TW202108678A - Composition, cured product, cured product production method, and additive - Google Patents

Abstract

A main problem addressed by the present invention is to provide a composition that provides excellent balance between curability and heat resistance of a cured product. The present invention solves said problem by providing a composition containing: a compound represented by general formula (A1); a sulfur-based antioxidant; and a curable component (refer to the description for R101, R102, R103, R104, n, a1, and X in the formula). The sulfur-based antioxidant is preferably a thioether-based antioxidant.

Description

Composition, hardened product, hardened product manufacturing method and additives

The present invention relates to a composition having an excellent balance between curability and heat resistance of the cured product.

In order to improve the heat resistance of thermoplastic resins, there are situations where antioxidants are added. For example, Patent Document 1 describes adding a sulfur-based antioxidant to a thermoplastic resin. In addition, Patent Document 2 describes adding both a sulfur-based antioxidant and a phenol-based antioxidant to a radical curable resin. Prior art literature Patent literature

Patent Document 1: Japanese Patent Application Publication No. 2017-128697 Patent Document 2: Japanese Patent Application Publication No. 2018-100403

[The problem to be solved by the invention]

However, Patent Document 1 has the following disadvantages: there are cases where it is difficult to pattern; there are cases where the resin melted by heating causes thermal deterioration of other components. The composition described in Patent Document 2 has disadvantages such as insufficient curing. In addition, there are the following disadvantages: there are cases where sufficient heat resistance cannot be obtained; there are cases where discoloration or cracks of the hardened material occur in a high-temperature environment.

The present invention was made in view of the above-mentioned problems, and its main subject is to provide a composition having an excellent balance of curability and heat resistance of the cured product. [Technical means to solve the problem]

The inventors of the present invention made diligent research to solve the above-mentioned problems, and found that by using a sulfur-based antioxidant and a compound of a specific structure in which a phenolic hydroxyl group has been protected by a protective group as an antioxidant, excellent curability and heat resistance are obtained. Excellent cured products, such as cured products with excellent long-term heat resistance in a temperature range of 80°C to 250°C. The inventors of the present invention completed the present invention based on these findings.

That is, the present invention provides a composition containing a compound represented by the following general formula (A1) (hereinafter, sometimes referred to as compound A1), a sulfur-based antioxidant, and a curable component.

[化1]

(In the formula, R ¹⁰¹ represents an unsubstituted or substituted aliphatic hydrocarbon group with 1 to 40 carbon atoms, an unsubstituted or substituted aromatic hydrocarbon-containing group with 6 to 40 carbon atoms, and a carbon atom An unsubstituted or substituted heterocyclic group containing 2-40, an unsubstituted or substituted silyl group with 0-40 carbon atoms, or the aliphatic hydrocarbon group or the aromatic hydrocarbon-containing group One or more of the heterocyclic group or the methylene group in the silyl group is substituted with a divalent group selected from the following group I, R ¹⁰² and R ¹⁰³ are each independently Represents a hydrogen atom or an unsubstituted or substituted aliphatic hydrocarbon group with 1-40 carbon atoms, R ¹⁰⁴ represents a halogen atom, a cyano group, a hydroxyl group, a nitro group, a carboxyl group, an unsubstituted or a C 1-40 aliphatic hydrocarbon group Substituent aliphatic hydrocarbon group, unsubstituted or substituted aromatic hydrocarbon-containing group with 6 to 40 carbon atoms, unsubstituted or substituted heterocyclic ring-containing group with 2 to 40 carbon atoms , Or one or more of the methylene groups in the aliphatic hydrocarbon group, the aromatic hydrocarbon-containing group or the heterocyclic group-containing group are substituted with a divalent group selected from the following group I when group R ¹⁰⁴ in the presence of a plurality of situation, there are plural R ¹⁰⁴ bonded to each other to form a benzene or naphthalene ring of the case, in case of presence of a plurality of R ^104, there are a plurality of R ¹⁰⁴ are the same case, There are also different situations, n represents an integer from 1 to 10, a1 represents an integer from 0 to 2, when n is 2 to 10, there are plural R ¹⁰¹ , R ¹⁰² , R ¹⁰³ , R ¹⁰⁴ and a1 They can be the same or different, and X represents the n-valent base) 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 invention, the curability of the above composition and the heat resistance of the cured product have an excellent balance.

In the present invention, R ^{101 is} preferably an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 40 carbon atoms, an unsubstituted or substituted aromatic hydrocarbon-containing group having 6 to 40 carbon atoms, Or an unsubstituted or substituted heterocyclic-containing group having 2 to 40 carbon atoms has a methylene group at the end of the oxygen atom side substituted with a divalent group selected from the above group I, or Unsubstituted or substituted silyl group with 0-40 carbon atoms. The reason is that by making R ¹⁰¹ the above-mentioned group, it becomes one having an excellent balance between curability and heat resistance of the cured product.

In the present invention, the sulfur-based antioxidant is preferably a thioether-based antioxidant. The reason for this is that the above-mentioned composition becomes more excellent in the balance of curability and heat resistance of the cured product.

In the present invention, the above-mentioned thioether antioxidant is preferably at least one selected from the group consisting of the following general formulas (B1), (B2), (B3) and (B4). The reason is that the thioether-based antioxidant is a compound represented by each of the above general formulas, so that the balance between the curability and the heat resistance of the cured product is more excellent.

[化2]

(In the formula, R ¹ and R ² each independently represent an aryl group with 6 to 20 carbon atoms, an alkyl group with 3 to 30 carbon atoms, or one or more of the methylene groups in the alkyl group. Substituted with -O- or -S-, R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ each independently represent a hydrogen atom and the number of carbon atoms is 1-8 The alkyl group, or one or more of the methylene groups in the alkyl group is substituted with -O- or -S-. One or more of the hydrogen atoms of the above-mentioned alkyl group may be Substitution is alkoxy, alkenyl, alkenyloxy, hydroxy or cyano, and one or more of the hydrogen atoms of the aryl group may be substituted with hydroxy or alkyl with 1 to 8 carbon atoms)

[化3]

(In the formula, R ¹¹ represents an aryl group with 6 to 20 carbon atoms, an alkyl group with 3 to 30 carbon atoms, or one or more of the methylene groups in the alkyl group are substituted with -O- or -S-, R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ and R ¹⁹ each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. One or more of the hydrogen atoms of the group may be substituted with alkoxy, alkenyl, alkenyloxy, hydroxy, or cyano, and one or more of the hydrogen atoms of the above aryl group may be substituted with hydroxy or Alkyl group with 1 to 8 carbon atoms)

[化4]

(In the formula, R ²¹ , R ²² , R ²³ and R ²⁴ each independently represent an alkyl group having 3 to 30 carbon atoms, or one or more of the methylene groups in the alkyl group are substituted with -O -Or -S-, one or more of the hydrogen atoms of the alkyl group may be substituted with alkoxy, alkenyl, alkenyloxy, hydroxyl or cyano

[化5]

(In the formula, R ³¹ and R ³² each independently represent a hydrogen atom, an aryl group with 6 to 20 carbon atoms, an alkyl group with 3 to 30 carbon atoms, or one or two of the methylene groups in the alkyl group. More than one group substituted with -O- or -S-, L ¹ and L ² each independently represent an alkylene group having 1 to 8 carbon atoms, 1 of the above-mentioned alkyl group and the hydrogen atom of the above-mentioned alkylene group One or two or more may be substituted with alkoxy, alkenyl, alkenyl, hydroxy, or cyano, and one or two of the hydrogen atoms of the aryl group may be substituted with hydroxy or with 1-8 carbon atoms Of alkyl)

^{In the present invention, R 1} and R ² in the formula (B1) are each independently an alkyl group having 8 to 20 carbon atoms, and R ¹¹ in the formula (B2) is an alkyl group having 8 to 20 carbon atoms, and the formula (B3) ) In R ²¹ , R ²² , R ²³ and R ²⁴ are each independently an alkyl group having 8 to 20 carbon atoms, and R ³¹ and R ³² in formula (B4) are each independently preferably having 8 to 20 carbon atoms alkyl. This is because the thioether-based antioxidant is a compound having the above-mentioned structure, and the balance between the curability and the heat resistance of the cured product is more excellent.

In the present invention, the above-mentioned thioether antioxidant is preferably a compound represented by the above-mentioned general formula (B3) or (B4). The reason is that the thioether-based antioxidant is a compound represented by each of the above general formulas, so that the balance between the curability and the heat resistance of the cured product is more excellent.

In the present invention, the content of the compound represented by the general formula (A1) in 100 parts by mass of the compound represented by the general formula (A1) and the sulfur-based antioxidant is preferably 10 parts by mass or more and 70 parts by mass the following. The reason is that by setting the content of the compound represented by the general formula (A1) and the sulfur-based antioxidant in the above range, the balance between the curability and the heat resistance of the cured product is more excellent.

In the present invention, the curable component preferably contains a radically polymerizable compound. The reason is that the effect of obtaining a cured product excellent in heat resistance can be effectively obtained.

The present invention provides a cured product obtained by curing the above-mentioned composition. According to the present invention, since the above-mentioned composition is used, it is excellent in heat resistance.

The present invention provides a method for manufacturing a hardened product, which has a hardening step for hardening the above-mentioned composition. According to the present invention, since the above-mentioned composition is used, a cured product excellent in heat resistance can be easily obtained.

The present invention provides an additive containing a compound represented by the following general formula (A1) and a sulfur-based antioxidant.

[化6]

(In the formula, R ¹⁰¹ represents an unsubstituted or substituted aliphatic hydrocarbon group with 1 to 40 carbon atoms, an unsubstituted or substituted aromatic hydrocarbon-containing group with 6 to 40 carbon atoms, and a carbon atom An unsubstituted or substituted heterocyclic group containing 2-40, an unsubstituted or substituted silyl group with 0-40 carbon atoms, or the aliphatic hydrocarbon group or the aromatic hydrocarbon-containing group , One or more of the heterocyclic group or the methylene group in the silyl group is substituted with a divalent group selected from the following group I, R ¹⁰² and R ¹⁰³ are each independently Represents a hydrogen atom or an unsubstituted or substituted aliphatic hydrocarbon group with 1-40 carbon atoms, R ¹⁰⁴ each independently represents a halogen atom, a cyano group, a hydroxyl group, a nitro group, a carboxyl group, and a C 1-40 Substituted or substituted aliphatic hydrocarbon groups, unsubstituted or substituted aromatic hydrocarbon-containing groups with 6 to 40 carbon atoms, unsubstituted or substituted heterogeneous groups with 2 to 40 carbon atoms One or more of the methylene groups in the cyclic group, or the aliphatic hydrocarbon group, the aromatic hydrocarbon-containing group, or the heterocyclic group-containing group is substituted with a divalent group selected from the following group I from the group, there is to the case where a plurality of R ^104, R ¹⁰⁴ has a plurality bonded to each other to form a benzene or naphthalene ring of the case, there is to the case where a plurality of R ^104, R ¹⁰⁴ each have a plurality of identical There are also different situations. n represents an integer from 1 to 10, and a1 represents an integer from 0 to 2. When n is 2 to 10, there are multiple R ¹⁰¹ , R ¹⁰² , R ¹⁰³ , R ¹⁰⁴ And a1 can be the same or different, respectively, X represents the n-valent base) 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 invention, since it contains the compound represented by the above general formula (A1) and the sulfur-based antioxidant, by adding it to a composition containing a curable component, a balance of curability and heat resistance of the cured product can be easily formed Excellent composition. [Effects of Invention]

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

The present invention relates to a composition and its hardened product, a method of manufacturing the hardened product, and additives added to the composition. Hereinafter, the composition, hardened product, hardened product manufacturing method and additives of the present invention will be described in detail.

A. Composition First, the composition of the present invention will be explained. One of the characteristics of the composition of the present invention is that it contains a compound represented by the following general formula (A1), a sulfur-based antioxidant, and a curable component.

[化7]

(In the formula, R ¹⁰¹ represents an unsubstituted or substituted aliphatic hydrocarbon group with 1 to 40 carbon atoms, an unsubstituted or substituted aromatic hydrocarbon-containing group with 6 to 40 carbon atoms, and a carbon atom An unsubstituted or substituted heterocyclic group containing 2-40, an unsubstituted or substituted silyl group with 0-40 carbon atoms, or the aliphatic hydrocarbon group or the aromatic hydrocarbon-containing group One or more of the heterocyclic group or the methylene group in the silyl group is substituted with a divalent group selected from the following group I, R ¹⁰² and R ¹⁰³ are each independently Represents a hydrogen atom or an unsubstituted or substituted aliphatic hydrocarbon group with 1-40 carbon atoms, R ¹⁰⁴ represents a halogen atom, a cyano group, a hydroxyl group, a nitro group, a carboxyl group, an unsubstituted or a C 1-40 aliphatic hydrocarbon group Substituent aliphatic hydrocarbon group, unsubstituted or substituted aromatic hydrocarbon-containing group with 6 to 40 carbon atoms, unsubstituted or substituted heterocyclic ring-containing group with 2 to 40 carbon atoms , Or one or more of the methylene groups in the aliphatic hydrocarbon group, the aromatic hydrocarbon-containing group or the heterocyclic group-containing group are substituted with a divalent group selected from the following group I when group R ¹⁰⁴ in the presence of a plurality of situation, there are plural R ¹⁰⁴ bonded to each other to form a benzene or naphthalene ring of the case, in case of presence of a plurality of R ^104, there are a plurality of R ¹⁰⁴ are the same case, There are also different situations. n represents an integer from 1 to 10, and a1 represents an integer from 0 to 2. When n is 2 to 10, there are plural R ¹⁰¹ , R ¹⁰² , R ¹⁰³ , R ¹⁰⁴ and a1 respectively Can be the same or different, X represents the base of n valence) 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 invention, by using the compound A1 as the compound represented by the general formula (A1) in combination with a sulfur-based antioxidant, the composition will have an excellent balance of curability and heat resistance of the cured product. Here, although the reason why the composition is excellent in the balance of curability and heat resistance of the cured product by using the compound A1 and the sulfur-based antioxidant in combination is not clear, it is presumed to be as follows.

That is, the compound A1 has a structure in which a phenolic hydroxyl group is protected, and the protective group R ¹⁰¹ can be removed to generate a phenolic hydroxyl group. The compound A1 that has formed a phenolic hydroxyl group (hereinafter referred to as compound A1') exhibits anti-oxidation ability by capturing peroxy radicals, etc., which can improve the heat resistance of the above-mentioned composition and its cured product . In addition, since the compound A1 has a structure in which the phenolic hydroxyl group is protected by the protective group R ¹⁰¹ , it can suppress the hardening inhibition of the curable component compared with, for example, an antioxidant having a phenolic hydroxyl group. Therefore, the composition is excellent in the sensitivity of the hardening reaction, and the occurrence of poor hardening is less, and a hardened product with a higher crosslink density can be obtained. The resulting cured product has a high crosslinking density, so oxygen can be prevented from penetrating into the cured product, and as a result, the oxidative degradation of the curable component and its polymer in a high-temperature environment can be suppressed. As a result, the above-mentioned cured product has excellent heat resistance. Sulfur-based antioxidants decompose hydrogen peroxide to suppress the oxidative degradation of the curable components and high molecular weight substances formed by the hardening of the curable components. In addition, the above-mentioned compound A1' may be decomposed due to the exertion of the antioxidant capacity, and the structure may be changed, and the oxidative degradation inhibitory capacity may disappear. However, the sulfur-based antioxidant can regenerate the compound A1' with oxidative degradation ability from the compound A1' whose oxidative degradation ability has disappeared in the process of inhibiting oxidative degradation. As described above, sulfur-based antioxidants can inhibit the loss of the oxidation degradation ability of compound A1', and obtain long-term heat resistance improvement effects. As mentioned above, by using compound A1 and sulfur-based antioxidants together, it exhibits excellent hardening properties and prevents oxygen from penetrating. It also exhibits antioxidant effects due to different mechanisms such as the capture of peroxy radicals and the decomposition of hydrogen peroxide. Sulfur-based antioxidants produce effects such as regeneration of compound A1', and as a result, the above-mentioned composition has an excellent balance of curability and heat resistance of the cured product. In addition, since the curability and heat resistance of the cured product are excellent, it can exhibit excellent heat resistance in a temperature range of, for example, 80°C or higher and 250°C or lower, among which 90°C or higher and 230°C or lower, especially 100°C or higher and 200°C or lower. Furthermore, due to the excellent curability and heat resistance, the above composition is useful for forming components that require long-term stability in a high-temperature environment, such as electronic equipment used in transportation equipment such as automobiles and aircraft.

The composition of the present invention contains compound A1, sulfur-based antioxidant, and curable component. Hereinafter, each component of the composition of the present invention will be described in detail.

1. Compound A1 Compound A1 is a compound represented by the above general formula (A1). ^{As the aliphatic hydrocarbon groups represented by R 101} , R ¹⁰² , R ¹⁰³ and R ¹⁰⁴ (hereinafter referred to as R ¹⁰¹ etc.) in the general formula (A1) (hereinafter, also collectively referred to as "R ¹⁰¹ etc.""Aliphatic hydrocarbon group") can be one that contains only hydrogen atoms and carbon atoms and does not contain an aromatic hydrocarbon ring or a heterocyclic ring. The hydrocarbon group is one 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 and the like include an alkyl group having 1 to 40 carbon atoms, an alkenyl group having 2 to 40 carbon atoms, a cycloalkyl group having 3 to 40 carbon atoms, and 4-40 cycloalkylalkyl groups and groups in which one or two or more of the hydrogen atoms of these groups are substituted with the substituents described below.

As ^{the C1-C40 alkyl group represented by R 101} etc., a group containing only a hydrogen atom and a carbon atom 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 linear alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and the like. Examples of branched alkyl groups include isopropyl, second butyl, tertiary butyl, isobutyl, isopentyl, tertiary pentyl, 2-hexyl, 3-hexyl, and 2-heptyl. Base, 3-heptyl, isoheptyl, third heptyl, 1-octyl, isooctyl and third octyl, etc.

As ^{the alkenyl group having 2 to 40 carbon atoms represented by R 101} and the like, a group containing only a hydrogen atom and a carbon atom can be used. The alkenyl group having 2 to 40 carbon atoms may be a straight-chain alkenyl group or a branched-chain alkenyl group. For example, vinyl, ethylene, 2-propenyl, 3-butenyl, 2-butenyl, 4-pentenyl, 3-pentenyl, and 4-dodecenyl can be mentioned. As a branched alkenyl group, 4,8,12-tetradecatrienyl allyl etc. are mentioned, for example.

As ^{the cycloalkyl group having 3 to 40 carbon atoms represented by R 101} etc., a group containing only a hydrogen atom and a carbon atom 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 two or more of the hydrogen atoms in the cycloalkyl group having 3 to 40 carbon atoms may be substituted with 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 cyclo Decyl and others. As the saturated polycyclic alkyl group, for example, adamantyl group, decahydronaphthyl group, octahydrocyclopentadienyl group, bicyclo[1.1.1]pentyl group, etc. may be mentioned. Examples of the alkyl group substituted by the hydrogen atom in the ring of the saturated monocyclic alkyl group or the saturated polycyclic alkyl group include those exemplified above as the alkyl group having 1 to 40 carbon atoms represented by ^{R 101 etc.} The same basis. As a group in which one or two or more of the hydrogen atoms in the ring of the saturated polycyclic alkyl group are substituted with an alkyl group, for example, a 𦯉 group can be mentioned.

The cycloalkylalkyl group having 4 to 40 carbon atoms represented by R ¹⁰¹ and the like means a group having 4 to 40 carbon atoms in which the hydrogen atom of the alkyl group is substituted by 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, 3-cyclopentylpropyl, and the like. Examples of the saturated polycyclic alkylalkyl group having 4 to 40 carbon atoms include 3-3-adamantylpropyl and decahydronaphthylpropyl.

In the present invention, the number of carbon atoms contained in a group refers to the number of carbon atoms contained in the substituted group when the hydrogen atom in the group is substituted by a substituent. For example, in the case where the hydrogen atoms of an alkyl group with 1-40 carbon atoms are substituted, the so-called carbon atoms 1-40 refers to the number of carbon atoms after the hydrogen atom is replaced, not the carbon atom before the hydrogen atom is replaced number. Furthermore, in the present invention, the number of carbon atoms in a group in which a methylene group in a group with a specific number of carbon atoms is substituted with a divalent group is defined as the number of carbon atoms in the group before the substitution Those with the same requirements. For example, in this specification, the number of carbon atoms of the group in which the methylene group in the alkyl group having 1 to 40 carbon atoms is substituted with a divalent group is set to 1 to 40.

As the above-mentioned R ¹⁰¹ and R ¹⁰⁴ (hereinafter, referred to as R ^104, etc.), the aromatic hydrocarbon-containing group having 6 to 40 carbon atoms (hereinafter, also collectively referred to as the aromatic-containing group represented by ^{R 104, etc.)} Group of hydrocarbons") can be those containing an aromatic hydrocarbon ring containing only hydrogen 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: an aryl group having 6 to 40 carbon atoms, an arylalkyl group having 7 to 40 carbon atoms, and the hydrogen atom of an aliphatic hydrocarbon group is substituted A group formed by an aryl group, and a group formed by substituting one or two or more of the hydrogen atoms of these groups with the substituent mentioned later. Furthermore, as for the aliphatic hydrocarbon group whose hydrogen atom is to be replaced by an aryl group, one that satisfies the specified number of carbon atoms among the aliphatic hydrocarbon groups represented by ^{R 101 and the like can be mentioned.}

The aryl group having 6 to 40 carbon atoms represented by the above-mentioned R ^{104 and the like may be an aromatic group.} The above-mentioned aryl group may have a monocyclic structure or may have a condensed ring structure. Furthermore, the above-mentioned aryl group may be formed by linking an aryl group of a monocyclic structure and an aryl group of a single ring structure, or may be formed by linking an aryl group of a monocyclic structure and an aryl group of a condensed structure, or may be It is formed by connecting the aryl group of the condensed structure and the aryl group of the condensed structure. As a linking group linking two aryl groups, a single bond and a carbonyl group may, for example, be mentioned. The hydrogen atom in the above aryl group may be substituted with an unsubstituted or substituted aliphatic hydrocarbon group. As an aryl group having a monocyclic structure, for example, a phenyl group, a biphenyl group, a benzophenone, etc. may be mentioned. Examples of the aryl group having a condensed ring structure include naphthyl, anthracenyl, phenanthryl, and pyrenyl. Examples of the unsubstituted or substituted aliphatic hydrocarbon group substituted for the hydrogen atom in the above aryl group include the unsubstituted or substituted aliphatic hydrocarbon group ^{shown as R 101} and the like above, which has 1 to 40 carbon atoms. The aliphatic hydrocarbon groups are the same as those exemplified. The unsubstituted or substituted aliphatic hydrocarbon group substituted by the hydrogen atom in the above aryl group is preferably an unsubstituted alkyl group having 1 to 4 carbon atoms and an alkyl group having 1 to 4 carbon atoms All hydrogen atoms are substituted with halogen atoms.

As the arylalkyl group having 7-40 carbon atoms represented by ^{R 104} and the like, one or more of the hydrogen atoms in the alkyl group represented by ^{R 101 and the like are substituted by R 104} and the like. The aryl group becomes the base and so on. Examples of the arylalkyl group having 7 to 40 carbon atoms include benzyl, stilbyl, indenyl, 9- stilbylmethyl, α-methylbenzyl, α,α-dimethylbenzyl , Phenylethyl and naphthylpropyl, or groups in which the hydrogen atoms in these groups are substituted with unsubstituted or substituted aliphatic hydrocarbon groups, etc. Examples of the unsubstituted or substituted aliphatic hydrocarbon group in which the alkyl group in the arylalkyl group and the hydrogen atom in the arylalkyl group are substituted include those with the number of carbon atoms shown ^{as R 101 and the like.} ~40 unsubstituted or substituted aliphatic hydrocarbon groups are the same as those exemplified.

As the heterocyclic ring-containing group having 2 to 40 carbon atoms represented by ^{R 104 and the like (hereinafter, also collectively referred to as "heterocyclic ring-containing group represented by R 104} and the like"), a group containing a hydrogen atom and carbon can be used. A heterocyclic group of a ring of atoms other than atoms. The above-mentioned heterocyclic ring-containing group may be unsubstituted or may have a substituent. Examples of the heterocyclic ring-containing group include: tetrahydrofuranyl, dioxolane, tetrahydropiperanyl, linolinylfuryl, thienyl, methylthienyl, hexylthienyl, and benzothienyl , Pyrrolyl, pyrrolidinyl, imidazolyl, imidazolidinyl, imidazolinyl, pyrazolyl, pyrazolidinyl, piperidinyl and piperidinyl and other heterocyclic rings; the hydrogen atoms in these heterocyclic rings are replaced by A group formed from an unsubstituted or substituted aliphatic hydrocarbon group; one or more of the hydrogen atoms of the aliphatic hydrocarbon group is substituted with the above-mentioned heterocyclic group; one of the hydrogen atoms of the aliphatic hydrocarbon group Or two or more groups which are substituted with the substituent mentioned later. As the aliphatic hydrocarbon group substituted with the heterocyclic ring-containing group, those exemplified as the unsubstituted or substituted aliphatic hydrocarbon group having 1 to 40 carbon atoms represented by ^{R 101 and the like can be mentioned.} In addition, in this specification, the "2-40" in the "heterocyclic ring-containing group having 2 to 40 carbon atoms" specifies the number of carbon atoms of the "heterocyclic ring-containing group" instead of the "heterocyclic ring".

The ^{silyl group with 0-40 carbon atoms represented by R 101} may be unsubstituted or may have a substituent. Examples of the above-mentioned silyl group include: a silyl group in which a hydrogen atom is not substituted, a substituted silyl group in which a hydrogen atom is substituted by another substituent, and one or more of the hydrogen atoms of these groups are substituted by the substituent described later The base and so on. Examples of the above-mentioned substituted silyl groups include: monoalkylsilyl groups such as monomethylsilyl groups, monoarylsilyl groups such as monophenylsilyl groups, dialkylsilyl groups such as diethylsilyl groups, and diphenyl groups. Diarylsilyl groups such as trimethylsilyl groups, trialkylsilyl groups such as trimethylsilyl groups, triarylsilyl groups such as triphenylsilyl groups, monoalkyldiarylsilyl groups such as methyldiphenylsilyl groups, Dialkyl monoarylsilyl groups such as dimethylphenylsilyl group.

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

Two or more of the aliphatic hydrocarbon group, aromatic hydrocarbon-containing group, or heterocyclic group-containing methylene group is substituted with a divalent group selected from the above group I, and a plurality of the divalent groups They may be the same or different from each other, and the divalent groups are not adjacent to each other.

As the above-mentioned aliphatic hydrocarbon group, one or two or more of the methylene groups are substituted with divalent groups selected from the above-mentioned group I. When the aliphatic hydrocarbon group is an alkyl group, for example: The methylene group at the end of the benzene ring side of the alkyl group is substituted with an -O- group, that is, an alkoxy group or the like. In addition, as the group represented by -OR ¹⁰¹ bonded to the benzene ring, the methylene group at the -O-side terminal of R ¹⁰¹ is substituted with -CO-O-, that is, -O-CO The group represented by -OR (R represents a group other than the methylene group at the end of the oxygen atom of ^{R 101) and the like.} In addition, the above-mentioned divalent group is selected so that the oxygen atoms are not adjacent to each other. For example, when the methylene group on the -O- side of R ^{101 of "-OR 101} " is substituted with a divalent group selected from the above group I, as the above divalent group, -O-, -OCO-, for example, select -COO-, _{-CO-, -CS-, -S-, -SO-, -SO 2} -, -NR ²³⁰ -, -NR ²³⁰ -CO-, -CO-NR ²³⁰ -, -NR ²³⁰ -COO- or -SiR ²³⁰ R ²³¹ -. In the present invention, usually the divalent group substituted with the methylene group is selected in a non-adjacent manner. That is, the methylene group substituted by the divalent group is selected in a non-adjacent manner. As the unsubstituted aliphatic hydrocarbon group with 1 to 40 carbon atoms used ^{in R 230} and R ²³¹ in the above group I, the ^{aliphatic hydrocarbon group used in the above R 101} and the like can be used with an unsubstituted hydrogen atom Substituted base.

One or more of the aliphatic hydrocarbon group, aromatic hydrocarbon-containing group, heterocyclic group-containing group, silyl group, and methylene groups in these groups described in the general formula (A1) are substituted with Substituents substituted with hydrogen atoms in groups formed from divalent groups selected from the above group I, more specifically, as the above-mentioned alkyl group, alkenyl group, cycloalkyl group, cycloalkylalkyl group, aryl group, One or more of arylalkyl groups, heterocyclic ring-containing groups and silyl groups, and one or more of the methylene groups in these groups are substituted with hydrogen in the group formed by the divalent group selected from the above group I Substituents with one or more atoms substituted, for example, ethylenically unsaturated groups such as vinyl, allyl, acrylic, and methacrylic; halogen atoms such as fluorine, chlorine, bromine, and iodine ; Acetyl, 2-chloroacetyl, propionyl, octyl, acryloyl, methacryloyl, phenylcarbonyl (benzyl), phthaloyl, 4-trifluoromethyl Benzyl, p-pentyl, o-hydroxybenzyl, oxalanyl, stearyl, methoxycarbonyl, ethoxycarbonyl, tertiary butoxycarbonyl, n-octadecyloxy Acetyl groups such as carbonyl and aminoformyl; acetoxy groups such as acetoxy and benzyloxy groups; amino groups, ethylamino groups, dimethylamino groups, diethylamino groups, butylamino groups, Cyclopentylamino, 2-ethylhexylamino, dodecylamino, anilino, chlorophenylamino, tolylin, methoxyanilin, N-methyl-anilino, diphenyl Amino, naphthylamino, 2-pyridylamino, methoxycarbonylamino, phenoxycarbonylamino, acetylamino, benzylamino, methylamino, p-pentyl Amino, laurylamino, carbamate, N,N-dimethylaminocarbonylamino, N,N-diethylaminocarbonylamino, linolinylcarbonylamino , Methoxycarbonylamino, ethoxycarbonylamino, tertiary butoxycarbonylamino, n-octadecyloxycarbonylamino, N-methyl-methoxycarbonylamino, phenoxycarbonyl Amine group, sulfamoylamino group, N,N-dimethylaminosulfonylamino group, methylsulfonylamino group, butylsulfonylamino group, phenylsulfonylamino group, etc. Substituted amine group; sulfonamide, sulfonyl, carboxyl, cyano, sulfo, hydroxyl, nitro, sulfhydryl, amide, carbamethan, sulfonamide, phosphonic acid, phosphoric acid group , Or carboxyl, sulfo, phosphonic acid, phosphoric acid, etc. That is, as the above-mentioned substituents, ethylenically unsaturated groups, halogen atoms, acyl groups, acyloxy groups, substituted amine groups, sulfonamide groups, sulfonyl groups, carboxyl groups, cyano groups, sulfo groups, Hydroxyl group, nitro group, sulfhydryl group, amide group, carbamethan group, sulfonamide group, phosphonic acid group, phosphoric acid group, or carboxyl, sulfo, phosphonic acid, phosphoric acid salt, etc.

^{Regarding R 101} in the above general formula (A1), from the viewpoint of being easily removed by heat treatment, it is preferably an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 40 carbon atoms, and the number of carbon atoms 6-40 unsubstituted or substituted aromatic hydrocarbon-containing group, or unsubstituted or substituted heterocyclic-containing group with 2-40 carbon atoms, the methylene group at the oxygen atom side terminal A group 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, the oxygen atom side terminal is preferably substituted by the above divalent group The unsubstituted or substituted aliphatic hydrocarbon group with 1-40 carbon atoms, the unsubstituted or substituted aromatic hydrocarbon-containing group with 6-40 carbon atoms, or the unsubstituted aromatic hydrocarbon group with 2-40 carbon atoms A substituted or substituted heterocyclic ring-containing group, or an unsubstituted or substituted silyl group having 0-40 carbon atoms, wherein the carbon atom at the end of the oxygen atom is preferably substituted by -CO-O- An unsubstituted or substituted aliphatic hydrocarbon group of 1-40, particularly preferably an unsubstituted or substituted alkyl group with 1-40 carbon atoms at the end of the oxygen atom substituted by -CO-O-, Among them, an unsubstituted or substituted alkyl group with 1-40 carbon atoms at the end of the oxygen atom substituted by -CO-O- is particularly preferred, that is, -CO-O-R''(R'' is a carbon atom The number 1 to 39 (unsubstituted or substituted alkyl group) represented by the group. In the present invention, the above-mentioned R" is preferably an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms, and particularly preferably an unsubstituted or substituted alkyl group having 1 to 8 carbon atoms , Particularly preferred are unsubstituted alkyl groups with 1 to 8 carbon atoms, and particularly preferred are unsubstituted alkyl groups with 3 to 6 carbon atoms, and particularly preferred are isopropyl, n-butyl, and second Butyl, tertiary butyl, isobutyl, n-pentyl, isopentyl, tertiary pentyl, particularly preferably n-butyl, second butyl, tertiary butyl, isobutyl, tertiary butyl The group, that is, R ¹⁰¹ is a group represented by -CO-OC ₄ H ₉ , among which R ″ is a tertiary butyl group, that is, R ¹⁰¹ is a -CO-O-tertiary butyl group. The reason is that by making the above-mentioned R ¹⁰¹ the above-mentioned group, the above-mentioned compound A1 becomes easy to control the detachment of ^{R 102 by heat treatment.}

^{The temperature at which the protective group R 101} contained in the above compound A1 is released by heat treatment is appropriately set according to the use of the above composition and the like. For example, it can be set to 80°C or higher and 300°C or lower, and 100°C or higher is preferable. 290°C or less, more preferably 120°C or more and 280°C or less, particularly preferably 150°C or more and 250°C or less, and more preferably 180°C or more and 240°C or less. The reason for this is that the balance between the curability and the heat resistance of the cured product becomes more excellent. The desorption temperature can be set to the temperature at which a loss on ignition of 5 mass% is shown by differential thermal analysis. As a measurement method, for example, using STA (differential thermal-thermogravimetric simultaneous measurement device), in an atmosphere of about 5 mg of the sample and 200 mL/min of nitrogen, the heating start temperature is 30℃, the heating end temperature is 500℃, and the heating rate is 10 Measure the loss on ignition of the sample when the temperature is raised at °C/min, and set the temperature at the time point when the weight of the sample at 30 °C is reduced by 5% by mass as the desorption temperature. As a differential calorimeter-thermogravimetry synchronous measuring device, STA7000 (manufactured by Hitachi High-Tech Science Co., Ltd.) can be used.

^{Regarding R 101} in the above general formula (A1), from the viewpoint of being easily released by light irradiation treatment, a photo-detachable protecting group such as o-nitrobenzyl can also be used. Furthermore, when the above-mentioned R ¹⁰¹ is a photo-detachable protecting group, ^{the wavelength of the light at which the protecting group R 101} will desorb from the compound A1 can be set to include, for example, a wavelength of 365 nm, more specifically, it can be set to include The light having a wavelength of 250 nm or more and 450 nm or less can preferably be set to include light having a wavelength of 280 nm or more and 380 nm or less. In order to separate R ¹⁰¹ from the above compound A1, the cumulative light quantity of the irradiated light can be, for example, 1000 mJ/cm ² or more and 10000 mJ/cm ² or less, preferably more than 1000 mJ/cm ² and 5000 mJ/cm ² or less , More preferably 2000 mJ/cm ² or more and 4000 mJ/cm ² or less. The reason for this is that the balance between the curability and the heat resistance of the cured product becomes more excellent.

^{R 102} and R ¹⁰³ in the above general formula (A1) are each independently preferably a hydrogen atom, an alkyl group having 1 to 40 carbon atoms, or one or more of the hydrogen atoms of the alkyl group is further substituted as the above Substituent groups are each independently preferably a hydrogen atom or an unsubstituted or substituted alkyl group having 1 to 40 carbon atoms, and among them, a hydrogen atom or an unsubstituted or substituted alkyl group having 1 to 40 carbon atoms is preferable. The substituted alkyl group is preferably an alkyl group having 1 to 40 carbon atoms, of which an alkyl group having 1 to 10 carbon atoms is preferred, an alkyl group having 2 to 6 carbon atoms is particularly preferred, and an alkyl group having 2 to 6 carbon atoms is particularly preferred. It is _{an alkyl group with 4 carbon atoms represented by -C 4} H ₉ , and a tertiary butyl group is particularly preferred. Preferably, at least one of R ¹⁰² and R ¹⁰³ is an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 40 carbon atoms, and it is preferable that both of R ¹⁰² and R ^{103 have} 1 to carbon atoms. A 40 alkyl group or a group in which one or more of the hydrogen atoms of the alkyl group are further substituted with the above-mentioned substituents, that is, it is preferable that both of R ¹⁰² and R ^{103 have} 1 to 40 carbon atoms The unsubstituted or substituted alkyl group is particularly preferably an unsubstituted alkyl group having 1 to 40 carbon atoms, among which an alkyl group having 1 to 10 carbon atoms is preferred, and an alkyl group having 2 to carbon atoms is particularly preferred. Among them, the alkyl group having ₄ carbon atoms represented by -C 4 H _{9 is} particularly preferred, and the tertiary butyl group is particularly preferred. The reason is that, by making the above-mentioned R ¹⁰² and R ¹⁰³ as the above-mentioned groups, the above-mentioned compound A1 becomes the one with a greater change in antioxidant capacity before and after the ^{protective group R 101 is removed.} Another reason is that the above compound A1 can inhibit the occurrence of hardening inhibition. Therefore, the balance between the curability and the heat resistance of the cured product becomes more excellent. Furthermore, the reason is that synthesis will become easy.

The above-mentioned R ^{104 is} preferably a halogen atom, an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 40 carbon atoms. The reason is that, by making the above-mentioned R ¹⁰⁴ as the above-mentioned group, the above-mentioned compound A1 becomes the one having a greater change in antioxidant capacity before and after the ^{protective group R 101 is removed.} Another reason is that the above compound A1 can inhibit the occurrence of hardening inhibition. Therefore, the balance between the curability and the heat resistance of the cured product becomes more excellent. Furthermore, the reason is that synthesis will become easy.

The above-mentioned a1 is an integer of 0-2, preferably 0-1, and preferably 0. The reason for this is that the above-mentioned composition becomes more excellent in the balance of curability and heat resistance of the cured product.

The above-mentioned n is an integer of 1-10, preferably an integer of 1-6, of which an integer of 1-4 is preferred, and an integer of 2-4 is particularly preferred. The reason is that, by setting the above n in the above range, the above composition becomes more excellent in the balance between the curability and the heat resistance of the cured product.

The above-mentioned X represents an atom or a group of n-valent. As such X, as long as it can obtain the desired curability and heat resistance of the cured product, for example, the group represented by X and the p-alkoxy group described in International Publication No. 2014/021023 may also be used. Substituents to be substituted, groups described as groups represented by X in general formula (1) in JP 2018-150301 A, etc. Regarding the above-mentioned X, more specifically, 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; The base shown in ); the base shown in (II-b); >C=O;>NR⁵³; -OR ⁵³ ; -SR ⁵³ ; -NR ⁵³ R ⁵⁴ ; carbon with the same valence as n An unsubstituted or substituted aliphatic hydrocarbon group with 1-40 atoms; an unsubstituted or substituted aromatic hydrocarbon-containing group with 6-40 carbon atoms with the same valence as n; An unsubstituted or substituted heterocyclic group containing 2-40 carbon atoms with the same number of valences as n; or the aliphatic hydrocarbon group, the aromatic hydrocarbon-containing group, or the heterocyclic-containing group One or two or more of the methylene groups in the group are substituted with divalent groups selected from the following group I, etc.

R ⁵³ and R ⁵⁴ each independently represent a hydrogen atom, an unsubstituted or substituted aliphatic hydrocarbon group with 1 to 40 carbon atoms, and an unsubstituted or substituted aromatic hydrocarbon group with 6 to 40 carbon atoms The group, the unsubstituted or substituted heterocyclic group containing 2-40 carbon atoms, or the aliphatic hydrocarbon group, the aromatic hydrocarbon-containing group or the methylene group in the heterocyclic group One or two or more are substituted with a divalent group selected from the following group I.

When X is a nitrogen atom, a phosphorus atom, a group shown in (II-a) below or a group shown in (II-b) below, n is 3. To X is an oxygen atom, a sulfur atom,> C = O, -NH- CO -, - CO-NH- or> NR ⁵³ of the case, is n-2. When the X group 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 also form a ring together with the benzene ring that is the bonding target of X.

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.

[化8]

(In the formula, * indicates the bonding position)

As an aliphatic hydrocarbon group having the same valence as n as shown by X in the general formula (A1), an aromatic hydrocarbon-containing group having the same valence as n, and having the same number as n The valence of the heterocyclic ring-containing group, for example, can be exemplified by ^{the aliphatic hydrocarbon group shown by R 101} , the aromatic hydrocarbon-containing group, and the heterocyclic ring-containing group after removing "n-1" hydrogen atoms. It meets the specified number of carbon atoms. Examples of the aliphatic hydrocarbon group, aromatic hydrocarbon-containing group, and heterocyclic ring-containing group represented by R ⁵³ and R ^{54 include aliphatic hydrocarbon groups, aromatic hydrocarbon-containing groups, and heterocyclic ring-containing groups represented by R 101} and the like. The base of which meets the specified number of carbon atoms. In addition, the content of the unsubstituted aliphatic hydrocarbon group with 1 to 20 carbon atoms represented ^{by R 230} and R ^{231 in group I can be set to be the same as R 230 in} group I used in ^{R 101 etc.} , R ^{231 is the} same base.

X in the general formula (A1) is preferably an unsubstituted or substituted aliphatic hydrocarbon group with 1-40 carbon atoms having the same valence as n when n is 2-10; An unsubstituted or substituted aromatic hydrocarbon-containing group with 6-40 carbon atoms having the same valence as n; a group with 2-40 carbon atoms having the same valence as n A substituted or substituted heterocyclic-containing group; or one or more of the methylene groups in the aliphatic hydrocarbon group, the aromatic hydrocarbon-containing group, or the heterocyclic-containing group are substituted to be selected from The group consisting of the above group I is a group composed of a divalent group, which 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-containing group with 6-30 carbon atoms having the same valence as n; a group with 3-30 carbon atoms having the same valence as n A substituted or substituted heterocyclic-containing group; or one or more of the methylene groups in the aliphatic hydrocarbon group, the aromatic hydrocarbon-containing group, or the heterocyclic-containing group are substituted to be selected from -O-, -COO-, -OCO- and -CO- group consisting of divalent groups. Particularly preferred is an unsubstituted or substituted aliphatic hydrocarbon group with 10 to 25 carbon atoms having the same valence as n; and an unsubstituted or substituted aliphatic hydrocarbon group with 4 to 25 carbon atoms having the same valence as n A substituted or substituted heterocyclic-containing group; or one or more of the methylene groups in the aliphatic hydrocarbon group or the heterocyclic-containing group are substituted to be selected from -O-, -COO-, -OCO- and -CO- are formed by the divalent group in the group. Particularly preferred is an unsubstituted or substituted aliphatic hydrocarbon group with 14-22 carbon atoms having the same valence as n; and 5-22 carbon atoms having the same valence as n A substituted or substituted heterocyclic-containing group; or one or more of the methylene groups in the aliphatic hydrocarbon group or the heterocyclic-containing group are substituted to be selected from -O-, -COO-, -OCO- and -CO- are formed by the divalent group in the group. The reason is that the balance between the curability of the composition and the heat resistance of the resulting cured product becomes more excellent. In the present invention, (1) when 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. (2) When n is 3, X in the general formula (A1) is preferably a group selected from the following group 2. (3) When n is 4, X in the general formula (A1) is preferably a group selected from the following group 3. (4) When n is 5, X in the general formula (A1) is preferably a group selected from the group 4 below. (5) When n is 6, X in the general formula (A1) is preferably a group selected from the following group 5. (6) When n is 1, X in the general formula (A1) is preferably a hydrogen atom, an unsubstituted or substituted aliphatic hydrocarbon group with 1 to 40 carbon atoms, or an aliphatic hydrocarbon group in the aliphatic hydrocarbon group. One or two or more of the methyl groups are substituted with divalent groups selected from the above group I. The reason for this is that the above-mentioned composition becomes more excellent in the balance of curability and heat resistance of the cured product.

[化9]

(In the formula, Y ¹¹¹ and Y ¹¹⁵ each independently represent an unsubstituted or substituted divalent aliphatic hydrocarbon group with 1 to 8 carbon atoms, or one or two methylene groups in the aliphatic hydrocarbon group The above is substituted with a divalent group selected from the above group I, Y ¹¹² and Y ¹¹⁴ each independently represent -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 with 1-40 carbon atoms, or the aliphatic One or two or more of the methylene groups in the hydrocarbon group are substituted with divalent groups selected from the above group I, Y ¹¹³ represents -CR ²¹⁴ R ²¹⁵ -, -NR ²¹⁶ -, the following general formula The group shown in (103), unsubstituted or substituted divalent aliphatic hydrocarbon group with 1-40 carbon atoms, unsubstituted or substituted divalent aromatic hydrocarbon with 6-40 carbon atoms One or more of the methylene groups in the aliphatic hydrocarbon group or the aromatic hydrocarbon-containing group are substituted with divalent groups selected from the above group I, R ²¹⁴ and R ²¹⁵ each independently represents 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, and R ²¹⁶ represents a hydrogen atom and 1 carbon atom. ~40 unsubstituted or substituted aliphatic hydrocarbon groups, unsubstituted or substituted aromatic hydrocarbon-containing groups with 6 to 40 carbon atoms, unsubstituted or substituted carbon atoms with 2 to 40 One or more of the methylene groups in the heterocyclic ring-containing group or the aliphatic hydrocarbon group, the aromatic hydrocarbon-containing group, or the heterocyclic group-containing group are substituted with those selected from the above group I The base formed by the bivalent base, * indicates the bonding site)

[化10]

(In the formula, Y ¹¹⁹ and Y ¹²⁰ each independently represent an unsubstituted or substituted divalent aliphatic hydrocarbon group with 1 to 8 carbon atoms or one or more methylene groups in the aliphatic hydrocarbon group Substituted with a divalent group selected from the above group I, * indicates the bonding site)

[化11] ＜Group 1＞

(In the formula, R ³¹ represents a hydrogen atom, an unsubstituted or substituted aliphatic hydrocarbon group with 1 to 40 carbon atoms, and an unsubstituted or substituted aromatic hydrocarbon-containing group with 6 to 40 carbon atoms , Unsubstituted or substituted heterocyclic-containing group with 2-40 carbon atoms, or one of the methylene groups in the aliphatic hydrocarbon group, the aromatic hydrocarbon-containing group, or the heterocyclic-containing group Or two or more groups are substituted with divalent groups selected from the above group I, * indicates the bonding site)

[化12] <Group 2>

(In the formula, R ³² represents a hydrogen atom, an unsubstituted or substituted aliphatic hydrocarbon group with 1 to 40 carbon atoms, and an unsubstituted or substituted aromatic hydrocarbon-containing group with 6 to 40 carbon atoms , Unsubstituted or substituted heterocyclic-containing group with 2-40 carbon atoms, or one of the methylene groups in the aliphatic hydrocarbon group, the aromatic hydrocarbon-containing group, or the heterocyclic-containing group Or two or more groups are substituted with divalent groups selected from the above group I. When there are two or more R ³² groups 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 , -PR ⁶³ -Unsubstituted or substituted divalent aliphatic hydrocarbon group with 1-40 carbon atoms, unsubstituted or substituted divalent aromatic hydrocarbon-containing group with 6-40 carbon atoms, number of carbon atoms 2-40 unsubstituted or substituted divalent heterocyclic ring-containing group, or 1 or 2 of the methylene group in the aliphatic hydrocarbon group, the aromatic hydrocarbon-containing group, or the heterocyclic ring-containing group At least one group is substituted with a divalent group selected from the above group I, R ⁶³ represents a hydrogen atom, an unsubstituted or substituted aliphatic hydrocarbon group with 1-40 carbon atoms, and a carbon 6- 40 unsubstituted or substituted aromatic hydrocarbon-containing group, unsubstituted or substituted heterocyclic-containing group with 2-40 carbon atoms, or the aliphatic hydrocarbon group, the aromatic hydrocarbon-containing group One or two or more of the methylene groups in the group or the heterocyclic ring-containing group are substituted with divalent groups selected from the above group I, * represents the bonding site)

[化13] ＜Group 3＞

(In the formula, R ³² represents the same group as R ³² in the above group 2. When there are more than two R ³² in the group, the two or more R ³² may be the same or different, and Z ¹¹ represents the same as the above The base shown by Z ¹¹ in group 2 is the base of the same range, * indicates the bonding position)

[化14] ＜Group 4＞

(In the formula, ^{the groups shown by Z 10} , Z ¹¹ , Z ¹² , Z ¹³ and Z ¹⁴ each independently represent the groups in the same range as the group shown by ^{Z 11 in the above group 2, and * represents the bonding site)}

[化15] <Group 5>

(In the above formula, ^{the groups shown by Z 10} , Z ¹¹ , Z ¹² , Z ¹³ , Z ¹⁴ and Z ¹⁵ each independently represent groups in the same range as the groups shown by ^{Z 11 in group 2 above, and * represents} Bonding site)

Furthermore, as the unsubstituted or substituted divalent aliphatic hydrocarbon group represented by ^{Y 111} , Y ¹¹³ , Y ¹¹⁵ , Y ¹¹⁹ and Y ¹²⁰ , and the unsubstituted or substituted divalent hydrocarbon group represented by Y ¹¹³ The aromatic hydrocarbon-containing group can be independently exemplified from the unsubstituted or substituted aliphatic hydrocarbon group and the unsubstituted or substituted aromatic hydrocarbon-containing group used ^{in R 101, etc. Remove one hydrogen} Those who meet the specified number of carbon atoms in the base after the atom. As the ^{unsubstituted or substituted divalent aliphatic hydrocarbon group represented by Y 111} , Y ¹¹³ , Y ¹¹⁵ , Y ¹¹⁹ and Y ¹²⁰ , one hydrogen atom can be removed from the unsubstituted or substituted alkyl group The following unsubstituted or substituted alkylene groups, etc. ^{Y 111} and Y ¹¹⁵ in the above formula (101) may be the same or different. ^{Y 119} and Y ¹²⁰ in the above formula (103) may be the same or different. Regarding unsubstituted or substituted aliphatic hydrocarbon groups, unsubstituted or substituted aromatic hydrocarbon-containing groups or unsubstituted or substituted aliphatic hydrocarbon groups represented by ^{R 213} , R ²¹⁶ , R ²¹⁷ , R ³¹ and R ³² The heterocyclic ring-containing group of the substituent can be a substituted aliphatic hydrocarbon group, an unsubstituted or substituted aromatic hydrocarbon-containing group or an unsubstituted or substituted aliphatic hydrocarbon group shown in ^{R 101, etc.} The same content for the heterocyclic group. Examples of the C and R ²¹⁵ R ²¹⁴ shown in the alkyl group of 1 to 8, R ²¹⁴ and R ²¹⁵ shown in the aryl and carbon atoms of 6 to 20 carbon atoms of 7 to 20 of the arylalkyl group can be Set the same content as those satisfying the specified number of carbon atoms among the alkyl group, aryl group, and arylalkyl group used in ^{R 101 and the like. The plural Z 11} contained in each formula of group 2 and group 3, ^{Z 10} to Z ¹⁴ contained in each formula of group 4, ^{and Z 10} to Z ¹⁵ contained in each formula of group 5 They may be the same or different.

In the present invention, when n is 2, X is preferably a group represented by the above general formula (101). In the above general formula (101), Y ¹¹¹ and Y ¹¹⁵ are each independently preferably an unsubstituted or substituted divalent aliphatic hydrocarbon group having 1 to 5 carbon atoms, and preferably having 1 to 3 carbon atoms The unsubstituted or substituted divalent aliphatic hydrocarbon group is particularly preferably an unsubstituted alkylene group having 1 to 3 carbon atoms. In the above general formula (101), Y ¹¹² and Y ¹¹⁴ are each independently preferably -O-, -CO-, -CO-O- or -O-CO-, and preferably -CO-O- or -O -CO-. In the above general formula (101), Y ^{113 is} preferably an unsubstituted or substituted divalent aliphatic hydrocarbon group having 1 to 40 carbon atoms, and one or more of the methylene groups in the aliphatic hydrocarbon group A group substituted with a divalent group selected from the above group I or a group represented by the above general formula (103), wherein the unsubstituted or substituted divalent group having 1 to 20 carbon atoms is preferred An aliphatic hydrocarbon group, one or more of the methylene groups in the aliphatic hydrocarbon group is substituted with a divalent group selected from the group I above or a group represented by the above general formula (103), especially Preferably, one or more of the methylene groups in the unsubstituted or substituted divalent aliphatic hydrocarbon group having 1 to 20 carbon atoms are substituted with a divalent group selected from the above group I Group or the group represented by the above general formula (103), and among them, the group represented by the above general formula (103) is particularly preferred.

In the above general formula (103), Y ¹¹⁹ and Y ¹²⁰ are each independently preferably an unsubstituted or substituted divalent aliphatic hydrocarbon group having 1 to 40 carbon atoms, or a methylene group in the aliphatic hydrocarbon group One or more groups are substituted with divalent groups selected from the above group I, and among them, unsubstituted or substituted divalent aliphatic hydrocarbon groups with 1 to 20 carbon atoms are preferred, especially It is preferably an unsubstituted or substituted divalent aliphatic hydrocarbon group with 1 to 10 carbon atoms, and particularly preferably an unsubstituted or substituted divalent aliphatic hydrocarbon group with 1 to 5 carbon atoms, especially It is preferably a linear or branched alkylene group having 2 to 5 carbon atoms.

In the present invention, when n is 3, X is preferably a group represented by general formula (II-2) in group 2, a group represented by general formula (II-3), or general formula (II- 6) The group represented by the general formula (II-6) is preferred among them.

The group represented by the general formula (II-2), the group represented by the general formula (II-3), and the Z ¹¹ in the general formula (II-6) are preferably direct bonds or carbon atoms of 1-40 A substituted or substituted divalent aliphatic hydrocarbon group, of which a direct bond or an unsubstituted or substituted divalent aliphatic hydrocarbon group with 1 to 20 carbon atoms is preferred, and a direct bond or a carbon atom number of 1 is particularly preferred. -10 unsubstituted or substituted alkylene groups, of which direct bond or unsubstituted alkylene groups having 1 to 5 carbon atoms are particularly preferred. ^{The plural Z 11} 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.

^{Among them, in the present invention, it is preferable that at least one of the three Z 11} in the group represented by the general formula (II-2) is a direct bond, and at least one is an unsubstituted or substituted group with 1 to 40 carbon atoms Of the divalent aliphatic hydrocarbon group, preferably at least one is a direct bond, at least one is an unsubstituted or substituted divalent aliphatic hydrocarbon group with 1 to 20 carbon atoms, particularly preferably at least one is a direct bond, At least one is an unsubstituted or substituted alkylene group having 1 to 10 carbon atoms, among which at least one is a direct bond, and at least one is an unsubstituted alkylene group having 1 to 5 carbon atoms. ^{In addition, it is preferable that all of Z 11} in the group represented by the general formula (II-3) and the group represented by (II-6) are unsubstituted or substituted divalent groups having 1 to 40 carbon atoms Aliphatic hydrocarbon groups, among them, unsubstituted or substituted divalent aliphatic hydrocarbon groups with 1 to 20 carbon atoms are preferred, and unsubstituted or substituted alkylene groups with 1 to 10 carbon atoms are particularly preferred Among them, an unsubstituted alkyl group with 1 to 5 carbon atoms is particularly preferred.

^{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 preferably a hydrogen atom or a carbon atom number The unsubstituted or substituted aliphatic hydrocarbon group of 1 to 5 is particularly preferably a hydrogen atom.

In the present invention, when n is 4, X is preferably the group represented by (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 one or more of the methylene groups in the aliphatic hydrocarbon group A group substituted with a divalent group selected from the above group I, among which an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, or a methylene group in the aliphatic hydrocarbon group is preferred One or two or more of the groups are substituted with divalent groups selected from the above group I, and particularly preferred is an unsubstituted or substituted alkylene group having 1 to 10 carbon atoms. One or two or more of the methyl groups are substituted with divalent groups selected from the above group I, among which the methylene group in the unsubstituted alkylene group having 1 to 10 carbon atoms is particularly preferred One or more of the groups are substituted with -O-, -COO-, -OCO- or -CO-, among which the methylene group in the alkylene group with 2 to 5 carbon atoms is particularly preferred One group is substituted with -O-CO- or -CO-O-. The reason is that by setting X as the above-mentioned group at each n, the above-mentioned compound A1 becomes the one with a greater change in antioxidant capacity before and after the ^{protective group R 101 is removed.} As a result, the above-mentioned composition has an excellent balance between curability and heat resistance of the cured product.

The bonding position of X to the benzene ring may be any position within the benzene ring that can be bonded, but for example, it is preferably a para position relative to the bonding position of ^{R 101 -O-.} The reason is that by setting the above-mentioned bonding position to the above-mentioned position, the above-mentioned compound A1 becomes the one with a greater change in antioxidant capacity before and after the ^{protective group R 101 is removed.} As a result, the above-mentioned composition has an excellent balance between curability and heat resistance of the cured product.

As a specific example of compound A1, specifically, the compound etc. which are specifically described in International Publication No. 2014/021023 can be mentioned.

The method for producing the compound A1 is not particularly limited as long as the method can obtain the desired structure. For example, it can be the same method as the method described in International Publication No. 2014/021023.

As the kind of the above-mentioned compound A1, there may be only one kind in the composition, or two or more kinds.

The content of the above-mentioned compound A1 may be as long as the desired curability and heat resistance of the cured product can be obtained, and it can be appropriately set according to the use of the above-mentioned composition and the like. The content of the compound A1 is, for example, in 100 parts by mass of the solid content of the composition, preferably 0.01 parts by mass or more and 20 parts by mass or less, among which 0.05 parts by mass or more and 10 parts by mass or less, and more preferably 0.1 Parts by mass or more and 5 parts by mass or less. The reason is that, by setting the above content within the above range, the above composition becomes more excellent in the balance of curability and heat resistance of the cured product. In addition, the so-called solid component includes all components other than the solvent. The content of the above-mentioned compound A1 varies according to 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, of which 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. The reason is that, by setting the above content within the above range, the above composition becomes more excellent in the balance of curability and heat resistance of the cured product. The content of the compound A1 in the total of 100 parts by mass of the compound A1 and the sulfur-based antioxidant is preferably 10 parts by mass or more and 70 parts by mass or less, wherein it is preferably 15 parts by mass or more and 60 parts by mass or less, and more preferably 20 parts by mass. Parts by mass or more and 55 parts by mass or less, particularly preferably 25 parts by mass or more and 50 parts by mass or less. The reason is that, by setting the above content within the above range, the above composition becomes more excellent in the balance of curability and heat resistance of the cured product. The content of the above-mentioned compound A1 in 100 parts by mass of the total of compound A1, sulfur-based antioxidants, and curable components is preferably 0.01 parts by mass or more and 20 parts by mass or less, and more preferably 0.05 parts by mass or more and 10 parts by mass or less, especially Preferably, it is not less than 0.1 part by mass and not more than 5 parts by mass. The reason is that, by setting the content of the compound A1 in the above range, the above-mentioned composition becomes more excellent in the balance between the curability and the heat resistance of the cured product.

The content of the compound A1 relative to 100 parts by mass of the curable ingredient is preferably 0.001 parts by mass or more and 20 parts by mass or less, among them, 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. the following. The reason is that, by setting the above content within the above range, the above composition becomes more excellent in the balance of curability and heat resistance of the cured product. The total content of the compound A1 and the sulfur-based antioxidant relative to 100 parts by mass of the curable ingredient is preferably 0.002 parts by mass or more and 20 parts by mass or less, and among them, 0.01 parts by mass or more and 10 parts by mass or less, and more preferably 0.1 parts by mass or more and 5 parts by mass or less. The reason is that, by setting the total content of the compound A1 and the sulfur-based antioxidant in the above range, the composition becomes more excellent in the balance of curability and heat resistance of the cured product. The total content of the compound A1 and the sulfur-based antioxidant in 100 parts by mass of the total of the compound A1, the sulfur-based antioxidant and the curable component is preferably 0.002 parts by mass or more and 20 parts by mass or less, and more preferably 0.01 parts by mass Part or more and 10 parts by mass or less, more preferably 0.1 part by mass or more and 5 parts by mass or less. The reason is that, by setting the total content of the compound A1 and the sulfur-based antioxidant in the above range, the composition becomes more excellent in the balance of curability and heat resistance of the cured product.

The total content of the compound A1, sulfur-based antioxidant, and curable component in 100 parts by mass of the solid content is preferably 10 parts by mass or more, preferably 30 parts by mass or more, and preferably 40 parts by mass or more. The reason is that, by setting the total content of the compound A1, sulfur-based antioxidant, and curable component within the above range, the composition becomes more excellent in the balance of curability and heat resistance of the cured product. The upper limit of the total content of the aforementioned compound A1, sulfur-based antioxidant, and curable component can be appropriately set according to the use of the composition of the present invention, etc., and can be set to 99 parts by mass or less. The reason is that, by setting the above content within the above range, the above composition becomes more excellent in the balance of curability and heat resistance of the cured product.

2. Sulfur-based antioxidants The above-mentioned sulfur-based antioxidants contain sulfur atoms and have antioxidant capacity. Such sulfur-based antioxidants may be those capable of obtaining the desired curability and heat resistance. For example, thiol-based antioxidants having a thiol group (-SH), and those having a sulfur atom (S ) A thioether antioxidant with a structure of 2 carbon atoms (C) bonded to it. In the present invention, the sulfur-based antioxidant is preferably a thioether-based antioxidant. The reason for this is that the above-mentioned composition becomes more excellent in the balance of curability and heat resistance of the cured product. In addition, the above-mentioned sulfur-based antioxidant may be any one containing a sulfur atom. It is preferable that the said sulfur-type antioxidant does not have a phenolic hydroxyl group. The reason for this is that it becomes one with more excellent curability. Moreover, as a result, it becomes a thing excellent also in heat resistance.

(1) Thioether antioxidant As the above-mentioned thioether-based antioxidant, any one that has a thioether structure and can obtain desired curability and heat resistance. Specifically, at least one selected from the group consisting of compounds represented by the following general formulas (B1), (B2), (B3), and (B4) can be preferably used. The reason is that by using the above compound and the above compound A1 in combination, the above composition becomes more excellent in the balance between the curability and the heat resistance of the cured product. In the present invention, it is preferable that the above-mentioned thioether-based antioxidant does not have a phenolic hydroxyl group from the viewpoint of easily forming a composition having more excellent curability. For example, it is preferably selected from the compounds represented by the general formulas (B1), (B2), (B3) and (B4), among the compounds represented by the general formulas (B1), (B3) and (B4). At least one of the group consisting of. Since these compounds do not contain a phenolic hydroxyl group as an essential structure, they tend to be compositions with more excellent curability. In the present invention, it is preferably at least one selected from the group consisting of compounds represented by the above general formulas (B3) and (B4). The reason is that by using the above compound and the above compound A1 in combination, the above composition becomes more excellent in the balance between the curability and the heat resistance of the cured product. In the present invention, the thioether antioxidant is preferably a compound represented by the general formula (B3) from the viewpoint of low volatility and easy production of a cured product with less change in heat resistance over time. In the present invention, the above-mentioned thioether-based antioxidant is relatively more compatible with the curable component, easy to produce a composition with excellent dispersion stability, and easy to produce a cured product in which the thioether-based antioxidant is well dispersed. It is preferably a compound represented by the above general formula (B4).

[化16]

(In the formula, R ¹ and R ² each independently represent an aryl group with 6 to 20 carbon atoms, an alkyl group with 3 to 30 carbon atoms, or one or more of the methylene groups in the alkyl group. Substituted with -O- or -S-, R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ each independently represent a hydrogen atom and the number of carbon atoms is 1-8 The alkyl group, or one or more of the methylene groups in the alkyl group is substituted with -O- or -S-. One or more of the hydrogen atoms of the above-mentioned alkyl group may be (Substituted with alkoxy, alkenyl, alkenyloxy, hydroxyl or cyano, one or more of the hydrogen atoms of the above aryl group may be substituted with a hydroxyl group or an alkyl group with 1 to 8 carbon atoms)

[化17]

(In the formula, R ¹¹ represents an aryl group with 6 to 20 carbon atoms, an alkyl group with 3 to 30 carbon atoms, or one or more of the methylene groups in the alkyl group are substituted with -O- or -S-, R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ and R ¹⁹ each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. One or more of the hydrogen atoms of the group may be substituted with alkoxy, alkenyl, alkenyloxy, hydroxy, or cyano, and one or more of the hydrogen atoms of the above aryl group may be substituted with hydroxy or Alkyl group with 1 to 8 carbon atoms)

[化18]

(In the formula, R ²¹ , R ²² , R ²³ and R ²⁴ each independently represent an alkyl group having 3 to 30 carbon atoms, or one or more of the methylene groups in the alkyl group are substituted with -O -Or -S-, one or more of the hydrogen atoms of the alkyl group may be substituted with alkoxy, alkenyl, alkenyloxy, hydroxyl or cyano)

[化19]

(In the formula, R ³¹ and R ³² each independently represent one or two of a hydrogen atom, an aryl group having 6 to 20 carbon atoms, an alkyl group having 3 to 30 carbon atoms, or the methylene group in the alkyl group. More than one group substituted with -O- or -S-, L ¹ and L ² each independently represent an alkylene group having 1 to 8 carbon atoms, 1 of the above-mentioned alkyl group and the hydrogen atom of the above-mentioned alkylene group One or two or more may be substituted with alkoxy, alkenyl, alkenyl, hydroxy, or cyano, and one or two of the hydrogen atoms of the aryl group may be substituted with hydroxy or with 1-8 carbon atoms Of alkyl)

As the alkyl group having 3 to 30 carbon atoms represented ^{by R 1} and R ² in the general formula (B1), those having a specific number of carbon atoms in the alkyl group represented by ^{R 101 and the like can be used.} As the aryl group having 6 to 20 carbon atoms represented ^{by R 1} and R ² in the general formula (B1), those having a specific number of carbon atoms in the aryl group represented by ^{R 101 and the like can be used.} As the alkyl group having 1 to 8 carbon atoms to which the hydrogen atom of the aryl group is substituted, the alkyl group having the specified number of carbon atoms in the alkyl group represented by ^{R 101 and the like can be used.} In the general formula (B1), as the alkyl group having 1 to 8 carbon atoms represented by ^{R 3} to R ¹⁰ , those having the specified number of carbon atoms in the aryl group ^{used in the above-mentioned R 101 and the like can be used.}

Regarding the alkoxy group and alkenyl group substituted for the hydrogen atom in the alkyl group represented by ^{R 1} to R ¹⁰ , those having the specified number of carbon atoms in the groups ^{used in the above-mentioned R 101 and the like can be used.} As the alkenyloxy group for substituting the hydrogen atom in the alkyl group represented by ^{R 1} to R ¹⁰ , one of the groups in which the methylene group at the end of the alkenyl group represented by ^{R 101 and the like is substituted with -O- can be used} Those with a specific number of carbon atoms.

The alkyl group having 3 to 30 carbon atoms and the aryl group having 6 to 20 carbon atoms represented ^{by R 11} in the above general formula (B2) ^{, R 12} , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ The alkyl group having 1 to 8 carbon atoms represented by R ¹⁸ and R ¹⁹ can be the same as those used for ^{R 1} and R ³ to R ^{10 in the general formula (B1).} In addition, the alkyl group having 1 to 8 carbon atoms substituted for the hydrogen atom in the aryl group represented by ^{R 11 can also be used with the one used for R 1} or R ² in the above general formula (B1) The hydrogen atom of the aryl group is the same as the alkyl group having 1 to 8 carbon atoms. Furthermore, regarding the alkoxy, alkenyl and alkenyloxy groups substituted with hydrogen atoms of the alkyl groups represented by ^{R 11} , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ and R ¹⁹ As the group, the same group as the one substituted for the hydrogen atom of the alkyl group represented by ^{R 1} to R ¹⁰ in the above general formula (B1) can also be used.

As the alkyl group having 3 to 30 carbon atoms represented ^{by R 21} , R ²² , R ²³ and R ²⁴ in the above general formula (B3), the ^{group represented by R 1} in the above general formula (B1) can be used The same base. In addition, with regard to the alkoxy and alkenyl groups that replace the hydrogen atoms in the alkyl groups used ^{in R 21} , R ²² , R ²³ and R ^{24 , specific carbons in the groups used in the above-mentioned R 101} and the like can be used Atomic number. As the alkenyloxy group for substituting the hydrogen atom in the alkyl group used in R ²¹ , R ²² , R ²³ and R ²⁴ , the methylene group at the end of the alkenyl group ^{used in the above-mentioned R 101 etc. can be substituted} It is the specific number of carbon atoms in the base of -O-.

As the alkyl group having 3 to 30 carbon atoms and the aryl group having 6 to 20 carbon atoms ^{represented by R 31} and R ³² in the above general formula (B4), the same ^{as R 1 in the above general formula (B1) can be used.} The same groups as those used in ^{R 3} to R ^10. As the alkoxy group, alkenyl group, and alkenyloxy group substituted for the hydrogen atom of the alkyl group represented by ^{R 31} and R ^{32, the same groups as those used in the above general formula (B1) can be used.} As the alkyl group having 1 to 8 carbon atoms substituted for the hydrogen atom of the aryl group represented ^{by R 31} and R ³² in the above general formula (B4), the same group as used in the above general formula (B1) can be used The same base. As the alkylene group having 1 to 8 carbon atoms used ^{in L 1} and L ² in the above general formula (B4), the ^{alkylene group having 1 to 40 carbon atoms used in R 101} and the like can be used to remove 1 A specific number of carbon atoms in the base after a hydrogen atom. Regarding the alkoxy group, alkenyl group, and alkenyloxy group substituted for the hydrogen atom of the alkylene group represented by ^{L 1} and L ^{2, the same groups as those used in the above general formula (B1) can be used.}

^{R 21} , R ²² , R ²³ and R ²⁴ in the above general formula (B3) are each independently preferably an alkyl group with 6 to 25 carbon atoms, and among them, an alkyl group with 8 to 20 carbon atoms is preferred, and most preferably It is an alkyl group having 10 to 15 carbon atoms. The reason for this is that the above-mentioned composition becomes more excellent in the balance of curability and heat resistance of the cured product. The alkyl group used in the above-mentioned R ²¹ , R ²² , R ²³ and R ²⁴ is preferably an unsubstituted alkyl group in which one or more of the hydrogen atoms in the alkyl group are not substituted with an alkoxy group or the like. In addition, the groups used in the above-mentioned R ²¹ , R ²² , R ²³ and R ²⁴ are preferably those with one or more methylene groups in the alkyl group that are not substituted with -O- or -S- Substituted alkyl. The above-mentioned R ²¹ , R ²² , R ²³ and R ²⁴ may be the same or different. R ²¹ , R ²² , R ²³ and R ^{24 are} preferably the same. The reason is that by making the above-mentioned R ²¹ , R ²² , R ^23, and R ²⁴ the above-mentioned group, the above-mentioned composition becomes a more excellent balance between the curability and the heat resistance of the cured product. In addition, the above-mentioned composition can stably exhibit the desired heat resistance.

^{R 31} and R ³² in the above general formula (B4) are each independently preferably an alkyl group having 6 to 25 carbon atoms, of which an alkyl group having 8 to 20 carbon atoms is preferred, and an alkyl group having 10 to carbon atoms is particularly preferred. The alkyl group of 18 is particularly preferably an alkyl group having 10 to 15 carbon atoms. The reason for this is that the above-mentioned composition becomes more excellent in the balance of curability and heat resistance of the cured product. The ^{alkyl groups and aryl groups used in R 31} and R ³² are preferably unsubstituted alkyl groups and aryl groups in which one or more of the hydrogen atoms in the alkyl group and the aryl group are not substituted by an alkoxy group, etc. base. In addition, the groups used in the above-mentioned R ³¹ and R ³² are preferably unsubstituted alkyl groups in which one or more of the methylene groups in the alkyl group are not substituted with -O- or -S-. In addition, the above-mentioned R ³¹ and R ³² may be the same or different, but are preferably the same. The reason is that by making the above-mentioned R ³¹ and R ³² as the above-mentioned group, the above-mentioned composition becomes one having a more excellent balance between the curability and the heat resistance of the cured product. In addition, the above-mentioned composition can stably exhibit the desired heat resistance.

In the above general formula (B4), L ¹ and L ^{2 are} preferably alkylene groups having 1 to 5 carbon atoms, and among them, alkylene groups having 1 to 3 carbon atoms are preferred, and particularly preferred are alkylene groups having 1 to 3 carbon atoms. The alkylene group of 2 is methylene or ethylene group, and ethylene group is particularly preferred. The reason for this is that by making the structure of the thioether-based antioxidant the above-mentioned structure, the above-mentioned composition becomes more excellent in the balance between the curability and the heat resistance of the cured product. In addition, the above-mentioned composition can stably exhibit the desired heat resistance. The alkylene group used in the above L ¹ and L ² is preferably an unsubstituted alkylene group in which the hydrogen atom in the alkylene group is not substituted with an alkoxy group or the like. The reason is that by making the above-mentioned L ¹ and L ² as the above-mentioned group, the above-mentioned composition becomes more excellent in the balance between the curability and the heat resistance of the cured product. In addition, the above-mentioned composition can stably exhibit the desired heat resistance.

As a specific compound that can be used as the above-mentioned thioether-based antioxidant, for example, the compound described in JP 2017-128697 A can be cited. In addition, as commercial products of thioether antioxidants, AO-412S and AO-503 manufactured by ADEKA Co., Ltd., K-NOX1520 and K-NOX1726 manufactured by Sanyo Trading Co., Ltd. can be mentioned.

The above-mentioned thioether-based antioxidant may be present in the composition by only one type or two or more types.

(2) Thiol-based antioxidants The aforementioned thiol-based antioxidant may be one having a thiol group, and for example, 2-mercaptobenzimidazole may be mentioned. As a commercial item of the said thiol-type antioxidant, Sumilizer MB etc. which are manufactured by Sumika Chemtex Co., Ltd. can be mentioned, for example.

(3) Other The content of the sulfur-based antioxidant in the composition of the present invention is based on 100 parts by mass of the solid content of the composition, preferably 0.01 parts by mass or more and 20 parts by mass or less, and more preferably 0.05 parts by mass or more and 10 parts by mass Below, it is especially preferable that it is 0.1 mass part or more and 5 mass parts or less. The reason is that, by setting the above content within the above range, the above composition becomes one having an excellent balance of curability and heat resistance of the cured product. The content of the sulfur-based antioxidant varies according to the content of the solvent, etc., for example, in 100 parts by mass of the composition, it can be set to 0.001 parts by mass or more and 20 parts by mass or less, and preferably 0.005 parts by mass or more and 10 parts by mass or less, especially Preferably it is 0.01 part by mass or more and 5 parts by mass or less. The reason is that, by setting the above content within the above range, the above composition becomes one having an excellent balance of curability and heat resistance of the cured product. The content of the above-mentioned sulfur-based antioxidant is in 100 parts by mass of the total of compound A1, sulfur-based antioxidant and hardenable components, preferably 0.01 part by mass or more and 20 parts by mass or less, and more preferably 0.05 part by mass or more and 10 parts by mass or less , Particularly preferably not less than 0.1 parts by mass and not more than 5 parts by mass. The reason is that, by setting the above content within the above range, the above composition becomes more excellent in the balance of curability and heat resistance of the cured product. The content of the sulfur-based antioxidant relative to 100 parts by mass of the curable component is preferably 0.001 parts by mass or more and 20 parts by mass or less, among them, 0.005 parts by mass or more and 10 parts by mass or less, and particularly preferably 0.01 parts by mass or more. Parts by mass or less. The reason is that, by setting the above content within the above range, the above composition becomes more excellent in the balance of curability and heat resistance of the cured product.

3. Hardening ingredients The above-mentioned curable component contains a curable compound. Moreover, the said curable component is what is contained in the said composition as a component other than the said compound A1, and the polymerizable thing as the said compound A1 is not included in the said curable component. Therefore, the compound A1 containing alkenyl group and the like does not belong to the curable component in the present invention. As the above-mentioned curable compound, two or more curable compounds can be used to bond to form a high molecular weight compound. For example, a polymerizable compound in which curable compounds can be directly bonded to each other to form a high molecular weight can be used. Heat-curable compounds with high molecular weight, etc. As said polymerizable compound, a radical polymerizable compound, a cation polymerizable compound, an anionic polymerizable compound, etc. are mentioned, for example. In the present invention, among others, in terms of the effect of obtaining a composition excellent in the balance of curability and heat resistance of the cured product, the curable component preferably contains a polymerizable compound, and preferably contains free Base polymerizable compound. In addition, in the present invention, the curable component also preferably contains both of a radical polymerizable compound and a thermosetting compound. The reason is that the above-mentioned composition becomes an excellent balance between the curability and the heat resistance of the cured product.

The above-mentioned radically polymerizable compound may be any compound that can undergo radical polymerization. As said radical polymerizable compound, the compound which has ethylenic unsaturated groups, such as an acrylic group, a methacryl group, and a vinyl group, is mentioned, for example. In the composition of the present invention, as the 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 radically polymerizable compound, known compounds can be used. For example, the radically polymerizable compound described in International Publication No. 2018/012383 and the radically polymerizable compound described in International Publication No. 2014/021023 can be used. Substances and so on.

As the above-mentioned radically polymerizable compound, it is preferable to use a compound having an acidic group such as a carboxyl group and an ethylenically unsaturated group from the viewpoint of imparting alkali developability. As the compound having an acidic group such as a carboxyl group and an ethylenically unsaturated group, for example, unsaturated monocarboxylic acids such as acrylic acid and methacrylic acid, and a carboxyl group-containing photosensitive resin described in JP 2016-180880 A can be used , The carboxyl-containing resin described in International Publication No. 2016/208187, the carboxyl-containing resin described in Japanese Patent Laid-Open No. 2018-53215, and the carboxyl-containing resin described in Japanese Patent Laid-Open No. 2016-151744 Polymers of structural units, and [A] copolymers described in Japanese Patent Laid-Open No. 2005-234362, etc.

As the compound having an acidic group such as a carboxyl group and an ethylenically unsaturated group, it is preferable to use a carboxyl group-containing resin. Examples of the above-mentioned carboxyl group-containing resin include: epoxy acrylate resin obtained by reacting a cresol novolac type epoxy resin with acrylic or methacrylic acid; reacting a multifunctional epoxy compound with an unsaturated carboxylic acid, and then reacting with An acid-modified unsaturated epoxy ester resin formed by the reaction of a polybasic acid or its anhydride; and an unsaturated modified acrylic resin, etc., which are contained in a structural unit obtained by polymerizing a compound selected from acrylic acid and methacrylic acid The acrylic resin reacts with the epoxy compound containing the ethylenically unsaturated group to introduce the ethylenically unsaturated group.

As the said polyfunctional epoxy compound, what has at least two epoxy groups in 1 molecule should just be sufficient. As the polyfunctional epoxy compound, for example, bisphenol type epoxy resin such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, and bisphenol AD type epoxy resin; biphenyl type epoxy resin ; Naphthalene type epoxy resin; Dicyclopentadiene type epoxy resin; Silicone modified epoxy resin and other rubber modified epoxy resin; ε-caprolactone modified epoxy resin; Bisphenol A type, bisphenol Phenolic novolac type epoxy resins such as F type and bisphenol AD type; cresol novolac type epoxy resins such as o-cresol novolac type; cycloaliphatic multifunctional epoxy resin; glycidyl ester type multifunctional ring Oxygen resin; glycidylamine type multifunctional epoxy resin; heterocyclic type multifunctional epoxy resin; bisphenol modified novolac epoxy resin; multifunctional modified novolac epoxy resin; phenolic and phenolic Hydroxyl aromatic aldehyde condensate type epoxy resin, etc. In addition, it is also possible to use those having halogen atoms such as Br and Cl introduced into these resins. These polyfunctional epoxy compounds may be used alone, or two or more of them may be mixed and used.

As said unsaturated carboxylic acid, unsaturated monocarboxylic acid, such as acrylic acid, methacrylic acid, crotonic acid, and cinnamic acid, can be mentioned, for example. Among these unsaturated monocarboxylic acids, acrylic acid or methacrylic acid is preferred. The reaction method of the polyfunctional epoxy compound and the unsaturated monocarboxylic acid is not particularly limited. For example, the polyfunctional epoxy compound and the unsaturated monocarboxylic acid can be reacted by heating in a suitable solvent.

As the polybasic acid or its anhydride, either polysaturated or unsaturated can be used. As the above-mentioned polybasic acid, for example, succinic acid, maleic acid, adipic acid, citric acid, phthalic acid, tetrahydrophthalic acid, 3-methyltetrahydrophthalic acid, 4-methyl Tetrahydrophthalic 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, internal Methylenetetrahydrophthalic acid, methylendomethyltetrahydrophthalic acid, trimellitic acid, pyromellitic acid and diglycolic acid, etc. As said polybasic acid anhydride, the acid anhydride of the said polybasic acid can be mentioned.

Regarding the above-mentioned ethylenically unsaturated group-containing epoxy compound, for example, glycidyl methacrylate, 4-hydroxybutyl (meth)acrylate glycidyl ether, and 3,4-epoxy (meth)acrylate may be mentioned. Cyclohexyl methyl ester and so on.

Furthermore, the (meth)acrylic group includes both an acrylic group and a methacrylic group. In addition, (meth)acrylate includes both acrylate and methacrylate.

As the carboxyl group-containing resin, commercially available products can be used. As a commercially available product of the carboxyl group-containing resin, for example, ZAR-2000, ZFR-1122, FLX-2089, ZCR-1601H, CCR-1171H, CCR-1235, CCR-1291H, CCR-1307H, CCR- 1309H (manufactured by Nippon Kayaku Co., Ltd.), Cyclomer P (ACA) Z-250 (manufactured by Daicel Chemical Industries Co., Ltd.), RIPOXY SP-4621, SPC-1000, SPC-3000, PR-300CP (Showa High (Manufactured by Molecule Co., Ltd.) and so on.

The acid value of the above-mentioned carboxyl group-containing resin may be a value capable of forming a cured product with excellent durability. For example, it is preferably 40 mgKOH/g or more and 150 mgKOH/g or less, and more preferably 50 mgKOH/g or more and 130 mgKOH/g. g or less. The reason is that, by setting the acid value of the carboxyl group-containing resin within the above range, the composition can easily form a cured product having excellent durability. In addition, the reason is that the above-mentioned composition is easy to pattern.

The weight average molecular weight of the above-mentioned carboxyl group-containing resin may be one that can obtain a cured product excellent in durability, and one of 1,000 or more can be used. Regarding the weight average molecular weight of the above-mentioned carboxyl group-containing resin, from the viewpoint of easy patterning, for example, it is preferably 2,000 or more and 150,000 or less, and particularly preferably 5,000 or more and 100,000 or less. The reason is that, by setting the average molecular weight of the carboxyl group-containing resin within the above range, the composition can easily form a cured product having excellent durability. In addition, the reason is that the above-mentioned composition is easy to pattern. For the weight average molecular weight Mw of the above-mentioned carboxyl-containing resin, for example, HLC-8120GPC manufactured by Tosoh Co., Ltd. can be used, and the elution solvent is set to N-methylpyrrolidone added with 0.01 mol/liter of lithium bromide, and the calibration curve Use polystyrene standards as Mw377400, 210500, 96000, 50400, 20650, 10850, 5460, 2930, 1300, 580 (the above are Easi PS-2 series manufactured by Polymer Laboratories) and Mw1090000 (manufactured by Tosoh Co., Ltd.), It is obtained by measuring the measurement column as TSK-GEL ALPHA-M×2 (manufactured by Tosoh Co., Ltd.). In addition, the measurement temperature can be set to 40°C, and the flow rate can be set to 1.0 mL/min.

The content of the compound having a carboxyl group may be one that can form a cured product with excellent durability. For example, in 100 parts by mass of the solid content of the composition, it is preferably 1 part by mass or more and 90 parts by mass or less, and more It is preferably 20 parts by mass or more and 80 parts by mass or less, and more preferably 40 parts by mass or more and 70 parts by mass or less. The reason is that the above composition can easily form a cured product having excellent curability and heat resistance. In addition, the reason is that the above-mentioned composition can be easily patterned.

It may be a compound having no carboxyl group among the above-mentioned radically polymerizable compounds (hereinafter, it may be referred to as a compound having no carboxyl group). As the compound having no carboxyl group, for example, a compound represented by the following general formula (14) can be preferably used. The reason is that by using this compound, the composition of the present invention is more excellent in the balance of curability and heat resistance of the cured product.

[化20]

(In the formula, R ¹⁴⁰¹ represents a hydrogen atom or a methyl group, and X ¹⁴ represents an unsubstituted or substituted aliphatic hydrocarbon group with the same number of valences as n14 and a carbon number of 1-40; Unsubstituted or substituted aromatic hydrocarbon-containing group with the number of valences of 6-40 carbon atoms; unsubstituted or substituted group with 2-40 carbons with the same valence as n14 Or one or more of the methylene groups in the aliphatic hydrocarbon group, the aromatic hydrocarbon-containing group, or the heterocyclic group-containing group are substituted with those selected from the above group I A base formed by a divalent base, n14 represents an integer from 1 to 10)

About X ¹⁴ has shown the number of non-n14 is the number of different substituted or divalent aliphatic hydrocarbon group having the substituent group; n14 having substituents having a substituted or without the same number of valence of the aromatic hydrocarbon containing The group; and the unsubstituted or substituted heterocyclic-containing group having the same valence as n14, the same group as X in the above general formula (A1) can be exemplified.

n14 is an integer from 1 to 10, preferably an integer from 1 to 6, wherein an integer from 1 to 3 is preferred, and an integer from 1 to 2 is particularly preferred. The reason for this is that the above-mentioned composition becomes more excellent in the balance of curability and heat resistance of the cured product. In addition, from the viewpoint of being more excellent in the curability of the composition, n14 is preferably an integer of 2-8, particularly preferably an integer of 3-7, and particularly preferably an integer of 4-6. ^{In the present invention, X 14} in the general formula (14) is preferably an aromatic hydrocarbon-containing group, a heterocyclic group-containing group, or one or more of the methylene groups in these groups are substituted to be selected from The base formed by the divalent base in the above group I. The reason is that the heat resistance of the cured product obtained can be more effectively exhibited. Furthermore, in the present invention, the above X ^{14 is} also preferably a group in which one or more of the alkyl group or the methylene group in the alkyl group is substituted with a divalent group selected from the above group I. The reason is that the curability of the composition will be more excellent.

The above-mentioned X ¹⁴ may be one that can obtain the desired curability and heat resistance, and is preferably an unsubstituted or substituted aromatic containing 6-40 carbon atoms having the same valence as n14 A hydrocarbon group; an unsubstituted or substituted heterocyclic group containing 2-40 carbon atoms with the same number of valences as n14; or the aromatic hydrocarbon-containing group or the heterocyclic group-containing group One or two or more of the methylene groups are substituted with divalent groups selected from the above group I. Among them, it is preferably an unsubstituted or substituted aromatic hydrocarbon-containing group having 10 to 30 carbon atoms with the same valence as n14; and 2 with the same valence as n14 ～20 unsubstituted or substituted heterocyclic ring-containing groups; or one or more of the methylene groups in the aromatic hydrocarbon-containing group or the heterocyclic ring-containing group are substituted as selected from the above A group composed of a divalent group in group I, particularly preferably methylene in an unsubstituted or substituted aromatic hydrocarbon-containing group with 15 to 30 carbon atoms with the same valence as n14 One or more of the groups are substituted with divalent groups selected from the above group I; or unsubstituted or substituted with 2-10 carbon atoms with the same valence as n14 The group contains a heterocyclic group. One or more methylene groups in the unsubstituted or substituted aromatic hydrocarbon-containing group having 15-30 carbon atoms and having the same number of valence as n14 shown in the above X ¹⁴ A group substituted with a divalent group selected from the above group I. When n14 is 2, it is preferably a methylene group in a linear or branched alkyl group with 15 to 30 carbon atoms One or two or more are substituted with a group obtained by removing one hydrogen atom from an aryl group, and among them, a group represented by the following general formula (14-1) is particularly preferred. The reason for this is that, by setting the above X ¹⁴ to the above structure, the above composition becomes more excellent in the balance between the curability and the heat resistance of the cured product.

[化21]

In the formula, R ^14a-1 and R ^14a-2 each independently represent a hydrogen atom or a linear or branched alkyl group with 1 to 20 carbon atoms, and L ¹¹ and L ¹² each independently represent a direct bond, the number of carbon atoms 1 to 10 linear or branched alkylene groups or one or more of the methylene groups in the alkylene groups are substituted with -O- groups, and * represents a bonding site.

As the linear or branched alkyl group having 1 to 20 carbon atoms represented ^{by R 14a-1} and R ^14a-2 in the general formula (14-1), a ^{linear or branched alkyl group represented by R 101} and the like can be exemplified The specific number of carbon atoms in the branched alkyl group. The linear or branched alkylene group having 1 to 10 carbon atoms represented by L ¹¹ and L ¹² can be exemplified by removing one hydrogen atom from the linear or branched alkyl group represented by ^{R 101 and the like} The specific number of carbon atoms in the alkylene group of the latter group.

In the above general formula (14-1), R ^14a-1 and R ^14a-2 are each independently preferably a hydrogen atom, or a linear or branched alkyl group having 1 to 10 carbon atoms, of which a carbon atom is preferred. The straight-chain alkyl group having 1 to 5 is particularly preferably a straight-chain alkyl group having 1 to 3 carbon atoms. In the above general formula (14-1), L ¹¹ and L ¹² are each independently preferably a linear or branched alkylene group having 1 to 5 carbon atoms or one of the methylene groups in the alkylene group or Two or more groups substituted with -O-, of which one or more of the linear alkylene groups having 2 to 4 carbon atoms or the methylene groups in the alkylene group are preferably substituted with- The O- group is particularly preferably one or more of the methylene groups in the linear alkylene group having 2 to 4 carbon atoms, which is substituted with -O-. The reason is that by making the above-mentioned R ^14a-1 and R ^14a-2 and L ¹¹ and L ¹² as the above-mentioned group, the above-mentioned composition becomes a more excellent balance between the curability and the heat resistance of the cured product.

X ¹⁴ as the number of carbon atoms and n14 is the valence of the same number of 2 to 10 shown without having a substituent or a heterocyclic group containing the substituent group, the case where the time is to n14. 1, preferably X ¹⁴ The unsubstituted or substituted heterocyclic ring-containing group having 3 to 7 carbon atoms is preferably an unsubstituted heterocyclic ring-containing group having 3 to 7 carbon atoms. As the heterocyclic ring contained in the heterocyclic ring-containing group, any of aromatic heterocyclic rings having aromaticity and aliphatic heterocyclic rings showing no aromaticity can be used, but aromatic heterocyclic rings are preferred. As the above-mentioned aromatic heterocyclic ring, as long as it contains atoms other than carbon atoms in the atoms forming the ring structure, it may be a single ring or a condensed ring. For example, a furan ring, a benzofuran ring, two Benzofuran ring, thiophene ring, etc.

^{In the present invention, X 14 is} preferably unsubstituted or substituted with 1 to 40 carbon atoms from the viewpoint that the balance between the curability and the heat resistance of the cured product is more excellent, and especially the curability is excellent One or two or more of the aliphatic hydrocarbon group or the methylene group in the aliphatic hydrocarbon group is substituted with a divalent group selected from the above group I, wherein the number of carbon atoms is preferably 3 to 20 unsubstituted or substituted aliphatic hydrocarbon groups, or groups in which one or more of the methylene groups in the aliphatic hydrocarbon group are substituted with divalent groups selected from the above group I, especially Preferably, 1 or 2 of the methylene group in the unsubstituted or substituted aliphatic hydrocarbon group with 4 to 10 carbon atoms, or the unsubstituted or substituted aliphatic hydrocarbon group with 5 to 15 carbon atoms More than one group substituted with a divalent group selected from the above group I, particularly preferably an unsubstituted or substituted aliphatic hydrocarbon group with 4 to 10 carbon atoms, or a group with 5 to 15 carbon atoms One or two or more of the methylene groups in the unsubstituted or substituted aliphatic hydrocarbon group are substituted with divalent groups selected from the above group I. In addition, in terms of the composition becoming more excellent in curability, the aliphatic hydrocarbon group used in the ^{above-mentioned X 14 is preferably an alkyl group.}

As a specific example of the above-mentioned compound having no carboxyl group, as long as it has one or more ethylenically unsaturated groups and does not have a carboxyl group, for example: 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate Ester, isobutyl acrylate, n-octyl acrylate, isooctyl acrylate, isononyl acrylate, stearyl acrylate, methoxyethyl acrylate, dimethylaminoethyl acrylate, zinc acrylate, 1,4- Butylene glycol diacrylate, neopentyl glycol diacrylate, 1,6-hexanediol diacrylate, trimethylolpropane triacrylate, 2-hydroxyethyl methacrylate, methacrylic acid-2 -Hydroxypropyl ester, butyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, 1,4-butanediol dimethacrylate, neopentyl glycol dimethacrylate, three Methylolpropane trimethacrylate, polyethylene glycol di(meth)acrylate, isocyanurate di(meth)acrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol tetraacrylate Ester, 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 radically polymerizable compound having no carboxyl group, (meth)acrylate having a phosphate structure such as acid phosphate mono(2-propenoxyethyl) ester can also be used. As the radically polymerizable compound which does not have a 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, those described in JP 2018-53215 A can be used.

Among the above-mentioned compounds having no carboxyl group, those that are liquid at room temperature (25°C) can also be used as a diluent for dissolving the above-mentioned carboxyl group-containing resin and the like.

When the above-mentioned radically polymerizable component contains a compound having an acidic group such as a carboxyl group as the radically polymerizable compound, it is preferable to use a compound having an acidic group and a compound not having an acidic group in combination. The reason for this is that the composition is excellent in the curability of the composition and the balance between the heat resistance of the cured product and the alkali developability. When the above-mentioned radically polymerizable component contains a compound having a carboxyl group as the radically polymerizable compound, it is preferable to use a compound having a carboxyl group and a compound not having a carboxyl group in combination. The reason for this is that the composition is excellent in the curability of the composition and the balance between the heat resistance of the cured product and the alkali developability.

When the above-mentioned curable component contains both a compound having an acidic group such as a carboxyl group and a compound having no acidic group such as a carboxyl group as a radically polymerizable compound, the content of the compound having no acidic group is greater than that of the compound having an acidic group and The total 100 parts by mass of the compound having no acidic group is preferably 1 part by mass or more and 90 parts by mass or less, more preferably 20 parts by mass or more and 70 parts by mass or less, and particularly preferably 30 parts by mass or more and 50 parts by mass or less. The reason is that the above-mentioned composition has excellent curability, and the obtained cured product has excellent heat resistance. In addition, the above-mentioned composition can be more easily patterned. When the above-mentioned curable component contains both of a compound having a carboxyl group and a compound not having a carboxyl group as a radically polymerizable compound, the content of the compound having no carboxyl group is equal to the total of the compound having a carboxyl group and the compound having no carboxyl group 100 Among the parts by mass, it is preferably 1 part by mass or more and 90 parts by mass or less, more preferably 20 parts by mass or more and 70 parts by mass or less, and particularly preferably 30 parts by mass or more and 50 parts by mass or less. The reason is that the above-mentioned composition has excellent curability, and the obtained cured product has excellent heat resistance. In addition, the above-mentioned composition can be more easily patterned.

The above-mentioned cationically polymerizable compound may be a compound capable of undergoing cation polymerization, and examples thereof include cyclic ether compounds such as epoxy compounds and oxetane compounds, cyclic sulfide compounds, and vinyl ether compounds. As such a cationically polymerizable compound, more specifically, cationically polymerizable compounds such as epoxy compounds, oxetane compounds, and vinyl ether compounds described in International Publication No. 2018/012383, and Japanese Patent Laid-Open The epoxy compound described in 2016-180880, and the thermosetting component described in Japanese Patent Laid-Open No. 2018-53215 as a thermosetting component having two or more cyclic ether groups and cyclic sulfide groups in a molecule, etc. Recorded compound.

As the above-mentioned anionic polymerizable compound, any compound capable of undergoing anionic polymerization may be used. For example, cyclic ether compounds such as epoxy compounds and oxetane compounds, cyclic sulfide compounds, acrylate compounds, and methyl ester compounds may be used. -Based acrylate compounds, etc. As the cyclic ether compound and cyclic sulfide compound used as such an anionic polymerizable compound, those exemplified as the above-mentioned cationic polymerizable compound can be used. Moreover, as an acrylate compound and a methacrylate compound used as an anionic polymerizable compound, the compound which has an acrylate group or a methacrylate group among those exemplified as the radical polymerizable compound can be used.

Examples of the above-mentioned thermosetting compound include phenol resins, urea resins, amino resins, epoxy compounds such as polyfunctional epoxy compounds, and cyclic ethers such as oxetane compounds such as polyfunctional oxetane compounds. Compounds, unsaturated polyester resins, benzoguanamine derivatives, isocyanate compounds, blocked isocyanate compounds, maleimide compounds, benzoimide compounds, oxazoline compounds, carbodiimide compounds, Cyclic sulfide compounds such as cyclic carbonate compounds, polyfunctional oxetane compounds, episulfide resins, and the like. As the above-mentioned polyfunctional epoxy compound, the same as those described in the examples used in the formation of the above-mentioned carboxyl group-containing resin can be used. As a commercially available product of the above-mentioned polyfunctional epoxy compound, for example, what is described in JP 2018-53215 A 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 described in JP 2017-111453 A can be used , Polyfunctional oxetane compounds, resins in which the oxygen atoms of the epoxy groups of the novolac type epoxy resins are replaced with sulfur atoms. As the above-mentioned amine-based resin, for example, melamine derivatives and benzoguanamine derivatives described in JP 2017-111453 A can be used. In the present invention, the thermosetting compound preferably contains a cyclic ether compound, a cyclic sulfide compound, etc., among them, a cyclic ether compound is preferably contained, an epoxy compound is particularly preferred, and a polyfunctional ring is particularly preferred. Oxygen compounds. The reason is that the above-mentioned composition becomes an excellent balance between the curability and the heat resistance of the cured product.

The content of the curable component in the composition of the present invention is appropriately set according to the use of the composition and the like. The content of the curable component in 100 parts by mass of the solid content of the composition is preferably 5 parts by mass or more, among which 20 parts by mass or more is preferable, and 30 parts by mass or more are particularly preferable. The reason is that, by setting the above content within the above range, the above composition becomes one having an excellent balance of curability and heat resistance of the cured product. In addition, the so-called solid component includes all components other than the solvent. The content of the above-mentioned sclerosing component varies according to the content of the solvent, etc., for example, in 100 parts by mass of the composition, preferably 1 part by mass or more, wherein preferably 5 parts by mass or more, and particularly preferably 10 parts by mass or more and 99 parts by mass the following. The reason is that, by setting the above content within the above range, the above composition becomes one having an excellent balance of curability and heat resistance of the cured product. The content of the curable component is preferably 5 parts by mass or more in the total of 100 parts by mass of the compound A1, sulfur-based antioxidant, and curable component, and more preferably 20 parts by mass or more, and particularly preferably 30 parts by mass or more 99 parts by mass or less. The reason for this is that by setting the content of the curable component within the above range, the composition will have an excellent balance of curability and heat resistance of the cured product.

4. Hardening catalyst The above composition may contain a hardening catalyst in addition to the hardening component. As long as the curing catalyst promotes the curing reaction of the curing component, it is easy to bond two or more curing compounds to form a high molecular weight product. It can be appropriately selected according to the type of the curing component, the application of the composition, etc. . When the curing component contains polymerizable compounds such as radical polymerizable compounds, cationic polymerizable compounds, and anionic polymerizable compounds, the curing catalyst may contain a radical polymerization initiator, a cationic polymerization initiator, and an anionic polymerization initiator, respectively. Starter and other polymerization initiators.

系化合物及肟酯系化合物之光自由基聚合起始劑，偶氮系化合物、過氧化物及過硫酸鹽等熱自由基聚合起始劑等。又，作為自由基聚合起始劑，亦可使用國際公開第2017/170493號公報、國際公開第2019/013112號公報等中記載之苯乙酮系化合物、二苯乙二酮化合物、二苯甲酮系化合物、9-氧硫𠮿

系化合物、雙咪唑系化合物、吖啶系化合物、醯基膦系化合物等。As a radical polymerization initiator, for example, acetophenone compounds, benzophenone compounds, benzophenone compounds, and 9-oxysulfur described in International Publication No. 2018/012383 etc. can be used.

Initiator for photo-radical polymerization of compound and oxime ester-based compound, thermal radical polymerization initiator such as azo compound, peroxide and persulfate, etc. In addition, as a radical polymerization initiator, acetophenone compounds, benzophenone compounds, and benzophenone compounds described in International Publication No. 2017/170493 and International Publication No. 2019/013112 can also be used. Ketone compounds, 9-oxysulfur𠮿

-Based compounds, bisimidazole-based compounds, acridine-based compounds, phosphine-based compounds, etc.

As the cationic polymerization initiator, for example, the photocationic polymerization initiator described in International Publication No. 2018/012383 etc. as the double salt of the onium salt of Lewis acid released by the irradiation of energy rays or its derivative can be used. Agents, sulfonium salts, thiophenium salts and other thermal cationic polymerization initiators. As an anionic polymerization initiator, when the curable component contains a cyclic ether compound, a cyclic sulfide compound, etc. as anionic polymerizable compounds, for example, imidazole derivatives, amine compounds such as dicyandiamide, hydrazine compounds, and phosphorus can be used. Thermal hardening catalysts such as compounds and S-tris derivatives. In addition, as the thermosetting catalyst and its commercially available products, for example, those described in JP 2017-11143 A can be used.

As the content of the polymerization initiator in the composition of the present invention, it is sufficient if the desired curability is obtained. For example, it is preferably 0.1 mass parts relative to 100 parts by mass of the polymerizable component contained as the curable component. Part or more and 30 parts by mass or less, and more preferably 1 part by mass or more and 20 parts by mass or less. The reason is that, by setting the above content within the above range, a composition having an excellent balance between curability and heat resistance of the cured product can be obtained.

The curing catalyst contains cyclic ether compounds such as polyfunctional epoxy compounds and polyfunctional oxetane compounds, and cyclic sulfide compounds having multiple cyclic sulfide groups, such as episulfide resins, in the curing component as the thermosetting In the case of a sexual compound, it is preferable to contain a thermosetting agent capable of forming a high molecular weight compound of the above-mentioned thermosetting compound. Examples of the thermosetting agent include imidazole derivatives, amine compounds such as dicyandiamide, hydrazine compounds, phosphorus compounds, S-triacetin derivatives, polythiols, acid anhydrides, phenol resins, carboxylic acid compounds, and the like. As such a thermosetting catalyst and its commercially available products, for example, those described as a thermosetting catalyst described in JP 2017-111453 A can be mentioned. In the present invention, it is preferable to contain an amine compound as the thermosetting agent, and it is particularly preferable to contain both an imidazole derivative and dicyandiamide. The reason is that the above-mentioned composition becomes an excellent balance between the curability and the heat resistance of the cured product. The content of the thermosetting agent may be one that can obtain the desired curability. For example, it may be 0.1 part by mass or more and 50 parts by mass relative to 100 parts by mass of the total of the cyclic ether compound and cyclic sulfide compound. Servings or less. The reason is that by setting the content of the thermosetting agent in the above range, a composition having an excellent balance between curability and heat resistance of the cured product can be obtained.

5. Solvent The composition of the present invention may contain a solvent for dispersing or dissolving compound A1, sulfur-based antioxidant, and curable component. The above-mentioned solvent can be one that is liquid at normal temperature (25°C) and atmospheric pressure. The above-mentioned solvent can disperse or dissolve each component in the composition such as compound A1, sulfur-based antioxidant, and curable component. Therefore, even if it is liquid at normal temperature (25°C) and atmospheric pressure, the above-mentioned compound A1 and the curable component are not included in the solvent. As the above-mentioned solvent, any of water, organic solvents, and mixtures thereof can be used.

As the organic solvent, a well-known solvent can be used. For example, carbonates such as propylene carbonate; ketones such as methyl ethyl ketone; ether solvents such as diethyl ether; ester solvents such as methyl acetate; methanol and ethanol Alcohol solvents; propylene glycol-1-monomethyl ether-2-acetate and other ether ester solvents; benzene and other BTX (Benzene-Toluene-Xylene, benzene-toluene-xylene) solvents; hexane and other aliphatic hydrocarbons Department of solvents and so on. As the organic solvent, for example, the solvent described in International Publication No. 2018/012383 that can dissolve or disperse each component in the curable composition, the organic solvent described in International Publication No. 2014/021023, and the like can also be used.

The content of the above-mentioned solvent in the composition of the present invention may be one that can obtain a composition having an excellent balance of curability and heat resistance of the cured product, and can be set to 1 part by mass in 100 parts by mass of the above-mentioned composition Above 99 parts by mass or less.

6. Other ingredients In addition to the compound A1, the sulfur-based antioxidant, the curable component, the curing catalyst, and the solvent, the above-mentioned composition may contain other components as necessary. Such other components can be selected according to the application of the composition, and examples include: benzotriazole-based, tri-triazole-based, and benzoate-based ultraviolet absorbers; phenol-based and phosphorus-based antioxidants; including Cationic surfactants, anionic surfactants, nonionic surfactants, amphoteric surfactants and other antistatic agents; halogen compounds, phosphate ester compounds, phosphamide compounds, melamine compounds, fluororesins Or metal oxides, (poly)melamine phosphate, piperazine (poly)phosphate and other flame retardants; lubricants of hydrocarbon series, fatty acid series, aliphatic alcohol series, aliphatic ester series, aliphatic amine series or metal soap series ;Dyes, pigments, carbon black and other colorants; smoked silica, particulate silica, silica, diatomaceous earth, clay, kaolin, diatomaceous earth, silica gel, calcium silicate, sericite , Kaolinite, flint, feldspar powder, vermiculite, Otepite, talc, mica, iron talc, pyrophyllite, silica and other silica-based inorganic additives; glass fiber, calcium carbonate and other fillers; nucleating agent , Crystallization accelerators and other crystallization agents, silane coupling agents, flexible polymers and other rubber elasticity imparting agents, sensitizers, etc. As the above-mentioned other components, an organic polymer can be used as a resin component other than the above-mentioned curable component. As such an organic polymer, what is exemplified as an organic polymer in International Publication No. 2014/021023 can be used.

As the filler used as the above-mentioned other components, more specifically, those 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, those formulated in sealing materials such as silicone resin compositions and epoxy resin compositions can be used. For example, examples include: fused silica, fused spherical silica, crystalline silica, colloidal silica, fuming silica, silica gel and other silicas; alumina, oxide Metal oxides such as iron, 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 modified by organic modification treatment, etc.; metal carbonates such as calcium carbonate, calcium silicate, magnesium carbonate, barium carbonate, etc.; metal salts such as barium sulfate, or modified by organic modification treatment, etc. Quality; metal borate, carbon black and other pigments; carbon fiber, graphite, whiskers, kaolin, talc, glass fiber, glass beads, glass microspheres, silica glass, layered clay minerals, clay, silicon carbide, Quartz, aluminum, zinc, etc. Examples of the above-mentioned organic fillers include acrylic beads, polymer particles, transparent resin beads, wood flour, pulp, and cotton yarn fragments. In the present invention, among them, the inorganic filler is preferably silica, metal oxide, metal acid salt, and talc, and particularly preferably crystalline silica, talc, barium sulfate, and titanium oxide.

The average particle size of the filler may be as long as the desired durability is obtained, and it also varies according to the use of the composition. For example, in the case of solder resist use, it is preferably 10 nm or more and 100 μm or less . Furthermore, as a method for measuring the above-mentioned average particle diameter, a laser diffraction-scattering method can be used. Specifically, a laser diffraction particle size distribution measuring device (SALD-2000J manufactured by Shimadzu Corporation) or the like can be used. The average particle size can be set as the particle size (median diameter) that becomes 50% of the cumulative particle size distribution from the particle side.

The content of the filler is, for example, preferably 5 parts by mass or more and 500 parts by mass or less, and more preferably 5 parts by mass or more and 200 parts by mass or less with respect to 100 parts by mass of the curable component. The reason is that by setting the content of the filler in the above range, a composition having an excellent balance between curability and heat resistance of the cured product can be obtained. In addition, a cured product with excellent durability can be easily formed, and for example, it can be easily used as a solder resist. As the content of the filler, for example, in 100 parts by mass of the solid content of the composition, it is preferably 1 part by mass or more and 90 parts by mass or less, of which 5 parts by mass or more and 70 parts by mass or less, and more preferably 10 parts by mass or more and 60 parts by mass or less. The reason is that, by setting the above content within the above range, a composition having an excellent balance between 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 is easy to use as a solder resist.

The content of the above-mentioned coloring agent is sufficient as long as the desired appearance and the like can be obtained, and it is preferably not less than 0.01 parts by mass and not more than 10 parts by mass, and more preferably not less than 0.1 parts by mass relative to 100 parts by mass of the curable component. Parts by mass or less. The reason is that, by setting the content of the colorant in the above range, a composition having an excellent balance between curability and heat resistance of the cured product can be obtained.

The total content of the other components in the composition of the present invention may be 50 parts by mass or less in 100 parts by mass of the composition when the other components are not included as the above-mentioned other components. When the above-mentioned other components contain a filler, the total content of the above-mentioned other components is preferably 90 parts by mass or less, and more preferably 70 parts by mass or less. The reason is that, by setting the above content within the above range, a composition having an excellent balance between curability and heat resistance of the cured product can be obtained.

7. Other The method for producing the above composition may be a method in which the above-mentioned components can be blended in the desired content, and the above-mentioned components may be added and mixed at the same time, or the components may be added and mixed in sequence.的方法。 The method.

The use of the above composition is preferably a use requiring curability and heat resistance of the cured product. It can be used for thermosetting paints, photocuring paints or varnishes, thermosetting adhesives, photocuring adhesives, and printed circuit boards. , Or color filters, CCD (Charge Coupled Device, Charge Coupled Device) image sensors in LCD panels with color displays such as color TVs, PC (pesonal computer) monitors, portable information terminals, digital cameras, etc. Color filters, photosensitive spacers, black tube cylindrical spacers, electrode materials for plasma display panels, touch panels, touch sensors, powder coatings, printing inks, printing plates, adhesives, Dental composition, photo-forming resin, gel coat, photoresist for electronic engineering, anti-plating agent, resist, both liquid and dry film, solder resist, for manufacturing various display applications Color filters or resists used to form structures in plasma display panels, electroluminescent display devices, and LCD (liquid crystal display, liquid crystal display devices) manufacturing steps, used to seal electrical and electronic parts The composition, solder resists, magnetic recording materials, micro mechanical parts, waveguides, optical switches, coating masks, etching masks, color test systems, glass fiber cable coatings, templates for screen printing, Materials for producing three-dimensional objects using stereolithography, holographic recording materials, image recording materials, microelectronic circuits, decolorizing materials, decolorizing materials for image recording materials, and decolorizing materials for image recording materials using microcapsules , Photoresist materials for printed wiring boards, photoresist materials for UV (ultraviolet) and visible light laser direct imaging systems, and photoresist materials for the formation of dielectric layers in the sequential build-up of printed circuit boards There are no particular restrictions on its use in various applications such as photoresist materials for 3D mounting or protective films. In the present invention, among them, it can be preferably used for color filters, photosensitive spacers, black tube columnar spacers, electrode materials, photoresists, solder resists, overcoats, insulating films, black matrices, and spacers. Next wall materials, etc. The reason is that it can more effectively exhibit an excellent balance of curability and heat resistance of the cured product. In addition, these components can be preferably used for forming parts in electronic equipment used in transportation equipment such as automobiles and aircrafts that require long-term heat resistance. The reason is that it can more effectively exhibit an excellent balance of curability and heat resistance of the cured product.

B. Hardening Next, the cured product of the present invention will be described. The cured product of the present invention is formed by curing the above-mentioned composition.

According to the present invention, since the above-mentioned composition is used, it becomes one having excellent heat resistance.

The cured product of the present invention is one using the above-mentioned composition. The said hardened|cured material contains the thing of a high molecular weight formed by the hardening component contained in the said composition. The content of such a composition can be the same as the content described in the item of "A. Composition" above, so the description here is omitted.

The compound A1 contained in the cured product may be a phenolic hydroxyl group protected by a protective group R ¹⁰¹ , or a protective group R ¹⁰¹ may be removed to generate a phenolic hydroxyl group. In the present invention, from the viewpoint of making the cured product excellent in heat resistance, the compound A1 is preferably one where the protective group R ^{101 is} removed and a phenolic hydroxyl group is generated.

Regarding the plan view shape of the cured product, it can be appropriately set in accordance with the use of the cured product, etc., and it can be, for example, a pattern shape such as a dot shape or a line shape.

Regarding the use of the above-mentioned cured product, etc., it may be the same as the content described in the section of "A. Composition" above.

The method for producing the above-mentioned cured product is not particularly limited as long as it is a method capable of forming a high-molecular weight product from the curable component in the above-mentioned composition. As such a manufacturing method, for example, the manufacturing method described in the section of "C. Manufacturing method of hardened product" mentioned later can be used.

C. Manufacturing method of hardened material Next, the manufacturing method of the cured product of the present invention will be described. One of the characteristics of the manufacturing method of the hardened object of the present invention is that it has a hardening step for hardening the above-mentioned composition.

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

1. Hardening step The hardening step in the present invention is a step of hardening the above-mentioned composition. As a method of hardening the above-mentioned composition, a method of forming a high-molecular-weight substance from a curable component can be used.

As the hardening method in this step, for example, a method of using a hardening catalyst as the above-mentioned composition together with a hardening component can be exemplified. Regarding the above-mentioned curing method, when a photopolymerization initiator such as a photoradical polymerization initiator and a photocationic polymerization initiator is contained as a curing catalyst, it is preferable to irradiate the composition with light to make the curable component The way to harden each other. The reason is that by the above-mentioned hardening method, hardening of the composition becomes easy. As the light irradiated to the composition, it is preferable to include light having a wavelength of 300 nm to 450 nm. The reason is that by using light of the above-mentioned wavelength, the curing of the composition becomes easy. As the light source for the above-mentioned light irradiation, for example, a light emitting diode (LED), ultra-high pressure mercury, mercury vapor arc, carbon arc, xenon arc, etc. can be preferably used. The reason is that by using the above-mentioned light source, the curing of the composition becomes easy. As the above-mentioned light to be irradiated, laser light can also be used. As the laser light, one containing light with a wavelength of 340 to 430 nm can be used. As the laser light source, argon ion lasers, helium-neon lasers, YAG (Yttrium Aluminium Garnet, Yttrium Aluminum Garnet) lasers, and semiconductor lasers that emit light in the visible to infrared range can also be used. Furthermore, when these lasers are used, the above-mentioned composition may contain a sensitizing pigment that absorbs visible light to infrared light.

Regarding the above-mentioned curing method, when a thermal polymerization initiator such as a thermal radical polymerization initiator and a thermal cationic polymerization initiator is contained as a curing catalyst, the composition can be preferably heated to make the composition hardenable. The way the ingredients harden each other. The reason is that heat treatment facilitates hardening of the composition. The heating temperature may be one that can stably harden the above composition, and is preferably 60°C or higher, and more preferably 100°C or higher and 300°C or lower. The reason is that by setting the heating temperature as described above, the curing of the composition becomes easy. The heating time can be about 10 seconds to 3 hours. The reason is that the curing of the composition becomes easy by setting the heating time as described above.

The above-mentioned curing method may use only the method of curing the curable component by light irradiation, or only the method of curing the curable component by heating, or the combination of the method of curing by light irradiation and the method of curing by heating. The method of hardening. When the method of curing by light irradiation and the method of curing by heating are used together, for example, light irradiation and heating treatment may be performed at the same time, or light irradiation and heating treatment may be performed sequentially.

2. Detachment step The production method of the present invention has the above-mentioned hardening step. From the viewpoint of obtaining a cured product with excellent heat resistance, it is preferable to have a detachment step for detaching the ^{protective group R 101 from the compound A1.}

As a method of removing the protecting group R ^{101 in} this step, for example, a method of heat-treating the above-mentioned compound A1, a method of light-irradiating the above-mentioned compound A1, and the like can be exemplified. In this step, the protective group R ¹⁰¹ is an unsubstituted or substituted aliphatic hydrocarbon group with 1 to 40 carbon atoms, and an unsubstituted or substituted aromatic hydrocarbon-containing group with 6 to 40 carbon atoms. Group, an unsubstituted or substituted heterocyclic group containing 2 to 40 carbon atoms or an unsubstituted or substituted silyl group with 0 to 40 carbon atoms at the oxygen atom side terminal methylene group In the case where it is substituted with a divalent group selected from the above group I, the method of the above-mentioned detachment is preferably a method of heat-treating the compound A1. The reason is that the above-mentioned protective group R ¹⁰¹ can be easily removed. In this step, when the protective group R ¹⁰¹ is a photo-releasable protective group such as o-nitrobenzyl, the method of the above-mentioned detachment is preferably a method of light irradiation treatment. The reason is that the above-mentioned protective group R ¹⁰¹ can be easily removed.

As a method of heat-treating the above-mentioned compound A1, for example, what is necessary is just a method which can remove the protective group R ¹⁰¹ from the compound A contained in a composition or its hardened|cured material. For example, a method of heating the composition or its hardened substance using a hot plate, an oven, etc., can be mentioned. The heating temperature for the above compound A1 can be set to a temperature higher than the temperature ^{at which the protective group R 101 will be released.} Specifically, the heating temperature is preferably 80°C or more and 300°C or less, preferably 100°C or more and 290°C or less, among which 120°C or more and 280°C or less, and particularly preferably 150°C or more and 250°C or less, especially Preferably, it is 180°C or more and 240°C or less. The reason for this is that the protective group R ^{101 is} easily removed from the compound A by setting the heating temperature as described above. In addition, when the above-mentioned heating temperature is the case where the above-mentioned composition contains an acid catalyst, an alkali catalyst, etc., it can be set to be equal to or lower than the desorption temperature observed ^{with the protecting group R 101 alone.} The heating temperature can be set to be the same as the content described in the item of "1. Compound A1" of the above "A. Composition". The heating time may be 5 minutes or more and 3 hours or less.

As a method of light-irradiating the above-mentioned compound A1, for example, a method of light-irradiating the composition or its cured product, etc. can be used. The wavelength of the light irradiated to the composition or the cured product can be the same as the content described in the item "1. Compound A1" of the above-mentioned "A. Composition". As the light source for the above-mentioned light irradiation, the light source described in the above-mentioned "1. Curing Step" can be used. As the cumulative light intensity with respect to the above compound A1, it can be set to be equal to or higher than the cumulative light intensity ^{at which the protecting group R 101 is released.} As the above-mentioned cumulative light quantity, it is preferably 1000 mJ/cm ² or more and 10000 mJ/cm ² or less, among which it is more than 1000 mJ/cm ² and 5000 mJ/cm ² or less, and more preferably 2000 mJ/cm ² or more 4000 mJ/cm ² or less. The reason for this is that the protective group R ^{101 is} easily removed from the compound A by being the above-mentioned accumulated light quantity. The above-mentioned accumulated light quantity can be made the same as the content described in the item of "1. Compound A1" of the above-mentioned "A. Composition", for example.

As the execution timing of this step, it is only necessary to obtain a cured product having the desired heat resistance. For example, regarding the above implementation sequence, when this step is a step of performing light irradiation treatment, and the curing method in the above curing step is a method of irradiating the composition with light to harden the curable components, it can be combined with the above curing step. Simultaneous implementation. In addition, regarding the above-mentioned implementation sequence, when this step is a step of heat treatment, and the curing method in the above-mentioned curing step is a method of irradiating the composition with light to harden the curable components, it is preferable to use the above-mentioned curing method. In the step, it is carried out after the light irradiation treatment for hardening the curable components to each other. The reason is that it becomes a person with excellent step passability. When this step is a step of heat treatment, and the hardening method in the above-mentioned hardening step is a method of heat-treating the composition to harden the curable components with each other, the execution timing of this step may be the same as that of the above-mentioned hardening step. The heat treatment to harden the curable components or the baking step described later are performed at the same time.

3. Other steps The method of manufacturing the above-mentioned hardened product may include other steps as necessary in addition to the above-mentioned hardening step and detachment step. As the above-mentioned other steps, for example: after the above-mentioned hardening step, the unhardened part of the coating film of the composition is removed to obtain a pattern-like hardened product; after the above-mentioned hardening step, the hardened product is heated and then baked Baking step; before the hardening step, the composition is heated to remove the solvent in the pre-baking step; before the hardening step, the step of forming a coating film of the composition, etc.

As a method of removing the unhardened portion in the above-mentioned development step, for example, a method of applying an alkaline developer to the unhardened portion can be exemplified. As the alkaline developer, those generally used as alkaline developer such as tetramethylammonium hydroxide (TMAH) aqueous solution or potassium hydroxide aqueous solution can be used. The execution timing of the above-mentioned developing step only needs to be after the above-mentioned hardening step. The heating conditions in the post-baking step may be those that can increase the strength of the cured product obtained in the hardening step. For example, it can be performed at 200°C or higher and 250°C or lower for 20 minutes to 90 minutes. The heating conditions in the above-mentioned pre-baking step may be those that can remove the solvent in the composition, and for example, it can be set at 70°C or higher and 150°C or lower for 30 seconds to 300 seconds. As a method of coating the composition in the step of forming the above-mentioned coating film, spin coating, roll coating, bar coating, die nozzle coating, curtain coating, various printing, and dipping methods can be used. And other well-known methods. The above-mentioned coating film may be formed on a substrate. As the above-mentioned base material, it can be appropriately set according to the use of the cured product, etc., and examples thereof include soda glass, quartz glass, semiconductor substrate, metal, paper, plastic, and the like. In addition, the above-mentioned cured product may be used after being peeled off from the base material after being formed on the base material, or may be used by transferring from the base material to other adherends.

3. Other Regarding the cured product manufactured by the above-mentioned manufacturing method and its use, etc., it can be made the same as the content described in the section of the above-mentioned "A. Composition".

D. Additives Next, the additive of the present invention will be explained. The additive of the present invention contains a compound represented by the above general formula (A1) and a sulfur-based antioxidant.

According to the present invention, since it contains the compound represented by the above general formula (A1) and the sulfur-based antioxidant, by adding it to a composition containing a curable component, a balance of curability and heat resistance of the cured product can be easily formed Excellent composition.

The additive of the present invention contains compound A1 and sulfur-based antioxidant.

1. Compound A1 and sulfur-based antioxidants As the total content of the compound A1 and sulfur-based antioxidant in the additive of the present invention, 100 parts by mass of the solid content of the additive can be set to 100 parts by mass, that is, the solid content of the additive is only the compound A1 and Sulfur-based antioxidants. In addition, the total content of the above-mentioned compound A1 and the sulfur-based antioxidant may be less than 100 parts by mass in 100 parts by mass of the solid content of the additive, that is, the additive may be a combination containing the above-mentioned compound A1 and the sulfur-based antioxidant. The substance can be, for example, more than 20 parts by mass and 99.99 parts by mass or less. The reason is that by setting the above content within the above range, it is easy to form a composition having more excellent curability and heat resistance of the cured product. In the present invention, the lower limit of the total content of the above-mentioned compound A1 and sulfur-based antioxidant is less than 100 masses of the solid content of the additive from the viewpoint of easily forming a composition having better curability and better heat resistance of the cured product. Among the parts, it is preferably 50 parts by mass or more, particularly preferably 70 parts by mass or more, and particularly preferably 90 parts by mass or more. The reason is that by setting the above content within the above range, it is easy to form a composition having an excellent balance of curability and heat resistance of the cured product. In addition, from the viewpoint of facilitating the particle size control of the additive, etc., the upper limit of the total content of the compound A1 and the sulfur-based antioxidant is preferably 99 parts by mass based on 100 parts by mass of the solid content of the additive. Parts or less, among them, 95 parts by mass or less is preferable, and 90 parts by mass or less is particularly preferable. The reason is that by setting the above content within the above range, it is easy to form a composition having an excellent balance of curability and heat resistance of the cured product.

In addition, the compound A1 and the sulfur-based antioxidant can be the same as those described in the items of "1. Compound A" and "2. Sulfur-based antioxidant" of the above-mentioned "A. Composition". The content of the compound A1 in a total of 100 parts by mass of the compound A1 and the sulfur-based antioxidant may be the same as the content described in the item of the above-mentioned "A. composition".

2. Solvent The above-mentioned additive may contain a solvent in addition to the above-mentioned compound A1 and sulfur-based antioxidant. As said solvent, what is necessary is just to disperse or dissolve each component in an additive, and can be made into the content described in the item of the said "A. Composition". In addition, the content can be 1 part by mass or more and 99 parts by mass or less in 100 parts by mass of the above-mentioned additives.

3. Other ingredients The above-mentioned additives may contain other components other than compound A1, sulfur-based antioxidant, and solvent. As the above-mentioned other components, the content described in the item of "5. Other components" of the above-mentioned "A. Composition" can be exemplified. The content of the above-mentioned other components can be appropriately set according to the use of the above-mentioned additive, etc., for example, in 100 parts by mass of the additive, it can be set to 50 parts by mass or less, preferably 10 parts by mass or less. The reason is that it is easy to make the content ratio of the compound A1 of the above additives and the sulfur-based antioxidant relatively large, and it is easy to form a composition having more excellent curability and heat resistance of the cured product.

4. Other The properties of the above-mentioned additives can be appropriately set according to the method of addition to the composition, etc., for example, it can be in the form of liquid, powder, granule, etc. in which compound A1 and sulfur-based antioxidants are dispersed or dissolved in a solvent. As a manufacturing method of the said additive, what is necessary is just a method which can contain compound A1 and a sulfur-type antioxidant in a desired compounding quantity.

The use of the above-mentioned additive includes a composition requiring heat resistance and the like. The use of adding to a composition containing a curable component is preferred, and the use of a curable component containing a radically polymerizable compound is particularly preferred. As the use of the above-mentioned composition, specifically, it can be made the same as the content described in the item of the above-mentioned "A. Composition".

The present invention is not limited to the above-mentioned embodiment. The above-mentioned embodiments are examples, and those having substantially the same constitution as the technical idea described in the scope of patent application of the present invention and exhibiting the same effects are included in the technical scope of the present invention. Example

Hereinafter, the present invention will be described in further detail with examples and the like, but the present invention is not limited to these examples.

[Production Example A1-1] A phenol compound (compound represented by the following formula (C1-1)) 0.01 mol, 0.05 mol di-tert-butyl dicarbonate, and 30 g of pyridine were mixed, and under a nitrogen atmosphere, 0.025 mol of 4-dimethylaminopyridine was added at room temperature, and the mixture was stirred at 60°C for 3 hours to obtain a reaction liquid. After cooling to room temperature, the reaction liquid was poured into 150 g of ion-exchange water, and 200 g of chloroform was added to perform oil-water separation. After the organic layer was dried with 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 product (the compound represented by the following general formula (A1-1)). It was ^{confirmed by 1} H-NMR that the obtained white powdery crystal was the target product.

[Production Examples A1-2 and A1-3] The following formulae (C1-2) to (C1-3) were used as the phenol compound, and the following formula (A1) was synthesized in the same manner as in Production Example A1-1, except that -2) Compounds shown in (A1-3). It was ^{confirmed by 1} H-NMR that the obtained white powdery crystal was the target product.

[化22]

[化23]

[Examples 1 to 5 and Comparative Examples 1 to 6] According to the formulation described in Table 1 below, compound A, sulfur-based antioxidants, non-sulfur-based antioxidants, hardening components, hardening catalysts, and additives were stirred in a defoaming mixer at an initial temperature of 25°C for 3 minutes. combination. In addition, the following materials are used for each component. Furthermore, the blending amount in the table represents the mass parts of each component.

(Compound A) A1-1: The compound represented by the above formula (A1-1) A1-2: The compound represented by the above formula (A1-2) A1-3: The compound represented by the above formula (A1-3)

(Sulfur-based antioxidant) B1-1: The compound represented by the following formula (B1-1) B1-2: The compound represented by the following formula (B1-2)

(Non-sulfur antioxidant) C2-1: The compound represented by the following formula (C2-1)

(Hardening ingredient) D-1: The compound represented by the following formula (D-1) D-2: The compound represented by the following formula (D-2)

(Hardening catalyst) E-1: Irgacure 907 (radical polymerization initiator, phosphine-based compound)

(additive) F-1: SH-29PA (silicone-based surfactant) manufactured by Toray Dow Corning

[化24]

[Evaluation] With respect to the obtained compositions of Examples and Comparative Examples, the heat resistance and curability were evaluated by the following methods.

1. Evaluation of heat resistance A spacer tape with a thickness of 0.13 mm is pasted on the four corners of a 10 cm square glass. Then, the compositions of the examples and comparative examples were coated on the glass in the area surrounded by the spacer tape, and clamped with 10 cm square glass to obtain a glass laminate. Next, an ultra-high pressure mercury lamp (UL-750: manufactured by HOYA, 20 mW/cm ² ) was used to irradiate the glass laminate with 200 mJ/cm ² to form a cured film of the composition sandwiched between two sheets of glass. Then, the cured film was taken out from the glass laminate. Then, the cured film was allowed to stand in an oven at 200° C. for 30 minutes to perform heat treatment to obtain a test piece. The obtained test piece was subjected to a heat treatment (heating test) in an oven at 150°C for 250 hours. According to ASTM (American Society for Testing Materials, American Society for Testing Materials) D1925, the YI of the test piece before and after the heating test was calculated. Use the following criteria to evaluate the YI change (ΔYI) before and after the heating test. The results are shown in Table 1. +: ΔYI is less than 10 -: ΔYI is 10 or more. The smaller the ΔYI, the better the heat resistance.

[Table 1] Example 1 Example 2 Example 3 Example 4 Example 5 Comparative example 1 Comparative example 2 Comparative example 3 Comparative example 4 Comparative example 5 Comparative example 6 Compound A A1-1 1 1 - - 1 - 1 3 - - 1 A1-2 - - 1 - - - - - - - - A1-3 - - - 1 - - - - - - - Sulfur-based antioxidants B1-1 1 3 3 3 - - - - 1 3 - B1-2 - - - - 3 - - - - - - Non-sulfur antioxidant C2-1 - - - - - - - - - - 1 Polymeric compound D-1 80 80 80 80 80 80 80 80 80 80 80 D-2 20 20 20 20 20 20 20 20 20 20 20 Polymerization initiator E-1 1 1 1 1 1 1 1 1 1 1 1 Surfactant F-1 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Evaluation Heat resistance evaluation + + + + + - - - - - -

[to sum up] Although not listed in Table 1, the composition of any of the examples can be hardened. In addition, from the results shown in Table 1, it was confirmed that the obtained cured product was excellent in heat resistance. For example, it was confirmed that a cured product exhibiting excellent heat resistance under temperature conditions of 80°C or higher and 250°C or lower was obtained. In contrast, although the cured product of Comparative Example 1 can be cured, the heat resistance of the cured product obtained is not sufficient. As described above, it is confirmed that the composition of the examples has an excellent balance between the curability of the composition and the heat resistance of the cured product.

[Examples 6-10 and Comparative Examples 7-25] According to the formulation described in Tables 2 to 4 below, compound A, sulfur-based antioxidants, non-sulfur-based antioxidants, hardenable ingredients, hardening catalysts, additives, and solvents are stirred in a defoaming mixer at an initial temperature of 25°C The composition was obtained in 3 minutes. In addition, the following materials are used for each component. Furthermore, the blending amount in the table represents the mass parts of each component.

(Compound A) A1-1: The compound represented by the above formula (A1-1) A1-2: The compound represented by the above formula (A1-2) A1-3: The compound represented by the above formula (A1-3)

(Sulfur-based antioxidant) B1-1: The compound represented by the above formula (B1-1) B1-2: The compound represented by the above formula (B1-2)

(Non-sulfur antioxidant) C1-1: The compound represented by the above formula (C1-1) C1-2: The compound represented by the above formula (C1-2) C1-3: The compound represented by the above formula (C1-3) C2-1: The compound represented by the above formula (C2-1)

(Hardening ingredient) D-3: SPC-1000 (radical polymerizable compound, unsaturated modified (meth)acrylic resin, PEGMEA (Poly(ethylene glycol) methacrylate) with a solid content of 29% by mass, manufactured by Showa Denko Co., Ltd. Polyethylene glycol methacrylate) solution) D-4: SPC-3000 manufactured by Showa Denko Co., Ltd. (free radical polymerizable compound, unsaturated modified (meth)acrylic resin, PEGMEA solution with a solid content of 43% by mass) D-5: Dipentaerythritol hexaacrylate (radical polymerizable compound, 6 functions)

(Hardening catalyst) E-1: NCI-930 (radical polymerization initiator) manufactured by ADEKA

(additive) F-1: FZ-2122 (Dimethylpolysiloxane with polyalkylene oxide unit) manufactured by Toray Dow Corning Corporation

(Solvent) G-1: Propylene glycol monomethyl ether acetate (PGMEA)

[Evaluation] With respect to the obtained compositions of Examples and Comparative Examples, the heat resistance and curability were evaluated by the following methods.

1. Heat resistance evaluation 2 Prepare 10 cm square glass. Then, the composition obtained in each example and each comparative example was coated on one surface of the glass by the spin coating method in such a way that the film thickness after heat treatment became 4 μm, and then it was allowed to stand in an oven at 90°C for 2 Pre-baking was performed in minutes to obtain a glass laminate. For the obtained glass laminate, a mirror projection aligner (product name: TME-150RTO, a high-pressure mercury lamp manufactured by TOPCON Co., Ltd.) was used to irradiate ultraviolet rays ^{to the coating film at an irradiance of 20 mJ/cm 2 without a mask.} , Form a hardened film on the glass. Then, the glass laminate on which the cured film was formed was allowed to stand in an oven at 200° C. for 30 minutes for heat treatment to obtain a test piece. The obtained test piece was subjected to heat treatment (heating test) in an oven at 150°C for 336 hours. Measure the 400 nm transmittance (%) of the cured film before and after the heating test of the test piece with the UV-Vis spectrophotometer V-760 (manufactured by JASCO), and calculate the difference in transmittance (400 nm transmittance of the cured film after the heating test -400 nm transmittance of the cured film before the heating test). Use the following criteria to evaluate the difference in transmittance calculated. The results are shown in Tables 2 to 4. +: less than 0.4% -: more than 0.4% and less than 2% --: more than 2%, the smaller the difference in transmittance, the better the heat resistance.

2. Evaluation of Hardness 2 The exposure gap was set to 100 μm, and ultraviolet rays were irradiated through a negative mask formed with a line pattern of 30 μm. Then, a developer containing a 0.04% by mass potassium hydroxide aqueous solution was sprayed at 23°C to perform spraying for 40 seconds Except for the development, a test piece was obtained by the same method as the above-mentioned "1. Heat resistance evaluation 2". The width (line width) of the pattern of the cured film of the obtained test piece was measured and evaluated using the following criteria. The results are shown in Tables 2 to 4. +: 30 μm or more -: less than 30 μm Furthermore, the wider the line width, the better the curability.

[Table 2] Example 6 Example 7 Example 8 Example 9 Example 10 Compound A A1-1 1 1 1 - - A1-2 - - - 1 - A1-3 - - - - 1 Sulfur-based antioxidants B1-1 1 3 - 3 - B1-2 - - 1 - 3 Non-sulfur antioxidant C1-1 - - - - - C1-2 - - - - - C1-3 - - - - - C2-1 - - - - - Polymeric compound D-3 137 137 137 137 137 D-4 40 40 40 40 40 D-5 43 43 43 43 43 Polymerization initiator E-1 1 1 1 1 1 Surfactant F-1 0.2 0.2 0.2 0.2 0.2 Solvent G-1 386 386 386 386 386 Evaluation Heat resistance evaluation + + + + + Hardening evaluation + + + + +

[table 3] Comparative example 7 Comparative example 8 Comparative example 9 Comparative example 10 Comparative example 11 Comparative example 12 Comparative example 13 Comparative example 14 Comparative example 15 Comparative example 16 Compound A A1-1 - 1 3 - - 1 1 - - - A1-2 - - - - - - - - - - A1-3 - - - - - - - - - - Sulfur-based antioxidants B1-1 - - - 1 3 - - - - - B1-2 - - - - - - - - - - Non-sulfur antioxidant C1-1 - - - - - - - - - 1 C1-2 - - - - - - - - - - C1-3 - - - - - - - - - - C2-1 - - - - - 1 3 1 3 - Polymeric compound D-3 137 137 137 137 137 137 137 137 137 137 D-4 40 40 40 40 40 40 40 40 40 40 D-5 43 43 43 43 43 43 43 43 43 43 Polymerization initiator E-1 1 1 1 1 1 1 1 1 1 1 Surfactant F-1 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 Solvent G-1 386 386 386 386 386 386 386 386 386 386 Evaluation Heat resistance evaluation - - - - - - - - - - Hardening evaluation + + + + + + + + + -

[Table 4] Comparative example 17 Comparative Example 18 Comparative Example 19 Comparative example 20 Comparative Example 21 Comparative example 22 Comparative example 23 Comparative example 24 Comparative example 25 Compound A A1-1 - 1 1 - - - - - - A1-2 - - - - - - - - - A1-3 - - - - - - - - - Sulfur-based antioxidants B1-1 - - - 1 1 1 - B1-2 - - - - - - - - - Non-sulfur antioxidant C1-1 3 1 3 1 3 - - - 1 C1-2 - - - - - 1 - - - C1-3 - - - - - - 1 - - C2-1 - - - - - - - 1 1 Polymeric compound D-3 137 137 137 137 137 137 137 137 137 D-4 40 40 40 40 40 40 40 40 40 D-5 43 43 43 43 43 43 43 43 43 Polymerization initiator E-1 1 1 1 1 1 1 1 1 1 Surfactant F-1 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 Solvent G-1 386 386 386 386 386 386 386 386 386 Evaluation Heat resistance evaluation - - + - - - - - - Hardening evaluation - - - - - - - + -

From the results shown in Tables 2 to 4, it was confirmed that the compositions of Examples 6 to 10 all had sufficient curability. In addition, it was confirmed that the obtained cured product was excellent in heat resistance. On the other hand, the curability of the compositions of Comparative Examples 7 to 25 was insufficient, or the heat resistance of the cured product obtained was poor, and it was impossible to obtain a composition having excellent curability and excellent heat resistance. As described above, it can be confirmed that the composition of Examples 6 to 10 has an excellent balance between the curability of the composition and the heat resistance of the cured product.

[Manufacturing Example 4-1] Using the same method as in Synthesis Example 1 of JP 2017-111453 A, a carboxyl group-containing resin with an acid value of 88 mgKOH/g of solid components other than the solvent and a solid component concentration of 71% by mass (cresol A resin solution of epoxy acrylate resin obtained by reacting novolac type epoxy resin with acrylic acid.

[Examples 11 to 17 and Comparative Examples 26 to 46] According to the formulations described in Tables 5-7 below, compound A, sulfur antioxidants, non-sulfur antioxidants, hardening ingredients, hardening catalysts, additives, and solvents are mixed in a defoaming mixer and stirred at an initial temperature of 25°C The composition was obtained in 3 minutes. In addition, each component in the table indicates the following materials. Furthermore, the blending amount in the table represents the mass parts of each component.

(Compound A) A1-1: The compound represented by the above formula (A1-1) A1-2: The compound represented by the above formula (A1-2) A1-3: The compound represented by the above formula (A1-3)

(Sulfur-based antioxidant) B1-1: The compound represented by the above formula (B1-1) B1-2: The compound represented by the above formula (B1-2)

(Non-sulfur antioxidant) C1-1: The compound represented by the above formula (C1-1) C1-2: The compound represented by the above formula (C1-2) C1-3: The compound represented by the above formula (C1-3) C2-1: The compound represented by the above formula (C2-1)

(Curable component: radical polymerizable compound) D-5: Dipentaerythritol hexaacrylate (radical polymerizable compound, 6 functions) D-6: Resin solution of the carboxyl group-containing resin produced in Production Example 4-1 (acid value of solid content 88 mgKOH/g, concentration of solid content 71% by mass)

(Curable ingredient: thermosetting compound) D2-1: Biphenyl type epoxy resin (NC3000 manufactured by Nippon Kayaku Co., Ltd., multifunctional epoxy compound) D2-2: Biphenyl type epoxy resin (YX-4000 manufactured by Mitsubishi Chemical Corporation, multifunctional epoxy compound)

(Hardening catalyst: radical polymerization initiator) E-2: IRGACURE TPO (manufactured by BASF Japan) E-3: IRGACURE OXE02 (manufactured by BASF Japan)

(Hardening catalyst: thermal hardening agent) E2-1: Dicyandiamide E2-2: Imidazole-based hardening catalyst (2PHZ manufactured by Shikoku Chemical Industry Co., Ltd.)

(Additive: filler) F2-1: Silicon dioxide (SO-E5 manufactured by Admatechs) F2-2: Titanium oxide (TIPAQUE R-820 manufactured by Ishihara Sangyo Co., Ltd.)

(Additive: colorant) F3-1: pigment blue 15 (pigment) F3-2: pigment yellow 14 (pigment)

(Solvent) G-1: Propylene glycol monomethyl ether acetate (PGMEA, ether ester solvent)

[Evaluation] With respect to the obtained compositions of Examples 11 to 17 and Comparative Examples 26 to 46, the heat resistance and curability were evaluated by the following methods.

1. Heat resistance evaluation 3 The compositions obtained in Examples 11-17 and Comparative Examples 26-46 were applied to FR-4 copper clad with a thickness of 1.6 mm so that the film thickness of the cured product after curing became 20 μm After the laminate is laminated, the coating film is dried at 80°C for 30 minutes. Then, the dried coating film is exposed to ultraviolet rays with a cumulative light quantity of ^{1000 mJ/cm 2.} Then, the coating film after ultraviolet exposure was heat-processed at 150 degreeC for 60 minutes, and the sample for evaluation was obtained. Then, the sample for evaluation was heat-processed (heating test) in 150 degreeC oven for 250 hours. Using a color difference meter, calculate the b ^* value of the evaluation sample before and after heating. Use the following criteria to evaluate the b ^* value change (Δb ^* ) before and after the heating test. The results are shown in Tables 5 to 7 below. +: Δb ^* less than 5 -: Δb ^* is 5 or more The ^{smaller the Δb *} , the more excellent heat resistance can be judged.

2. Curability evaluation 3 The compositions of Examples 11-17 and Comparative Examples 26-46 were coated on a glass substrate so that the film thickness of the cured product after curing became 20 μm, and the coating film was dried at 80°C 30 minutes. After that, use a high-pressure mercury lamp to expose the dried coating film through a mask (mask opening 30 μm) (exposure gap 300 μm, exposure amount 500 mJ/cm ² ). A 1.0% by mass sodium carbonate aqueous solution was used as a developer, and the exposed coating film was developed for 60 seconds, then thoroughly washed with water, and post-baked at 150°C for 60 minutes in a clean oven to fix the pattern to obtain a sample for evaluation. Observe the pattern on the obtained evaluation sample with an optical microscope, and measure the line width of the part corresponding to the opening of the mask. The pattern on the obtained evaluation sample was observed with an optical microscope, the width (line width) of the pattern was measured, and the evaluation was performed using the following criteria. The results are shown in Tables 5 to 7 below. +: 30 μm or more -: 27.5 μm or more and less than 30 μm. --: Less than 27.5 μm. The wider the line width, the better the curability. In addition, the smaller the difference with respect to the set line width, the better it can be judged that the photolithography property is also excellent.

[table 5] Example 11 Example 12 Example 13 Example 14 Example 15 Example 16 Example 17 Compound A A1-1 1 1 - - 1 1 1 A1-2 - - 1 - - - - A1-3 - - - 1 - - - Sulfur-based antioxidants B1-1 1 3 3 3 - 1 1 B1-2 - - - - 3 - - Non-sulfur antioxidant C1-1 - - - - - - - C1-2 - - - - - - - C1-3 - - - - - - - C2-1 - - - - - - - Hardening ingredients D-5 15 15 15 15 15 15 15 D-6 141 141 141 141 141 141 141 D2-1 25 25 25 25 25 25 25 D2-2 20 20 20 20 20 20 20 Hardening catalyst E-2 7.5 7.5 7.5 7.5 7.5 7.5 7.5 E-3 1 1 1 1 1 1 1 E2-1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 E2-2 0.1 0.1 0.1 0.1 0.1 0.1 0.1 additive F2-1 155 155 155 155 155 155 - F2-2 - - - - - - 155 F3-1 - - - - - 1.5 - F3-2 - - - - - 2 - Solvent G-1 5 5 5 5 5 5 5 Evaluation Heat resistance evaluation 3 + + + + + + + Hardening evaluation 3 + + + + + + +

[Table 6] Comparative Example 26 Comparative Example 27 Comparative Example 28 Comparative Example 29 Comparative example 30 Comparative example 31 Comparative example 32 Comparative Example 33 Comparative Example 34 Comparative Example 35 Compound A A1-1 - 1 3 - - 1 1 - - - A1-2 - - - - - - - - - - A1-3 - - - - - - - - - - Sulfur-based antioxidants B1-1 - - - 1 3 - - - - - B1-2 - - - - - - - - - - Non-sulfur antioxidant C1-1 - - - - - - - - - 1 C1-2 - - - - - - - - - - C1-3 - - - - - - - - - - C2-1 - - - - - 1 3 1 3 - Hardening ingredients D-5 15 15 15 15 15 15 15 15 15 15 D-6 141 141 141 141 141 141 141 141 141 141 D2-1 25 25 25 25 25 25 25 25 25 25 D2-2 20 20 20 20 20 20 20 20 20 20 Hardening catalyst E-2 7.5 7.5 7.5 7.5 7.5 7.5 7.5 7.5 7.5 7.5 E-3 1 1 1 1 1 1 1 1 1 1 E2-1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 E2-2 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 additive F2-1 155 155 155 155 155 155 155 155 155 155 F2-2 - - - - - - - - - - F3-1 - - - - - - - - - - F3-2 - - - - - - - - - - Solvent G-1 5 5 5 5 5 5 5 5 5 5 Evaluation Heat resistance evaluation 3 - - - - - - - - - - Hardening evaluation 3 + + + + + + + + + -

[Table 7] Comparative Example 36 Comparative Example 37 Comparative Example 38 Comparative Example 39 Comparative example 40 Comparative Example 41 Comparative example 42 Comparative example 43 Comparative example 44 Comparative Example 45 Comparative Example 46 Compound A A1-1 1 1 - - - - - - 1 1 A1-2 - - - - - - - - - - - A1-3 - - - - - - - - - - - Sulfur-based antioxidants B1-1 - - - 1 1 - - 1 3 - - B1-2 - - - - - - - - - - - Non-sulfur antioxidant C1-1 3 1 3 1 3 1 3 - - - - C1-2 - - - - - - - - - - - C1-3 - - - - - - - - - - - C2-1 - - - - - 1 1 1 1 - - Hardening ingredients D-5 15 15 15 15 15 15 15 15 15 15 15 D-6 141 141 141 141 141 141 141 141 141 141 141 D2-1 25 25 25 25 25 25 25 25 25 25 25 D2-2 20 20 20 20 20 20 20 20 20 20 20 Hardening catalyst E-2 7.5 7.5 7.5 7.5 7.5 7.5 7.5 7.5 7.5 7.5 7.5 E-3 1 1 1 1 1 1 1 1 1 1 1 E2-1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 E2-2 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 additive F2-1 155 155 155 155 155 155 155 155 155 155 - F2-2 - - - - - - - - - - 155 F3-1 - - - - - - - - - 1.5 - F3-2 - - - - - - - - - 2 - Solvent G-1 5 5 5 5 5 5 5 5 5 5 5 Evaluation Heat resistance evaluation 3 - - + + + - - - - - - Hardening evaluation 3 - - - - - - - + + + +

According to the results shown in Table 5 to Table 7, it can be confirmed that the composition of the examples has an excellent balance between the curability of the composition and the heat resistance of the cured product. In addition, as shown in Tables 5 to 7, it can be confirmed that the compositions of the examples can also be preferably used for coloring hardening containing various coloring agents, such as color filters, photosensitive spacers, and black tube columnar spacers. Compositions, solder resists and other filler-containing compositions.

Claims (15)

A composition comprising: a compound represented by the following general formula (A1); a sulfur-based antioxidant; and a hardening component;

(In the formula, R ¹⁰¹ represents an unsubstituted or substituted aliphatic hydrocarbon group with 1 to 40 carbon atoms, an unsubstituted or substituted aromatic hydrocarbon-containing group with 6 to 40 carbon atoms, and a carbon atom An unsubstituted or substituted heterocyclic group containing 2-40, an unsubstituted or substituted silyl group with 0-40 carbon atoms, or the aliphatic hydrocarbon group or the aromatic hydrocarbon-containing group One or more of the heterocyclic group or the methylene group in the silyl group is substituted with a divalent group selected from the following group I, R ¹⁰² and R ¹⁰³ are each independently Represents a hydrogen atom or an unsubstituted or substituted aliphatic hydrocarbon group with 1-40 carbon atoms, R ¹⁰⁴ represents a halogen atom, a cyano group, a hydroxyl group, a nitro group, a carboxyl group, an unsubstituted or a C 1-40 aliphatic hydrocarbon group Substituent aliphatic hydrocarbon group, unsubstituted or substituted aromatic hydrocarbon-containing group with 6 to 40 carbon atoms, unsubstituted or substituted heterocyclic ring-containing group with 2 to 40 carbon atoms , Or one or more of the methylene groups in the aliphatic hydrocarbon group, the aromatic hydrocarbon-containing group or the heterocyclic group-containing group are substituted with a divalent group selected from the following group I when group R ¹⁰⁴ in the presence of a plurality of situation, there are plural R ¹⁰⁴ bonded to each other to form a benzene or naphthalene ring of the case, in case of presence of a plurality of R ^104, there are a plurality of R ¹⁰⁴ are the same case, There are also different situations. n represents an integer from 1 to 10, and a1 represents an integer from 0 to 2. When n is 2 to 10, there are plural R ¹⁰¹ , R ¹⁰² , R ¹⁰³ , R ¹⁰⁴ and a1 respectively Can be the same or different, X represents the base of n valence) 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 unsubstituted aliphatic hydrocarbon group with 1-40 carbon atoms. The composition of claim 1, wherein R ¹⁰¹ is an unsubstituted or substituted aliphatic hydrocarbon group with 1 to 40 carbon atoms, and an unsubstituted or substituted aromatic hydrocarbon group with 6 to 40 carbon atoms The methylene group at the end of the oxygen atom in an unsubstituted or substituted heterocyclic group containing 2 to 40 carbon atoms is substituted with a divalent group selected from the above group I Group, or unsubstituted or substituted silyl group having 0-40 carbon atoms. The composition of claim 1, wherein R ¹⁰² and R ¹⁰³ are each independently a hydrogen atom, an unsubstituted or substituted alkyl group having 1 to 40 carbon atoms. Such as the composition of claim 1, wherein n represents an integer from 2 to 4, X is an unsubstituted or substituted aliphatic hydrocarbon group with 10-25 carbon atoms having the same valence as n; an unsubstituted or substituted aliphatic hydrocarbon group with 4-25 carbon atoms having the same valence as n A substituted or substituted heterocyclic ring-containing group; or one or more of the methylene groups in the aliphatic hydrocarbon group or the heterocyclic ring-containing group are substituted to be selected from -O-, -COO-,- OCO- and -CO- are formed by the divalent group in the group. The composition of claim 1, wherein the sulfur-based antioxidant is a thioether-based antioxidant. The composition of claim 5, wherein the thioether antioxidant is at least one selected from the group consisting of the following general formulas (B1), (B2), (B3) and (B4),

(In the formula, R ¹ and R ² each independently represent an aryl group with 6 to 20 carbon atoms, an alkyl group with 3 to 30 carbon atoms, or one or more of the methylene groups in the alkyl group. Substituted with -O- or -S-, R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ each independently represent a hydrogen atom and the number of carbon atoms is 1-8 The alkyl group, or one or more of the methylene groups in the alkyl group is substituted with -O- or -S-. One or more of the hydrogen atoms of the above-mentioned alkyl group may be (Substituted with alkoxy, alkenyl, alkenyloxy, hydroxyl or cyano, one or more of the hydrogen atoms of the above aryl group may be substituted with a hydroxyl group or an alkyl group with 1 to 8 carbon atoms)

(In the formula, R ¹¹ represents an aryl group with 6 to 20 carbon atoms, an alkyl group with 3 to 30 carbon atoms, or one or more of the methylene groups in the alkyl group are substituted with -O- or -S-, R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ and R ¹⁹ each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. One or more of the hydrogen atoms of the group may be substituted with alkoxy, alkenyl, alkenyloxy, hydroxy, or cyano, and one or more of the hydrogen atoms of the above aryl group may be substituted with hydroxy or Alkyl group with 1 to 8 carbon atoms)

(In the formula, R ²¹ , R ²² , R ²³ and R ²⁴ each independently represent an alkyl group having 3 to 30 carbon atoms, or one or more of the methylene groups in the alkyl group are substituted with -O -Or -S-, one or more of the hydrogen atoms of the alkyl group may be substituted with alkoxy, alkenyl, alkenyloxy, hydroxyl or cyano)

(In the formula, R ³¹ and R ³² each independently represent one or two of a hydrogen atom, an aryl group having 6 to 20 carbon atoms, an alkyl group having 3 to 30 carbon atoms, or the methylene group in the alkyl group. More than one group substituted with -O- or -S-, L ¹ and L ² each independently represent an alkylene group having 1 to 8 carbon atoms, 1 of the above-mentioned alkyl group and the hydrogen atom of the above-mentioned alkylene group One or two or more may be substituted with alkoxy, alkenyl, alkenyl, hydroxy, or cyano, and one or two of the hydrogen atoms of the aryl group may be substituted with hydroxy or with 1-8 carbon atoms的alkyl). Such as the composition of claim 6, wherein R ¹ and R ² in formula (B1) are each independently an alkyl group having 8-20 ^{carbon atoms, and R 11} in formula (B2) is an alkane having 8-20 carbon atoms In formula (B3), R ²¹ , R ²² , R ²³ and R ²⁴ are each independently an alkyl group having 8 to 20 carbon atoms, and R ³¹ and R ³² in formula (B4) are independently 8 carbon atoms. ~20 alkyl group. The composition of claim 6, wherein the above-mentioned thioether antioxidant is a compound represented by the above-mentioned general formula (B3) or (B4). The composition of claim 1, wherein the content of the compound represented by the general formula (A1) is 10 parts by mass or more in 100 parts by mass of the compound represented by the general formula (A1) and the sulfur-based antioxidant 70 parts by mass or less. The composition according to claim 1, wherein the curable component contains a radical polymerizable compound. The composition according to claim 10, wherein the radically polymerizable compound contains a compound having an acidic group and an ethylenically unsaturated group. The composition according to claim 10, wherein the curable component further contains a thermosetting compound. A hardened product obtained by hardening the composition according to claim 1. A method for manufacturing a hardened product, which has a hardening step of hardening the composition of claim 1. An additive comprising: a compound represented by the following general formula (A1); and a sulfur-based antioxidant;

(In the formula, R ¹⁰¹ represents an unsubstituted or substituted aliphatic hydrocarbon group with 1 to 40 carbon atoms, an unsubstituted or substituted aromatic hydrocarbon-containing group with 6 to 40 carbon atoms, and a carbon atom An unsubstituted or substituted heterocyclic group containing 2-40, an unsubstituted or substituted silyl group with 0-40 carbon atoms, or the aliphatic hydrocarbon group or the aromatic hydrocarbon-containing group , One or more of the heterocyclic group or the methylene group in the silyl group is substituted with a divalent group selected from the following group I, R ¹⁰² and R ¹⁰³ are each independently Represents a hydrogen atom or an unsubstituted or substituted aliphatic hydrocarbon group with 1-40 carbon atoms, R ¹⁰⁴ each independently represents a halogen atom, a cyano group, a hydroxyl group, a nitro group, a carboxyl group, and a C 1-40 aliphatic hydrocarbon group Substituted or substituted aliphatic hydrocarbon groups, unsubstituted or substituted aromatic hydrocarbon-containing groups with 6 to 40 carbon atoms, unsubstituted or substituted heterogeneous groups with 2 to 40 carbon atoms One or more of the methylene groups in the cyclic group, or the aliphatic hydrocarbon group, the aromatic hydrocarbon-containing group, or the heterocyclic group-containing group is substituted with a divalent group selected from the following group I from the group, there is to the case where a plurality of R ^104, R ¹⁰⁴ has a plurality bonded to each other to form a benzene or naphthalene ring of the case, there is to the case where a plurality of R ^104, R ¹⁰⁴ each have a plurality of identical There are also different situations. n represents an integer from 1 to 10, and a1 represents an integer from 0 to 2. When n is 2 to 10, there are multiple R ¹⁰¹ , R ¹⁰² , R ¹⁰³ , R ¹⁰⁴ And a1 can be the same or different, respectively, X represents the n-valent base) 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 are independently Represents a hydrogen atom or an unsubstituted aliphatic hydrocarbon group with 1-40 carbon atoms.