or silyl-substituted hydrocarbon group having 1 to 20 carbon atoms, or a silyl group having 0 to 20 carbon atoms,

^R2 represents an unsubstituted or substituted hydrocarbon group having 1 to 20 carbon atoms,

nb1 represents an integer from 0 to 4. )

Examples of the hydrocarbon group used for ^R1 and ^R2 include hydrocarbon groups satisfying the prescribed number of carbon atoms among the hydrocarbon groups described as the aliphatic hydrocarbon group or aromatic hydrocarbon group used for ^R101 , etc. Examples of the substituent in the hydrocarbon group having a substituent used for ^R2 include the groups listed above as substituents that can replace hydrogen atoms in the aliphatic hydrocarbon group used for ^R101 , etc.

As the silyl group substituting for the hydrogen atom in the hydrocarbon group used in ^R1 , a silyl group having 0 to 20 carbon atoms can be used. As the silyl group used in ^R1 or substituting for the hydrogen atom in the hydrocarbon group used in ^R1 , there can be mentioned those silyl groups satisfying the prescribed number of carbon atoms among those described as the silyl groups used in ^R101 and the like.

In the present application, ^R1 is preferably a hydrogen atom, a hydroxyl group or a hydrocarbon group having 1 to 20 carbon atoms substituted by a silyl group. This is because the balance between the curability of the above-mentioned composition and the heat resistance of the cured product becomes better. In the case where ^R1 is a hydrocarbon group having 1 to 20 carbon atoms substituted by a silyl group, the number of carbon atoms here refers to the number of atoms including the number of carbon atoms of the silyl group in the hydrocarbon group substituted by a silyl group. In the case where ^R1 is a hydrocarbon group having 1 to 20 carbon atoms substituted by a silyl group, the silyl group is preferably a substituted silyl group, and particularly preferably a group represented by ^-SiR117t ( ^OR118 ) _{3-t (} ^R117 and ^R118 each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. t represents an integer of 0 to 3.). In particular, it is preferred that t in -SiR ¹¹⁷ _t (OR ¹¹⁸ ) _3-t is 0 or 1, and it is preferred that t is 0, i.e., -Si(OR ¹¹⁷ ) ₃ . This is because the balance between the curability of the composition and the heat resistance of the cured product becomes better. Furthermore, R ¹¹⁷ and R ¹¹⁸ are each independently preferably an alkyl group having 1 to 4 carbon atoms, and it is preferably an alkyl group having 1 to 2 carbon atoms. This is because the balance between the curability of the composition and the heat resistance of the cured product becomes better.

In the present application, R ² is preferably a hydrogen atom or an unsubstituted hydrocarbon group having 1 to 20 carbon atoms, and a hydrogen atom is particularly preferred because the balance between the curability of the composition and the heat resistance of the cured product is further improved.

Specific examples of the benzotriazole compound include benzotriazole and tolyltriazole.

Examples of commercially available products of the benzotriazole compound include X12-1214A manufactured by Shin-Etsu Silicone Co., Ltd.

The hydrazide compound is a reaction product of a hydrazine compound and an oxo acid, and examples thereof include compounds having a hydrazine structure (—CO—NH—NH—CO—).

The hydrazide compound is generally a compound having no benzotriazole ring, and further, a compound having no salicylic acid structure represented by formula (B3a) described later.

In the present application, the hydrazide compound is preferably a compound having a hydrazine structure and a phenolic hydroxyl group, and is preferably a compound represented by the following general formula (B2). This is because the balance between the curability of the composition and the heat resistance of the cured product is further improved.

(wherein, R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom or an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 40 carbon atoms,

^R7 and ^R8 each independently represent an unsubstituted or substituted hydrocarbon group having 1 to 40 carbon atoms,

^R9 and ^R10 each independently represent a hydrogen atom, an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 40 carbon atoms, an unsubstituted or substituted aromatic hydrocarbon group having 6 to 40 carbon atoms, an unsubstituted or substituted heterocyclic group having 2 to 40 carbon atoms, an unsubstituted or substituted silyl group having 0 to 40 carbon atoms, or a group having 1 to 40 carbon atoms in which one or more methylene groups in an unsubstituted or substituted aliphatic hydrocarbon group are substituted with a divalent group selected from the following group I-B2, an unsubstituted or a group having 6 to 40 carbon atoms obtained by replacing one or more methylene groups in a substituted aromatic hydrocarbon-containing group with a divalent group selected from the following group I-B2, a group having 2 to 40 carbon atoms obtained by replacing one or more methylene groups in an unsubstituted or substituted heterocyclic-containing group with a divalent group selected from the following group I-B2, or a group having 0 to 40 carbon atoms obtained by replacing one or more methylene groups in an unsubstituted or substituted silyl group with a divalent group selected from the following group I-B2.)

Group I-B2: -O-, -COO-, -OCO-, -CO-, -CS-, -S-, -SO-, -SO ₂ -, -NR ^230-B2 -, -NR ^230-B2 -CO-, -CO-NR ^230-B2 -, -NR ²³⁰ -COO-, -OCO-NR ^230-B2 -, or -SiR ^230-B2 R ^231-B2 -. R ^230-B2 and R ^231-B2 each independently represent a hydrogen atom or an unsubstituted aliphatic hydrocarbon group having 1 to 40 carbon atoms.

As the aliphatic hydrocarbon group used for R ³ , R ⁴ , R ⁵ and R ⁶ , the same groups as those exemplified as the unsubstituted or substituted aliphatic hydrocarbon group used for R ¹⁰¹ etc., as long as they satisfy the prescribed number of carbon atoms, can be used.

The hydrocarbon group used in ^R7 and ^R8 is a divalent group. Examples of such hydrocarbon groups used in ^R7 and ^R8 include hydrocarbon groups satisfying the prescribed number of carbon atoms among groups obtained by removing one hydrogen atom from the aliphatic hydrocarbon groups and aromatic hydrocarbon groups used in ^R101 or ^R104 .

As the aliphatic hydrocarbon group, aromatic hydrocarbon group, heterocyclic ring-containing group and silyl group used for ^R9 and ^R10 , the same groups as those listed as the unsubstituted or substituted aliphatic hydrocarbon group, unsubstituted or substituted aromatic hydrocarbon group, unsubstituted or substituted heterocyclic ring-containing group or silyl group represented by ^R101 etc. or ^R104 etc., which groups satisfying the prescribed number of carbon atoms can be used.

As the group obtained by replacing the methylene group in the unsubstituted or substituted aliphatic hydrocarbon group, aromatic hydrocarbon group, heterocyclic group or silyl group with a divalent group selected from Group I-B2 used in ^R9 and ^R10 , the same groups as those listed above as the group obtained by replacing the methylene group in the unsubstituted or substituted aliphatic hydrocarbon group, aromatic hydrocarbon group, heterocyclic group or silyl group represented by ^R101 etc. or ^R104 etc. with a divalent group selected from Group I can be used.

In the group obtained by replacing two or more methylene groups of the above-mentioned aliphatic hydrocarbon group, aromatic hydrocarbon group-containing group or heterocyclic group-containing group with a divalent group selected from the above-mentioned group I-B2, the multiple divalent groups may be the same as or different from each other, but the divalent groups are set to be non-adjacent.

As the aliphatic hydrocarbon group used for R ^230-B2 and R ^231-B2 , the same groups as those exemplified as the unsubstituted aliphatic hydrocarbon group used for R ¹⁰¹ etc. as long as they satisfy the prescribed number of carbon atoms can be used.

R ³ , R ⁴ , R ⁵ and R ⁶ are each independently preferably a hydrogen atom, an alkyl group having 1 to 40 carbon atoms, or a group in which one or more hydrogen atoms of the alkyl group are further substituted with the above-mentioned substituent, that is, each independently a hydrogen atom or an unsubstituted or substituted alkyl group having 1 to 40 carbon atoms, and preferably a hydrogen atom or an unsubstituted alkyl group having 1 to 40 carbon atoms, preferably an alkyl group having 1 to 40 carbon atoms, preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 2 to 6 carbon atoms, more preferably an alkyl group having 4 carbon atoms represented by -C ₄ H ₉ , and more preferably a tert-butyl group. This is because when R ³ , R ⁴ , R ⁵ and R ⁶ are the above-mentioned groups, the balance between the curability of the composition and the heat resistance of the cured product is further improved.

The above ^R7 and ^R8 are each independently preferably an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 40 carbon atoms, and among them, an unsubstituted or substituted alkylene group having 1 to 40 carbon atoms is preferred, and an unsubstituted or substituted alkylene group having 1 to 10 carbon atoms is particularly preferred, and an unsubstituted or substituted alkylene group having 1 to 5 carbon atoms is particularly preferred, and among them, an unsubstituted alkylene group having 1 to 5 carbon atoms such as methylene, ethylene, propylene, butylene, and pentyl is particularly preferred. This is because the balance between the curability of the above composition and the heat resistance of the cured product is further improved.

^R9 and ^R10 are each independently preferably a hydrogen atom, an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 40 carbon atoms, or a group in which one or more methylene groups in the unsubstituted or substituted aliphatic hydrocarbon group are substituted with a divalent group selected from the above group I-B2. Among them, a group in which the methylene group at the terminal of the oxygen atom side of the hydrogen atom or the unsubstituted or substituted aliphatic hydrocarbon group is substituted with a divalent group selected from the above group I-B2 is preferred, and a group in which the methylene group at the terminal of the oxygen atom side of the unsubstituted or substituted alkyl group is substituted with -CO-O-, i.e., a group represented by -CO-OR" ^-B2 (R" ^-B2 is an unsubstituted or substituted alkyl group having 1 to 39 carbon atoms) is particularly preferred. This is because the balance between the curability of the above composition and the heat resistance of the cured product is further improved.

The group represented by -CO-OR" ^-B2 used independently in ^R9 and ^R10 can be set to the same group as the group preferably used as -CO-OR" used in ^R101 . Specifically, -CO-OR" ^-B2 used in ^R9 and ^R10 is preferably -CO-O-tert-butyl. This is because the balance between the curability of the above-mentioned composition and the heat resistance of the cured product is further improved.

Examples of the hydrazide compound include N,N'-bis((3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl))propionohydrazide and the like.

Examples of commercially available products of the hydrazide compound include CDA-10 manufactured by IDICO Co., Ltd. and "Qunox" (registered trademark) manufactured by Mitsui Toatsu Fine Co., Ltd.

Examples of the salicylic acid compound include compounds having the following structure B3a as a structure derived from salicylic acid (wherein * represents a bonding site).

Furthermore, the salicylic acid compound is generally a compound not having a benzotriazole ring.

In the present application, the salicylic acid compound is preferably a compound represented by the following general formula (B3-1) or (B3-2). This is because the balance between the curability of the composition and the heat resistance of the cured product is further improved.

(In the formula, R ¹¹ represents a hydrogen atom or an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 40 carbon atoms.)

As the aliphatic hydrocarbon group used for R ¹¹ , the same groups as those exemplified as the unsubstituted or substituted aliphatic hydrocarbon group used for R ¹⁰¹ etc. as long as the aliphatic hydrocarbon group has the prescribed number of carbon atoms can be used.

In the present application, R ¹¹ is preferably a hydrogen atom or an unsubstituted or substituted alkyl group having 1 to 40 carbon atoms, and is preferably a hydrogen atom or an unsubstituted alkyl group having 1 to 10 carbon atoms, and is particularly preferably a hydrogen atom. This is because the balance between the curability of the composition and the heat resistance of the cured product is further improved.

(In the formula, ^R12 represents an unsubstituted or substituted hydrocarbon group having 1 to 40 carbon atoms.)

The hydrocarbon group used in R ¹² is a divalent group. Examples of such hydrocarbon groups used in R ¹² include groups obtained by removing one hydrogen atom from the groups listed as the aliphatic hydrocarbon groups and the unsubstituted or substituted aromatic hydrocarbon groups used in R ¹⁰¹ , etc., which have a predetermined number of carbon atoms.

In the present application, ^R12 is preferably an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 40 carbon atoms, and is preferably an unsubstituted alkylene group having 1 to 40 carbon atoms, and is particularly preferably an unsubstituted alkylene group having 2 to 20 carbon atoms, and is particularly preferably an unsubstituted alkylene group having 5 to 15 carbon atoms, and is particularly preferably an unsubstituted alkylene group having 7 to 13 carbon atoms. This is because the balance between the curability of the composition and the heat resistance of the cured product becomes better.

Examples of the salicylic acid compound include 3-(N-salicyloyl)amino-1,2,4-triazole, decamethylenedicarboxylic acid disalicylohydrazide, and salicylidene salicylohydrazide.

Examples of commercially available products of the salicylic acid compound include ADK STAB CDA-1 and ADK STAB CDA-6S manufactured by ADK CORPORATION and Chel-180 manufactured by BASF.

Examples of the triazine compound include compounds having a triazine ring.

As the triazine compound, a compound having no benzotriazole ring, no hydrazine structure, or no structure represented by the above formula (B3a) is generally used.

In the present application, the triazine compound is preferably a compound represented by the following general formula (B4).

This is because the balance between the curability of the composition and the heat resistance of the cured product is further improved.

(In the formula, R ¹⁴ represents a single bond or a linking group.

R ^13-1 , R ^13-2 , R ^13-3 and R ^13-4 each independently represent a hydrogen atom or an alkyl group having 1 to 12 carbon atoms.

R ^15-1 and R ^15-2 each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a hydroxyl group, or a methoxy group.

R ¹⁶ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a hydroxyl group, a methoxy group, or a group represented by -SiR ¹⁷ _s (OR ¹⁸ ) _3-s .

R ¹⁷ and R ¹⁸ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

nb4 represents an integer from 0 to 16.

s represents an integer from 0 to 3. )

Examples of the alkyl groups used for R ^13-1 , R ^13-2 , R ^13-3 and R ^13-4 , R ^15-1 and R ^15-2 , R ¹⁶ and R ¹⁷ and R ¹⁸ include, independently of one another, those listed as the alkyl groups used for R ¹⁰¹ and the like, which satisfy the prescribed number of carbon atoms.

Examples of the linking group used for ^R14 include an unsubstituted or substituted hydrocarbon group having 1 to 40 divalent carbon atoms, a carbonyl group, an ether bond, an ester bond, a carbonate group, an amide group, a thioether group, an amino group, and a group obtained by linking a plurality of these.

Examples of the divalent hydrocarbon group having 1 to 40 carbon atoms include groups satisfying the prescribed number of carbon atoms among those obtained by removing one hydrogen atom from the aliphatic hydrocarbon groups and unsubstituted or substituted aromatic hydrocarbon groups listed as R ¹⁰¹ and the like.

Examples of carbonyl groups, ether bonds, ester bonds, carbonate groups, amide groups, thioether groups, amino groups, and groups formed by connecting multiple groups thereof include -CO-; -O-CO-O-; -COO-; -O-; -CONH-; -S-; -NH-, and groups formed by connecting one or more of these groups to one or more of divalent hydrocarbon groups.

In the present application, R ^13-1 , R ^13-2 , R ^13-3 and R ^13-4 are each independently preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and a hydrogen atom is particularly preferred because the balance between the curability of the composition and the heat resistance of the cured product is further improved.

It should be noted that R ^13-1 , R ^13-2 , R ^13-3 and R ^13-4 may be the same group or different groups, but are preferably the same group because the balance between the curability of the composition and the heat resistance of the cured product is further improved.

In the present application, R ^15-1 and R ^15-2 are each independently preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and a hydrogen atom is particularly preferred because the balance between the curability of the composition and the heat resistance of the cured product is further improved.

It should be noted that, when nb4 is 2 or more, a plurality of R ^15-1 may be the same group or different groups. Similarly, when nb4 is 2 or more, a plurality of R ^15-2 may be the same group or different groups.

In the present application, R ¹⁶ is preferably a hydrogen atom, a hydroxyl group, a methoxy group, or a group represented by -SiR ¹⁷ _s (OR ¹⁸ ) _3-s , and is preferably a hydroxyl group or -SiR ¹⁷ _s (OR ¹⁸ ) _3-s . This is because the balance between the curability of the composition and the heat resistance of the cured product is further improved.

In the present application, s in -SiR ¹⁷ _s (OR ¹⁸ ) _3-s used in R ¹⁶ is preferably 0 or 1, and s is preferably 0, that is, -Si(OR ¹⁷ ) ₃ . This is because the balance between the curability of the composition and the heat resistance of the cured product is further improved.

In the present application, R ¹⁷ and R ¹⁸ are each independently preferably an alkyl group having 1 to 4 carbon atoms, and particularly preferably an alkyl group having 1 to 2 carbon atoms. This is because the balance between the curability of the composition and the heat resistance of the cured product is further improved.

The linking group R ¹⁴ is preferably a divalent hydrocarbon group, and among these, a divalent aliphatic hydrocarbon group is preferred, and an alkylene group which is a group obtained by removing one hydrogen atom from an alkyl group is particularly preferred.

When the linking group ^R14 is a divalent hydrocarbon group, the number of carbon atoms of ^R14 is preferably 2 or more, and preferably 3 or more. The linking group is preferably -S-; -NH-; or _{-CH2CH2 -} S-. This is because the balance between the curability of the composition and the heat resistance of the cured product is further improved.

In the present application, nb4 is preferably an integer of 1 to 8, more preferably an integer of 1 to 6, and particularly preferably an integer of 1 to 3. This is because the balance between the curability of the composition and the heat resistance of the cured product becomes more excellent.

As the triazine compound, specifically, the compounds listed as the triazine-based adhesion agent (D) described in JP-A-2020-70391 can be used.

Examples of commercially available products of the triazine compound include products sold under the trade names “VD-3”, “VD-4”, and “VD-5” (all manufactured by Shikoku Chemicals Co., Ltd.).

Examples of the oxalic acid compound include compounds having a structure derived from oxalic acid (eg, -CO-CO-).

As the oxalic acid compound, for example, compounds described as oxalic acid derivatives in Japanese Patent No. 6266964 can be used.

Examples of the oxalic acid compound include oxalyl-bis-1,2-hydroxybenzylhydrazide (N,N'-bis(2-(2-(3,5-di-tert-butyl-4-hydroxyphenyl)ethylcarbonyloxy)ethyl)oxalamide, oxalanilide, and N-(2-ethylphenyl)-N'-(2-ethoxyphenyl)oxalic acid diamide.

Specific examples of commercially available products of the oxalic acid compound include Eastman Inhibitor, OABH from Eastman Kodak and Naugard XL-1 from Uniroyal Chemical.

Examples of the imidazole compound include 4,4'-methylenebis(2-undecyl-5-methylimidazole and bis[(N-methyl)imidazol-2-yl]methanol octyl ether.

Examples of the above-mentioned phosphite compounds include tris(2-tert-butyl-5-methyl-4-thio-5'-tert-butyl-4'-hydroxy-2-methylphenyl)phenyl phosphite), tris[2-tert-butyl-4-thio(2'-methyl-4'-hydroxy-5'-tert-butyl)phenyl-5-methyl]-phenyl phosphite, and the like.

Examples of the guanidine compound include guanidine hydrochloride, guanidine nitrate, guanidine carbonate, guanidine phosphate, and guanidine sulfamate as guanidine salts.

The content of the metal deactivator is preferably 5 parts by mass or more and 90 parts by mass or less in a total of 100 parts by mass of the compound A and the metal deactivator, wherein preferably 10 parts by mass or more and 80 parts by mass or less, particularly preferably 15 parts by mass or more and 60 parts by mass or less, preferably 20 parts by mass or more and 50 parts by mass or less. This is because: by the above content being the above range, the balance of the curability of the composition and the heat resistance of the cured product becomes more excellent.

The content of the metal deactivator may be any content that can obtain desired curability and heat resistance of the cured product, and can be appropriately set according to the application of the composition and the like.

The content of the metal passivator is preferably 0.01 parts by mass or more and 20 parts by mass or less, preferably 0.05 parts by mass or more and 10 parts by mass or less, and particularly preferably 0.1 parts by mass or more and 5 parts by mass or less, in 100 parts by mass of the solid content of the composition. This is because the balance of the curability of the composition and the heat resistance of the cured product becomes more excellent when the content is within the above range.

In addition, the so-called solid content includes all components other than the solvent.

The content of the metal deactivator is different according to the content of the solvent, etc., for example, preferably 0.001 mass part or more and 20 mass parts or less in 100 mass parts of the composition, wherein preferably 0.005 mass part or more and 10 mass parts or less, particularly preferably 0.01 mass part or more and 5 mass parts or less. This is because: by the above-mentioned content being the above-mentioned range, the balance of the curability of the above-mentioned composition and the heat resistance of the cured product becomes more excellent.

The content of the metal deactivator is preferably 0.01 mass part or more and 20 mass parts or less in the total 100 mass parts of the compound A, the metal deactivator and the curable component, wherein preferably 0.05 mass part or more and 10 mass parts or less, particularly preferably 0.1 mass part or more and 5 mass parts or less, particularly preferably 0.5 mass part or more and 3 mass parts or less. This is because: by the content of compound A being within the above range, the balance of the curability of the composition and the heat resistance of the cured product becomes more excellent.

3. Curing ingredients

The curable component is formed of a curable compound.

In addition, the curable component is a component contained in the composition as a component other than the compound A and the metal deactivator, and a polymerizable compound as the compound A and the metal deactivator is not included in the curable component. Therefore, a compound containing an alkenyl group as the compound A does not belong to the curable component in the present application.

As the curable compound, a compound in which two or more curable compounds can be bonded to form a high molecular weight body can be used, for example, a radical polymerizable compound that can be directly bonded to each other to increase the molecular weight, a thermosetting compound that can be increased in molecular weight by heating, etc.

In the present application, the curable component preferably contains a radical polymerizable compound, because the effect of obtaining a composition having an excellent balance between curability and heat resistance of a cured product becomes more significant.

In the present application, the curable component preferably includes both a radical polymerizable compound and a thermosetting compound, because the balance between the curability of the composition and the heat resistance of the cured product becomes excellent.

The above-mentioned free radical polymerizable compound can be any compound capable of free radical polymerization. As the above-mentioned free radical polymerizable compound, for example, compounds having ethylenically unsaturated groups such as acryloyl, methacryloyl, and vinyl can be cited. In the composition of the present application, as a compound having one or more ethylenically unsaturated groups, a monofunctional compound having one ethylenically unsaturated group and a polyfunctional compound having two or more ethylenically unsaturated groups can be used. As the above-mentioned free radical polymerizable compound, a known compound can be used, for example, a free radical polymerizable compound described in International Publication No. 2018/012383, a free radical polymerizable organic substance described in International Publication No. 2014/021023, etc. can be used.

As the radical polymerizable compound, a compound having an acidic group such as a carboxyl group and an ethylenically unsaturated group is preferably used from the viewpoint of imparting alkali developability.

Examples of the compound having an acidic group such as a carboxyl group and an ethylenically unsaturated group include unsaturated carboxylic acids such as acrylic acid and methacrylic acid, and carboxyl group-containing resins.

As the carboxyl group-containing resin, for example, a carboxyl group-containing photosensitive resin described in Japanese Patent Application Publication No. 2016-180880, a carboxyl group-containing resin described in International Publication No. 2016/208187, a carboxyl group-containing resin described in Japanese Patent Application Publication No. 2017-11453, a carboxyl group-containing resin described in Japanese Patent Application Publication No. 2018-53215, a polymer containing a structural unit having a carboxyl group described in Japanese Patent Application Publication No. 2016-151744, and a copolymer (A) described in Japanese Patent Application Publication No. 2005-234362 can be used.

Specific examples of the carboxyl group-containing resin include epoxy acrylate resins obtained by reacting acrylic acid or methacrylic acid with a resol novolac type epoxy resin; acid-modified unsaturated epoxy ester resins obtained by reacting an unsaturated carboxylic acid with a polyfunctional epoxy compound and further reacting a polyacid or an anhydride thereof; and unsaturated modified acrylic resins into which an ethylenically unsaturated group is introduced by reacting an epoxy compound containing an ethylenically unsaturated group with an acrylic resin having a structural unit obtained by polymerizing a compound selected from acrylic acid and methacrylic acid.

The polyfunctional epoxy compound may be any compound as long as it has at least two epoxy groups in one molecule. Examples of the polyfunctional epoxy compound include bisphenol-type epoxy resins such as bisphenol A-type epoxy resins, bisphenol F-type epoxy resins, and bisphenol AD-type epoxy resins, biphenyl-type epoxy resins, naphthalene-type epoxy resins, dicyclopentadiene-type epoxy resins, rubber-modified epoxy resins such as silicone-modified epoxy resins, ε-caprolactone-modified epoxy resins, linear novolac-type epoxy resins such as bisphenol A-type, bisphenol F-type, and bisphenol AD-type, resol-type novolac-type epoxy resins such as o-resole novolac-type, cyclic aliphatic polyfunctional epoxy resins, glycidyl ester-type polyfunctional epoxy resins, glycidyl amine-type polyfunctional epoxy resins, heterocyclic polyfunctional epoxy resins, bisphenol-modified novolac-type epoxy resins, polyfunctional modified novolac-type epoxy resins, and epoxy resins which are condensates of phenols and aromatic aldehydes having phenolic hydroxyl groups. Furthermore, resins obtained by introducing halogen atoms such as Br and Cl into these resins may also be used. The polyfunctional epoxy compound may be a glycidyl-type epoxy compound having a glycidyl group, or an epoxy compound having an oxidized cycloolefin structure.

These polyfunctional epoxy compounds may be used alone or in combination of two or more.

As the unsaturated carboxylic acid, for example, unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, and cinnamic acid can be cited. Of these unsaturated monocarboxylic acids, acrylic acid or methacrylic acid is preferred. This is because the balance between the curability of the composition and the heat resistance of the cured product is more excellent.

The reaction method of the polyfunctional epoxy compound and the unsaturated monocarboxylic acid is not particularly limited, and for example, the polyfunctional epoxy compound and the unsaturated monocarboxylic acid can be reacted by heating them in an appropriate solvent.

As the polybasic acid or its anhydride, any of polysaturated and unsaturated ones may be used.

Examples of the polyacid include succinic acid, maleic acid, adipic acid, citric acid, phthalic acid, tetrahydrophthalic acid, 3-methyltetrahydrophthalic acid, 4-methyltetrahydrophthalic acid, 3-ethyltetrahydrophthalic acid, 4-ethyltetrahydrophthalic acid, hexahydrophthalic acid, 3-methylhexahydrophthalic acid, 4-methylhexahydrophthalic acid, 3-ethylhexahydrophthalic acid, 4-ethylhexahydrophthalic acid, methyltetrahydrophthalic acid, methylhexahydrophthalic acid, methylenetetrahydrophthalic acid, methylmethylenetetrahydrophthalic acid, trimellitic acid, pyromellitic acid, and diglycolic acid.

Examples of the polybasic acid anhydride include anhydrides of the polybasic acids described above.

Examples of the ethylenically unsaturated group-containing epoxy compound include glycidyl methacrylate, 4-hydroxybutyl (meth)acrylate glycidyl ether, and 3,4-epoxycyclohexyl methyl (meth)acrylate.

In addition, the (meth)acryloyl group includes both an acryloyl group and a methacryloyl group.

In addition, (meth)acrylate includes both acrylate and methacrylate.

As the carboxyl-containing resin, a commercially available product can be used. As the commercially available product of the carboxyl-containing resin, for example, ZAR-2000, ZFR-1122, FLX-2089, ZCR-1601H, CCR-1171H, CCR-1235, CCR-1291H, CCR-1307H, CCR-1309H (the above are made by Nippon Kayaku (Co., Ltd.)), CYCLOMER P (ACA) Z-250 (made by Daicel Chemical Industries, Ltd.), Ripoxy SP-4621, SPC-1000, SPC-3000, PR-300CP (made by Showa Polymer (Co., Ltd.)), etc. can be listed.

The acid value of the carboxyl-containing resin can be any value that can form a cured product with excellent durability, for example, preferably 40 mgKOH/g or more and 150 mgKOH/g or less, preferably 50 mgKOH/g or more and 130 mgKOH/g or less. This is because: when the acid value of the carboxyl-containing resin is within the above range, the composition becomes easy to form a cured product with excellent durability. In addition, the composition becomes easy to pattern.

The weight average molecular weight of the carboxyl group-containing resin may be any one that provides a cured product having excellent durability, and a carboxyl group-containing resin of 1,000 or more may be used.

From the viewpoint of easy patterning, the weight average molecular weight of the above-mentioned carboxyl-containing resin is preferably, for example, 2,000 or more and 150,000 or less, and preferably 5,000 or more and 100,000 or less. This is because: the above-mentioned composition becomes easy to form a cured product with excellent durability by having the average molecular weight of the above-mentioned carboxyl-containing resin in the above-mentioned range. In addition, the above-mentioned composition becomes easy to pattern.

The weight average molecular weight Mw of the above-mentioned carboxyl group-containing resin can be measured, for example, using HLC-8120GPC manufactured by Tosoh Corporation, setting the elution solvent to N-methylpyrrolidone added with 0.01 mol/L lithium bromide, setting the calibration curve to polystyrene standards of Mw377,400, 210,500, 96,000, 50,400, 20,650, 10,850, 5,460, 2,930, 1,300, 580 (the above are EasiPS-2 series manufactured by Polymer Laboratories) and Mw1,090,000 (manufactured by Tosoh Corporation), and setting the measurement column to TSK-GEL ALPHA-M×2 (manufactured by Tosoh Corporation). In addition, the measurement temperature can be set to 40°C and the flow rate can be set to 1.0 mL/min.

As the content of the free radical polymerizable compound having a carboxyl group, any content that can form a cured product with excellent durability can be used, for example, preferably 1 mass part or more and 90 mass parts or less, more preferably 20 mass parts or more and 80 mass parts or less, preferably 30 mass parts or more and 70 mass parts or less in 100 mass parts of the solid content of the above-mentioned composition. This is because the above-mentioned composition can easily form a cured product with excellent curability and heat resistance. In addition, the above-mentioned composition can easily form a pattern.

It may also be a compound without a carboxyl group among the above-mentioned free radical polymerizable compounds (hereinafter sometimes referred to as a compound without a carboxyl group). As the compound without a carboxyl group, for example, a compound represented by the following general formula (1) may be preferably used. This is because: by using such a compound, the balance between the curability of the composition of the present application and the heat resistance of the cured product becomes better.

(wherein, R ¹¹¹ represents a hydrogen atom or a methyl group,

X ¹ represents an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 40 carbon atoms and having the same valence as n1; an unsubstituted or substituted aromatic hydrocarbon group having 6 to 40 carbon atoms and having the same valence as n1; an unsubstituted or substituted heterocyclic group having 2 to 40 carbon atoms and having the same valence as n1; or a group having 1 to 40 carbon atoms obtained by replacing one or more methylene groups in the unsubstituted or substituted aliphatic hydrocarbon group having the same valence as n1 with a divalent group selected from the above Group I, a group having 6 to 40 carbon atoms obtained by replacing one or more methylene groups in the unsubstituted or substituted aromatic hydrocarbon group having the same valence as n1 with a divalent group selected from the above Group I, or a group having 2 to 40 carbon atoms obtained by replacing one or more methylene groups in the unsubstituted or substituted heterocyclic group having the same valence as n1 with a divalent group selected from the above Group I,

n1 represents an integer from 1 to 10. )

Examples of the unsubstituted or substituted aliphatic hydrocarbon group having the same valence as ⁿ¹ , the unsubstituted or substituted aromatic hydrocarbon group having the same valence as n1, and the unsubstituted or substituted heterocyclic group having the same valence as n1, or a group in which one or more methylene groups in the above-mentioned aliphatic hydrocarbon group, aromatic hydrocarbon group or heterocyclic group are substituted with a divalent group selected from Group I, include the same groups as X in the above-mentioned general formula (A1).

From the viewpoint of improving the curability of the composition, n1 is preferably an integer of 2 to 8, more preferably an integer of 3 to 7, and particularly preferably an integer of 4 to 6. This is because the effect of improving the heat resistance of the obtained cured product can be more effectively exerted.

In the present application, ^X1 in the general formula (1) is preferably an aliphatic hydrocarbon group, or a group in which one or more methylene groups in an aliphatic hydrocarbon group are substituted with a divalent group selected from the above group I, preferably a group in which one or more methylene groups in an aliphatic hydrocarbon group are substituted with a divalent group selected from -O-, -COO-, or -CO-, and particularly preferably a group in which one or more methylene groups in an aliphatic hydrocarbon group are substituted with a divalent group selected from -O-. This is because the effect of achieving a better heat resistance of the obtained cured product can be more effectively exerted.

In the present application, when ^X1 in the general formula (1) is an aliphatic hydrocarbon group, or a group obtained by replacing one or more methylene groups in an aliphatic hydrocarbon group with a divalent group selected from the above group I, the aliphatic hydrocarbon group used is preferably a group obtained by removing n1-1 hydrogen atoms from an alkyl group. This is because the effect of achieving better heat resistance of the obtained cured product can be more effectively exerted.

In the present application, when ^X1 in the general formula (1) is an aliphatic hydrocarbon group, or a group in which one or more methylene groups in an aliphatic hydrocarbon group are substituted with a divalent group selected from the above group I, the number of carbon atoms of ^X1 is preferably 2 to 30, particularly preferably 4 to 20, and particularly preferably 6 to 15. This is because the effect of achieving better heat resistance of the obtained cured product can be more effectively exerted.

As the compound without a carboxyl group, any compound having one or more ethylenically unsaturated groups and without a carboxyl group may be used, and examples thereof include compounds obtained by adding α,β-unsaturated carboxylic acids to polyols, compounds obtained by adding α,β-unsaturated carboxylic acids to glycidyl-containing compounds, etc. For such compounds, for example, compounds described as (D) reactive diluents described in Japanese Patent Application Laid-Open No. 2018-053215 may be used.

Specific examples of the compound not having a carboxyl group include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, isobutyl acrylate, n-octyl acrylate, isooctyl acrylate, isononyl acrylate, stearyl acrylate, methoxyethyl acrylate, dimethylaminoethyl acrylate, zinc acrylate, 1,4-butanediol diacrylate, neopentyl glycol diacrylate, 1,6-hexanediol diacrylate, trimethylolpropane triacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, butyl methacrylate, tert-butyl methacrylate, cyclohexanediol diacrylate, Ester, 1,4-butanediol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, polyethylene glycol di(meth)acrylate, isocyanurate di(meth)acrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol tetraacrylate, pentaerythritol triacrylate, caprolactone-modified dipentaerythritol hexa(meth)acrylate, bisphenol A diglycidyl ether (meth)acrylate, bisphenol F diglycidyl ether (meth)acrylate, bisphenol Z diglycidyl ether (meth)acrylate, tripropylene glycol di(meth)acrylate, etc.

As the radical polymerizable compound having no carboxyl group, (meth)acrylate having a phosphate structure such as mono(2-acryloyloxyethyl) acid phosphate may be used.

As the free radical polymerizable compound having no carboxyl group, urethane acrylate, polyester acrylate, epoxy acrylate, etc. can also be used. As commercially available products of such urethane acrylate, polyester acrylate, and epoxy acrylate, for example, compounds described in Japanese Patent Application Laid-Open No. 2018-53215 can be used.

Among the above compounds not having a carboxyl group, a compound that is liquid at room temperature (25° C.) may be used as a diluent for dissolving the above carboxyl group-containing resin or the like.

In the case of containing a compound having an acidic group such as a carboxyl group as a free radical polymerizable compound, the free radical polymerizable component preferably uses a compound having an acidic group and a compound having no acidic group in combination. For example, in the case of containing a compound having a carboxyl group as a free radical polymerizable compound, the free radical polymerizable component preferably uses a compound having a carboxyl group and a compound having no carboxyl group in combination. This is because the curability of the composition and the balance between the heat resistance and alkali developability of the cured product become excellent.

In the case where the curable component includes a compound having an acidic group such as a carboxyl group and a compound not having an acidic group such as a carboxyl group as the free radical polymerizable compound, the content of the free radical polymerizable compound not having an acidic group is preferably 1 mass part or more and 90 mass parts or less, more preferably 5 mass parts or more and 40 mass parts or less, and particularly preferably 10 mass parts or more and 25 mass parts or less in a total of 100 mass parts of the free radical polymerizable compound having an acidic group and the free radical polymerizable compound not having an acidic group. This is because: the curability of the above-mentioned composition becomes excellent, and the heat resistance of the obtained cured product becomes excellent. In addition, the above-mentioned composition can be more easily patterned.

The content of the radical polymerizable component in the composition of the present invention is preferably 10 parts by mass or more and 80 parts by mass or less in 100 parts by mass of the solid content of the above-mentioned composition, more preferably 20 parts by mass or more and 70 parts by mass or less, more preferably 30 parts by mass or more and 60 parts by mass or less, and particularly preferably 40 parts by mass or more and 50 parts by mass or less. This is because: the curability of the above-mentioned composition becomes excellent, and the heat resistance of the obtained cured product becomes excellent. It should be noted that in this specification, for thermosetting compounds, it is set to not contain compounds with free radical polymerizability, and even if it has thermosetting properties, the compound with free radical polymerizability is set to be included in the free radical polymerizable compound rather than the thermosetting compound.

As the thermosetting compound, a compound other than a compound that can be converted to a high molecular weight by radicals can be used. In addition, as the thermosetting compound, a compound that can be converted to a high molecular weight at a temperature of 25° C. or higher is preferred because it is easy to set the curing conditions.

Examples of the thermosetting compound include phenolic resins, urea resins, amino resins, epoxy compounds such as polyfunctional epoxy compounds, cyclic ether compounds such as polyfunctional oxetane compounds, unsaturated polyester resins, benzoguanamine derivatives, isocyanate compounds, blocked isocyanate compounds, maleimide compounds, benzoxazine compounds, oxazoline compounds, carbodiimide compounds, cyclic carbonate compounds, polyfunctional oxetane compounds, and cyclic sulfide compounds such as episulfide resins.

As the above-mentioned polyfunctional epoxy compound, the same compounds as those described as examples used in the formation of the above-mentioned carboxyl-containing resin can be used. As a commercially available product of the above-mentioned polyfunctional epoxy compound, for example, the compound described in Japanese Patent Laid-Open No. 2018-53215 can be used.

As the above-mentioned isocyanate compound, blocked isocyanate compound, polyfunctional oxetane compound, and episulfide resin, for example, a compound having an isocyanate group or a blocked isocyanate group, a polyfunctional oxetane compound, and a resin obtained by replacing the oxygen atom of the epoxy group of a novolac type epoxy resin with a sulfur atom as described in JP-A-2017-111453 can be used.

As the amino resin, for example, melamine derivatives and benzoguanamine derivatives described in JP-A-2017-111453 can be used.

In the present application, the thermosetting compound preferably includes a cyclic ether compound, a cyclic thioether compound, etc., and preferably includes a cyclic ether compound, and particularly preferably includes an epoxy compound, and particularly preferably includes a multifunctional epoxy compound. This is because the balance between the curability of the composition and the heat resistance of the cured product becomes excellent.

The content of the thermosetting compound in the composition of the present invention is preferably 1 part by mass or more and 50 parts by mass or less, more preferably 5 parts by mass or more and 40 parts by mass or less, and particularly preferably 8 parts by mass or more and 20 parts by mass or less, based on 100 parts by mass of the solid content of the composition. This is because the curability of the composition becomes excellent and the heat resistance of the obtained cured product becomes excellent.

The content of the thermosetting compound in the composition of the present invention is preferably 5 parts by mass or more and 60 parts by mass or less, more preferably 10 parts by mass or more and 40 parts by mass or less, and particularly preferably 15 parts by mass or more and 30 parts by mass or less in 100 parts by mass of the total of the free radical polymerizable component and the thermosetting compound. This is because the curability of the above-mentioned composition becomes excellent, and the heat resistance of the obtained cured product becomes excellent.

The content of the curable component in the composition of the present application is appropriately set according to the use of the composition, etc. The content of the curable component is preferably 5 parts by mass or more, preferably 20 parts by mass or more, and particularly preferably 30 parts by mass or more and 99 parts by mass or less in 100 parts by mass of the solid content of the composition. This is because the balance of the curability of the composition and the heat resistance of the cured product becomes excellent when the content is within the above range.

In addition, the so-called solid content includes all components other than the solvent.

The content of the curable component varies depending on the content of the solvent, etc., and is preferably 1 part by mass or more and 99 parts by mass or less in 100 parts by mass of the composition, preferably 10 parts by mass or more and 90 parts by mass or less, and particularly preferably 30 parts by mass or more and 80 parts by mass or less. This is because: by the above content being within the above range, the balance of the curability of the composition and the heat resistance of the cured product becomes excellent.

The content of the curable component is preferably 60 parts by mass or more in 100 parts by mass of the total of the compound A, the metal deactivator and the curable component, preferably 90 parts by mass or more and 99.5 parts by mass or less, and particularly preferably 95 parts by mass or more and 99 parts by mass or less. This is because: when the content of the curable component is within the above range, the balance of the curability of the composition and the heat resistance of the cured product becomes excellent.

4. Curing catalyst

The above composition may contain a curing catalyst in addition to the curable component.

The curing catalyst may be any one that can promote the curing reaction of the curable component and easily form a high molecular weight body composed of two or more curable compounds bonded together, and may be appropriately selected depending on the type of the curable component, the application of the composition, and the like.

When the curable component contains a radical polymerizable compound, the curing catalyst may contain a radical polymerization initiator.

As the radical polymerization initiator, for example, the photo-radical polymerization initiator of the acetophenone-based compounds, benzyl-based compounds, benzophenone-based compounds, thioxanthone-based compounds and oxime ester-based compounds described in International Publication No. 2018/012383, thermal radical polymerization initiators such as azo compounds, peroxides and persulfates, etc. can be used. In addition, as the radical polymerization initiator, the acetophenone-based compounds, benzyl-based compounds, benzophenone-based compounds, thioxanthone-based compounds, bisimidazole-based compounds, acridine-based compounds, acylphosphine-based compounds, etc. described in International Publication No. 2017/170493, International Publication No. 2019/013112, etc. can also be used.

The content of the free radical polymerization initiator in the composition of the present application may be any content that can obtain the desired curability, for example, preferably 0.1 parts by mass or more and 30 parts by mass or less, and preferably 1 part by mass or more and 20 parts by mass or less, relative to 100 parts by mass of the free radical polymerizable compound included as a curable component. This is because: by having the above content within the above range, a composition having an excellent balance of curability and heat resistance of the cured product can be obtained.

When the curable component contains a cyclic ether compound such as a polyfunctional epoxy compound, a polyfunctional oxetane compound, or a cyclic sulfide compound having a plurality of cyclic sulfide groups such as an episulfide resin as a thermosetting compound, the curing catalyst preferably contains a thermosetting agent capable of forming a high molecular weight body of the thermosetting compound. This is because the balance between the curability of the composition and the heat resistance of the cured product is further improved.

Examples of the thermosetting agent include melamine derivatives, imidazole derivatives, amine compounds such as dicyandiamide, hydrazine compounds, phosphorus compounds, S-triazine derivatives, polythiol, acid anhydrides, phenolic resins, and carboxylic acid compounds.

Examples of such a thermosetting agent and commercially available products thereof include compounds described as thermosetting catalysts described in JP-A-2017-111453.

In addition, as melamine derivatives, compounds listed as melamine derivatives described as thermosetting components in Japanese Patent Application Publication No. 2017-111453 can be used. Specifically, as melamine derivatives, specifically, alkoxyalkylated melamine compounds such as methylol melamine compounds, methylol benzoguanamine compounds, methylol glycoluril compounds, methylol urea compounds, and alkoxymethylated melamine compounds, alkoxymethylated benzoguanamine compounds, alkoxymethylated glycoluril compounds, and alkoxymethylated urea compounds can be listed. There is no particular limitation on the type of the above-mentioned alkoxymethyl group, and for example, it can be set to methoxymethyl, ethoxymethyl, propoxymethyl, butoxymethyl, etc.

In the present application, the melamine derivative is preferably an alkoxyalkylated melamine compound because the balance between the curability of the composition and the heat resistance of the cured product becomes excellent.

Commercially available products of melamine derivatives include Nikalac Mx-750, Mx-032, Mx-270, Mx-280, Mx-290, Mx-706, Mx-708, Mx-40, Mx-31, Ms-11, Mw-30, Mw-30HM, Mw-390, Mw-100LM, and Mw-750LM (all manufactured by Sanwa Chemical Co., Ltd.).

In the present application, the heat curing agent is preferably an amine compound, and among them, melamine derivatives, dicyandiamide, etc. are preferred because the balance between the curability of the composition and the heat resistance of the cured product becomes excellent.

The content of the thermosetting agent may be any content that can obtain desired curability, and may be, for example, 0.1 to 50 parts by mass based on 100 parts by mass of the total of the thermosetting composition, and more preferably 0.1 to 50 parts by mass based on 100 parts by mass of the total of the cyclic ether compound and the cyclic sulfide compound. This is because when the content of the thermosetting agent is within the above range, a composition having an excellent balance between curability and heat resistance of the cured product can be obtained.

The preferred amount of the curing catalyst in the present invention is preferably 0.1 to 30 parts by mass, more preferably 1 to 10 parts by mass, relative to 100 parts by mass of the curing component. This is because: by setting the content of the curing catalyst to the above range, a composition having an excellent balance of curability and heat resistance of the cured product can be obtained.

5. Solvent

The composition of the present application may contain a solvent for dispersing or dissolving the compound A, the metal deactivator, and the curable component.

The above-mentioned solvent can be a solvent that is liquid at room temperature (25° C.) and atmospheric pressure.

The solvent is a solvent that can disperse or dissolve the components in the composition such as compound A, metal deactivator and curing component. Therefore, even if it is liquid at room temperature (25°C) and atmospheric pressure, the compound A, metal deactivator and curing component are not included in the solvent. As the solvent, any one of water, organic solvent and mixtures thereof can be used.

As the organic solvent, a known solvent can be used, for example, carbonates such as propylene carbonate; ketones such as methyl ethyl ketone; ether solvents such as ethyl ether; ester solvents such as methyl acetate; alcohol solvents such as methanol and ethanol; ether ester solvents such as propylene glycol-1-monomethyl ether-2-acetate; BTX solvents such as benzene; aliphatic hydrocarbon solvents such as hexane, etc.

As the organic solvent, for example, a solvent that can dissolve or disperse each component in the curable composition described in International Publication No. 2018/012383, an organic solvent described in International Publication No. 2014/021023, etc. can also be used.

The content of the above-mentioned solvent in the composition of the present application can be any content of a composition that can obtain an excellent balance between curability and heat resistance of the cured product, and can be set to 1 part by mass or more and 99 parts by mass or less in 100 parts by mass of the above-mentioned composition, preferably 10 parts by mass or more and 50 parts by mass or less, preferably 20 parts by mass or more and 45 parts by mass or less. This is because: by setting the content of the solvent to the above-mentioned range, the adjustment of the coating properties of the above-mentioned composition becomes easy.

6. Fillers

The composition preferably includes a filler in addition to compound A, a metal deactivator, a curing component, a curing catalyst and a solvent. This is because: by including the filler, the composition becomes a composition excellent in insulation, for example, and can be preferably used as a solder resist used in a printed wiring board, etc.

More specifically, as the filler, fillers used in solder resists and the like can be used, and inorganic fillers and organic fillers can be used.

As the above-mentioned inorganic filler, inorganic fillers formulated in sealing materials such as silicone resin compositions and epoxy resin compositions can be used. For example, silicas such as fused silica, fused spherical silica, crystalline silica, colloidal silica, fumed silica, and silica gel can be listed; metal oxides such as aluminum oxide, iron oxide, titanium oxide, and antimony trioxide; ceramics such as silicon nitride, aluminum nitride, boron nitride, and silicon carbide; minerals such as mica or montmorillonite; metal hydroxides such as aluminum hydroxide and magnesium hydroxide, or substances obtained by modifying them through organic modification treatments, etc.; metal carbonates such as calcium carbonate, calcium silicate, magnesium carbonate, and barium carbonate; metal acid salts such as barium sulfate, or substances obtained by modifying them through organic modification treatments, etc.; pigments such as metal borates and carbon black; carbon fibers, graphite, whiskers, kaolin, talc, glass fibers, glass beads, glass microspheres, silica glass, layered clay minerals, clay, silicon carbide, quartz, aluminum, zinc, etc.

Examples of the organic filler include acrylic beads, polymer fine particles, transparent resin beads, wood powder, pulp, and cotton scraps.

In the present application, among the inorganic fillers, silica, metal oxides, metal acid salts, and talc are preferred, and crystalline silica, talc, barium sulfate, and titanium oxide are particularly preferred because the cured product of the above composition has excellent heat resistance.

The average particle size of the filler may be any average particle size that can achieve the desired durability, and varies depending on the application of the composition. For example, in the case of solder resist application, it is preferably set to 10 nm or more and 100 μm or less. This is because the composition makes the cured product excellent in heat resistance.

It should be noted that, as a method for measuring the above-mentioned average particle size, a laser diffraction scattering method can be used. Specifically, a laser diffraction particle size distribution measuring device (SALD-2000J manufactured by Shimadzu Corporation) etc. can be used. The average particle size can be set to a particle size (median particle size) that reaches 50% of the cumulative particle size distribution from the microparticle side in the number basis.

The content of the filler is preferably 5 parts by mass or more and 500 parts by mass or less, preferably 5 parts by mass or more and 200 parts by mass or less, and preferably 10 parts by mass or more and 150 parts by mass or less, relative to 100 parts by mass of the curable component. This is because: by setting the content of the filler to the above range, a composition having an excellent balance of curability and heat resistance of the cured product can be obtained. In addition, it is easy to form a cured product with excellent durability, for example, it becomes easy to use in solder resists, etc.

As the content of the above-mentioned filler, for example, in 100 parts by mass of the solid content of the above-mentioned composition, it is preferably 1 part by mass or more and 90 parts by mass or less, wherein it is preferably 5 parts by mass or more and 70 parts by mass or less, preferably 10 parts by mass or more and 60 parts by mass or less, and preferably 20 parts by mass or more and 40 parts by mass or less. This is because: by the above-mentioned content being within the above-mentioned range, a composition having an excellent balance of curability and heat resistance of the cured product can be obtained. In addition, it is easy to form a cured product with excellent durability, for example, it becomes easy to use in solder resists, etc.

7. Other ingredients

The composition may contain other components as necessary in addition to the compound A, the metal deactivator, the curing component, the curing catalyst, the solvent, and the filler.

Such other components can be selected according to the purpose of the composition, for example, benzotriazole-based, triazine-based, benzoate-based ultraviolet absorbers; phenol-based, phosphorus-based antioxidants; antistatic agents including cationic surfactants, anionic surfactants, nonionic surfactants, amphoteric surfactants, etc.; flame retardants such as halogen compounds, phosphate ester compounds, phosphoric acid amide compounds, fluororesins or metal oxides, (poly) melamine phosphate, (poly) piperazine phosphate; lubricants such as hydrocarbons, fatty acids, aliphatic alcohols, aliphatic esters, aliphatic amides or metal soaps; colorants such as dyes, pigments, carbon black; crystallizing agents such as nucleating agents and crystallization accelerators, rubber elasticity imparting agents such as silane coupling agents and flexible polymers, sensitizers, etc.

As the other components, an organic polymer may be included as a resin component other than the curable component. As such an organic polymer, an organic polymer listed as an organic polymer in International Publication No. 2014/021023 may be used.

The total content of other components in the composition of the present application can be set to 30 parts by mass or less in 100 parts by mass of the above-mentioned composition.

8. Others

The method for producing the composition may be any method as long as the components can be blended in desired contents, and may be a method in which the components are added simultaneously and mixed, or a method in which the components are added sequentially and mixed.

As the use of the above-mentioned composition, it is preferably used for the use that requires curability and heat resistance of the cured product, and can be used for thermosetting coatings, photocuring coatings or varnishes, thermosetting adhesives, photocuring adhesives, printed substrates, or color filters in liquid crystal display panels for color displays such as color TVs, PC monitors, portable information terminals, and digital cameras, color filters for CCD image sensors, photo spacers, black columnar spacers, electrode materials for plasma display panels, touch panels, touch sensors, powder coatings, printing inks, printing plates, adhesives, dental compositions, photoforming resins, gel coatings, photoresists for electronic engineering, plating resists, etching resists, both liquid and dry films, solder resists, color filters for various display applications or in plasma display panels, electroluminescent display devices The present invention can be used in various applications, such as resists for forming structures in the manufacturing processes of devices, and LCDs, compositions for encapsulating electrical and electronic components, solder resists, magnetic recording materials, micromechanical parts, waveguides, optical openings, masks for plating, etching masks, color test systems, glass fiber cable coatings, templates for screen printing, materials for manufacturing three-dimensional objects by stereolithography, materials for holographic recording, image recording materials, fine circuits, decolorizing materials, decolorizing materials for image recording materials, decolorizing materials for image recording materials using microcapsules, photoresist materials for printed circuit boards, photoresist materials for UV and visible laser direct imaging systems, photoresist materials for forming dielectric layers in successive stacks of printed circuit boards, photoresist materials or protective films for 3D installation, and the like, without any particular limitation on their uses.

In the present application, it can be preferably used for color filters, photo spacers, black columnar spacers, electrode materials, photoresists, solder resists, outer coatings, insulating films, black matrices, partition materials, etc. This is because the effect of excellent balance between curability and heat resistance of the cured product can be more effectively exerted.

Furthermore, these components can be preferably used for forming parts of electronic devices used in transportation equipment such as automobiles and airplanes that require long-term heat resistance, because the effects of excellent balance between curability and heat resistance of the cured product can be more effectively exerted.

B. Solidified

Next, the cured product of the present application will be described.

The cured product of the present application is a cured product formed by curing the above-mentioned composition.

According to the present application, since the above-mentioned composition is used, heat resistance becomes excellent.

The cured product of the present application is a cured product using the above-mentioned composition.

The cured product includes a high molecular weight body formed from the curable component contained in the composition.

The contents of such a composition can be set to be the same as those described in the above-mentioned "A. Composition", and therefore the description here is omitted.

The compound A contained in the cured product may be a compound in which the phenolic hydroxyl group is protected by the protecting group R ¹⁰¹ , or may be a compound in which the protecting group R ¹⁰¹ is removed to generate a phenolic hydroxyl group.

In the present application, from the viewpoint of making a cured product excellent in heat resistance, the compound A is preferably a compound in which the protecting group R ¹⁰¹ is removed to generate a phenolic hydroxyl group.

The plan view shape of the cured product can be appropriately set according to the purpose of the cured product, and can be set to a pattern such as dots or lines, for example.

The uses and the like of the cured product can be the same as those described in the above-mentioned section "A. Composition".

The method for producing the cured product is not particularly limited as long as it is a method that can form a high molecular weight body using the curable component in the composition.

As such a production method, for example, the production method described in the section "C. Production method of cured product" described later can be used.

C. Method for producing cured product

Next, the method for producing the cured product of the present application will be described.

One of the characteristics of the method for producing a cured product of the present application is that it comprises a curing step of curing the above-mentioned composition.

According to the present application, since the above-mentioned composition is used, a cured product having excellent heat resistance can be easily obtained.

1. Curing process

The curing step in the present application is a step of curing the above-mentioned composition.

As a method for curing the above-mentioned composition, a method of forming a high molecular weight body from a curable component can be used.

As a curing method in this step, a method of using a curing catalyst together with the curable component as the above-mentioned composition is mentioned, for example.

When a photopolymerization initiator such as a photoradical polymerization initiator or a photocationic polymerization initiator is included as a curing catalyst, the curing method is preferably a method of curing the curable components by irradiating the composition with light. This is because the curing of the composition becomes easy by using the above curing method.

The light irradiated on the composition is preferably light having a wavelength of 300 nm to 450 nm, because the composition can be easily cured by using light having such a wavelength.

As the light source for the light irradiation, for example, a light emitting diode (LED), ultrahigh pressure mercury, mercury vapor arc, carbon arc, xenon arc, etc. can be preferably used. This is because the use of the above light source facilitates curing of the composition.

Laser light may be used as the irradiation light. As the laser light, laser light including light having a wavelength of 340 to 430 nm may be used.

As a laser light source, a light source that emits light in the visible to infrared region, such as an argon ion laser, a helium-neon laser, a YAG laser, and a semiconductor laser, may be used.

When using these lasers, the composition may contain a sensitizing dye that absorbs in the visible to infrared region.

In the case where a thermal polymerization initiator such as a thermal free radical polymerization initiator or a thermal cationic polymerization initiator is used as a curing catalyst, a thermal curing agent is used as a curing catalyst, a thermal curing compound is used as a curing component, etc., the curing method may preferably use a method of curing the curing components by heating the composition. This is because the curing of the composition becomes easier by performing a heating treatment.

The heating temperature may be any temperature at which the composition can be stably cured, and is preferably set to 60° C. or higher, and preferably 100° C. or higher and 300° C. or lower. This is because the composition can be easily cured by setting the heating temperature to the above range.

The heating time may be about 10 seconds to 3 hours. This is because the composition can be easily cured by heating for such a time.

The above-mentioned curing method may be a method of curing the curable component by light irradiation alone, a method of curing the curable component by heating alone, or a method of curing by light irradiation and a method of curing by heating may be used in combination. When a method of curing by light irradiation and a method of curing by heating are used in combination, for example, light irradiation and heating treatment may be performed simultaneously, or light irradiation and heating treatment may be performed sequentially.

2. Separation process

The production method of the present application includes the above-mentioned curing step, but preferably includes a detachment step of detaching the protecting group R ¹⁰¹ from the compound A from the viewpoint of obtaining a cured product having excellent heat resistance.

Examples of the method for removing the protecting group R ¹⁰¹ in this step include a method of heating the compound A and a method of irradiating the compound A with light.

In this step, when the protecting group ^R101 is an unsubstituted or substituted aliphatic hydrocarbon group, an unsubstituted or substituted aromatic hydrocarbon group, an unsubstituted or substituted heterocyclic group, or an unsubstituted or substituted silyl group having 1 to 40 carbon atoms in which the terminal methylene group on the oxygen atom side is substituted with a divalent group selected from the above group I, the removal method is preferably a method of heating the compound A. This is because the protecting group ^R101 can be easily removed.

In this step, when the protecting group ^R101 is a photo-detachable protecting group such as o-nitrobenzyl, the detachment method is preferably a method of performing a photoirradiation treatment because the detachment of the protecting group ^R101 is easy.

The method for heat-treating the compound A may be any method as long as the protecting group R ¹⁰¹ can be removed from the compound A contained in the composition or its cured product. For example, the method includes heating the composition or its cured product on a hot plate, in an oven, or the like.

The heating temperature for the compound A can be set to a temperature higher than the temperature at which the protecting group R ¹⁰¹ is detached. Specifically, the heating temperature is preferably 80° C. to 300° C., preferably 100° C. to 290° C., preferably 120° C. to 280° C., particularly preferably 150° C. to 250° C., particularly preferably 180° C. to 240° C. This is because the protecting group R ¹⁰¹ is easily detached from the compound A by the heating temperature.

When the composition contains an acid catalyst, a base catalyst or the like, the heating temperature may be set to be lower than the temperature at which the protective group R ¹⁰¹ is separated independently.

The heating temperature can be set in the same manner as described in the section "1. Compound A" of the above "A. Composition".

The heating time can be set to 5 minutes or more and 3 hours or less.

As a method for subjecting the compound A to light irradiation treatment, for example, a method of subjecting a composition or a cured product thereof to light irradiation may be used.

The wavelength of light irradiated on the composition or the cured product can be set in the same manner as described in the above-mentioned "1. Compound A" of "A. Composition".

As the light source for the light irradiation, the light source described in the above-mentioned "1. Curing step" can be used.

The cumulative light amount relative to the compound A can be set to be greater than the cumulative light amount at which the protecting group R ¹⁰¹ is released. The cumulative light amount (cumulative light amount at a wavelength of 300 nm to 430 nm) is preferably 1,000 mJ/cm ² or more and 10,000 mJ/cm ² or less, preferably more than 1,000 mJ/cm ² and 5,000 mJ/cm ² or less, and more preferably 2,000 mJ/cm ² or more and 4,000 mJ/cm ² or less. This is because the protecting group R ¹⁰¹ is easily released from the compound A by setting the cumulative light amount to be greater than the cumulative light amount.

The cumulative light amount can be set to be the same as that described in the item "1. Compound A" of the above-mentioned "A. Composition", for example.

This step may be performed at any timing as long as a cured product having desired heat resistance can be obtained.

For example, when the present step is a step of performing light irradiation treatment, and the curing method in the curing step is a method of curing the curable components by irradiating the composition with light, the implementation timing may be a timing simultaneously with the curing step.

In addition, when this step is a step of performing a heat treatment, and the curing method in the curing step is a method of curing the curable components by irradiating the composition with light, the timing of the implementation is preferably after the light irradiation treatment for curing the curable components in the curing step. This is because the process passing property becomes excellent.

When this step is a step of performing a heat treatment, and the curing method in the above-mentioned curing step is a method of performing a heat treatment on the composition to cure the curable components with each other, the timing of implementing this step can also be to implement it simultaneously with the heat treatment for curing the curable components with each other in the above-mentioned curing step or the post-baking step described later.

3. Other processes

The method for producing the cured product may include other steps as necessary in addition to the curing step and the releasing step.

Examples of the other steps include a developing step of removing uncured portions in a coating film of the composition after the curing step to obtain a patterned cured product, a post-baking step of heat-treating the cured product after the curing step, a pre-baking step of heat-treating the composition before the curing step to remove a solvent in the composition, and a step of forming a coating film of the composition before the curing step.

As a method of removing the uncured portion in the above-mentioned development step, there is mentioned, for example, a method of applying an alkaline developer to the uncured portion.

As the alkali developer, a solution generally used as an alkali developer, such as a tetramethylammonium hydroxide (TMAH) aqueous solution, a potassium hydroxide aqueous solution, and a sodium hydroxide aqueous solution, can be used.

The development step may be performed after the curing step.

The heating conditions in the post-baking step may be any conditions that can improve the strength of the cured product obtained in the curing step, and can be set to, for example, 100° C. to 200° C. for 20 minutes to 90 minutes.

The heating conditions in the prebaking step may be any conditions that can remove the solvent in the composition, and can be set to, for example, 70° C. or higher and 150° C. or lower for 10 minutes to 60 minutes.

As a method for applying the composition in the step of forming a coating film, a known method such as a spin coater, a roll coater, a bar coater, a die coater, a curtain coater, various printings, and dipping can be used.

The above-mentioned coating film can be formed on a substrate.

The substrate may be appropriately selected depending on the application of the cured product, and examples thereof include substrates made of soda glass, quartz glass, semiconductor substrates, metals, paper, and plastics.

Furthermore, the above-mentioned cured product may be formed on a substrate and then peeled from the substrate for use, or may be transferred from the substrate to another adherend for use.

3. Others

The cured product produced by the above production method and its uses and the like can be the same as those described in the above section "A. Composition".

D. Additives

Next, the additive of the present application will be described.

The additive of the present application comprises the compound represented by the above general formula (A1) and a metal deactivator.

According to the present application, since the compound represented by the general formula (A1) and the metal deactivator are contained, by adding to a composition containing a curable component, a composition having an excellent balance between curability and heat resistance of a cured product can be easily formed.

The additive of the present application comprises compound A and a metal deactivator.

1. Compound A and metal passivator

The total content of the compound A and the metal deactivator in the additive of the present application may be set to 100 parts by mass based on 100 parts by mass of the solid content of the additive. That is, the solid content of the additive may be only the compound A and the metal deactivator.

In addition, the total content of the compound A and the metal deactivator can be less than 100 parts by mass in 100 parts by mass of the solid content of the additive, that is, the additive is a composition comprising other components other than the compound A and the metal deactivator, and can be set to, for example, more than 20 parts by mass and less than 99.99 parts by mass. This is because: by the above content being within the above range, it becomes easy to form a composition with further excellent curability and heat resistance of the cured product.

In the present application, from the viewpoint of becoming easy to form a composition with further excellent curability and heat resistance of a cured product, the lower limit of the total content of the above-mentioned compound A and the metal deactivator is preferably 50 parts by mass or more in 100 parts by mass of the solid content of the additive, wherein, preferably 70 parts by mass or more, and particularly preferably 90 parts by mass or more. This is because: by the above-mentioned content being the above-mentioned range, it becomes easy to form a composition with excellent balance of curability and heat resistance of a cured product. In addition, from the viewpoint of becoming easy to control the particle size of the additive, etc., the upper limit of the total content of the above-mentioned compound A and the metal deactivator is preferably 99 parts by mass or less in 100 parts by mass of the solid content of the additive, wherein, preferably 95 parts by mass or less, and particularly preferably 90 parts by mass or less. This is because: by the above-mentioned content being the above-mentioned range, it becomes easy to form a composition with excellent balance of curability and heat resistance of a cured product.

In addition, the compound A and the metal deactivator can be set to the same as the contents described in the items "1. Compound A" and "2. Metal deactivator" in the above-mentioned "A. Composition".

The content of the compound A in 100 parts by mass of the total of the compound A and the metal deactivator can also be set in the same manner as described in the above-mentioned section "A. Composition".

2. Solvent

The additive may include a solvent in addition to the compound A and the metal deactivator.

The solvent may be any solvent capable of dispersing or dissolving the components in the additive, and may be the same as described in the above-mentioned "A. Composition".

The content thereof can be set to 1 part by mass or more and 99 parts by mass or less in 100 parts by mass of the above additives.

3. Other ingredients

The additives may include other components besides the compound A, the metal deactivator and the solvent.

Examples of the other components include those described in the section "5. Other components" of the above-mentioned "A. Composition".

The content of the above-mentioned other components can be appropriately set according to the use of the above-mentioned additives, but can be set to, for example, 50 parts by mass or less, preferably 10 parts by mass or less in 100 parts by mass of the additive. This is because: the above-mentioned additives easily increase the content ratio of compound A and the metal deactivator, and easily form a composition with further excellent curability and heat resistance of the cured product.

4. Others

The properties of the additives can be appropriately set depending on the method of adding to the composition, and can be, for example, liquid, powder, or granular form obtained by dispersing or dissolving the compound A and the metal deactivator in a solvent.

The method for producing the additive may be any method as long as it can produce a composition containing the compound A and the metal deactivator in desired blending amounts.

Examples of uses of the additive include uses in which the additive is added to a composition requiring heat resistance or the like, and preferably uses in which the additive is added to a composition containing a curable component, and particularly preferably uses in which the curable component contains a radical polymerizable compound.

Specifically, the use of the composition can be the same as described in the above-mentioned "A. Composition".

The present application is not limited to the above-mentioned embodiments. The above-mentioned embodiments are merely examples, and any embodiments having substantially the same configuration and exhibiting the same functions and effects as the technical concept described in the claims of the present application are included in the technical scope of the present application.

Example

Hereinafter, the present application will be described in more detail with reference to Examples and the like, but the present application is not limited to these Examples.

[Production Example A1-1]

0.01 mol of a phenolic compound (a compound represented by the following formula (C1-1)), 0.05 mol of di-tert-butyl dicarbonate and 30 g of pyridine were mixed, 0.025 mol of 4-dimethylaminopyridine was added under a nitrogen atmosphere at room temperature, and the mixture was stirred at 60°C for 3 hours to obtain a reaction solution. After cooling to room temperature, the reaction solution was injected into 150 g of ion exchange water, and 200 g of chloroform was added to separate oil and water. After the organic layer was dried over anhydrous sodium sulfate, the solvent was distilled off, and 100 g of methanol was added to the residue for crystallization. The obtained white powdery crystals were dried under reduced pressure at 60°C for 3 hours to obtain the target compound (a compound represented by the following general formula (A1-1)). The obtained white powdery crystals were confirmed to be the target compound by ¹ H-NMR.

[Production Examples A1-2 and A1-3]

Compounds represented by the following formulae (A1-2) to (A1-3) were synthesized in the same manner as in Production Example A1-1 except that the following formulae (C1-2) to (C1-3) were used as phenolic compounds. The obtained white powdery crystals were confirmed to be the target product by ¹ H-NMR.

[Examples 1 to 10 and Comparative Examples 1 to 8]

According to the formulations described in Tables 1 to 4 below, compound A, a metal deactivator, an antioxidant, a curable component, a curing catalyst, a filler, and a solvent were stirred in a degassing stirrer at an initial temperature of 25° C. for 3 minutes to obtain a composition.

In addition, the following materials were used for each component.

In addition, the compounding amount in a table|surface shows the mass part of each component.

(Compound A)

A-1: Compound represented by the above formula (A1-1) produced in Production Example A1-1

A-2: Compound represented by the above formula (A1-2) produced in Production Example A1-2

A-3: Compound represented by the above formula (A1-3) produced in Production Example A1-3

(Metal passivator)

B-1: Compound represented by the following formula (B-1) (benzotriazole compound)

B-2: Compound represented by the following formula (B-2) (benzotriazole compound)

B-3: Compound represented by the following formula (B-3) (hydrazide compound)

B-4: VD-5 (triazine compound) manufactured by Shikoku Chemical Industry Co., Ltd.

B-5: X12-1214A manufactured by Shin-Etsu Silicone Co., Ltd. (benzotriazole compound)

(Antioxidant)

C-1: Compound represented by the above formula (C1-1)

C-2: Compound represented by the above formula (C1-2)

C-3: Compound represented by the above formula (C1-3)

(Curing component: polymerizable compound (radical polymerizable compound))

D1-1: Carboxyl-containing epoxy acrylate resin (radical polymerizable compound, carboxyl-containing resin, solid content acid value 100 mgKOH/g, solid content concentration 67.2 mass %, CCR-1711H manufactured by Nippon Kayaku Co., Ltd., epoxy acrylate obtained by reacting acrylic acid with a carboxyl-containing resol novolac type epoxy resin)

D1-2: Compound represented by the following formula (D1-2) (radical polymerizable compound, compound having no carboxyl group, DPHA, manufactured by Nippon Kayaku Co., Ltd.)

(Curing component: thermosetting compound (epoxy compound))

D2-1: Compound represented by the following formula (D2-1) (thermosetting compound, EPPN-201 manufactured by Nippon Kayaku Co., Ltd., novolac-type epoxy resin)

D2-2: EP-4100 manufactured by IDICO Co., Ltd. (bisphenol A type epoxy resin, epoxy equivalent 190)

(Curing catalyst: free radical polymerization initiator)

E-1: Irgacure 184 (a compound represented by the following formula (E-1), a radical polymerization initiator, manufactured by BASF, an acetophenone compound)

E-2: Irgacure 907 (a compound represented by the following formula (E-2), a radical polymerization initiator, manufactured by BASF, an acetophenone compound)

E-3: Irgacure TPO (a compound represented by the following formula (E-3), a radical polymerization initiator, manufactured by BASF, an acylphosphine oxide compound)

E-4: Irgacure OXE02 (a compound represented by the following formula (E-4), a radical polymerization initiator, manufactured by BASF, an oxime ester compound)

(Curing catalyst: thermal curing agent)

F-1: melamine derivative (Nikala MW-390 manufactured by Sanwa Chemical, alkoxyalkylated melamine compound)

F-2: Dicyandiamide (DICY)

(Bulking Agent)

G-1: Titanium oxide (TIPAQUE CR-80 manufactured by Ishihara Sangyo Co., Ltd., titanium oxide particles surface-treated with Al and Si, average particle size (D50): 0.25 μm)

G-2: Silica (SO-E5 manufactured by Admatechs, silicon oxide particles, average particle size (D50) 1.3 to 1.7 μm)

(Solvent)

H-1: Propylene glycol monomethyl ether acetate (PGMEA)

[evaluate]

The heat resistance and curability of the obtained compositions of Examples and Comparative Examples were evaluated by the following methods.

1. Heat resistance evaluation

(1) Preparation of evaluation samples

Each composition obtained in Examples and Comparative Examples was applied to a 1.6 mm thick FR-4 copper-clad laminate so that the film thickness after curing would be 20 μm, and then dried at 80° C. for 30 minutes.

Next, ultraviolet exposure was performed using a high-pressure mercury lamp at a cumulative light intensity of 500 mJ/cm ² (cumulative light intensity of light with a wavelength of 320 nm to 400 nm).

Next, a heat treatment was performed at 150° C. for 60 minutes to obtain a sample for evaluation.

(2) Heat resistance evaluation

The evaluation sample was exposed to additional ultraviolet light at a cumulative light intensity of 1,000 mJ/ ^cm2 (cumulative light intensity of light with a wavelength of 320 nm to 400 nm), and then heated in a 200°C oven for 90 minutes (heating test). The b* value before and after heating was determined using a colorimeter. The change in b* value (Δb*) before and after the heating test was evaluated according to the following criteria.

++: Δb* less than 5

+: Δb* is 5 or more and less than 10

-: Δb* is 10 or more

It should be noted that the smaller Δb* is, the better the heat resistance can be judged to be.

2. Curing evaluation

(1) Preparation of evaluation samples

The compositions of Examples and Comparative Examples were applied onto a glass substrate so that the film thickness after curing would be 20 μm, and then dried at 80° C. for 30 minutes.

Thereafter, exposure was performed using a high pressure mercury lamp through a photomask (mask opening: 30 μm) (exposure gap: 300 μm, exposure amount: 500 mJ/cm ² (cumulative light amount of light with a wavelength of 320 nm to 400 nm)).

After development was performed for 60 seconds using a 1.0 mass % sodium carbonate aqueous solution as a developer, the resulting film was thoroughly washed with water and post-baked in a clean oven at 150° C. for 60 minutes to fix the pattern, thereby obtaining a sample for evaluation.

(2) Curing evaluation

The obtained pattern of the evaluation sample was observed with an optical microscope, and the line width of the portion corresponding to the mask opening was measured.

+: The obtained line width is 30 μm or more.

-: The obtained line width is less than 30 μm.

It should be noted that the wider the width of the pattern of the cured product is than the set line width, the better the curability can be judged to be.

Table 1

Table 2

Table 3

Table 4

The results shown in Tables 1 to 4 confirm that the curability and heat resistance of the compositions of the embodiments are excellent. As in Comparative Examples 4 to 6, when an antioxidant having a phenolic hydroxyl group other than Compound A is used, the curability is poor even if a metal deactivator is contained. In addition, by comparing Comparative Example 4 with Comparative Example 8, when an antioxidant other than Compound A is contained, the heat resistance improvement effect brought about by the inclusion of the metal deactivator cannot be obtained. On the other hand, as can be judged by comparing Comparative Example 2 with Example 1, in the present invention, by having a metal deactivator in the presence of a compound of formula (A1), curability can be obtained, and a significant heat resistance improvement effect can be obtained. It can also be judged by comparing Comparative Examples 1, 2, 7 and Example 2 that in the present invention, by using the compound of formula (A1) and the metal deactivator in combination, the heat resistance is synergistically improved.

Industrial Applicability

The present application exerts an effect of providing a composition having an excellent balance between curability and heat resistance of a cured product.

Claims (10)

1. A composition comprising:

a compound represented by the following general formula (A1),

Metal deactivator

A curable component which is capable of curing the curable composition,

wherein R is ¹⁰¹ Represents an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 40 carbon atoms, an unsubstituted or substituted aromatic hydrocarbon group having 6 to 40 carbon atoms, an unsubstituted or substituted heterocyclic group having 2 to 40 carbon atoms, or an unsubstituted or substituted silyl group having 0 to 40 carbon atoms, or R ¹⁰¹ Represents an unsubstituted or substituted aliphatic hydrocarbon group, an unsubstituted or substituted aromatic hydrocarbon group, an unsubstituted or substituted heterocyclic group, or an unsubstitutedOr a group having 1 to 40 carbon atoms, wherein 1 or 2 or more methylene groups in the substituted silyl group are substituted with a divalent group selected from the group I,

R ¹⁰² r is R ¹⁰³ Each independently represents a hydrogen atom or an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 40 carbon atoms,

R ¹⁰⁴ represents a halogen atom, a cyano group, a hydroxyl group, a nitro group, a carboxyl group, an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 40 carbon atoms, an unsubstituted or substituted aromatic hydrocarbon group having 6 to 40 carbon atoms, or an unsubstituted or substituted heterocyclic group having 2 to 40 carbon atoms, or R ¹⁰⁴ Represents a group having 1 to 40 carbon atoms in which 1 or more methylene groups in the unsubstituted or substituted aliphatic hydrocarbon group, the unsubstituted or substituted aromatic hydrocarbon-containing group, or the unsubstituted or substituted heterocyclic group are substituted with a divalent group selected from group I,

at R ¹⁰⁴ Where there are plural, plural R' s ¹⁰⁴ And are bonded to each other to form a benzene ring or a naphthalene ring,

at R ¹⁰⁴ Where there are plural, plural R' s ¹⁰⁴ Are sometimes identical, sometimes different,

n represents an integer of 1 to 10,

a1 represents an integer of 0 to 2,

in the case where n is 2 to 10, a plurality of R's are present ¹⁰¹ 、R ¹⁰² 、R ¹⁰³ 、R ¹⁰⁴ And a1 may be the same or different,

x represents a group having a valence of n,

group I: -O-, -COO-, -OCO-, -CO-, -CS-, -S-, -SO ₂ -、-NR ²³⁰ -、-NR ²³⁰ -CO-、-CO-NR ²³⁰ -、-NR ²³⁰ -COO-、-OCO-NR ²³⁰ -or-SiR ²³⁰ R ²³¹ -, where R is ²³⁰ R is R ²³¹ Each independently represents a hydrogen atom or an unsubstituted aliphatic hydrocarbon group.

2. The composition of claim 1, wherein the R ¹⁰¹ Is selected from unsubstituted or substituted aliphatic hydrocarbon groups an unsubstituted or substituted aromatic hydrocarbon-containing group, an unsubstituted or substituted heterocyclic group-containing group wherein the methylene group at the oxygen atom side end is selected from the group consisting of-COO-; -CO-, -CS-, -S-, -SO ₂ -、-NR ²³⁰ -、-NR ²³⁰ -CO-、-CO-NR ²³⁰ -、-NR ²³⁰ COO-and SiR ²³⁰ R ²³¹ The divalent group in (a) is substituted with a group having 1 to 40 carbon atoms or an unsubstituted or substituted silyl group having 0 to 40 carbon atoms.

3. The composition of claim 1 or 2, wherein the metal deactivator comprises at least 1 of a benzotriazole compound, a hydrazide compound, a salicylic acid compound, and a triazine compound.

4. The composition according to any one of claims 1 to 3, wherein the content of the metal deactivator is 5 parts by mass or more and 90 parts by mass or less based on 100 parts by mass of the total of the compound represented by the general formula (A1) and the metal deactivator.

5. The composition according to any one of claims 1 to 4, wherein the total content of the compound represented by the general formula (A1) and the metal deactivator is 0.01 to 10 parts by mass based on 100 parts by mass of the total of the compound represented by the general formula (A1), the metal deactivator and the curable component.

6. The composition according to any one of claims 1 to 5, wherein the curable component comprises a radical polymerizable compound and a thermosetting compound.

7. The composition according to any one of claims 1 to 6, which is for a solder resist.

8. A cured product of the composition according to any one of claims 1 to 7.

9. A method for producing a cured product comprising a curing step of curing the composition according to any one of claims 1 to 7.

10. An additive, comprising:

a compound represented by the following general formula (A1), and

the metal passivation agent is used for the passivation of the metal,

wherein R is ¹⁰¹ Represents an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 40 carbon atoms, an unsubstituted or substituted aromatic hydrocarbon group having 6 to 40 carbon atoms, an unsubstituted or substituted heterocyclic group having 2 to 40 carbon atoms, or an unsubstituted or substituted silyl group having 0 to 40 carbon atoms, or R ¹⁰¹ Represents a group having 1 to 40 carbon atoms, wherein 1 or 2 or more methylene groups in the unsubstituted or substituted aliphatic hydrocarbon group, the unsubstituted or substituted aromatic hydrocarbon-containing group, the unsubstituted or substituted heterocyclic group, or the unsubstituted or substituted silyl group are substituted with a divalent group selected from group I,

R ¹⁰² r is R ¹⁰³ Each independently represents a hydrogen atom or an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 40 carbon atoms,

R ¹⁰⁴ Represents a halogen atom, a cyano group, a hydroxyl group, a nitro group, a carboxyl group, an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 40 carbon atoms, an unsubstituted or substituted aromatic hydrocarbon group having 6 to 40 carbon atoms, or an unsubstituted or substituted heterocyclic group having 2 to 40 carbon atoms, or R ¹⁰⁴ Represents an unsubstituted or substituted lipidA group having 1 to 40 carbon atoms, which is obtained by substituting 1 or more methylene groups in an aliphatic hydrocarbon group, an unsubstituted or substituted aromatic hydrocarbon-containing group, or an unsubstituted or substituted heterocyclic group with a divalent group selected from group I,

at R ¹⁰⁴ Where there are plural, plural R' s ¹⁰⁴ And are bonded to each other to form a benzene ring or a naphthalene ring,

at R ¹⁰⁴ Where there are plural, plural R' s ¹⁰⁴ Are sometimes identical, sometimes different,

n represents an integer of 1 to 10,

a1 represents an integer of 0 to 2,

in the case where n is 2 to 10, a plurality of R's are present ¹⁰¹ 、R ¹⁰² 、R ¹⁰³ 、R ¹⁰⁴ And a1 may be the same or different,

x represents a group having a valence of n,

group I: -O-, -COO-, -OCO-, -CO-, -CS-, -S-, -SO ₂ -、-NR ²³⁰ -、-NR ²³⁰ -CO-、-CO-NR ²³⁰ -、-NR ²³⁰ -COO-、-OCO-NR ²³⁰ -or-SiR ²³⁰ R ²³¹ -, where R is ²³⁰ R is R ²³¹ Each independently represents a hydrogen atom or an unsubstituted aliphatic hydrocarbon group.