WO2019069961A1

WO2019069961A1 - Compound, latent antioxidant, composition, cured product and method for producing cured product

Info

Publication number: WO2019069961A1
Application number: PCT/JP2018/036959
Authority: WO
Inventors: 有希子金原; 光裕岡田; 哲千中屋敷
Original assignee: 株式会社Adeka
Priority date: 2017-10-05
Filing date: 2018-10-02
Publication date: 2019-04-11
Also published as: KR20200058327A; JP7293119B2; TWI788428B; CN110869343A; KR102587531B1; TW201922684A; JPWO2019069961A1

Abstract

Provided is a compound represented by general formula (I-1). (In the formula, A denotes an atomic group having an antioxidant function, B denotes a photo-releasable group, and k denotes an integer between 1 and 10.) Also provided is a composition that contains a compound represented by general formula (I-2) and an elimination product derived from a photo-releasable group. (In the formula, A denotes an atomic group having an antioxidant function, and k denotes an integer between 1 and 10.)

Description

Compound, latent antioxidant, composition, cured product and method for producing cured product

The present invention relates to, for example, a compound which has less inhibition of curing and which can easily impart an antioxidant function to a cured product.

In order to improve the oxidation preventing ability and the heat resistance of the curable composition, methods are known in which a UV absorber and an antioxidant are added to the cured product to be stabilized (Patent Documents 1 to 3).

JP, 2011-048382, A US2016016919A1 JP, 2015-108649, A

However, there has been a problem that the antioxidants described in Patent Documents 1 to 3 may inhibit the curing of the curable composition.
With respect to such problems, the present inventors have found that the phenolic antioxidant has an action of trapping radicals which greatly affect the deterioration of the polymer, and because of such an action, the phenolic oxidation is It has been found that adding an inhibitor into the polymerization system generally acts as a so-called polymerization inhibitor and may cause curing inhibition.

As means for solving the above-mentioned problems, latent additives which can be activated after curing are inactivated in the above-mentioned light absorbing action in the polymerization system.
On the other hand, latent additives that can be activated after curing may require high temperature heating and the like for activation, and there has been a demand for latent additives that can be more easily activated.

This invention is made in view of the said subject, for example, there is little hardening inhibition and makes it a main purpose to provide the compound which can provide antioxidant ability etc. easily with respect to hardened | cured material.

As a result of intensive investigations to solve the above problems, the present inventors used a photoleaving group as a protecting group to protect the phenolic hydroxyl group contained in the antioxidant with the photoleaving group. It has been found that the adjustment of the time to develop the antioxidant ability is easy and the above-mentioned problems can be solved, and the present invention has been completed.

That is, the present invention provides a compound represented by the following general formula (I-1).

(Wherein, A represents a group having an antioxidant ability, B represents a photoleaving group, and k represents an integer of 1 to 10).

The present invention also provides a latent antioxidant comprising a compound represented by the above general formula (I-1).

The present invention also provides a composition comprising the compound represented by the above general formula (I-1).

The present invention also provides a cured product of a composition comprising a compound represented by the above general formula (I-1) and a polymerizable compound.

In the present invention, a composition containing the compound represented by the general formula (I-1) and a polymerizable compound is cured to form a cured product, and the cured product is irradiated with light. And a step of removing the photoleaving group contained in the compound represented by the general formula (I-1).

The present invention also relates to a compound represented by the following general formula (I-2) (hereinafter sometimes referred to as “compound I-2”) and a leaving substance derived from a photoleaving group (hereinafter referred to as “compound And B) (hereinafter, may be referred to as “second composition”).

(Wherein, A represents a group having an antioxidant ability, and k represents an integer of 1 to 10).

The present invention relates to a compound and a latent antioxidant using the same, a composition, a cured product thereof and a method for producing the cured product. These will be described in detail below.

A. Compounds First, the compounds of the present invention will be described.
The compound of the present invention is represented by the following general formula (I-1) (hereinafter, the compound of the present invention is also referred to as compound I-1).

In the compound I-1 of the present invention, the atomic group A has an antioxidant ability. The compound I-1 of the present invention has low antioxidant ability before the elimination of the photoleaving group B, but exhibits excellent antioxidant ability based on the atomic group A after elimination of the photoleaving group B.
Therefore, when the compound I-1 before elimination of the photoleaving group B is added, for example, into the polymerization system, the compound I-1 has a low ability to trap radicals generated for the polymerization, and Hard to inhibit hardening.
In addition, the compound I-1 of the present invention is exposed to light, whereby the photoleaving group is released to exhibit excellent antioxidant performance. Therefore, by irradiating the cured product containing the compound I-1 with light, the cured product can be easily provided with an antioxidant ability. Since compound I-1 does not need to be heat-treated to develop its antioxidant capacity, it has the advantage of being less likely to cause damage to the cured product and its peripheral members such as the substrate due to heating.
Due to the above reasons, the compound I-1 has, for example, little inhibition of curing and can easily impart an antioxidant ability to a cured product.

Further, by having the photoleaving group B, the compound I-1 can easily adjust, for example, the dispersion stability in the composition.
The compound I-1 can impart excellent dispersibility in the composition by selecting the photoleaving group B such that the affinity with other components contained in the composition is improved.
Therefore, the compound I-1 can impart excellent antioxidant performance to the composition, and can also impart excellent dispersion stability during storage before use.

Hereinafter, the compound I-1 of the present invention will be described in detail.

1. Photo leaving group B
The compound I-1 of the present invention has a photoleaving group B.
The photoleaving group in the present invention can be a group which can be eliminated from compound I-1 by being irradiated with light of a specific wavelength. When compound I-1 is irradiated with light of a specific wavelength, the photoleaving group B is eliminated from compound I-1, and an atomic group having a hydroxyl group and an antioxidant ability represented by the following general formula (I-2) A compound having A is formed.

The wavelength of the light from which the photoleaving group B leaves the compound I-1 is, for example, the wavelength range of ultraviolet light or visible light. Specifically, the wavelength of 365 nm can be included, more specifically, the light of wavelength of 250 nm or more and 450 nm or less can be included, and preferably, the light of wavelength of 280 nm or more and 380 nm or less can be included. Can.
Integrated light quantity of the light irradiated to detach the light leaving group B from above Compound I-1, for example, be a 1000 mJ / cm ² or more 10000 mJ / cm ² or less, 1000 mJ / cm ² or more 5000mJ / Cm ² or less is preferable, and 2000 mJ / cm ² or more and 4000 mJ / cm ² or less is more preferable. The integrated light quantity of the light irradiated for curing the composition containing the polymerizable compound etc. can be usually less than 1000 mJ / cm ² . Therefore, when the integrated light amount is in the above-mentioned range, for example, application to a photocurable composition becomes easy.
The elimination of the photoleaving group B is sufficient as long as it can impart a desired antioxidant ability, and for example, the elimination rate of the photoleaving group can be 50% or more. Especially, it is preferable that it becomes 80% or more.
On the other hand, the compound I-1 may have an integrated light quantity that suppresses photodetachment as long as a desired curing inhibition suppressing effect can be obtained, and can be less than 1000 mJ / cm ² . It is because application to a photocurable composition becomes easy.
Further, to suppress photodetachment may be any as long as a desired curing inhibition inhibitory effect can be obtained. For example, the desorption rate of the photoleaving group B can be less than 50%. Especially, it is preferable that it becomes 20% or less. It is because application to a photocurable composition becomes easy.
The integrated light quantity can be measured by preparing a 0.01% by mass acetonitrile solution of compound I-1 and using the same method as the method of measuring the desorption rate described in the examples.

Specifically, the photoleaving group B satisfying the above requirements is represented by the following general formulas (B-1), (B-2), (B-3), (B-4), (B-5) And groups represented by (B-6), (B-7) and (B-8). Among them, the following general formulas (B-1-a), (B-2-a), (B-3-a), (B-4), (B-5), (B-6), (B) -7-a), (B-7-b) and (B-8-a) are preferable, and a group represented by the following general formula (B-1-a) Is preferred. By employing these photoleaving groups, the compound I-1 can be easily released, and the cured product can be easily imparted with an antioxidant ability and the like. Further, as the photoleaving group B satisfying the above-mentioned requirements, specifically, groups represented by the following general formulas (B-9) and (B-10) can also be mentioned.

(Wherein, R ¹¹ , R ¹³ , R ¹⁶ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²³ , R ²⁶ and R ²⁸ each independently represent a halogen atom, a cyano group, a hydroxyl group, a nitro group, a carboxyl group, An alkyl group having 1 to 40 carbon atoms, an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, or a heterocycle-containing group having 2 to 20 carbon atoms,
^{^{^{^{R 12, R 14, R 17}}}} , R 21, R 22, R 24, R 25, R 27, R 29 and ^{R 30} each independently represent a hydrogen atom, a halogen atom, a cyano group, a hydroxyl group, a nitro group, a carboxyl A group, an alkyl group having 1 to 40 carbon atoms, an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms or a heterocycle-containing group having 2 to 20 carbon atoms,
R ¹⁵ represents an alkyl group having 1 to 40 carbon atoms, an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms or a heterocycle-containing group having 2 to 20 carbon atoms,
^{^{^{^{R 11, R 12, R 13}}}} , R 14, R 15, R 16, R 17, R 18, R 19, R 20, R 21, R 22, R 23, R 24, R 25, R 26, R 27 And the methylene group in the alkyl group and arylalkyl group represented by R ²⁸ , R ²⁹ and R ³⁰ is a carbon-carbon double bond, -O-, -S-, -CO-, -O-CO-, -CO-O-, -O-CO-O-, -O-CO-O-, -S-CO-, -CO-S-, -S-CO-O-, -O-CO-S-, -CO-NH-, -NH-CO-, -NH-CO-O-, -NR'-,> P = O, -S-S-, -SO ₂ -or a combination thereof, Yes,
R ′ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms,
Multiple R ¹¹ each other, multiple R ¹³ each other, multiple R ¹⁶ each other, multiple R ¹⁸ each other, multiple R ¹⁹ each other, multiple R ²⁰ each other, multiple R ²³ each other, multiple R ²⁶ each other and multiple R ²⁸ may be bonded to each other to form a benzene ring or a naphthalene ring,
Plural R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²³ , R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ , R ²⁹ and R ³⁰ , Each may be the same, may be different,
b1, b2, b3, b6, b7, b8 and b9 each independently represent an integer of 0 to 4;
b4 and b5 each independently represent an integer of 0 to 5;
** represents the bonding position with the AO-. )

(Wherein, each of R ³¹ and R ⁴⁰ independently represents a halogen atom, a cyano group, a hydroxyl group, a nitro group, a carboxyl group, an alkyl group having 1 to 40 carbon atoms, an aryl group having 6 to 20 carbon atoms, carbon Represents an arylalkyl group having 7 to 20 atoms or a heterocycle-containing group having 2 to 20 carbon atoms,
R ³² , R ³³ , R ⁴¹ , R ⁴² , R ⁴³ and R ⁴⁴ are each independently a hydrogen atom, a halogen atom, a cyano group, a hydroxyl group, a nitro group, a carboxyl group, an alkyl group having 1 to 40 carbon atoms, An aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, or a heterocycle-containing group having 2 to 20 carbon atoms,
The methylene group in the alkyl group and arylalkyl group represented by R ³¹ , R ³² , R ³³ , R ⁴⁰ , R ⁴¹ , R ⁴² , R ⁴³ and R ⁴⁴ is a carbon-carbon double bond, -O-, -S-, -CO-, -O-CO-, -CO-O-, -O-CO-O-, -O-CO-O-, -S-CO-, -CO-S-, -S -CO-O-, -O-CO-S-, -CO-NH-, -NH-CO-, -NH-CO-O-, -NR'-,> P = O, -SS-, -SO ₂ -or a combination of these may be substituted,
The alkyl group, aryl group, arylalkyl group and heterocycle-containing group may have a substituent,
c1 represents an integer of 0 to 5;
c2 represents an integer of 0 to 4;
** represents the bonding position with the AO-. )

R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ , R ²⁹ , R ³⁰ , R ³¹ , R ³² , R ³³ , R ⁴⁰ , R ⁴¹ , R ⁴² , R ⁴³ and R ⁴⁴ (hereinafter, these functional groups are collectively referred to as R ¹¹ etc. As the alkyl group having 1 to 40 carbon atoms represented by (C), there are methyl group, ethyl group, propyl group, iso-propyl group, butyl group, sec-butyl group, tert-butyl group, iso-butyl group. Group, amyl group, iso-amyl group, tert-amyl group, cyclopentyl group, hexyl group, 2-hexyl group, 3-hexyl group, cyclohexyl group, 4-methylcyclohexyl group, heptyl group, 2 Heptyl, 3-heptyl group, iso- heptyl, tert- heptyl, 1-octyl group, iso- octyl group, and a tert- octyl group and adamantyl group.

Examples of the aryl group having 6 to 20 carbon atoms represented by R ^{11 and the} like include a phenyl group, a naphthyl group and an anthracenyl group.

Examples of the arylalkyl group having 7 to 20 carbon atoms represented by R ^{11 and the} like include a benzyl group, a fluorenyl group, an indenyl group and a 9-fluorenylmethyl group.

Examples of the heterocycle-containing group having 2 to 20 carbon atoms represented by R ^{11 and the} like described above include, for example, pyridyl group, pyrimidyl group, pyridazyl group, piperidyl group, pyranyl group, pyrazolyl group, triazyl group, pyrrolyl group, quinolyl group , Isoquinolyl group, imidazolyl group, benzimidazolyl group, triazolyl group, furyl group, furanyl group, benzofuranyl group, thienyl group, thiophenyl group, benzothiophenyl group, thiadiazolyl group, thiazolyl group, benzothiazolyl group, oxazolyl group, benzoxazolyl group , Isothiazolyl group, isoxazolyl group, indolyl group, 2-pyrrolidinone-1-yl group, 2-piperidone-1-yl group, 2,4-dioxyimidazolidin-3-yl group and 2,4-dioxyoxazolidine- A 3-yl group etc. can be mentioned.

Examples of the alkyl group having 1 to 8 carbon atoms represented by R ′ include those exemplified for the alkyl group represented by R ^{11 and the} like, and those having 1 to 8 carbon atoms.

The alkyl group, the aryl group, the arylalkyl group and the heterocyclic group may have a substituent. The compounds I-1 of the present invention include those having no substituent and those having a substituent, unless otherwise specified.

Examples of the substituent which may substitute a hydrogen atom such as an alkyl group, an aryl group, an arylalkyl group and a heterocycle-containing group include, for example, ethylenic unsaturated groups such as a vinyl group, an allyl group, an acryl group and a methacryl group; Halogen atoms such as fluorine, chlorine, bromine and iodine; acetyl group, 2-chloroacetyl group, propionyl group, octanoyl group, acryloyl group, methacryloyl group, phenylcarbonyl (benzoyl) group, phthaloyl group, 4-trifluoromethylbenzoyl group And acyl groups such as pivaloyl, salicyloyl, oxaloyl, stearoyl, methoxycarbonyl, ethoxycarbonyl, t-butoxycarbonyl, n-octadecyloxycarbonyl and carbamoyl; acetyloxy and benzoyloxy Aclio Amino group, ethylamino group, dimethylamino group, diethylamino group, butylamino group, cyclopentylamino group, 2-ethylhexylamino group, dodecylamino group, anilino group, chlorophenylamino group, toluidino group, anisidino group, N- Methyl-anilino group, diphenylamino group, naphthylamino group, 2-pyridylamino group, methoxycarbonylamino group, phenoxycarbonylamino group, acetylamino group, benzoylamino group, formylamino group, pivaloylamino group, lauroylamino group, carbamoylamino group , N, N-dimethylaminocarbonylamino group, N, N-diethylaminocarbonylamino group, morpholino carbonylamino group, methoxycarbonylamino group, ethoxycarbonylamino group, t-butoxycal Nylamino group, n-octadecyloxycarbonylamino group, N-methyl-methoxycarbonylamino group, phenoxycarbonylamino group, sulfamoylamino group, N, N-dimethylaminosulfonylamino group, methylsulfonylamino group, butylsulfonylamino group And substituted amino groups such as phenylsulfonylamino group; sulfonamide group, sulfonyl group, sulfonyl group, carboxyl group, cyano group, sulfo group, hydroxyl group, nitro group, mercapto group, imide group, carbamoyl group, sulfonamide group, phosphonic acid group, phosphorus Examples thereof include salts of acid groups or carboxyl groups, sulfo groups, phosphonic acid groups and phosphoric acid groups.

In the present invention, when the hydrogen atom in the group is substituted by a substituent, the number of carbon atoms of the group defines the number of carbon atoms of the group after the substitution. For example, when the hydrogen atom of the alkyl group having 1 to 40 carbon atoms is substituted, the term "C1 to 40 carbon atoms" refers to the number of carbon atoms after the hydrogen atom has been substituted, and the hydrogen atom is substituted Does not refer to the number of carbon atoms before the

In the present invention, when the methylene group in the group is replaced by the above divalent group, the number of carbon atoms of the group defines the number of carbon atoms of the group after the replacement. For example, in the present specification, when a methylene group in an alkyl group having 1 to 40 carbon atoms is replaced by the above divalent group, the “1 to 40 carbon atoms” means a group after a methylene group is replaced. It does not refer to the number of carbon atoms before the methylene group is replaced. Accordingly, “—O—C ₄₀ H ₈₁ ” corresponds to “an alkyl group having 40 carbon atoms (= an alkoxy group having 40 carbon atoms) in which the terminal methylene group is replaced by —O— It is. Similarly, “—CO—O—C ₃₉ H ₇₉ ” corresponds to “an alkyl group having 40 carbon atoms in which the terminal methylene group is replaced by —CO—O—”.

The methylene group in the alkyl group and arylalkyl group used for R ^{11 and the} like is a carbon-carbon double bond, -O-, -S-, -CO-, -O-CO-, -CO-O-,- O-CO-O-, -O-CO-O-, -S-CO-, -CO-S-, -S-CO-O-, -O-CO-S-, -CO-NH-,- NH—CO—, —NH—CO—O—, —NR′—,> P = O, —S—S—, —SO ₂ — or a combination thereof may be substituted.
In addition, the combination which substitutes the said methylene group can be made into the combination on the conditions which oxygen atom does not adjoin.

In the alkyl group having 1 to 40 carbon atoms represented by R ¹¹ or the like, the terminal methylene group on the proximal side may be replaced by -O- to form an alkoxy group. As such an alkoxy group, for example, an alkoxy group having 1 to 10 carbon atoms can be mentioned. Specifically, methyloxy, ethyloxy, iso-propyloxy, butyloxy, sec-butyloxy, tert-butyloxy, iso-butyloxy, amyloxy, iso-amyloxy, tert-amyloxy, hexyl Oxy group, 2-hexyloxy group, 3-hexyloxy group, cyclohexyloxy group, 4-methylcyclohexyloxy group, heptyloxy group, 2-heptyloxy group, 3-heptyloxy group, iso-heptyloxy group, tert- A heptyloxy group, 1-octyloxy group, iso-octyloxy group, tert-octyloxy group and the like can be mentioned.

R ¹¹ , R ¹³ , R ¹⁶ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²³ , R ²⁶ and R ²⁸ are preferably groups other than a hydroxyl group, and examples thereof include a halogen atom, a cyano group and a nitro group, A carboxyl group, an alkyl group having 1 to 40 carbon atoms, an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, a heterocyclic group having 2 to 20 carbon atoms, etc. preferable. By using a group other than a hydroxyl group, the photoleaving group B is easily released from the compound I-1, and the synthesis of the compound I-1 becomes easy.
It is preferable that said R < ¹¹ > and R < ²³ > is an alkoxy group. This is because the photoleaving group B is easily released from the compound I-1 and the synthesis of the compound I-1 is facilitated.
The R ¹³ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²⁶ and R ²⁸ are preferably an alkyl group having 1 to 40 carbon atoms. This is because the photoleaving group B is easily released from the compound I-1 and the synthesis of the compound I-1 is facilitated.
Among the above R ^{16 's} , two adjacent R ¹⁶ ' s are preferably bonded to form a benzene ring. This is because the photoleaving group B is easily released from the compound I-1 and the synthesis of the compound I-1 is facilitated.

When the methylene group in the alkyl group and the arylalkyl group represented by R ¹⁸ and R ¹⁹ is -O-substituted, -O- replacing the methylene group is such that the alkyl group and the arylalkyl group are interrupted respectively In other words, it may be substituted by a methylene group other than the ends of the alkyl group and the arylalkyl group.

R ¹² is preferably a hydrogen atom, a carboxyl group, or an alkyl group having 1 to 5 carbon atoms, and among them, a hydrogen atom or a methyl group is preferable.
R ¹⁴ , R ¹⁷ , R ²¹ , R ²⁴ , R ²⁵ , R ²⁷ , R ²⁹ and R ^{30 each} is preferably a hydrogen atom or an alkyl group having 1 to 40 carbon atoms, and particularly preferably a hydrogen atom Is particularly preferred. This is because the photoleaving group B is easily released from the compound I-1 and the synthesis of the compound I-1 is facilitated.
The above R ¹⁵ and R ²² are preferably an alkyl group having 1 to 5 carbon atoms, and particularly preferably a methyl group. This is because a compound which is less in inhibition of curing and which can easily impart an antioxidant ability or the like to a cured product can be provided.

The above b 1, b 2, b 3, b 6, b 7, b 8 and b 9 can be each independently an integer of 0 to 4 but preferably an integer of 0 to 3 from the viewpoint of easiness of synthesis, It is more preferably an integer of 0 to 2, still more preferably 0 to 1, and particularly preferably 0. This is because a compound which is less in inhibition of curing and which can easily impart an antioxidant ability or the like to a cured product can be provided.
The above b 4 and b 5 can be each independently an integer of 0 to 5, but from the viewpoint of easiness of synthesis, it is preferably an integer of 0 to 3 and more preferably an integer of 0 to 2 Preferably, it is 0 to 1, more preferably 0. This is because a compound which is less in inhibition of curing and which can easily impart an antioxidant ability or the like to a cured product can be provided.

When k is 2 or more, the type of photoleaving group B contained in compound I-1 of the present invention may be one type per compound I-1, and may be two or more types. From the viewpoint of facilitating the synthesis of the compound I-1, one type is preferable from the viewpoints of being less susceptible to curing, capable of easily imparting an antioxidant ability to a cured product, and the like.

The content number k of the photoleaving group is an integer of 1 to 10, but the curing inhibition is small, and the cured product can be easily provided with an antioxidant ability and the like, and from the viewpoint of synthesis ease, It is preferably an integer of 1 to 5, more preferably an integer of 1 to 4, and particularly preferably an integer of 1 to 3.

2. A group having the ability to prevent oxidation The group A is a group having the ability to prevent oxidation.
The compound I-1 of the present invention is irradiated with light of a specific wavelength, whereby the photoleaving group B is eliminated to produce a compound I-2 having a hydroxyl group. In the present invention, to have the ability to prevent oxidation means to exhibit, for example, a radical scavenging function having the function of preventing or suppressing oxidation by heat, light and other energy of a substance. In the present invention, the radical scavenging action means that Compound I-2 reacts with the chain support peroxy radical of autoxidation to stop the oxidation. In the present invention, the atomic group having the antioxidant ability can be a group of atoms having at least one group having the antioxidant ability or a group having the antioxidant ability.

Such atomic group A can be the same as the atomic group generally used for the antioxidant having a phenolic hydroxyl group.
That is, the compound I-2 can be generally used as an antioxidant having a phenolic hydroxyl group.
Examples of the compound I-2 include phenol-based antioxidants described in JP-A-6-17998, JP-A-11-71355, JP-A-2002-97224, etc., JP-A-7-109380 The alkyl-substituted phenolic antioxidant described in the above can be used.

Specifically, the atomic group A having the antioxidant ability is a protected phenol structure, that is, an atom obtained by removing the B—O— from the benzene ring in which the phenolic hydroxyl group is protected by the photoleaving group B. There is a group. More specifically, a benzene ring to which the B-O- is directly bonded, an alkyl group having 1 to 40 carbon atoms, an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, or There can be mentioned an atomic group containing a first substituent which is a heterocycle-containing group having 2 to 20 carbon atoms. The first substituent is preferably directly bonded to the benzene ring, and the bonding position of the first substituent to the benzene ring is an ortho position relative to the bonding position of the B-O-. It is more preferred that The atomic group A is a hydrogen atom, an alkyl group having 1 to 40 carbon atoms, an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms or a heterocyclic ring having 2 to 20 carbon atoms It is preferable that the second substituent represented by the group be further directly bonded to the benzene ring to which the first substituent is directly bonded, and the bonding position of the second substituent to the benzene ring is preferably More preferably, the compound is ortho to the bonding position of B—O—. That is, in the atomic group A, a first substituent is bonded to one ortho position relative to the bonding position of the B-O-, and a second substituent is bonded to the other ortho position. Is particularly preferred. It is because it is easy to set it as a compound which has few hardening inhibition and can easily provide an antioxidant etc. with respect to hardened | cured material.

Examples of the compound (I-1) of the present invention include those represented by the following general formula (A-1), (A-2) or (A-3).

(Wherein, R ¹ represents a halogen atom, a cyano group, a hydroxyl group, a nitro group, a carboxyl group, an alkyl group having 1 to 40 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryl having 7 to 20 carbon atoms Represents an alkyl group or a heterocycle-containing group having 2 to 20 carbon atoms,
R ² , R ³ and R ⁴ each independently represent an alkyl group having 1 to 40 carbon atoms, an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms or 2 to 6 carbon atoms Represents 20 heterocyclic containing groups,
The methylene group in the alkyl group and arylalkyl group used for R ¹ , R ² , R ³ and R ⁴ is a carbon-carbon double bond, -O-, -S-, -CO-, -O-CO- , -CO-O-, -O-CO-O-, -O-CO-O-, -S-CO-, -CO-S-, -S-CO-O-, -O-CO-S- When substituted by -CO-NH-, -NH-CO-, -NH-CO-O-, -NR'-,> P = O, -S-S-, -SO ₂ -or a combination thereof There is
R ′ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms,
Several R ¹ may be combined to form a benzene ring or a naphthalene ring,
Several R ¹ may be the same or different.
m represents an integer of 1 to 10,
n represents an integer of 2 to 10,
a represents an integer of 0 to 2;
X ¹ represents an m-valent linking group,
X ² represents an n-valent bonding group. )

The alkyl group having 1 to 40 carbon atoms, the aryl group having 6 to 20 carbon atoms, the arylalkyl group having 7 to 20 carbon atoms, and the carbon atom having 2 carbon atoms used for R ¹ , R ² , R ³ and R ⁴ As the hetero ring-containing group of to 20 and the alkyl group having 1 to 8 carbon atoms which is used for R ′, those exemplified as R ^{11 and the} like and R ′ described in the above “1. It can be mentioned.

R ¹ is an alkyl group having 1 to 40 carbon atoms, an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, or a heterocycle-containing group having 2 to 20 carbon atoms Among them, an alkyl group having 1 to 40 carbon atoms is preferable, and an alkyl group having 1 to 5 carbon atoms is particularly preferable. This is because the compound I-1 exerts an excellent antioxidizing ability after elimination of the photoleaving group B.

R ² , R ³ and R ⁴ are preferably an alkyl group having 1 to 40 carbon atoms, particularly preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, among which methyl It is preferably a group or t-butyl group. This is because the compound I-1 exerts an excellent antioxidizing ability after elimination of the photoleaving group B.

The above m is an integer of 1 to 10, but from the viewpoint of easiness of synthesis, it is preferably an integer of 1 to 6, and among them, an integer of 1 to 5 is preferable, in particular It is preferably an integer of -4. This is because the compound I-1 exerts an excellent antioxidizing ability after elimination of the photoleaving group B.

The above n is an integer of 2 to 10, but from the viewpoint of easiness of synthesis, it is preferably an integer of 2 to 6, and in particular, an integer of 2 to 5 is preferable, in particular It is preferably an integer of to 4, and is preferably an integer of 2 to 3. This is because the compound I-1 exerts an excellent antioxidizing ability after elimination of the photoleaving group B.

Although the above a is an integer of 0 to 2, the compound I-1 exerts an excellent antioxidizing ability after elimination of the photoleaving group B, and further, from the viewpoint of easiness of synthesis, 0 to 1 Is preferred.

The compound I-1 represented by the above general formula (A-1) has a structure in which a specific m-valent atom represented by X ¹ and m specific groups are bonded. The m specific groups may be identical to one another or may be different.

The above X ¹ represents an m-valent bonding group.
Specifically, the bonding group X ¹ is a direct bond, a hydrogen atom, a nitrogen atom, an oxygen atom, a sulfur atom, a phosphorus atom, a group represented by the following (II-a) or (II-b), C = O,> NR ⁵³ , -OR ⁵³ , -SR ⁵³ , -NR ⁵³ R ⁵⁴ or an aliphatic hydrocarbon group having 1 to 120 carbon atoms and having the same number of valences as m, having 6 to 35 carbon atoms It represents an aromatic ring-containing hydrocarbon group or a heterocyclic ring-containing group having 2 to 35 carbon atoms. R ⁵³ and R ^{54 each} represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 35 carbon atoms, an aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms, or a heterocyclic group having 2 to 35 carbon atoms And the aliphatic hydrocarbon group, the aromatic ring-containing hydrocarbon group and the heterocycle-containing group are represented by -O-, -S-, -CO-, -O-CO-, -CO-O-, -O-CO -O-, -O-CO-O-, -S-CO-, -CO-S-, -S-CO-O-, -O-CO-S-, -CO-NH-, -NH-CO -, - NH-CO-O -, - NH-CO-O -, - NR '-, - S-S -, - SO 2 -, sometimes are replaced by nitrogen atoms, or combinations thereof, the aromatic The ring or heterocycle may be fused to another ring.
However, in the case where X ¹ is a nitrogen atom, a phosphorus atom or a bonding group represented by (II-a) or (II-b) below, m is 3 and X ¹ is an oxygen atom or a sulfur atom,> C = In the case of O, -NH-CO-, -CO-NH- or> NR ⁵³ , m is 2, and when X ¹ is -OR ⁵³ , -SR ⁵³ or -NR ⁵³ R ⁵⁴ , m is 1 And X ¹ may form a ring together with the benzene ring.

(* Indicates that it is a bond to an adjacent group in the * part.)

As the aliphatic hydrocarbon group having 1 to 120 carbon atoms and having the same number of valences as m, which is represented by the aforementioned linking group X ¹ , when m is monovalent and m is monovalent, for example, , Methyl group, ethyl group, propyl group, isopropyl group, cyclopropyl group, butyl group, secondary butyl group, tertiary butyl group, tertiary butyl group, isobutyl group, amyl group, isoamyl group, tertiary amyl group, cyclopentyl group, hexyl group, 2-hexyl group, 3-hexyl group, cyclohexyl group, bicyclohexyl group, 1-methylcyclohexyl group, heptyl group, 2-heptyl group, 3-heptyl group, isoheptyl group, tertiary heptyl group, n-octyl group, isooctyl Alkyl groups such as octyl group, tertiary octyl group, 2-ethylhexyl group, nonyl group, isononyl group and decyl group; methyloxy group, ethyloxy group, propylo group Xy group, isopropyloxy group, butyloxy group, sec-butyloxy group, tert-butyloxy group, isobutyloxy group, amyloxy group, isoamyloxy group, tert-amyloxy group, hexyloxy group, cyclohexyloxy group, heptyloxy group, isoheptyl Alkoxy groups such as oxy, tertiary heptyloxy, n-octyloxy, isooctyloxy, tertiary octyloxy, 2-ethylhexyloxy, nonyloxy and decyloxy; methylthio, ethylthio, propylthio Isopropylthio group, butylthio group, sec-butylthio group, tert-butylthio group, isobutylthio group, amylthio group, isoamylthio group, tertiary amylthio group, hexylthio group, cyclohexylthio group, heptylthio group, isoheptylthio group, Alkylthio groups such as triheptylthio, n-octylthio, isooctylthio, tertiary octylthio and 2-ethylhexylthio; vinyl, 1-methylethenyl, 2-methylethenyl, 2-propenyl, 1-methyl -3-propenyl group, 3-butenyl group, 1-methyl-3-butenyl group, isobutenyl group, 3-pentenyl group, 4-hexenyl group, cyclohexenyl group, bicyclohexenyl group, heptenyl group, octenyl group, decenyl group, And alkenyl groups such as pentadecenyl group, eicosenyl group and tricosenyl group; and groups in which these groups are substituted by a substituent described later.

The aliphatic hydrocarbon group having 1 to 120 carbon atoms and having the same number of valences as m, which is represented by the above linking group X ¹ , is a methylene group, an ethylene group, a propylene group, a butylene, as the one where m is divalent And alkylene groups such as butyldiyl group; those in which the methylene chain of the above alkylene group is replaced with -O-, -S-, -CO-O-, -O-CO-; ethanediol, propanediol, butanediol, Residues of diol groups such as pentanediol and hexanediol; Residues of dithiol groups such as ethanedithiol, propanedithiol, butanedithiol, pentanedithiol, hexanedithiol and the like, and groups in which these groups are substituted by a substituent described later It can be mentioned.

The aliphatic hydrocarbon group having 1 to 120 carbon atoms and having the same number of valences as m, which is represented by the above linking group X ¹ , is, for example, a propyridine group and 1,1, Alkylidine groups such as 3-butylidine propyridine group; and groups in which these groups are substituted by a substituent described later.

The aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms and having the same number of valences as m, which is represented by the aforementioned linking group X ¹ , is preferably a benzyl group, a phenethyl group or a diphenylmethyl group, as m is a monovalent group Arylalkyl groups such as triphenylmethyl, styryl and cinnamyl; aryl groups such as phenyl and naphthyl; aryloxy groups such as phenoxy and naphthyloxy; arylthio such as phenylthio and naphthylthio: And groups in which these groups are substituted by a substituent described later, and the like.

The aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms and having the same number of valences as m, which is represented by the aforementioned linking group X ¹ , is an arylene group such as a phenylene group and a naphthylene group, as m is a divalent one Residues of bifunctional phenol groups such as catechol groups and bisphenol groups; 2,4,8,10-tetraoxaspiro [5,5] undecane groups; and groups in which these groups are substituted by substituents described later It can be mentioned.

The aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms and having the same number of valences as m, which is represented by the aforementioned linking group X ¹ , is a phenyl 1,3,5-trimethylene group in which m is a trivalent group. Examples thereof include groups and groups in which this group is substituted by a substituent described later.

The heterocycle-containing group having 2 to 35 carbon atoms and having the same number of valences as m, which is represented by the aforementioned linking group X ¹ , is a pyridyl group, a pyrimidyl group, a pyridazyl group, a piperidyl group, as m is a monovalent , Pyranyl group, pyrazolyl group, triazyl group, pyrrolyl group, quinolyl group, isoquinolyl group, imidazolyl group, benzimidazolyl group, triazolyl group, furyl group, furanyl group, benzofuranyl group, thienyl group, thiophenyl group, benzothiophenyl group, thiadiazolyl group , Thiazolyl group, benzothiazolyl group, oxazolyl group, benzoxazolyl group, isothiazolyl group, isoxazolyl group, indolyl group, 2-pyrrolidin-1-yl group, 2-piperidone-1-yl group, 2,4-dioxyimidazo Lysin-3-yl group, 2,4-dioxazolidine-3-yl Groups and the like, and groups in which these groups are substituted by a substituent described later, and the like.

The heterocycle-containing group having 2 to 35 carbon atoms and having the same number of valences as m, which is represented by the above linking group X ¹ , is a pyridine ring, a pyrimidine ring, a piperidine ring, a piperazine ring, as m is a divalent one And a divalent group having a triazine ring, a furan ring, a thiophene ring, an indole ring and the like, and a group in which these groups are substituted by a substituent described later.

Examples of the aliphatic hydrocarbon group having a carbon number of 1 to 35 for use in R ⁵³ and R ^54, an aliphatic hydrocarbon group or the aliphatic hydrocarbon group having a carbon number of 1 to 120 used in the above X ¹ is described below Among the groups substituted by the substituents, there may be mentioned those having 1 to 35 carbon atoms.
The aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms or the heterocyclic ring-containing group having 2 to 35 carbon atoms represented by R ⁵³ and R ⁵⁴ has 6 to 35 carbon atoms represented by X ^1. Or an aromatic ring-containing hydrocarbon group, a heterocyclic ring-containing group having 2 to 35 carbon atoms, or a group in which these groups are substituted by a substituent described later.

Each functional group such as the above-mentioned aliphatic hydrocarbon group, aromatic ring-containing hydrocarbon group and heterocyclic group-containing group may have a substituent, and compound I-1 of the present invention is not particularly limited. And those having no substituent and those having a substituent.
Examples of the substituent such as an aliphatic hydrocarbon group, an aromatic ring-containing hydrocarbon group, and a heterocycle-containing group include the same substituents as those for substituting a hydrogen atom such as an alkyl group used for R ^{11 and the} like. It can be mentioned.

When m is 2, X ¹ can be a group represented by the following general formula (1).
When m is 3, X ¹ can be a group represented by the following general formula (2).
When m is 4 as the above X ¹ , a group represented by the following general formula (3) can be used.
When m is 5 as X ¹ , a group represented by the following general formula (4) can be used.
When m is 6, X ¹ can be a group represented by the following general formula (5).

(In the above general formula (1), Y ¹ represents a single bond, —CR ⁵⁵ R ⁵⁶ —, —NR ⁵⁷ —, divalent aliphatic hydrocarbon group having 1 to 35 carbon atoms, 6 to 35 carbon atoms Or an aromatic ring-containing hydrocarbon group, a heterocyclic ring-containing group having 2 to 35 carbon atoms, or any substituent represented by the following (1-1) to (1-3): And an aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms and a hetero ring-containing group having 2 to 35 carbon atoms are -O-, -S-, -CO-, -COO-, -OCO- or -NH. -Or in some cases replaced by a combination of these groups,
R ⁵⁵ and R ^{56 each} represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an arylalkyl group having 7 to 20 carbon atoms,
Z ¹ and Z ² are each independently a direct bond, -O-, -S-,> CO, -CO-O-, -O-CO-, -SO _2- , -SS-, -SO-, Represents> NR ⁵⁸ or> PR ⁵⁸ ,
R ⁵⁷ and R ^{58 each} represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 35 carbon atoms, an aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms, or a heterocycle containing group having 2 to 35 carbon atoms ,
The * means that at the * part, it bonds to an adjacent group. )

(Wherein, R ⁵⁹ represents a hydrogen atom, a phenyl group which may have a substituent, or a cycloalkyl group having 3 to 10 carbon atoms,
R ⁶⁰ represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or a halogen atom, and the above alkyl group, alkoxy group and alkenyl group have a substituent In some cases, c1 is an integer of 0 to 5, and * means that the * part is to be bonded to an adjacent group. )

(* Indicates that it is a bond to an adjacent group in the * part.)

(In the above formula, R ⁶¹ and R ⁶² each independently represent an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, or the like An arylthio group of 6 to 20, an arylalkenyl group of 6 to 20 carbon atoms, an arylalkyl group of 7 to 20 carbon atoms, a heterocycle-containing group of 2 to 20 carbon atoms, or a halogen atom; The methylene group in the arylalkyl group may be replaced by an unsaturated bond, -O- or -S-,
R ⁶¹ may form a ring between adjacent R ⁶¹ in some cases,
c2 represents a number from 0 to 4;
c3 represents a number from 0 to 8,
c4 represents a number from 0 to 4;
c5 represents a number from 0 to 4;
The sum of the numbers of c4 and c5 is 2 to 4,
The * means that at the * part, it bonds to an adjacent group. )

(In the above general formula (2), Y ¹¹ is a trivalent aliphatic hydrocarbon group having 3 to 35 carbon atoms, an alicyclic hydrocarbon group having 3 to 35 carbon atoms, or 6 to 35 carbon atoms Represents an aromatic ring-containing hydrocarbon group or a heterocyclic ring-containing group having 2 to 35 carbon atoms,
Z ¹ , Z ² and Z ³ are each independently a direct bond, -O-, -S-,> CO, -CO-O-, -O-CO-, -SO _2- , -SS-,- SO—,> NR ⁶² , PR ⁶² , an aliphatic hydrocarbon group having 1 to 35 carbon atoms, an aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms, or a heterocyclic ring-containing group having 2 to 35 carbon atoms ,
R ⁶² represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 35 carbon atoms, an aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms or a heterocycle containing group having 2 to 35 carbon atoms,
The aliphatic hydrocarbon group, the aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms, and the heterocyclic group having 2 to 35 carbon atoms have a carbon-carbon double bond, -O-, -CO-,- It may be replaced by O-CO-, -CO-O- or -SO _2- . )

(In the above general formula (3), Y ¹² represents a carbon atom or a tetravalent aliphatic hydrocarbon group having 1 to 35 carbon atoms, an aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms, or 2 carbon atoms And an aliphatic hydrocarbon group, an aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms, or a heterocyclic group having 2 to 35 carbon atoms represented by —COO—, —O. -, -OCO-, -NHCO-, -NH- or -CONH- may be substituted, and Z ¹ to Z ⁴ are each independently a table represented by Z ¹ to Z ³ in the above general formula (2) In the same range as the

(In the above general formula (4), Y ¹³ is a pentavalent aliphatic hydrocarbon group having 2 to 35 carbon atoms, an aromatic ring-containing hydrocarbon group having 6 to 30 carbon atoms, or 2 to 30 carbon atoms And an aliphatic hydrocarbon group, an aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms and a heterocyclic group having 2 to 35 carbon atoms represented by the formula: -COO-, -O-,- It may be substituted by OCO-, -NHCO-, -NH- or -CONH-, and Z ¹ to Z ⁵ each independently represents a group represented by Z ¹ to Z ³ in the above general formula (2). In the same range as

(In the above general formula (5), Y ¹⁴ is a single bond, a hexavalent aliphatic hydrocarbon group having 2 to 35 carbon atoms, an aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms, or 2 carbon atoms And an aliphatic hydrocarbon group, a C6-C35 aromatic ring-containing hydrocarbon group or a C2-C35 heterocycle-containing group is a group represented by the formula -COO-, -O. -, -OCO-, -NHCO-, -NH- or -CONH- may be substituted, and Z ¹ to Z ⁶ are each independently a table of Z ¹ to Z ³ in the general formula (7). In the same range as the

Examples of the divalent aliphatic hydrocarbon group having 1 to 35 carbon atoms represented by Y ¹ in the group represented by the above general formula (1) include methane, ethane, propane, iso-propane, butane, sec- Butane, tert-butane, iso-butane, hexane, 2-methylhexane, 3-methylhexane, heptane, 2-methylheptane, 3-methylheptane, iso-heptane, tert-heptane, 1-methyloctane, iso-octane And tert-octane, cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, 2,4-dimethylcyclobutane, 4-methylcyclohexane and the like, and divalent groups substituted with Z ¹ and Z ² . These groups may be interrupted by —O—, —S—, —CO—, —COO—, —OCO—, —NH— or a combination thereof.

The divalent aromatic ring-containing hydrocarbon group having a carbon number of 6-35 represented by Y ¹ in the group represented by the general formula (1), phenylene, naphthylene, a group of biphenyl, Z ¹ and Examples thereof include divalent groups substituted by Z ² and the like.

Examples of the divalent heterocyclic group having 2 to 35 carbon atoms represented by Y ¹ in the group represented by the above general formula (1) include pyridine, pyrazine, piperidine, piperazine, pyrimidine, pyridazine, triazine, and hexa Hydrotriazines, furans, tetrahydrofurans, chromans, xanthenes, thiophenes, thiolanes and the like include divalent groups substituted by Z ¹ and Z ² .

The aliphatic hydrocarbon group, aromatic ring-containing hydrocarbon group and heterocycle-containing group represented by Y ¹ in the group represented by the above general formula (1) have a halogen atom, a cyano group, a nitro group or one carbon atom It may be further substituted by an alkoxy group of -8.
Each functional group such as the above aliphatic hydrocarbon group, aromatic ring-containing hydrocarbon group and heterocyclic group-containing group may have a substituent, and unless otherwise specified, has a substituent. Not substituted or substituted.
Examples of the substituent such as an aliphatic hydrocarbon group, an aromatic ring-containing hydrocarbon group, and a heterocycle-containing group include the same substituents as those for substituting a hydrogen atom such as an alkyl group used for R ^{11 and the} like. .

The alkyl group having 1 to 8 carbon atoms represented by R ⁵⁵ and R ⁵⁶ in the group represented by the above general formula (1) is a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an s- group Butyl, t-butyl, isobutyl, amyl, isoamyl, t-amyl, hexyl, 2-hexyl, 3-hexyl, cyclohexyl, 4-methylcyclohexyl, heptyl, 2-heptyl Groups, 3-heptyl group, isoheptyl group, t-heptyl group, 1-octyl group, isooctyl group, t-octyl group and the like.
The arylalkyl group having 7 to 20 carbon atoms represented by R ⁵⁵ and R ⁵⁶ in the group represented by the above general formula (1) includes a benzyl group, a phenethyl group, a 2-phenylpropan-2-yl group, And diphenylmethyl group, triphenylmethyl group, styryl, cinnamyl and the like.

An aliphatic hydrocarbon group having 1 to 35 carbon atoms, an aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms, or a carbon atom represented by R ⁵⁷ and R ⁵⁸ in a group represented by the above general formula (1) Examples of the heterocycle-containing group of the formulas 2 to 35 may be the same as those exemplified as R ⁵³ and R ⁵⁴ .

The cycloalkyl group having 3 to 10 carbon atoms represented by R ⁵⁹ in the group represented by the above general formula (1-1) is a cyclopropyl group, cyclobutyl group, cyclopentyl group, cycloheptyl group, cyclo Examples thereof include an octyl group and the like, and a group in which these groups are substituted with an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms.

Examples of the alkyl group having 1 to 10 carbon atoms represented by R ⁶⁰ in the group represented by the above general formula (1-1) include R ^{11 and the} like in the above “1. Photoleaving group B” Among the exemplified alkyl groups, those having 1 to 10 carbon atoms can be mentioned.
The alkoxy group having 1 to 10 carbon atoms represented by R ⁶⁰ in the group represented by the above general formula (1-1) is exemplified by R ^{11 and the} like in the above “1. Photoleaving group B” Among the exemplified alkoxy groups, those having 1 to 10 carbon atoms can be mentioned.
The alkenyl group having 2 to 10 carbon atoms in the group represented by the above general formula (1-1) includes vinyl, allyl, 1-propenyl, isopropenyl, 2-butenyl, 1, 3 -Butadienyl group, 2-pentenyl group, 2-octenyl group and the like.

The phenyl group, the alkyl group, the alkoxy group and the alkenyl group in the general formula (1-1) may have a substituent. As such a substituent, the same ones as those exemplified as the substituent for substituting a hydrogen atom such as an alkyl group used for R ^{1 and the} like can be mentioned.
The alkyl group, alkoxy group and alkenyl group in the above R ⁶⁰ may be, for example, those substituted with a halogen atom, and the position of substitution is not limited.

In the group represented by the above general formula (1-3), an alkyl group having 1 to 10 carbon atoms represented by R ⁶¹ and R ⁶² , an aryl group having 6 to 20 carbon atoms, and 7 to carbon atoms As the arylalkyl group of 20, among the contents exemplified as R ^{11 and the} like in the section of “1. Photoleaving group B”, those having a predetermined number of carbon atoms can be mentioned.

As a C6-C20 aryloxy group represented by R ⁶¹ and R ⁶² in the group represented by the above general formula (1-3), a phenyloxy group, a naphthyloxy group, 2-methylphenyloxy Group, 3-methylphenyloxy group, 4-methylphenyloxy group, 4-vinylphenyldioxy group, 3-iso-propylphenyloxy group, 4-iso-propylphenyloxy group, 4-butylphenyloxy group, 4 -Tert-butylphenyloxy group, 4-hexylphenyloxy group, 4-cyclohexylphenyloxy group, 4-octylphenyloxy group, 4- (2-ethylhexyl) phenyloxy group, 2,3-dimethylphenyloxy group, 2,4-Dimethylphenyloxy, 2,5-dimethylphenyloxy, 2,6-dimethyl Phenyloxy, 3,4-dimethylphenyloxy, 3,5-dimethylphenyloxy, 2,4-di-tert-butylphenyloxy, 2,5-di-tert-butylphenyloxy, 2,6-di tert-Butylphenyloxy, 2,4-di-tert-pentylphenyloxy, 2,5-tert-amylphenyloxy, 4-cyclohexylphenyloxy, 2,4,5-trimethylphenyloxy and A ferrocenyl oxy group and the group by which these groups were substituted by the halogen atom are mentioned.

As a C6-C20 arylthio group represented by R ⁶¹ and R ⁶² in the group represented by the above general formula (1-3), the number of carbon atoms which may be substituted by the above halogen atom What substituted the oxygen atom of the 6-20 aryloxy group by the sulfur atom is mentioned.

The arylalkenyl group having 8 to 20 carbon atoms represented by R ⁶¹ and R ⁶² in the group represented by the above general formula (1-3) is a carbon atom which may be substituted by the above halogen atom Groups in which the oxygen atom of the aryloxy group of formulas 6 to 20 is substituted with an alkenyl group such as vinyl, allyl, 1-propenyl, isopropenyl, 2-butenyl, 1,3-butadienyl, 2-pentenyl, 2-octenyl, etc. It can be mentioned.

The heterocyclic group containing 2 to 20 carbon atoms represented by R ⁶¹ and R ⁶² in the group represented by the above general formula (1-3) includes a pyridine group, a pyrazine group, a piperidine group, a piperazine group, A pyrimidine group, a pyridazine group, a triazine group, a hexahydro triazine group, a furan group, a tetrahydrofuran group, a chromane group, a xanthene group, a thiophene group and a thiofuran group, and groups in which these groups are substituted with a halogen atom are listed.

Each functional group in the group represented by the above general formula (1-3), such as aryloxy group, arylthio group, arylalkenyl group, heterocycle-containing group, represented by R ⁶¹ and R ⁶² has a substituent. And, unless otherwise specified, they are unsubstituted ones having no substituent or ones having a substituent.
The substituent that substitutes a hydrogen atom such as an aryloxy group, an arylthio group, an arylalkenyl group, and a heterocycle-containing group has the same content as the substituent that substitutes a hydrogen atom such as an alkyl group used for R ¹¹ and the like. be able to.

The trivalent aliphatic hydrocarbon group having 3 to 35 carbon atoms represented by Y ¹¹ in the group represented by the above general formula (2) is exemplified in the description of X ¹ in the above general formula (1) Aliphatic hydrocarbon groups include trivalent groups substituted with Z ¹ , Z ² and Z ³ , and these groups include -O-, -S-, -CO-, -CO-O-, It may be replaced by a group of -O-CO-, -SO _2- , -NH- or a combination thereof.

The trivalent aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms represented by Y ¹¹ in the group represented by the general formula (2) is exemplified in the description of X ¹ in the general formula (1) And a substituted aromatic ring-containing hydrocarbon group is a trivalent group substituted with Z ¹ , Z ² and Z ³ .

Examples of the trivalent group having a carbon number of 2 to 35 represented by Y ¹¹ in the group represented by the general formula (2) include the complexes exemplified in the description of X ¹ in the general formula (1) A trivalent group in which the ring-containing group is substituted by Z ¹ , Z ² and Z ³ can be mentioned.

The aliphatic hydrocarbon group having 1 to 35 carbon atoms and the aromatic ring having 6 to 35 carbon atoms represented by Z ¹ , Z ² and Z ³ and R ⁶² in the group represented by the above general formula (2) The hydrocarbon group or the heterocycle-containing group having 2 to 35 carbon atoms can be the same as the contents exemplified as R ⁵³ and R ⁵⁴ described above.

The tetravalent aliphatic hydrocarbon group having 1 to 35 carbon atoms represented by Y ¹² in the group represented by the general formula (3) is exemplified in the description of X ¹ in the general formula (1) Aliphatic hydrocarbon groups include tetravalent groups substituted with Z ¹ , Z ² , Z ³ and Z ⁴ , and -O-, -S-, -CO-, -COO-, -OCO-, It may be replaced by -NH- or a combination of these.

The tetravalent aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms represented by Y ¹² in the group represented by the above general formula (3) is exemplified by the description of X ¹ in the above general formula (1) And the aromatic ring-containing hydrocarbon group is a tetravalent group substituted with Z ¹ , Z ² , Z ³ and Z ⁴ .

Examples of the tetravalent heterocyclic group having 2 to 35 carbon atoms represented by Y ¹² in the group represented by the general formula (3) include the complexes exemplified in the description of X ¹ in the general formula (1) A tetravalent group in which the ring-containing group is substituted with Z ¹ , Z ² , Z ³ and Z ⁴ can be mentioned.

Examples of the pentavalent aliphatic hydrocarbon group having 2 to 35 carbon atoms used for Y ¹³ in the group represented by the general formula (4) include the fats exemplified in the description of X ¹ in the general formula (1) Group hydrocarbon group is substituted by Z ¹ , Z ² , Z ³ , Z ⁴ and Z ⁵ and examples thereof include -O-, -S-, -CO-, -CO-O-, It may be replaced by a group of -O-CO-, -SO _2- , -NH- or a combination thereof.

Examples of the pentavalent aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms in the group represented by the general formula (4) include the aromatic ring-containing hydrocarbons exemplified in the description of X ¹ in the general formula (1) A pentavalent group in which the group is substituted by Z ¹ , Z ² , Z ³ , Z ⁴ and Z 5 can be mentioned.

Examples of the pentavalent heterocyclic group having a carbon number of 2 to 35 in the group represented by the above general formula (4) include the heterocycle containing groups exemplified in the description of X ¹ in the above general formula (1). ^And pentavalent groups substituted with ¹ , Z ² , Z ³ , Z ⁴ and Z 5.

Examples of the aliphatic hydrocarbon group having 2 to 35 carbon atoms having a hexavalent carbon atom represented by Y ¹⁴ in the general formula (5) include the aliphatic hydrocarbon groups exemplified in the description of X ¹ in the general formula (1). And a hexavalent group substituted with Z ¹ , Z ² , Z ³ , Z ⁴ , Z 5 and Z ⁶ , and -O-, -S-, -CO-, -COO-, -OCO-, It may be replaced by -SO _2- , -NH- or a combination thereof.

Examples of the hexavalent aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms represented by Y ¹⁴ in the general formula (5) include the aromatic ring-containing carbon atoms exemplified in the description of X ¹ in the general formula (1) A hexavalent group in which a hydrogen group is substituted by Z ¹ , Z ² , Z ³ , Z ⁴ , Z 5 and Z ⁶ can be mentioned.

Examples of the hexavalent heterocyclic group having 2 to 35 carbon atoms represented by Y ¹⁴ in the general formula (5) include the heterocyclic groups exemplified in the description of X ¹ in the general formula (1). ^{^{^{^{Z 1, Z 2, Z 3}}}} , Z 4, Z 5 and hexavalent group substituted by ^{Z 6} and the like.

When m is 2, the linking group X ¹ is any ^one of the following general formulas (1-4), (1-5) and (1-6-a) to (1-6-e) It is preferable that it is a substituent of
When m is 3, the bonding group X ¹ is preferably a group selected from the following group 1.
When m is 4, the above bonding group X ¹ is preferably a group selected from the following group 2.
When m is 5, the linking group X ¹ is preferably a group selected from the following group 3.
When m is 6, the bonding group X ¹ is preferably a group selected from the following group 4.
These substituents can be such that the compound I-1 can exhibit excellent antioxidative ability after elimination of the photoleaving group B, and at the same time, it is easy to obtain and manufacture raw materials.

(In the above general formula (1-4), Y ¹ and Y ⁵ each independently represent an alkylene group having 1 to 4 carbon atoms, and Y ² and Y ⁴ each independently represent an oxygen atom or —NR 1 ^And R ¹¹³ represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 20 carbon atoms, and Y ³ represents —CR ¹¹⁴ R ¹¹⁵ —, —NR ¹¹⁶ —, a divalent carbon atom having 1 Represents an aliphatic hydrocarbon group of to 35, an aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms, or a substituent represented by the following general formula (1-7), and the aliphatic hydrocarbon group, carbon atom The aromatic ring-containing hydrocarbon group having 6 to 35 and the heterocyclic group having 6 to 35 carbon atoms are substituted by -COO-, -O-, -OCO-, -NHCO-, -NH- or -CONH- R ¹¹⁴ and R ¹¹⁵ are each independently hydrogen R represents 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 ¹¹⁶ represents a hydrogen atom or a fat having 1 to 35 carbon atoms Group hydrocarbon group, an aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms, or a heterocyclic ring-containing group having 2 to 35 carbon atoms.

(In the above general formula (1-5), Y ⁶ and Y ⁸ each independently represent —NR ¹¹⁷ — or an alkylene group having 1 to 4 carbon atoms which may be replaced by an oxygen atom, Y ⁷ Represents a direct bond, -O-, -S-, -SO _2- , -CR ¹¹⁸ R ¹¹⁹ -or any of the substituents represented by the above general formulas (1-1) to (1-3) R ¹¹⁷ represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 20 carbon atoms, and R ¹¹⁸ and R ¹¹⁹ each independently represent a carbon atom number which may be substituted with a hydrogen atom or a halogen atom Represents 1 to 8 alkyl groups)

(In the general formulas (1-6-a) to (1-6-e), R ³¹ represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 35 carbon atoms, an aromatic ring having 6 to 35 carbon atoms) Represents a containing hydrocarbon group or a heterocyclic group having 2 to 35 carbon atoms.)

(In the above general formula (1-7), Y ⁹ and Y ¹⁰ each independently represent an alkylene group having 1 to 4 carbon atoms.)

(Wherein, R 32 is the same group as R ⁶² in the general formula (2), and when there are two or more in the group, it may be the same or different, and Z ¹¹ is Z ¹ to Z Represents the same range of groups as the group represented by ^3. )

(In the above formulae, R ³² is the same group as R ⁶² in the above general formula (2), and when there are two or more in the group, it may be the same or different, and Z ¹¹ is Z ¹ It represents a group of the same range as the group represented by ~ Z ^3.)

(In the above formulae, Z ¹⁰ , Z ¹¹ , Z ¹² , Z ¹³ and Z ¹⁴ represent the same range of groups as the groups represented by Z ¹ to Z ^3. )

Alkylene group having 1 to 4 carbon atoms used for Y ¹ , Y ⁵ , Y ⁶ , Y ⁸ , Y ⁹ and Y ¹⁰ used as a substituent in the above general formulas (1-4) to (1-7) Examples of the group include a methylene group, an ethylene group, a propylidene group, an isopropylidene group and a butylidene group.
The aliphatic hydrocarbon group having 1 to 20 carbon atoms used for R ¹¹³ and R ¹¹⁷ includes, as the aliphatic hydrocarbon group having 1 to 120 carbon atoms used for the bonding group X ¹ , m is monovalent Among the contents exemplified as those, those having a predetermined number of carbon atoms can be mentioned.
The divalent aliphatic hydrocarbon group having 1 to 35 carbon atoms and the aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms represented by Y ³ are the same as the contents exemplified as Y ¹ described above. be able to.

The alkyl group having 1 to 8 carbon atoms used for R ¹¹⁴ , R ¹¹⁵ , R ¹¹⁸ and R ¹¹⁹ and the aryl group having 6 to 20 carbon atoms used for R ¹¹⁴ and R ¹¹⁵ and 7 to 20 carbon atoms The arylalkyl group can be the same as the contents exemplified as R ⁵⁵ and R ⁵⁶ described above.
Examples of the aliphatic hydrocarbon group having 1 to 35 carbon atoms, the aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms, and the heterocyclic ring-containing group having 2 to 35 carbon atoms which are used for R ¹¹⁶ and R ³¹ include The same contents as those exemplified as R ⁵³ and R ⁵⁴ described above can be used.

Each functional group such as the above aliphatic hydrocarbon group, aromatic ring-containing hydrocarbon group and heterocyclic group-containing group may have a substituent, and unless otherwise specified, has a substituent. Not substituted or substituted.
The substituent such as an aliphatic hydrocarbon group, an aromatic ring-containing hydrocarbon group, and a heterocycle-containing group has the same content as a substituent that substitutes a hydrogen atom such as an alkyl group used for R ¹¹ and the like. be able to.

Furthermore, the linking group X ^1, if m is 2, can also be preferably used aliphatic hydrocarbon group having 1 to 10 carbon atoms, among others, aliphatic hydrocarbon groups having 1 to 6 carbon atoms Is preferred. This is because the compound can be made to be a compound which has less inhibition of curing and can easily impart an antioxidant ability or the like to a cured product, and furthermore, the production of the compound I-1 is easy.
When m is 1, the aforementioned bonding group X is preferably a hydrogen atom or an aliphatic hydrocarbon group having 1 to 120 carbon atoms, and is preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. More preferable. This is because the compound I-1 exerts excellent antioxidative ability after elimination of the photoleaving group B, and the compound I-1 can be easily produced.

The bonding position of the bonding group X ^{1 to} the benzene ring may be any bonding position in the benzene ring, and for example, the ortho position or para to the bonding position of the B—O— may be used. It can be a position and can be a para position. This is because the compound I-1 exerts an excellent antioxidizing ability after elimination of the photoleaving group B.

The above X ¹ is preferably a hydrogen atom or a group similar to R 1 when m = 1.

The compound I-1 represented by the general formula (A-2) or (A-3) has a structure in which a specific n-valent atom represented by X ² and n specific groups are bonded. The n specific groups are identical to or different from one another.

The X ² can be the same as the one having m of 2 or more among the linking groups used for the X ¹ .
The bonding position of the benzene ring of the bonding group X ^2, can be similar to the X ^1.

The above X ² is preferably a hydrogen atom or a group similar to R 1 when n = 1.

The above atomic group A may be one containing a phenolic hydroxyl group, that is, one in which the compound I-1 contains a phenolic hydroxyl group not protected by the photoleaving group B, but the number of phenolic hydroxyl groups is 2 The number is preferably not more than one, more preferably zero. This is because the compound I-1 has less inhibition of curing.

3. Compound The compound of the present invention may be any compound represented by the above general formula (I-1), but is represented by the above general formula (A-1), (A-2) or (A-3) It is preferably a compound, and as the photoleaving group B, one represented by the above general formula (B-1-a) is preferable. It is because synthesis is easy, and furthermore, photodetachment is easy. Moreover, it is because an antioxidant ability etc. can be easily provided with respect to hardened | cured material. In addition, since compound I-1 is the above general formula (A-1), (A-2) or (A-3), radicals etc. can be trapped stably by elimination of photoleaving group B. It is.

Specific examples of the compound I-1 include the compounds shown below.

The molecular weight of the compound I-1 can be set according to the application of the compound I-1.
The molecular weight can be, for example, 250 or more and 5000 or less, can be 300 or more and 2500 or less, and can be 350 or more and 1500 or less.
When the compound I-1 is a polymer having a repeating structure as its structure, the above molecular weight can be represented by weight average molecular weight (Mw).
The weight average molecular weight (Mw) can be determined as a standard polystyrene equivalent value by gel permeation chromatography (GPC).
The weight average molecular weight Mw is, for example, HLC-8120 GPC manufactured by Tosoh Corp., and the elution solvent is N-methylpyrrolidone to which 0.01 mol / liter of lithium bromide is added, and the polystyrene standard for calibration curve is Mw 377400 210500, 96000, 50400, 20650, 10850, 5460, 2930, 1300, 580 (above, Easi PS-2 series manufactured by Polymer Laboratories) and Mw 1090000 (manufactured by Tosoh Corp.), and the measurement column is TSK-GEL ALPHA- It can be obtained by measurement as M × 2 (made by Tosoh Corp.). Also, the measurement temperature can be 40 ° C., and the flow rate can be 1.0 mL / min.

The method for producing the compound I-1 is not particularly limited as long as it can obtain a desired structure. For example, JP-A-57-111375, JP-A-3-173843, JP-A-6-128195, It can be obtained by reacting a phenolic compound produced by the method described in each publication of JP-A-7-206,771, JP-A-7-252191, and JP-A-2004-501128 with an alkyl halide compound or the like.

The compound I-1 is inactive before light irradiation, and the light leaving group is eliminated by light irradiation to generate a compound I-2 having a hydroxyl group. The above compound I-2 exerts an antioxidant ability.
The application of the compound I-1 is preferably an application that is required to exhibit an antioxidant ability by light irradiation, and, for example, an antioxidant etc. to be used by adding to a composition Can.
Further, the compound I-1 is to generate a compound I-2 having a hydroxyl group by light irradiation. Examples of applications of such compound I-1 include antioxidants that require high dispersion stability.

B. Potential Antioxidant Next, the potential antioxidant of the present invention will be described.
The latent antioxidants of the invention include the compounds I-1 of the invention.

According to the latent antioxidant of the present invention, for example, the curing inhibition is small, and the cured product can be easily provided with the antioxidant ability and the like.

The content of the compound I-1 in the latent antioxidant of the present invention can be appropriately set according to the use of the latent antioxidant and the like.
The latent antioxidant of the present invention comprises 100 parts by mass of the compound I-1 in 100 parts by mass of the latent antioxidant, ie, the latent antioxidant comprises only the compound I-1 It can be done.
In addition to the compound I-1, the latent antioxidant of the present invention may contain other components. When the latent antioxidant of the present invention contains other components, the content of the compound I-1 is, for example, more than 20 parts by mass and 99 parts by mass or less in 100 parts by mass of the latent antioxidant. It is preferably 25 parts by mass or more and 99 parts by mass or less, more preferably 50 parts by mass or more and 99 parts by mass or less, and particularly preferably 80 parts by mass or more and 99 parts by mass or less. It is because the effects such as less hardening inhibition can be exhibited more effectively.

The type of the compound I-1 contained in the latent antioxidant may be only one type, or two or more types. When the latent antioxidant contains several types of compound I-1, the number of types can be, for example, 2 or more and 5 or less.

The compound I-1 described above can be the same as the contents described in the section “A. Compound”, and thus the description thereof is omitted here.

As said other components, it can be set as the content as described in the term of "2. other components" of "C. composition" mentioned later, for example.
The latent antioxidant may include, as another component, a resin component such as a polymer having no polymerizable group.

The latent antioxidant may be in the form of powder or pellet.
When it is in the form of a pellet, as a method of producing the latent antioxidant, for example, a method may be used in which the compound I-1 and the resin component are mixed using an extruder etc. it can.

C. Composition Next, the composition of the present invention will be described.
The composition of the present invention contains the compound I-1 of the present invention.

According to the composition of the present invention, for example, a cured product having a small amount of inhibition of curing and having excellent antioxidant performance and the like can be obtained. Moreover, the composition of the present invention can be easily imparted with photosensitivity and can be easily imparted to a cured product. Hereinafter, each component contained in the composition of this invention is demonstrated.

1. Compound The content of the compound I-1 in the composition of the present invention is not particularly limited as long as it is an amount capable of imparting a desired antioxidant capacity and the like to the composition.
As said content, it can be set as 0.01 mass part or more and 20 mass parts or less in 100 mass parts of solid content of a composition, for example, and it is preferable that it is 0.05 mass part or more and 5 mass parts or less. It is because it is easy to set it as a composition which has few hardening inhibition and can easily give antioxidant ability etc. with respect to hardened | cured material.
In addition, solid content is what contains all the components other than a solvent.
Further, in the present invention, the content is on a mass basis unless otherwise noted.
The content of the compound I-1 varies depending on the content of the solvent and the like, and can be, for example, 0.001 parts by mass or more and 20 parts by mass or less in 100 parts by mass of the composition. And 0.005 parts by mass or more and 10 parts by mass or less. It is because it is easy to set it as a composition which has few hardening inhibition and can easily give antioxidant ability etc. with respect to hardened | cured material.

The type of the compound I-1 contained in the composition may be only one type or two or more types. The type can be, for example, two or more and five or less.

2. Other Components The above composition may contain other components other than the above compound I-1 depending on its use and the like.
As said other component, the resin component is mentioned, for example.
By including the resin component, for example, the curability can be easily imparted to the composition, for example.
Moreover, as said other components, it is preferable to contain a polymerization initiator with the said resin component. This is because, for example, the curability can be easily imparted by containing the resin component, the polymerization initiator and the like as other components.

(1) Resin component The above-mentioned compound I-1 can be held as the above-mentioned resin component, and although it is suitably set up according to the use etc. of a composition, it has a polymeric group, for example Examples thereof include polymerizable compounds, polymers having no polymerizable group, and the like.
By including a polymerizable compound as the resin component, the composition can be used as, for example, a photocurable composition, a thermosetting composition, and the like.

(A) Polymerizable Compound The above-mentioned polymerizable compound has a polymerizable group.
The polymerizable compound is usually used together with a polymerization initiator.
Such polymerizable compounds differ depending on the type of polymerizable group, that is, the type of polymerization reaction, and examples thereof include radically polymerizable compounds, cationically polymerizable compounds, and anionically polymerizable compounds.
It is preferable that the said polymeric compound contains a radically polymerizable compound from a viewpoint of demonstrating the effect that hardening inhibition decreases effectively.

(I) Radically Polymerizable Compound The radically polymerizable compound may have one or more radically polymerizable group and may contain two or more radically polymerizable group.
The above-mentioned radical polymerizable compound is usually used together with a radical polymerization initiator.
As a radically polymerizable polymerizable group, ethylenic unsaturated double bond groups, such as a (meth) acryl group and a vinyl group, can be mentioned, for example.
In addition, (meth) acryl is used by the meaning containing an acryl and methacryl. Also, (meth) acrylate is used in the meaning including acrylate and methacrylate.

The radically polymerizable compound may be a compound having an acid value, or may be a compound having no acid value.
As a compound which has an acid value, the compound etc. which have a carboxyl group can be mentioned, for example.
By containing the compound which has an acid value as a radically polymerizable compound, the said composition reduces the solubility to the alkali developing solution of a light irradiation site | part. Therefore, the composition can be used, for example, as a photosensitive composition whose solubility in a solvent such as an alkaline developer changes before and after light irradiation. More specifically, the above-mentioned composition can be used as a negative working composition by including a compound having an acid value.
As an alkali developing solution, what is generally used as alkali developing solutions, such as tetramethyl ammonium hydroxide (TMAH) aqueous solution and potassium hydroxide aqueous solution, can be used.

The radically polymerizable compound has, for example, an ethylenically unsaturated double bond group, and as a compound having an acid value, (meth) acrylic acid, α-chloroacrylic acid, itaconic acid, maleic acid, citraconic acid, Fumaric acid, hymic acid, crotonic acid, isocrotonic acid, vinyl acetic acid, allyl acetic acid, cinnamic acid, sorbic acid, sorbic acid, mesaconic acid, mono [2- (meth) acryloyloxyethyl] succinate, mono [2- (metha] phthalic acid 1) Mono (meth) acrylates of polymers having a carboxy group and a hydroxyl group at both ends such as acryloyloxyethyl] and ω-carboxypolycaprolactone mono (meth) acrylate; hydroxyethyl (meth) acrylate malate, hydroxypropyl (meth) ) Acrylate malate, dicyclopentadiene malate or a single powder Unsaturated monobasic acids such as polyfunctional (meth) acrylates having a voxyl group and two or more (meth) acryloyl groups; phenol and / or cresol novolac epoxy resin, novolac epoxy resin having a biphenyl skeleton and a naphthalene skeleton, bisphenol Anovolak type epoxy compounds, novolac type epoxy compounds such as dicyclopentadiene novolac type epoxy compounds, polyphenylmethane type epoxy resins having a multifunctional epoxy group, epoxy resins such as epoxy compounds represented by the following general formula (III) An epoxy group of an epoxy resin such as a resin obtained by reacting an unsaturated monobasic acid with an epoxy group or an epoxy compound represented by the following general formula (III) is reacted with an unsaturated monobasic acid, and a polybasic acid anhydride is further Resin obtained by reaction, pentaerythritol tria Polyfunctional acrylates having an acid value, which are reaction products of hydroxyl group-containing polyfunctional acrylates such as acrylates and dipentaerythritol pentaacrylates and dibasic acid anhydrides such as succinic anhydride, phthalic anhydride and tetrahydrophthalic anhydride .

(Wherein, X ⁴¹ represents a direct bond, an alkylidene group having 1 to 4 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, -O-, -S-, -SO _2- , -SS- Or —SO—, —CO—, —OCO— or a substituent represented by (1-1) to (1-3) above,
R ⁴¹ , R ⁴² , R ⁴⁴ and R ⁴⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkenyl group having 2 to 5 carbon atoms or Represents a halogen atom,
d is an integer of 0 to 10; )

Examples of the alkyl group having 1 to 5 carbon atoms, the alkoxy group having 1 to 8 carbon atoms, and the alkenyl group having 2 to 5 carbon atoms include those exemplified as R ^{11 and the} like in the above-mentioned “A. And those having a predetermined number of carbon atoms.
Examples of the alkylidene group having 1 to 4 carbon atoms include methylidene, ethylidene, propylidene and butylidene.
Examples of the alicyclic hydrocarbon group include cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl and the like.
The above-mentioned alkyl group, alkoxy group, alkenyl group, alkylidene group, alicyclic hydrocarbon group etc. may have a substituent, and unless otherwise noted, has a substituent. There are no unsubstituted or substituted ones.
As a substituent which substitutes hydrogen atoms, such as an alkyl group, an alkoxy group, an alkenyl group, an alkylidene group, and an alicyclic hydrocarbon group, a substituent which substitutes hydrogen atoms, such as an alkyl group used for R ¹¹ grade | etc., It can be the same as

The above-mentioned radically polymerizable compound has, for example, an ethylenically unsaturated double bond group, and as a compound having no acid value, 2-hydroxyethyl (meth) acrylate, 2-hydroxy (meth) acrylate Propyl, glycidyl (meth) acrylate, the following compound No. 1 A1 to No. A4, methyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, n-octyl (meth) acrylate ( (Meth) acrylate isooctyl, (meth) acrylate isononyl, (meth) acrylate stearyl, (meth) acrylate lauryl, (meth) acrylate methoxyethyl, (meth) acrylate dimethylaminomethyl, (meth) acrylate dimethyl (meth) acrylate Aminoethyl, aminopropyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, ethoxyethyl (meth) acrylate, poly (ethoxy) ethyl (meth) acrylate, butoxyethoxyethyl (meth) acrylate, (meth ) Ethyl hexyl acrylate, (meth) acrylic acid Phenoxyethyl, tetrahydrofuryl (meth) acrylate, vinyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (Meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, trimethylolethane tri ( Meta) acrylate, trimethylolpropane tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, pentaerythritol Unsaturated monobasic acids such as tra (meth) acrylate, pentaerythritol tri (meth) acrylate, tricyclodecane dimethylol di (meth) acrylate, tri [(meth) acryloyl ethyl] isocyanurate, polyester (meth) acrylate oligomers and the like Polyhydric alcohol or ester of polyhydric phenol; Metal salt of unsaturated polybasic acid such as zinc (meth) acrylate and magnesium (meth) acrylate; maleic anhydride, itaconic anhydride, citraconic anhydride, methyl Tetrahydrophthalic anhydride, tetrahydrophthalic anhydride, trialkyltetrahydrophthalic anhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trialkyltetrahydrofuran Phthalic anhydride-anhydrous Acid anhydride of unsaturated polybasic acid such as leic acid adduct, dodecenyl succinic anhydride, methyl hymic acid anhydride; (meth) acrylamide, methylene bis (meth) acrylamide, diethylene triamine tris (meth) acrylamide, xylylene bis (meth) Unsaturated monobasic acids such as acrylamide, α-chloroacrylamide, N-2-hydroxyethyl (meth) acrylamide and amides of polyhydric amines; unsaturated aldehydes such as acrolein; (meth) acrylonitrile, α-chloroacrylonitrile, cyanation Unsaturated nitriles such as vinylidene and allyl cyanide; styrene, 4-methylstyrene, 4-ethylstyrene, 4-methoxystyrene, 4-hydroxystyrene, 4-chlorostyrene, divinylbenzene, vinyltoluene, vinylbenzoic acid, vinylene Unsaturated aromatic compounds such as 2-phenol, vinyl sulfonic acid, 4-vinyl benzene sulfonic acid, vinyl benzyl methyl ether, vinyl benzyl glycidyl ether; unsaturated ketones such as methyl vinyl ketone; vinyl amine, allylamine, N-vinyl pyrrolidone, vinyl Unsaturated amine compounds such as piperidine; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, n-butyl vinyl ether, isobutyl vinyl ether, allyl glycidyl ether; unsaturated imides such as maleimide, N-phenyl maleimide, N-cyclohexyl maleimide; And indenes such as 1-methylindene; aliphatic conjugated dienes such as 1,3-butadiene, isoprene and chloroprene; polystyrene, polymethyl (meth) acrylate, poly-n- Macromonomers having a mono (meth) acryloyl group at the end of polymer molecular chain such as chill (meth) acrylate and polysiloxane; (meth) acrylonitrile, other vinyl such as ethylene, propylene, butylene, vinyl chloride and vinyl acetate Compounds, and macromonomers such as polymethyl methacrylate macromonomer and polystyrene macromonomer, monomethacrylate of tricyclodecane skeleton, N-phenylmaleimide, methacryloyloxymethyl-3-ethyl oxetane, etc., and (meth) acrylic acid Polymers and copolymers of (meth) acrylic acid obtained by reacting an isocyanate compound having an unsaturated bond such as Karenz MOI manufactured by Showa Denko KK and AOI with these, vinyl chloride, vinylidene chloride, divinyl succ Nath, Allyl phthalate, triallyl phosphate, triallyl isocyanurate, vinyl thioether, vinyl imidazole, vinyl oxazoline, vinyl carbazole, vinyl pyrrolidone, vinyl pyridine, vinyl urethane compound of hydroxyl group-containing vinyl monomer and polyisocyanate compound, hydroxyl group-containing vinyl monomer And vinyl epoxy compounds of polyepoxy compounds, and reaction products of hydroxyl group-containing polyfunctional acrylates such as pentaerythritol triacrylate and dipentaerythritol pentaacrylate with polyfunctional isocyanates such as tolylene diisocyanate and hexamethylene diisocyanate.

The said radically polymerizable compound can be used individually or in mixture of 2 or more types. In addition, the radically polymerizable compound has an ethylenically unsaturated double bond group, and uses a compound having an acid value and a compound having an ethylenically unsaturated double bond group and not having an acid value in combination. Can.
When a radically polymerizable compound is used in mixture of 2 or more types, they may be copolymerized beforehand and it may be used as a copolymer.
The content of the radically polymerizable compound can be appropriately set according to the application etc. of the composition, but for example, it can be 1 part by mass or more and 99 parts by mass or less in 100 parts by mass of the composition, and 10 parts It is preferable that it is a part or more and 90 mass parts or less, Especially, it is preferable that it is 40 mass parts or more and 80 mass parts or less. When the content is in the above-mentioned range, for example, the composition can be used as a negative composition excellent in sensitivity. Moreover, it is because there can be provided a composition which has less inhibition of curing and can easily impart oxidation prevention and the like to a cured product.
The content of the polymerizable compound may be any one as long as the composition can be used as a curable composition, but 1 part by mass or more to 99 parts in total of 100 parts by mass of the compound I-1 and the polymerizable compound. It can be made into parts by mass or less, preferably 50 parts by mass or more and 99.9 parts by mass or less, and more preferably 80 parts by mass or more and 99.7 parts by mass or less, 90 parts by mass or more and 99. It is preferably 5 parts by mass or less. When the content is in the above-mentioned range, the composition can provide a composition which has less inhibition of curing and can easily impart an antioxidant ability and the like to a cured product.
The content of the compound I-1 and the radically polymerizable compound can be appropriately set according to the application of the composition and the like, and for example, 1 part by mass or more and 99 parts by mass or less in 100 parts by mass of the composition. The amount is preferably 10 parts by mass or more and 90 parts by mass or less, and more preferably 40 parts by mass or more and 80 parts by mass or less. When the content is in the above-mentioned range, for example, the composition can be used as a negative composition excellent in sensitivity. Moreover, it is because there can be provided a composition which has less inhibition of curing and which can easily impart antioxidizing ability and the like to a cured product.

(Ii) Cationic Polymerizable Compound and Anionic Polymerizable Compound The cationic polymerizable compound may be one having one or more cationically polymerizable groups.
The cationically polymerizable compound is usually used together with a cationic polymerization initiator.
Examples of the cationically polymerizable polymerizable group include cyclic ether groups such as an epoxy group and an oxetane group, and a vinyl ether group.
That is, as a cationically polymerizable compound, cyclic ether compounds, such as an epoxy compound and an oxetane compound, a vinyl ether compound, etc. are mentioned.

Examples of the above epoxy compounds include methyl glycidyl ether, 2-ethylhexyl glycidyl ether, butyl glycidyl ether, decyl glycidyl ether, C12 to 13 mixed alkyl glycidyl ether, phenyl 2-methyl glycidyl ether, cetyl glycidyl ether, stearyl glycidyl ether, p-sec-butylphenyl glycidyl ether, p-tert-butylphenyl glycidyl ether, glycidyl methacrylate, isopropyl glycidyl ether, allyl glycidyl ether, ethyl glycidyl ether, 2-methyloctyl glycidyl ether, phenyl glycidyl ether, 4-n-butylphenyl Glycidyl ether, 4-phenylphenol glycidyl ether, cresyl glycidyl Ether, dibromocresyl glycidyl ether, decyl glycidyl ether, methoxy polyethylene glycol monoglycidyl ether, ethoxy polyethylene glycol monoglycidyl ether, butoxy polyethylene glycol monoglycidyl ether, phenoxy polyethylene glycol monoglycidyl ether, dibromophenyl glycidyl ether, 1,4-butane Diol diglycidyl ether, 1,5-pentanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,1,2,2-tetrakis (glycidyloxyphenyl) ethane and pentaerythritol Glycidyl ether compounds such as tetraglycidyl ether; glycidyl acetate, Glycidyl esters such as sidyl stearate; 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-metadioxane, methylene bis (3,4-epoxycyclohexane), propane-2, 2-Diyl-bis (3,4-epoxycyclohexane), 2,2-bis (3,4-epoxycyclohexyl) propane, ethylene bis (3,4-epoxycyclohexane carboxylate), bis (3,4-epoxycyclohexyl) Methyl) adipate, 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-1-methylcyclohexyl 3,4-epoxy-1-methylhexanecarboxylate, 6-methyl-3,4 -Epoxycyclohexyl 6-Methyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-3-methylcyclohexylmethyl 3,4-epoxy-3-methylcyclohexanecarboxylate, 3,4-epoxy-5-methylcyclohexylmethyl , 4-Epoxy-5-methylcyclohexanecarboxylate, 1-epoxyethyl-3,4-epoxycyclohexane, 1,2-epoxy-2-epoxyethylcyclohexane, dicyclopentadiene diepoxide, 3,4-epoxy-6- Examples thereof include epoxy cycloalkyl type compounds such as methyl cyclohexyl carboxylate, α-pinene oxide, styrene oxide, cyclohexene oxide and cyclopentene oxide, and N-glycidyl phthalimide.

Moreover, an epoxidized polyolefin can also be used as said epoxy compound. The epoxidized polyolefin is a polyolefin in which an epoxy group is introduced by modifying the polyolefin with an epoxy group-containing monomer. It can be produced by copolymerizing ethylene or an α-olefin having 3 to 20 carbon atoms, an epoxy group-containing monomer, and, if necessary, another monomer, by any of a copolymerization method and a graft method. Ethylene or an α-olefin having 3 to 20 carbon atoms, an epoxy group-containing monomer and another monomer may be polymerized alone or in combination with other monomers. Also, the double bond of a non-conjugated polybutadiene having a hydroxyl group at the end can be obtained by epoxidation by the peracetic acid method, and one having a hydroxyl group in the molecule may be used. Moreover, a hydroxyl group can be urethane-ized with isocyanate, and a primary hydroxyl group-containing epoxy compound can be made to react here, and an epoxy group can be introduce | transduced.

Examples of ethylene or α-olefins of 3 to 20 carbon atoms include ethylene, propylene, butylene, isobutylene, 1,3-butadiene, 1,4-butadiene, 1,3-pentadiene, 2,3-dimethyl-1,3 -Butadiene, piperylene, 3-butyl-1,3-octadiene, isoprene and the like can be mentioned.

Examples of the epoxy group-containing monomer include glycidyl esters of α, β-unsaturated acids, vinyl benzyl glycidyl ether and allyl glycidyl ether. Specific examples of glycidyl esters of α, β-unsaturated acids include glycidyl acrylate, glycidyl methacrylate and glycidyl ethacrylic acid, with glycidyl methacrylate being particularly preferred.

Examples of the other monomers include unsaturated aliphatic hydrocarbons such as vinyl chloride, vinylidene chloride, vinylidene fluoride and tetrafluoroethylene; (meth) acrylic acid, α-chloroacrylic acid, itaconic acid, maleic acid, citraconic acid, Fumaric acid, hymic acid, crotonic acid, isocrotonic acid, vinyl acetic acid, allyl acetic acid, cinnamic acid, sorbic acid, sorbic acid, mesaconic acid, mono [2- (meth) acryloyloxyethyl] succinate, mono [2- (metha] phthalic acid ) Acryloyloxyethyl], ω-carboxypolycaprolactone mono (meth) acrylate, etc. Mono (meth) acrylate of a polymer having a carboxy group and a hydroxyl group at both ends, hydroxyethyl (meth) acrylate malate, hydroxypropyl (meth) ) Acrylate malate, dicyclopentadiene · And unsaturated polybasic acids such as polyfunctional (meth) acrylates having one carboxyl group and two or more (meth) acryloyl groups; 2-hydroxyethyl (meth) acrylate, (meth) acrylate -2-Hydroxypropyl, methyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, n (meth) acrylate -Octyl, isooctyl (meth) acrylate, isononyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, methoxyethyl (meth) acrylate, dimethylaminomethyl (meth) acrylate, (meth ) Dimethylaminoethyl acrylate, aminopropyl (meth) acrylate, (meth) acrylic Dimethylaminopropyl, ethoxyethyl (meth) acrylate, poly (ethoxy) ethyl (meth) acrylate, butoxyethoxyethyl (meth) acrylate, ethylhexyl (meth) acrylate, phenoxyethyl (meth) acrylate, (meth) Tetrahydrofuryl acrylate, vinyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, Polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, trimethylolethane Tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, tri Unsaturated monobasic acids such as cyclodecane dimethylol di (meth) acrylate, tri [(meth) acryloylethyl] isocyanurate and polyester (meth) acrylate oligomers and esters of polyhydric alcohols or polyhydric phenols; (meth) acrylic acid Zinc, metal salts of unsaturated polybasic acids such as magnesium (meth) acrylate; maleic anhydride, itaconic anhydride, citraconic anhydride, methyltetrahydrophthalic anhydride, tetrahydroanhydride Water phthalic acid, trialkyltetrahydrophthalic anhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trialkyltetrahydrophthalic anhydride-maleic anhydride Acid adducts, acid anhydrides of unsaturated polybasic acids such as dodecenyl succinic anhydride and methylhymic anhydride; (meth) acrylamides, methylenebis- (meth) acrylamides, diethylenetriaminetris (meth) acrylamides, xylylene bis (meth) acrylamides , Amides of unsaturated monobasic acids and polyvalent amines such as α-chloroacrylamide and N-2-hydroxyethyl (meth) acrylamide; unsaturated aldehydes such as acrolein; (meth) acrylonitrile, α-chloroacrylonitrile, and vinylidene cyanide , Shea Unsaturated nitriles such as allyl chloride; styrene, 4-methylstyrene, 4-ethylstyrene, 4-methoxystyrene, 4-hydroxystyrene, 4-chlorostyrene, divinylbenzene, vinyltoluene, vinylbenzoic acid, vinylphenol, vinyl Unsaturated aromatic compounds such as sulfonic acid, 4-vinylbenzenesulfonic acid, vinyl benzyl methyl ether and vinyl naphthalene; unsaturated ketones such as methyl vinyl ketone; unsaturated amines such as vinyl amine, allylamine, N-vinyl pyrrolidone and vinyl piperidine Compounds; vinyl alcohols such as allyl alcohol and crotyl alcohol; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, n-butyl vinyl ether and isobutyl vinyl ether; maleimide, N-phenyl maleate Unsaturated imides such as nmid and N-cyclohexyl maleimide; indens such as indene and 1-methyl indene; polymer molecular chains such as polystyrene, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate and polysiloxane Macromonomers having a mono (meth) acryloyl group at the terminal of: vinyl chloride, vinylidene chloride, divinyl succinate, diallyl phthalate, triallyl phosphate, triallyl isocyanurate, vinyl thioether, vinyl imidazole, vinyl oxazoline, Vinylcarbazole, vinylpyrrolidone, vinylpyridine, vinyl urethane compound of hydroxyl group-containing vinyl monomer and polyisocyanate compound, vinyl epoxy compound of hydroxyl group-containing vinyl monomer and polyepoxy compound Hydroxyl group-containing polyfunctional acrylate such as pentaerythritol triacrylate and dipentaerythritol pentaacrylate; reaction product of polyfunctional isocyanate such as tolylene diisocyanate and hexamethylene diisocyanate; hydroxyl group-containing multiple such as pentaerythritol triacrylate and dipentaerythritol pentaacrylate A multifunctional acrylate having an acid value which is a reaction product of a functional acrylate and a dibasic acid anhydride such as succinic anhydride, phthalic anhydride and tetrahydrophthalic anhydride can be mentioned.

A commercial item can also be used as said epoxidized polyolefin, For example, Epolide PB3600, Epolide PB4700 (made by Daicel); BF-1000, FC-3000 (made by ADEKA); Bond first 2C, bond first E, bond First CG 5001, Bond First CG 5004, Bond First 2 B, Bond First 7 B, Bond First 7 L, Bond First 7 M, Bond First VC 40 (Sumitomo Chemical Co., Ltd.); JP-100, JP-200 (Nippon Soda Co., Ltd.); Poly bd R And -45 HT, Poly bd R-15 HT (manufactured by Idemitsu Kosan Co., Ltd.) and Ricon 657 (manufactured by Arkema).

From the viewpoint of good heat resistance, it is more preferable to use a compound having a cardo skeleton as the above-mentioned epoxy compound.

Examples of the above-mentioned oxetane compounds include 3,7-bis (3-oxetanyl) -5-oxa-nonane, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, and 1,2-bis [(3-Ethyl-3-oxetanylmethoxy) methyl] ethane, 1,3-bis [(3-ethyl-3-oxetanylmethoxy) methyl] propane, ethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, Triethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, tetraethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, 1,4-bis (3-ethyl-3-oxetanylmethoxy) butane, 1 , 6-Bis (3-ethyl-3-oxetanylmethoxy) hexane, 3-ethyl-3- (Phenoxy) methyl] oxetane, 3-ethyl-3- (hexyloxymethyl) oxetane, 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane, 3-ethyl-3- (hydroxymethyl) oxetane and 3- Ethyl 3- (chloromethyl) oxetane and the like can be mentioned.

Examples of the vinyl ether compounds include diethylene glycol monovinyl ether, triethylene glycol divinyl ether, n-dodecyl vinyl ether, cyclohexyl vinyl ether, 2-ethylhexyl vinyl ether, 2-chloroethyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, triethylene glycol vinyl ether, 2- Examples thereof include hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, 1,6-cyclohexanedimethanol monovinyl ether, ethylene glycol divinyl ether, 1,4-butanediol divinyl ether and 1,6-cyclohexane dimethanol divinyl ether.

As the above-mentioned anionically polymerizable compound, those having one or more polymerizable groups capable of anionic polymerization may be used.
The above-mentioned anionically polymerizable compound is usually used together with an anionic polymerization initiator.
As said anionizable polymerizable group, an epoxy group, a lactone group, a (meth) acryl group etc. can be mentioned, for example.
That is, as the above-mentioned anion polymerization compound, an epoxy compound, a lactone compound, a compound which has a (meth) acryl group, etc. are mentioned.
Examples of the lactone compound include β-propiolactone and ε-caprolactone.
In addition, as an epoxy compound, the epoxy compound illustrated as said cationically polymerizable compound can be used. Moreover, as a compound which has a (meth) acryl group, what was illustrated as said radically polymerizable compound can be used.

The said cationically polymerizable compound and anionically polymerizable compound can be used individually or in mixture of 2 or more types, respectively.

(B) Polymer The weight average molecular weight (Mw) of the above-mentioned polymer is suitably set according to the use etc. of a composition, but can be made into 1500 or more, for example, and is 1500 or more and 300000 or less be able to.
Moreover, the said polymer is a thing which does not have a polymeric group.
As such a polymer, any polymer having a repeating structure may be used, and a photosensitive resin having photosensitivity, a non-photosensitive resin having no photosensitivity, and the like can be mentioned.
The said composition can be used as a photosensitive composition, for example by including photosensitive resin as a resin component.

(I) Photosensitive resin The above-mentioned photosensitive resin has photosensitivity, and is used together with an acid generator, for example, it dissolves in a developer such as cleavage of chemical bond such as ester group or acetal group by action of acid Mention may be made of positive resins which change in the direction in which the properties increase.
The composition described above contains a positive resin as a resin component, whereby the solubility of the light-irradiated portion in the alkali developer is increased.
Therefore, the composition can be used, for example, as a positive type composition, more specifically, as a photosensitive composition whose solubility in a solvent such as an alkaline developer changes before and after light irradiation.

As the positive resin, those obtained by partially replacing a high molecular weight polymer with an acid labile group having alkali solubility control ability can be used.
As the above-mentioned polymer, polyhydroxystyrene and derivatives thereof; polyacrylic acid and derivatives thereof; polymethacrylic acid and derivatives thereof; hydroxystyrene, acrylic acid, methacrylic acid and derivatives thereof and two or more formed Copolymer: two or more copolymers selected from hydroxystyrene, styrene and their derivatives, cycloolefin and its derivatives, maleic anhydride, and three or more copolymers selected from acrylic acid and its derivatives Combined; cycloolefin and derivatives thereof, maleimide, and three or more copolymers selected from acrylic acid and derivatives thereof; polynorbornene; at least one polymer selected from the group consisting of metathesis ring-opening polymers Etc. can be mentioned.
The acid labile group to be introduced into the above-mentioned polymer includes heteroalicyclic groups such as tertiary alkyl group, trialkylsilyl group, oxoalkyl group, aryl group substituted alkyl group, tetrahydropyran-2-yl group, etc. Tertiary alkylcarbonyl groups, tertiary alkylcarbonylalkyl groups, alkyloxycarbonyl groups and the like can be mentioned.

Detailed examples of the positive resin are the same as the contents described in, for example, JP-A-2003-192665, JP-A-2004-323704, claim 3, JP-A-10-10733, etc. Can.

A well-known acid generator can be used as an acid generator used with said positive resin. Specifically as said acid generator, the photocationic polymerization initiator mentioned later, a thermal cationic polymerization initiator, etc. can be mentioned.

(Ii) Non-Photosensitive Resin The above-mentioned non-photosensitive resin may be any one not having photosensitivity, for example, polystyrene, polymethyl methacrylate, methyl methacrylate-ethyl acrylate copolymer, poly (meth) acrylic acid, styrene -(Meth) acrylic acid copolymer, (meth) acrylic acid-methyl methacrylate copolymer, ethylene-vinyl chloride copolymer, ethylene-vinyl copolymer, polyvinyl chloride resin, ABS resin, nylon 6, nylon 66 Nylon 12, urethane resin, polycarbonate polyvinyl butyral, cellulose ester, polyacrylamide, saturated polyester, phenol resin, phenoxy resin, polyamide imide resin, polyamic acid resin, epoxy resin and the like.
As the non-photosensitive resin, for example, a polymer of the above-mentioned polymerizable compound can also be used.

(Iii) Polymer The weight average molecular weight (Mw) of the above-mentioned polymer is suitably set according to the use etc. of a composition, but can be made into 1500 or more, for example, and is 1500 or more and 300000 or less be able to.

(C) Resin component The content of the above-mentioned resin component is appropriately set according to the application etc. of the composition, and for example, 1 part by mass and 99 parts by mass or less in 100 parts by mass of the solid content of the composition. The amount is preferably 10 parts by mass or more and 90 parts by mass or less, and more preferably 20 parts by mass or more and 80 parts by mass or less. It is because the said composition can hold | maintain the said compound I-1 stably, for example, because the said content is the above-mentioned range.
The content of the resin component can be appropriately set according to the application etc. of the composition, but can be, for example, 1 part by mass or more and 99 parts by mass or less, and 10 parts by mass or more in 100 parts by mass of the composition. The content is preferably 90 parts by mass or less, and more preferably 40 parts by mass or more and 80 parts by mass or less. When the content is in the above-mentioned range, for example, the composition can be used as a negative composition excellent in sensitivity. Moreover, it is because there can be provided a composition which has less inhibition of curing and which can easily impart antioxidizing ability and the like to a cured product.
The content of the above resin component varies depending on the application etc. of the composition, but it is 1 part by mass or more and 99.9 parts by mass or less in 100 parts by mass in total of the compound I-1 and the resin component. And is preferably 50 parts by weight or more and 99.7 parts by weight or less, more preferably 80 parts by weight or more and 99.5 parts by weight or less and 90 parts by weight or more and 98 parts by weight or less preferable. When the content is in the above-mentioned range, the composition can provide a composition which can easily impart the antioxidant ability and the like to the cured product.
Further, the content of the compound I-1 and the resin component can be appropriately set according to the application etc. of the composition, but for example, it is 1 part by mass or more and 99 parts by mass or less in 100 parts by mass of the composition. It is preferably 10 parts by mass or more and 90 parts by mass or less, and more preferably 40 parts by mass or more and 80 parts by mass or less. When the content is in the above-mentioned range, for example, the composition can be used as a negative composition excellent in sensitivity. Moreover, it is because there can be provided a composition which has less inhibition of curing and which can easily impart antioxidizing ability and the like to a cured product.

The type of the resin component may be only one type or a combination of two or more types.
The resin component may contain, for example, only one or both of the polymerizable compound and the polymer.
When the resin component contains both a polymerizable compound and a polymer, the content of the polymerizable compound can be appropriately set according to the application etc. of the composition, for example, the polymerizable compound and the polymer 1 part by weight or more and 99 parts by weight or less can be contained in 100 parts by weight in total.

(2) Polymerization initiator The above-mentioned polymerization initiator is contained as a curable component, and is usually used together with a polymerizable compound or the like.
The above-mentioned polymerization initiator may be any one capable of polymerizing a polymerizable compound, for example, a photopolymerization initiator capable of polymerizing a polymerizable compound by receiving light irradiation, and can polymerize a polymerizable compound by heating And thermal polymerization initiators.

(A) Photopolymerization initiator The above-mentioned photopolymerization initiator may be any one capable of polymerizing the polymerizable compound by receiving light irradiation, for example, photo radical polymerization initiator, photo cationic polymerization initiator, photo anion A polymerization initiator etc. can be mentioned.
It is preferable that the said photoinitiator contains a radical photopolymerization initiator from a viewpoint of demonstrating the effect that a composition becomes what has few hardening inhibition effectively.

The photo radical polymerization initiator is not particularly limited as long as it generates radicals by light irradiation, and conventionally known compounds can be used.
As said photo radical polymerization initiator, an acetophenone type compound, a benzyl type compound, a benzophenone series compound, a thioxanthone type compound, an oxime ester type compound etc. can be illustrated as a preferable thing, for example.

Examples of the above-mentioned acetophenone compounds include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 4'-isopropyl-2-hydroxy-2-methylpropiophenone, 2-hydroxymethyl- 2-Methylpropiophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one, p-dimethylaminoacetophenone, p-tertiary butyl dichloroacetophenone, p-tertiary butyl trichloroacetophenone, p-azidoben Salacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1,2-benzyl-2-dimethylamino-1- (4-morpholinophenyl ) -Butanone-1, b Zoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin isobutyl ether and 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propane -1- on and the like.

Examples of the above-mentioned benzyl compound include benzyl and the like.

Examples of the benzophenone compounds include benzophenone, methyl o-benzoylbenzoate, Michler's ketone, 4,4'-bisdiethylaminobenzophenone, 4,4'-dichlorobenzophenone and 4-benzoyl-4'-methyldiphenyl sulfide. Be

Examples of the thioxanthone compound include thioxanthone, 2-methyl thioxanthone, 2-ethyl thioxanthone, 2-chloro thioxanthone, 2-isopropyl thioxanthone, 2,4-diethyl thioxanthone and the like.

As said oxime type compound, the compound represented by the following general formula (IV) can be mentioned, for example.

(Wherein, R ⁷¹ and R ⁷² each independently represent a hydrogen atom, a cyano group, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an arylalkyl having 7 to 30 carbon atoms A group or a heterocycle-containing group having 2 to 20 carbon atoms,
R ⁷³ and R ⁷⁴ each independently represent a halogen atom, a nitro group, a cyano group, a hydroxyl group, a carboxyl group, R ⁷⁵ , OR ⁷⁶ , SR ⁷⁷ , NR ⁷⁸ R ⁷⁹ , COR ⁸⁰ , SOR ⁸¹ , SO ₂ R ⁸² or It represents CONR ⁸³ ^{R ^84,} R ⁷³ and ^{R 74} are, sometimes are bonded to each other to form a ring,
R ⁷⁵ , R ⁷⁶ , R ⁷⁷ , R ⁷⁸ , R ⁷⁹ , R ⁸⁰ , R ⁸¹ , R ⁸² , R ⁸³ and R ⁸⁴ are each independently an alkyl group having 1 to 20 carbon atoms and 6 to 6 carbon atoms 30 aryl groups, arylalkyl groups having 7 to 30 carbon atoms, or heterocycle-containing groups having 2 to 20 carbon atoms,
X ³ represents an oxygen atom, a sulfur atom, a selenium atom, CR ⁸⁵ R ⁸⁶ , CO, NR ⁸⁷ or PR ⁸⁸ ,
X ⁴ represents a single bond or CO;
R ⁸⁵ , R ⁸⁶ , R ⁸⁷ and R ⁸⁸ each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms or an arylalkyl group having 7 to 20 carbon atoms And the methylene group in the alkyl group or the arylalkyl group may be substituted with a halogen atom, a nitro group, a cyano group, a hydroxyl group, a carboxyl group or a heterocyclic group, and may be substituted with -O- May be
R ⁷³ and R ⁷⁴ may independently form a ring together with either of adjacent benzene rings,
e1 represents an integer of 0 to 4;
e2 represents an integer of 0 to 5; )

The carbon number of 1 used in R ⁷¹ , R ⁷² , R ⁷⁵ , R ⁷⁶ , R ⁷⁷ , R ⁷⁸ , R ⁷⁹ , R ⁸⁰ , R ⁸⁵ , R ⁸⁶ , R ⁸⁷ and R ⁸⁸ in the above general formula (IV) As the alkyl group of to 20, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, a heterocycle-containing group having 2 to 20 carbon atoms, and a substituent thereof, the above-mentioned "1. Among the contents exemplified as R ^{11 and the} like in the section of “photoleaving group B”, those having a predetermined number of carbon atoms can be mentioned.

Examples of the oxime-based compound include: ethanone-1- [9-ethyl-6- (2-methylbenzoyl-9H-carbazol-3-yl] -1- (O-acetyloxime), 1- [9-ethyl -6-Benzoyl-9H-carbazol-3-yl-octan-1-one oxime-O-acetate, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -ethane- 1-one oxime-O-benzoate, 1- [9-n-butyl-6- (2-ethylbenzoyl) -9H-carbazol-3-yl] -ethan-1-one oxime-O-benzoate, ethanone-1- [ 9-ethyl-6- (2-methyl-4-tetrahydrofuranylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), Non-1- [9-ethyl-6- (2-methyl-4-tetrahydropyranylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl -6- (2-Methyl-5-tetrahydrofuranylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- {2-methyl-4 -(2,2-Dimethyl-1,3-dioxolanyl) methoxybenzoyl} -9H-carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- (2-) Carbazole-based ox having a carbazole structure such as methyl-4-tetrahydrofuranyl methoxybenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime) Muesuteru compounds.

As the oxime compound, for example, an indole oxime ester compound having an indole structure can also be used.
As an indole type oxime ester compound, the oxime ester compound etc. which are represented by the following general formula (V) described in international publication 2017/051680 can be mentioned, for example.

(Wherein, R ²⁰¹ and R ²⁰² each independently represent R ²¹¹ , OR ²¹¹ , COR ²¹¹ , SR ²¹¹ , CONR ²¹² R ²¹³ or CN,
R ²¹¹ , R ²¹² and R ²¹³ each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a carbon atom Represents a heterocycle-containing group of 2 to 20,
The hydrogen atoms of the groups represented by R ²¹¹ , R ²¹² and R ²¹³ are further R ²²¹ , OR ²²¹ , COR ²²¹ , SR ²²¹ , NR ²²² R ²²³ , CONR ²²² R ²²³ , NR ²²² OR ²²³ , NCOR ²²² OCOR ²²³ , NR ²²² COR ²²¹ , OCOR ²²¹ , COOR ²²¹ , SCOR ²²¹ , OCSR ²²¹ , COSR ²²¹ , CSOR ²²¹ , hydroxyl group, nitro group, CN, halogen atom, or COOR ²²¹ in some cases,
R ²²¹ , R ²²² and R ²²³ each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a carbon atom Represents a heterocycle-containing group of 2 to 20,
The hydrogen atom of the group represented by R ²²¹ , R ²²² and R ²²³ may be further substituted by a hydroxyl group, a nitro group, CN, a halogen atom, a hydroxyl group or a carboxyl group,
Methylene groups in the alkylene portion of the group represented by ^{^{^{^{R 211, R 212, R 213}}}} , R 221, R 222 and ^{R 223} is, -O -, - S -, - COO -, - OCO -, - OCOO-, ^{^{^{^{-CONR 224 -, - NR 224 -}}}} , - NR 224 CO -, - NR 224 COO -, - OCONR 224 -, - SCO -, - COS -, - OCS- or -SCOO- by sometimes replaced ,
R ²²⁴ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocycle-containing group having 2 to 20 carbon atoms Represent
The alkyl part of the group represented by R ²¹¹ , R ²¹² , R ²¹³ , R ²²¹ , R ²²² , R ²²³ and R ²²⁴ may have a branched side chain or may be a cyclic alkyl,
R ²⁰³ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms or a heterocycle-containing group having 2 to 20 carbon atoms And the alkyl moiety of the group represented by R ²⁰³ may be branched side chain or cyclic alkyl, and R ²⁰³ and R ²⁰⁷ and R ²⁰³ and R ²⁰⁸ together respectively. May form a ring,
The hydrogen atom of the group represented by R ²⁰³ further includes R ²²¹ , OR ²²¹ , COR ²²¹ , SR ²²¹ , NR ²²² R ²²³ , CONR ²²² R ²²³ , NR ²²² OR ²²³ , NCOR ²²² OCOR ²²³ , NR ²²² COR ²²¹ , It may be substituted by OCOR ²²¹ , COOR ²²¹ , SCOR ²²¹ , OCSR ²²¹ , COSR ²²¹ , CSOR ²²¹ , a hydroxyl group, a nitro group, CN, a halogen atom, or COOR ²²¹ ,
R ²⁰⁴ , R ²⁰⁵ , R ²⁰⁶ and R ²⁰⁷ are each independently R ²¹¹ , OR ²¹¹ , SR ²¹¹ , COR ²¹⁴ , CONR ²¹⁵ R ²¹⁶ , NR ²¹² COR ²¹¹ , OCOR ²¹¹ , COOR ²¹⁴ , SCOR ²¹¹ , OCSR ²¹¹ , COSR ²¹⁴ , CSOR ²¹¹ , a hydroxyl group, CN or a halogen atom, and R ²⁰⁴ and R ²⁰⁵ , R ²⁰⁵ and R ^206, and R ²⁰⁶ and R ²⁰⁷ may together form a ring, respectively.
The hydrogen atoms of the groups represented by R ²⁰⁴ , R ²⁰⁵ , R ²⁰⁶ and R ²⁰⁷ are further selected from R ²²¹ , OR ²²¹ , COR ²²¹ , SR ²²¹ , NR ²²² R ²²³ , CONR ²²² R ²²³ , NR ²²² OR ²²³ , NCOR ²²² OCOR ²²³ , NR ²²² COR ²²¹ , OCOR ²²¹ , COOR ²²¹ , SCOR ²²¹ , OCSR ²²¹ , COSR ²²¹ , CSOR ²²¹ , and may be substituted with a hydroxyl group, a nitro group, CN, a halogen atom or COOR ²²¹ ,
R ²¹⁴ , R ²¹⁵ and R ^{216 each} represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms,
The alkyl part of the group represented by R ²¹⁴ , R ²¹⁵ and R ²¹⁶ may be branched side chain or cyclic alkyl;
R ²⁰⁸ represents R ²¹¹ , OR ²¹¹ , SR ²¹¹ , COR ²¹¹ , CONR ²¹² R ²¹³ , NR ²¹² COR ²¹¹ , OCOR ²¹¹ , COOR ²¹¹ , SCOR ²¹¹ , OCSR ²¹¹ , COSR ²¹¹ , CSOR ²¹¹ , a hydroxyl group, CN or a halogen atom Represents
n1 represents 0 or 1; )

The number of carbon atoms used in R ²⁰³ , R ²¹¹ , R ²¹² , R ²¹³ , R ²¹⁴ , R ²¹⁵ , R ²¹⁶ , R ²²¹ , R ²²² , R ²²³ and R ²²⁴ in the above general formula (V) Examples of the alkyl group, the aryl group having 6 to 30 carbon atoms, the arylalkyl group having 7 to 30 carbon atoms, and the heterocycle-containing group having 2 to 20 carbon atoms include the items of the above-mentioned “1. Among the contents exemplified as R ^{11 and the} like, those having a predetermined number of carbon atoms can be mentioned.

Other radical polymerization initiators include phosphine oxide compounds such as 2,4,6-trimethylbenzoyl diphenyl phosphine oxide and bis (cyclopentadienyl) -bis [2,6-difluoro-3- (pill-1) -Yl)] Titanocene compounds such as titanium etc. may be mentioned.

Commercially available radical polymerization initiators include Adeka optomer N-1414, N-1717, N-1919, Adeka Arkles NCI-831, NCI-930 (manufactured by ADEKA Corporation), IRGACURE 184, IRGACURE 369, IRGACURE 651, IRGACURE 907, IRGACURE OXE 01, IRGACURE OXE 02, OXE 03, OXE 04, IRGACURE 784 (manufactured by BASF), TR-PBG-304, TR-PBG-305, TR-PBG-309, TR-PBG-314 and TR-PBG-327 (Tronly Company) and the like.

These photo radical polymerization initiators may be used alone or in combination of two or more depending on the desired performance.
The content of the photo radical polymerization initiator may be any as long as it can impart desired curability and photosensitivity. For example, 0.001 parts by mass or more and 20 parts by mass with respect to 100 parts by mass of the polymerizable compound The amount may be as follows, preferably 0.1 to 30 parts by mass, and more preferably 0.5 to 10 parts by mass. It is because a composition is excellent in curability etc. and is excellent also in dispersibility etc. by being said content.

The photocationic polymerization initiator is not particularly limited as long as it is a compound capable of releasing a substance that causes cationic polymerization to be initiated by light irradiation, and it is possible to use an existing compound, and preferably an energy ray. The compound is a double salt which is an onium salt that releases a Lewis acid upon irradiation with or a derivative thereof. Representative examples of such compounds include the following general formula:
[A1] ^{r +} [B1] ^r-
And salts of cations and anions represented by

The cation [A1] ^{r +} is preferably onium, and the structure thereof can be represented by, for example, the following general formula.
[(R ¹⁰¹ ) _{f 1} Q] ^{r +}

Furthermore, here, R ¹⁰¹ is an organic group having 1 to 60 carbon atoms and which may contain several atoms other than carbon atoms. f1 is an integer of 1 to 5; Each of e R ⁵⁸ is independent of each other and may be the same or different. Further, at least one of R ¹⁰¹ is preferably an organic group as described above having an aromatic ring. For example, even when substituted by an alkyl group, an alkoxy group, a hydroxy group, a hydroxyalkoxy group, a halogen atom, a benzyl group, a thiophenoxy group, a 4-benzoylphenylthio group, a 2-chloro-4-benzoylphenylthio group, etc. A certain phenyl group is mentioned. Q is an atom or atomic group selected from the group consisting of S, N, Se, Te, P, As, Sb, Bi, O, I, Br, Cl, F, and N = N. Also, when the valence of Q in the cation [A1] ^{r +} is q, it is necessary that the relationship r = f1-q holds (where N = N is treated as having a valence of 0).

The anion [B1] ^r- is preferably a halide complex, and its structure can be represented, for example, by the following general formula, [LX _f2 ] ^r- .

Furthermore, here, L is a metal or metalloid (Metalloid) which is a central atom of a halide complex, and B, P, As, Sb, Fe, Sn, Bi, Al, Ca, In, Ti, Zn, Sc, V, Cr, Mn, Co and the like.
X _f2 is a halogen atom or a phenyl group which may be substituted by a halogen atom, an alkoxy group or the like. f2 is an integer of 3 to 7;
Also, when the valence of L in the anion [B1] ^r -is p, it is necessary that the relationship r = f2-p holds.

Specific examples of the anion [LX _f2 ] ^r- of the above general formula include tetrakis (pentafluorophenyl) borate, tetra (3,5-difluoro-4-methoxyphenyl) borate, tetrafluoroborate (BF ₄ ) ⁻ , Hexafluorophosphate (PF ₆ ) ⁻ , hexafluoroantimonate (SbF ₆ ) ⁻ , hexafluoroarsenate (AsF ₆ ) ⁻ and hexachloroantimonate (SbCl ₆ ) ⁻ can be mentioned.

Further, the anion [B1] ^r- has the following general formula,
[LX _f2-1 (OH)] ^r-
The thing of the structure represented by can also be used preferably. L, X and f2 are the same as above. Other anions that can be used include perchlorate ion (ClO ₄ ) ⁻ , trifluoromethyl sulfite ion (CF ₃ SO ₃ ) ⁻ , fluorosulfonate ion (FSO ₃ ) ⁻ , toluene sulfonate anion And trinitrobenzenesulfonic acid anion, camphorsulfonate, nonafluorobutanesulfonate, hexadecafluorooctanesulfonate, tetraaryl borate and tetrakis (pentafluorophenyl) borate.

In the present invention, among such onium salts, it is particularly effective and preferable to use an aromatic onium salt of the following (e) to (t). Among these, 1 type can be used individually or in mixture of 2 or more types.

(E) aryldiazonium salts such as phenyldiazonium hexafluorophosphate, 4-methoxyphenyldiazonium hexafluoroantimonate and 4-methylphenyldiazonium hexafluorophosphate.

(F) Diaryls such as diphenyliodonium hexafluoroantimonate, di (4-methylphenyl) iodonium hexafluorophosphate, di (4-tert-butylphenyl) iodonium hexafluorophosphate and tolycamyliodonium tetrakis (pentafluorophenyl) borate Iodonium salt.

(G) Sulfonium salts represented by the following Group I or Group II: sulfonium salts such as hexafluoroantimony ion, tetrakis (pentafluorophenyl) borate ion and the like.

In addition, other preferable ones are (η5-2, 4-cyclopentadien-1-yl) [(1, 2, 3, 4, 5, 6 η)-(1-methylethyl) benzene] -iron- Iron-arene complexes such as hexafluorophosphate; aluminum complexes such as tris (acetylacetonato) aluminum, tris (ethylacetonatoacetato) aluminum, tris (salicylaldehyde) aluminum; mixtures with silanols such as triphenylsilanol : Etc. can also be mentioned.

A commercial item can also be used as said photocationic polymerization initiator, For example, IRUGACURE 261 (made by BASF Corporation), Adeka optomer SP-150, SP-151, SP-152, SP-170, SP-171, SP -172 (made by Adeka), UVE-1014 (made by General Electronics), CD-1012 (made by Sartmar), CI-2064, CI-2481 (made by Nippon Soda Co., Ltd.), Uvacure 1590, 1591 (Daicel UCB), CYRACUREUVI -6990 (manufactured by Union Carbide), BBI-103, MPI-103, TPS-103, MDS-103, DTS-103, NAT-103 and NDS-103 (manufactured by Midori Chemical Co., Ltd.), and the like.

Among these, aromatic iodonium salts, aromatic sulfonium salts and iron-arene complexes are preferably used from the viewpoint of practical use and light sensitivity.

As said photoanion polymerization initiator, what generate | occur | produces a base with light can be used, and what is well-known as a photoanion polymerization initiator can be used.
Examples of the photoanion polymerization initiator include acetophenone O-aroyloxime (acetophenone O-aroyloxime), nifedipine and the like.

(B) Thermal polymerization initiator The thermal polymerization initiator may be any one capable of polymerizing a polymerizable compound by heating, and a thermal radical polymerization initiator, a thermal cationic polymerization initiator, a thermal anionic polymerization initiator, etc. Can be mentioned.
It is preferable that the said thermal-polymerization initiator contains a thermal radical polymerization initiator from a viewpoint which exhibits the effect that hardening inhibition decreases effectively.

As said thermal radical polymerization initiator, what generate | occur | produces a radical can be used by heating, and a well-known thing can be used as a thermal radical polymerization initiator.
As said thermal radical polymerization initiator, an azo compound, a peroxide, a persulfate, etc. can be illustrated as a preferable thing, for example.

Examples of the above azo compounds include 2,2'-azobisisobutyronitrile, 2,2'-azobis (methylisobutyrate), 2,2'-azobis-2,4-dimethylvaleronitrile, 1,1 ' And -azobis (1-acetoxy-1-phenylethane) and the like.

Examples of peroxides include benzoyl peroxide, di-t-butyl benzoyl peroxide, t-butyl peroxypivalate and di (4-t-butylcyclohexyl) peroxy dicarbonate.

Examples of the persulfate include persulfates such as ammonium persulfate, sodium persulfate and potassium persulfate.

As said thermal cationic polymerization initiator, what generate | occur | produces cationic seed | species or a Lewis acid by heating can be used, and a well-known thing can be used as a thermal cationic polymerization initiator.
Specific examples of the thermal cationic polymerization initiator include salts such as sulfonium salts, thiophenium salts, thiolanium salts, benzyl ammonium, pyridinium salts and hydrazinium salts; and polyalkylpolyamines such as diethylenetriamine, triethylenetriamine and tetraethylenepentamine. Alicyclic polyamines such as 1,2-diaminocyclohexane, 1,4-diamino-3,6-diethylcyclohexane and isophorone diamine; Aromatic polyamines such as m-xylylenediamine, diaminodiphenylmethane and diaminodiphenyl sulfone Glycidyl ethers such as the above polyamines and phenyl glycidyl ether, butyl glycidyl ether, bisphenol A-diglycidyl ether and bisphenol F-diglycidyl ether Or a polyepoxy adduct modified product produced by reaction with various epoxy resins such as glycidyl esters of carboxylic acid according to a conventional method; the above organic polyamines and carboxylic acids such as phthalic acid, isophthalic acid and dimer acid Amidated modified products produced by reaction according to a conventional method; the above-mentioned polyamines and aldehydes such as formaldehyde and the like, aldehydes such as formaldehyde, and nuclei of phenol, cresol, xylenol, tert-butylphenol and resorcin etc. Mannich modified products produced by reacting with phenols having the same according to a conventional method; Multivalent carboxylic acids (oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacine Acid, dodecanedioic acid, 2 Methylsuccinic acid, 2-methyladipic acid, 3-methyladipic acid, 3-methylpentanedioic acid, 2-methyloctanedioic acid, 3,8-dimethyldecanedioic acid, 3,7-dimethyldecanedioic acid, hydrogenated dimer Aliphatic dicarboxylic acids such as acid and dimer acid; aromatic dicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid and naphthalene dicarboxylic acid; alicyclic dicarboxylic acids such as cyclohexane dicarboxylic acid; trimellitic acid, trimesic acid and castor oil fatty acid Etc .; acid anhydrides of tetracarboxylic acids such as pyromellitic acid etc.); dicyandiamide, imidazoles, carboxylic acid esters, sulfonic acid esters, amine imides and the like.
A commercial item can also be used as said thermal cationic polymerization initiator, For example, Adeka opton CP-77, Adeka opton CP-66 (made by ADEKA), CI-2639, CI-2624 (made by Nippon Soda Co., Ltd.), Sun Aid SI -60 L, San Aid SI-80 L, San Aid SI-100 L (manufactured by Sanshin Chemical Industry Co., Ltd.), and the like.

As said thermal anion polymerization initiator, what generate | occur | produces a base by heat can be used, and what is well-known as a thermal anion polymerization initiator can be used.
Specific examples of the anionic polymerization initiator include aliphatic amine compounds, aromatic amine compounds, secondary or tertiary amine compounds, imidazole compounds, polymercaptan compounds, and boron trifluoride-amine complex. , Dicyandiamide, organic acid hydrazide and the like can be used.

(C) Content of Polymerization Initiator The content of the polymerization initiator may be any as long as it can impart desired curability and photosensitivity. For example, 0.1 part by mass in 100 parts by mass of solid content It can be 30 parts by mass or less and preferably 0.5 parts by mass or more and 10 parts by mass or less. It is because a composition is excellent in curability etc. and is excellent also in dispersibility etc. by being said content.
The content of the polymerization initiator may be any as long as it can impart desired curability and photosensitivity, and for example, 0.001 to 20 parts by mass with respect to 100 parts by mass of the polymerizable compound It is preferable that it is 0.1 mass part or more and 30 mass parts or less, and it is preferable that it is 0.5 mass part or more and 10 mass parts or less. It is because a composition is excellent in curability etc. and is excellent also in dispersibility etc. by being said content.

(3) Others As the above other components, in addition to the resin component and the polymerization initiator, if necessary, a colorant, a solvent, a chain transfer agent, a sensitizer, a surfactant, a silane coupling agent, a melamine compound, etc. Can be included.
In addition to the above, the other components may be, if necessary, a thermal polymerization inhibitor such as p-anisole, hydroquinone, pyrocatechol, t-butyl catechol or phenothiazine; plasticizer; adhesion promoter; filler; Foaming agents; leveling agents; surface conditioners; antioxidants such as phenolic antioxidants, phosphite antioxidants, thioether antioxidants other than the compounds represented by the above compound I-1; ultraviolet absorbers; Dispersion aids; aggregation inhibitors; catalysts; effects accelerators; crosslinkers; additives such as thickeners etc. can be included.

(A) Colorant As the above-mentioned colorant, for example, a dye or a pigment may be mentioned as long as it can impart a desired color to a composition or a cured product thereof or the like.
As the dye, a compound having absorption at 380 to 1200 nm can be used, and for example, azo compound, anthraquinone compound, indigoid compound, triarylmethane compound, xanthene compound, alizarin compound, acridine compound, stilbene compound, thiazole compound, naphthol Compound, quinoline compound, nitro compound, indamine compound, oxazine compound, phthalocyanine compound, cyanine compound, diimmonium compound, cyanoethenyl compound, dicyanostyrene compound, rhodamine compound, perylene compound, polyene naphtholactam compound, coumarin compound, squalilium compound, squarylium compound, Spiropyran compounds, spirooxazine compounds, merocyanine compounds, oxonol compounds, styryl compounds, pi Lithium compounds, rhodanine compounds, oxazolone compounds, phthalimide compounds, cinnoline compounds, naphthoquinone compounds, azaanthraquinone compounds, porphyrin compounds, azaporphyrin compounds, pyromethene compounds, quinacridone compounds, diketopyrrolopyrrole compounds, indigo compounds, acridine compounds, azine compounds, Azomethine compounds, aniline compounds, quinacridone compounds, quinophthalone compounds, quinone imine compounds, iridium complex compounds, dyes such as europium complex compounds, and the like may be mentioned, and a plurality of these may be mixed and used.

As the pigment, an inorganic pigment or an organic pigment can be used. For example, nitroso compound, nitro compound, azo compound, diazo compound, xanthene compound, quinoline compound, anthraquinone compound, coumarin compound, phthalocyanine compound, isoindolinone compound, iso Indoline compounds, quinacridone compounds, anthrone compounds, perinone compounds, perylene compounds, diketopyrrolopyrrole compounds, thioindigo compounds, dioxazine compounds, triphenylmethane compounds, quinophthalone compounds, naphthalenetetracarboxylic acids; metal complex compounds of azo dyes, cyanine dyes; Lake pigment; carbon black obtained by furnace method, channel method, thermal method, or acetylene black, ketjen black or lamp black -Carbon black prepared by coating the above carbon black with an epoxy resin, coated with the carbon black in advance in a solvent, and adsorbed with a resin of 20 to 200 mg / g, the carbon black having an acidic or alkaline surface Treated, with an average particle diameter of 8 nm or more and a DBP oil absorption of 90 ml / 100 g or less, CO in volatiles at 950 ° C., total oxygen amount calculated from CO ₂ is 9 mg or more per 100 m ² of surface area of carbon black Graphite, graphitized carbon black, activated carbon, carbon fiber, carbon nanotube, carbon micro coil, carbon nanohorn, carbon aerogel, fullerene; aniline black, pigment black 7, titanium black; hydrophobic resin, chromium oxide green, miloli blue , Co Ruthe green, cobalt blue, manganese base, ferrocyanide, phosphate group blue, bitumen, ultramarine, cerulian blue, pyridian, emerald green, lead sulfate, yellow lead, zinc yellow, red iron oxide (red iron oxide (III)), Inorganic contents such as cadmium red, synthetic iron black, amber and organic pigments can be used. These pigments may be used alone or in combination of two or more.

Commercially available pigments can also be used as the above-mentioned inorganic pigment or organic pigment, and for example, pigment red 1, 2, 3, 9, 10, 14, 17, 22, 22, 31, 31, 38, 41, 48, 49, 88, 90, 97, 112, 119, 122, 123, 144, 149, 166, 168, 169, 171, 177, 179, 180, 184, 185, 192, 200, 202, 209, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, 254; pigment oranges 13, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 65, 71; pigment yellow 1, 3, 12, 13, 14, 16, 17, 20, 24, 55, 60, 73, 81, 83, 86 93, 95, 97, 98, 100, 109, 110, 113, 114, 117, 120, 126, 127, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 154, 154, 154, 154, 154, 154, 166, 168, 175, 180, 185; pigment green 7, 10, 36; pigment blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 5, 15: 6, 22, 24, 56, 60, 61, 62, 64; pigment violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 50 and the like.

As content of the said coloring agent, it can be referred to as 0.01 mass part or more and 50 mass parts or less with respect to 100 mass parts of solid content of a composition.
The content of the coloring agent can be 0.01 parts by mass or more and 20 parts by mass or less in 100 parts by mass of the composition.

(B) Solvent The solvent may be any solvent as long as it can dissolve or disperse the above-mentioned components. For example, methyl ethyl ketone, methyl amyl ketone, diethyl ketone, acetone, methyl isopropyl ketone, methyl isobutyl ketone, cyclohexanone, 2- Ketones such as heptanone; ether solvents such as ethyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane, dipropylene glycol dimethyl ether; methyl acetate, ethyl acetate, n-propyl acetate, Ester solvents such as isopropyl acetate, n-butyl acetate, cyclohexyl acetate, ethyl lactate, dimethyl succinate and texanol; cellosolve solvents such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; Alcohol solvents such as ethanol, iso- or n-propanol, iso- or n-butanol, amyl alcohol and diacetone alcohol; ethylene glycol monomethyl acetate, ethylene glycol monoethyl acetate, propylene glycol-1-monomethyl ether-2 -Ether ester solvents such as acetate (PGMEA), dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, ethoxyethyl propionate, 1-t-butoxy-2-propanol, 3-methoxybutyl acetate, cyclohexanol acetate, etc. BTX solvents such as benzene, toluene and xylene; aliphatic hydrocarbon solvents such as hexane, heptane, octane and cyclohexane; turpentine oil, D-limonene, Terpene-based hydrocarbon oils such as Nene; paraffin spirits such as Mineral Spirit, Swazor # 310 (Cosmo Matsuyama Oil Co., Ltd.), Solvesso # 100 (Exxon Chemical Co., Ltd.); Carbon tetrachloride, chloroform, trichloroethylene, methylene chloride Halogenated aliphatic hydrocarbon solvents such as 1,2-dichloroethane; halogenated aromatic hydrocarbon solvents such as chlorobenzene; carbitol solvents, aniline, triethylamine, pyridine, acetic acid, acetonitrile, carbon disulfide, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, water and the like can be mentioned, and these solvents can be used as one or two or more mixed solvents.
The content of the solvent varies depending on the application of the composition, etc., and can be 1 part by mass or more and 99 parts by mass or less in 100 parts by mass of the composition, and 10 parts by mass or more and 70 parts by mass It is preferable that it is less than part. It is because it is easy to make it excellent in coating property etc.

(C) Chain Transfer Agent and Sensitizer As the chain transfer agent and the sensitizer, the sensitivity of the composition can be adjusted, and a sulfur atom-containing compound is generally used. For example, thioglycolic acid, thiomalic acid, thiosalicylic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, 3-mercaptobutyric acid, N- (2-mercaptopropionyl) glycine, 2-mercaptonicotinic acid, 3- [N- ( 2-mercaptoethyl) carbamoyl] propionic acid, 3- [N- (2-mercaptoethyl) amino] propionic acid, N- (3-mercaptopropionyl) alanine, 2-mercaptoethanesulfonic acid, 3-mercaptopropanesulfonic acid, 4-Mercaptobutanesulfonic acid, dodecyl (4-methylthio) phenyl ether, 2-mercaptoethanol, 3-mercapto-1,2-propanediol, 1-mercapto-2-propanol, 3-mercapto-2-butanol, mercaptophenol , 2-me Captoethylamine, 2-mercaptoimidazole, 2-mercaptobenzimidazole, 2-mercapto-3-pyridinol, 2-mercaptobenzothiazole, mercaptoacetic acid, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3- 3- Mercapto compounds such as mercapto propionate), disulfide compounds obtained by oxidizing the mercapto compounds, iodoacetic acid, iodopropionic acid, 2-iodoethanol, 2-iodoethanesulfonic acid, iodomethane such as 3-iodopropanesulfonic acid Alkylated compounds, trimethylolpropane tris (3-mercaptoisobutyrate), butanediol bis (3-mercaptoisobutyrate), hexanedithiol, decanedithiol, 1,4- Methyl mercaptobenzene, butanediol bisthiopropionate, butanediol bisthioglycolate, ethylene glycol bisthioglycolate, trimethylolpropane tristhioglycolate, butanediol bisthiopropionate, trimethylolpropane tristhiopropionate Trimethylolpropane tristhioglycolate, pentaerythritol tetrakisthiopropionate, pentaerythritol tetrakisthioglycolate, tris hydroxyethyl tris thiopropionate, compound No. 1 below. C1, aliphatic polyfunctional thiol compounds, such as tri-mercaptopropionic acid tris (2-hydroxyethyl) isocyanurate, manufactured by Showa Denko KK Karenz MT BD1, PE1, NR ^1, and the like.

(D) Surfactant As said surfactant, what can improve the dispersion stability of a composition, coating property, etc. can be used, Fluorine, such as perfluoro alkyl phosphate ester and perfluoro alkyl carboxylic acid salt Surfactants, anionic surfactants such as higher fatty acid alkali salts, alkyl sulfonates and alkyl sulfates, cationic surfactants such as higher amine halides and quaternary ammonium salts, polyethylene glycol alkyl ether, polyethylene Nonionic surfactants such as glycol fatty acid esters, sorbitan fatty acid esters, fatty acid monoglycerides, surfactants such as amphoteric surfactants and silicone surfactants can be used, and these may be used in combination.

(E) Silane Coupling Agent The above silane coupling agent is a silane compound having a reactive group chemically bonded to an inorganic material such as glass and a reactive group chemically bonded to an organic material such as a synthetic resin, What can improve the adhesiveness etc. of a thing or its hardened | cured material can be used. As the silane coupling agent, for example, a silane coupling agent manufactured by Shin-Etsu Chemical Co., Ltd. can be used. Among them, KBE-9007, KBM-502, KBE-403, etc., silane coupling having an isocyanate group, methacryloyl group or epoxy group An agent is preferably used.

(F) Melamine compound As the above-mentioned melamine compound, those which can improve the curability can be used, for example, (poly) methylolmelamine, (poly) methylolglycoluril, (poly) methylolbenzoguanamine, (poly) methylolurea and the like of active methylol groups of the nitrogen compound (CH ₂ OH groups) of all or part (at least two) can be exemplified compounds alkyl etherified. Here, as an alkyl group which comprises an alkyl ether, a methyl group, an ethyl group, or a butyl group is mentioned, It may mutually be same or different. Moreover, the methylol group which is not alkyletherified may be self-condensing within one molecule, and may be condensed between two molecules, and as a result, an oligomer component may be formed. Specifically, hexamethoxymethylmelamine, hexabutoxymethylmelamine, tetramethoxymethylglycoluril, tetrabutoxymethylglycoluril and the like can be used. Among these, alkyletherified melamines such as hexamethoxymethylmelamine and hexabutoxymethylmelamine are preferable.

3. Composition The viscosity of the composition may be, for example, 200 mPa · s or less, and 1 mPa · s or more and 200 mPa · s or less from the viewpoint of having coatability. It is because the said composition is excellent in coatability.
The viscosity, JIS Z 8803: according to the 2011, rotational viscometer (e.g., Anton Paar, Physica ^MCR 3 01, etc.) using, refers to the measured values. In the present specification, in particular, processing without temperature designation and measurement may be performed at 25 ° C.

The method for producing the above composition may be any method as long as the above-mentioned components can be blended at a desired content, and may be a method in which the above-mentioned components are simultaneously added and mixed. It may be a method of mixing.

Applications of the above composition are thermosetting coatings, photocurable coatings or varnishes, thermosetting adhesives, photocurable adhesives, printed circuit boards, or color televisions such as color televisions, PC monitors, personal digital assistants, digital cameras, etc. Color filters for liquid crystal display panels for display, color filters for CCD image sensors, photo spacers, black column spacers, electrode materials for plasma display panels, touch panels, touch sensors, powder coatings, printing inks, printing plates, adhesives, for dental use Composition, resin for photolithography, gel coat, photoresist for electronics, electroplating resist, etching resist, both liquid and dry film, solder resist, for manufacturing color filters for various display applications or plasma display In the manufacturing process of panels, electroluminescent displays and LCDs Resist for forming a structure, composition for encapsulating electric and electronic components, solder resist, magnetic recording material, micro mechanical component, waveguide, optical switch, plating mask, etching mask, color test system, glass Fiber cable coatings, stencils for screen printing, materials for producing three-dimensional objects by stereolithography, materials for holographic recording, image recording materials, microelectronics, bleaching materials, bleaching materials for image recording materials, microcapsules Decoloring materials for image recording materials using the same, photoresist materials for printed wiring boards, photoresist materials for UV and visible laser direct imaging systems, photoresist materials used for forming a dielectric layer in sequential lamination of printed circuit boards, Various kinds of photoresist materials or protective films for 3D mounting It can be used for developing, and there is no particular limitation on the application.

D. Cured Product Next, the cured product of the present invention will be described.
The cured product of the present invention is a cured product of a composition, and the composition is characterized in that it contains the above-mentioned compound and a polymerizable compound.

According to the present invention, since the above-mentioned composition is used, the curing is easy and the antioxidant ability can be easily given.

The cured product of the present invention uses the composition described above.
Hereinafter, the cured product of the present invention will be described in detail.

The composition contains the compound I-1 and a polymerizable compound.
The composition may also contain components other than the compound I-1 and the polymerizable compound.
About the content of each component of such a composition, it can be made to be the same as the content as described in the term of "2. other components" of the above-mentioned "C. composition".

The compound I-1 contained in the composition may be before or after elimination of the photoleaving group B in the cured product, but is preferably after elimination . It is because the said hardened | cured material will have the outstanding antioxidant performance.

The above-mentioned cured product usually contains a polymer of a polymerizable compound.
The remaining amount of the polymerizable compound contained in the cured product is appropriately set according to the application of the cured product and the like, and is, for example, 10 parts by mass or less with respect to 100 parts by mass of the cured product. It is preferable that it is below a mass part.

The cured product may be substantially free of a solvent.
As content of the solvent contained in the said hardened | cured material, it can be 1 mass part or less with respect to 100 mass parts of hardened | cured material, for example, can be 0.5 mass part or less.

The elastic modulus of the cured product is usually higher than that of the composition, and can be, for example, 10 ^-3 M or more, and can be 10 MPa or more. With the elastic modulus, the cured product can stably hold the compound I-1 and the like.
About the upper limit of the above-mentioned elastic modulus, although it can set suitably according to the use etc. of hardened material, it can be made into 10 ⁶ MPa or less, for example.
Hereinafter, the elastic modulus refers to the compressive elastic modulus and can be measured at 23 ° C. in accordance with JIS K7181.
For the measurement sample, for example, a cube-shaped test piece having a side length of 6 mm can be prepared or cut out, and measurement can be performed at a test speed of 1 ± 0.2 mm / min according to JIS K7181.

The method for producing the above-mentioned cured product may be any method as long as the above-mentioned composition can be cured, for example, it may be the same as the method described in “F. Method for producing a cured product” described later. it can.

About the use etc. of the said hardened | cured material, it can be made to be the same as that of the content as described in the term of the said "C. composition".

E. Composition Next, the second composition of the present invention will be described.
The second composition of the present invention is characterized by containing a compound represented by the following general formula (I-2), and a photo-eliminating group-derived eliminated substance.

(Wherein, A represents an atomic group having an antioxidant ability, and k represents an integer of 1 to 10).

According to the present invention, the second composition can be easily formed, for example, using the composition described above. Further, the second composition can easily impart an antioxidant ability and the like.

The second composition of the present invention comprises the compound I-2 and the compound B ′.
Hereinafter, the second composition of the present invention will be described in detail.

1. Compound I-2
The above compound I-2 exerts the ability to prevent oxidation.
The compound I-2 is the compound I-1 in which the B—O— is substituted with an —OH group.
The contents of such compound I-1 can be the same as the contents described in the section “A. Compound” above, so the description thereof is omitted here.

The content of the compound I-2 in the composition may be any as long as it can impart a desired antioxidant ability and the like. For example, the compound I-1 described in the section "C. Composition" above It can be the same as the content in the solid content of

2. Compound B '
The compound B ′ is a leaving substance derived from a photoleaving group.
The photoleaving group may be any group capable of binding to the phenolic hydroxyl group as a protecting group, and the same as the contents described in “1. Photoleaving group B” of the above “A. Compound”. be able to.
Such a compound B ′ may be any compound as long as it can be taken after the photoleaving group is eliminated from the phenolic hydroxyl group.
The photoleaving group B after leaving the phenolic hydroxyl group is usually highly reactive and can have various structures.
As the compound B ′, the photoleaving group B is preferably a compound represented by the general formulas (B-1-a), (B-2), (B-3), (B-4), (B-5), When it is represented by B-6), (B-7), etc., for example, the following general formulas (B-111-a), (B-112), (B-113), (B) -114), (B-115), (B-116), (B-117) and the like can be included.

^R 11 contained in the compound ^{^{^{B ', R 12, R 13}}} , R 14, R 15, R 16, R 17, R 18, R 19, R 20, R 21, R 22, R 23, R 24, R ²⁵ , R ²⁶ and R ²⁷ and b 1, b 2, b 3, b 4, b 5, b 6, b 7 and b 8 can be the same as the contents described in the section “A. Compound” above, The description is omitted.

The type of the compound B ′ may be only one type or a combination of two or more types.

The compound B ′ may contain one derived from one type of photoleaving group B, or may contain one derived from two or more types of photoleaving group B.

3. Others The above second composition comprises the compound I-2 and the compound B ′, and usually comprises other components.
Examples of such other components include the contents described in the section "2. Other components" of the above "C. composition".
Among the above, the other components preferably include a resin component, and particularly preferably include a polymer having no polymerizable group such as a polymer of a polymerizable compound. This is because, for example, the second composition can effectively exert the effect of being able to easily impart the antioxidant ability and the like to the cured product.
In addition, the number of kinds of resin components may be one, or two or more kinds may be used in combination.

The second composition contains a solvent, a polymerizable compound, etc., and may have a coating property, and the viscosity in that case is the same as the content described in the above-mentioned "C. composition". It can be done.
When the second composition is a cured product containing a polymer of a polymerizable compound, the elastic modulus of the second composition is the same as the content described in the section "D. cured product". can do.

About the use etc. of the said 2nd composition, it can be made to be the same as that of the content as described in the term of said "D. hardened | cured material".

The method for producing the second composition may be any method capable of producing those containing the above-mentioned components. For example, the composition containing the compound I-1 or the cured product of the composition is irradiated with light. Can be used.
In addition, about the manufacturing method of the hardened | cured material of a composition, the method of light-irradiating, etc., the method similar to the content as described in the term of "the manufacturing method of hardened | cured material" mentioned later can be used.

F. Method of Producing Cured Product Next, a method of producing the cured product of the present invention will be described.
The method for producing a cured product of the present invention comprises the steps of curing a composition containing the compound I-1 of the present invention and a polymerizable compound to form a cured product, and irradiating the cured product with light. And d) removing the photoleaving group B contained in the compound.

According to the method for producing a cured product of the present invention, the composition can be easily cured, and a cured product having excellent antioxidant performance and the like can be easily produced.

The production method of the present invention includes the steps of forming a cured product and removing it. Each step will be described in detail below.

1. Step of forming a cured product The step of forming the cured product is a step of forming a cured product of the composition described above.

As a method of forming the hardened | cured material of the composition in this process, what is necessary is just a method which can form the hardened | cured material of desired hardness, and it changes according to the component contained in a composition.
For example, when the composition contains a photopolymerization initiator as a polymerization initiator together with a polymerizable compound, the curing method uses a method of irradiating the composition with light to polymerize the polymerizable compounds. Can.
The light irradiated to the composition may include light with a wavelength of 300 nm to 450 nm.
As a light source of the said light irradiation, an ultra-high pressure mercury, a mercury vapor arc, a carbon arc, a xenon arc etc. can be mentioned, for example.
Laser light may be used as the light to be irradiated. As the laser light, one containing light with a wavelength of 340 to 430 nm can be used.
As a light source of laser light, those emitting light in the visible to infrared region such as argon ion laser, helium neon laser, YAG laser, and semiconductor laser can also be used.
In addition, when using these lasers, the said composition can contain the sensitizing dye which absorbs the said area | region of visible to infrared.

The total light quantity of the irradiated light is preferably one that can suppress the detachment of the photoleaving group B, and can be, for example, less than 1000 mJ / cm ² and not more than 800 mJ / cm ^2. And can be 500 mJ / cm ² or less.

When the composition contains a thermal polymerization initiator as a polymerization initiator together with a polymerizable compound, for example, the above curing method uses a method of subjecting the composition to a heat treatment to polymerize the polymerizable compounds. Can.
The heating temperature may be any temperature as long as the composition can be cured stably, and can be 60 ° C. or more, preferably 100 ° C. or more and 300 ° C. or less.
In addition, heating temperature can be made into the temperature of the coating-film surface of a composition.
The heating time can be about 10 seconds to 3 hours.

The type of the curing method may include only one type, or may include two or more types.

The composition used in this step contains the compound I-1 and a polymerizable compound.
In addition, the composition may include other components other than the compound I-1 and the polymerizable compound.
About the content of each component of such a composition, since it can be made to be the same as the content as described in the item of "2. other components" of the above-mentioned "C. composition", explanation here is omitted. .

2. Step of Leaving The step of leaving is a step of leaving the photoleaving group B contained in the compound I-1.
As a method of removing the photoleaving group B contained in the compound I-1, any method may be used as long as the cured product is irradiated with light.
The light irradiated to the cured product and the total light amount thereof are not particularly limited as long as the light leaving group B can be removed, but the light of the above “1. light leaving group B” is not particularly limited. It can be the same as the contents described in the section.
In addition, as a light source of light irradiation, although it is suitably selected according to the wavelength of the light irradiated, it shall be the same as the content as described in the term of said "1. Process of forming hardened material", for example. be able to.

The temperature of the cured product in this step can be appropriately set according to the heat resistance and the like of the cured product and the substrate supporting the cured product, but can be, for example, 200 ° C. or less, 0 ° C. or more, The temperature is preferably 150 ° C. or less, and more preferably 0 ° C. or more and 100 ° C. or less. It is because detachment | desorption of the photoleaving group B becomes easy because the said temperature is the above-mentioned range. Also, as a result, for example, the cured product and its peripheral members such as the substrate can be less damaged by heating.
In addition, the temperature of the said hardened | cured material can be made into the temperature of the hardened | cured material surface.

3. Other Steps The above-mentioned production method includes the step of forming a cured product and the step of desorbing, but may include other steps as required.
As said other process, the process of apply | coating the said composition on a base material etc. can be mentioned, for example.
As a method of applying the composition, known methods such as spin coater, roll coater, bar coater, die coater, curtain coater, various printing, immersion and the like can be used.
The substrate can be appropriately set depending on the application of the cured product and the like, and examples thereof include soda glass, quartz glass, semiconductor substrates, metals, paper, plastics and the like.
In addition, after the cured product is formed on a substrate, it may be used after being peeled off from the substrate or may be transferred from the substrate to another adherend.

4. Others The cured product produced according to the above-mentioned production method, the use and the like can be the same as the contents described in the section of "D.

The present invention is not limited to the above embodiment. The above embodiment is an exemplification, and it has substantially the same configuration as the technical idea described in the claims of the present invention, and any one having the same function and effect can be used. It is included in the technical scope of the invention.

EXAMPLES Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples.

The various measurements were performed according to the following method.

Example 1
0.003 mol of a phenol compound in scheme 1 below, 0.0062 mol of potassium carbonate and 10 g of DMF are mixed, 0.0075 mol of o-nitrobenzyl chloride is added dropwise at room temperature under a nitrogen atmosphere, and the mixture is stirred for 10 hours. A compound I-1-161 represented by the following general formula (I-1-161) corresponding to I-1 was obtained. Oil-water separation was performed by adding 50 g of ethyl acetate and 50 g of ion-exchanged water to the reaction solution. The organic layer was dried over anhydrous sodium sulfate, then the solvent was evaporated and separated on a silica column (hexane: ethyl acetate = 9: 1). After separation, the solid was washed with methanol, and the obtained white solid was dried under reduced pressure at 40 ° C. for 2 hours to obtain the desired product. It was confirmed by H-NMR that the obtained white solid was the desired product.

[Evaluation]
A 0.01% by mass solution of Compound I-1 (Compound I-1-161) in acetonitrile was prepared and placed in a 1 cm square quartz cell. Ultra-high pressure mercury lamp UL750 (manufactured by HOYA) was adjusted to 20 mW / cm ^2, in a quartz cell filled with the solution was irradiated with light quantity of ^{^{100mJ / cm 2, 3000mJ / cm}} 2, 10000mJ / cm 2.
The liquid after irradiation was analyzed by high performance liquid chromatography (HPLC), and the desorption rate was calculated from the following equation. The results are shown in Table 2 below.
In the analysis by HPLC, calculation was made on the assumption that 100% desorption occurred when all the 230 nm peak derived from compound I-1 disappeared.
Elimination rate (%) = phenol compound (compound I-2) / phenol compound (compound I-2) + compound I-1) × 100

From Table 2, compound I-1 was confirmed to be desorbed from the photoleaving group B by light irradiation.
As a result, it has been confirmed that the compound I-1 can impart an antioxidant ability to a cured product by light irradiation.
In addition, it was confirmed that the compound I-1 had the phenolic hydroxyl group protected by the photoleaving group B before light irradiation, and could inhibit inhibition of curing.

[Example 2 and Comparative Examples 1 and 2]
The components shown in Table 3 below were mixed in the proportions shown in Table 3 to obtain the compositions of Example 2 and Comparative Examples 1 and 2. The symbols in Table 3 indicate the following compounds. In addition, the numerical value in a table represents a mass part.

A-1: Radical polymerizable compound (NK Oligo EA-1020 (bisphenol A epoxy acrylate) manufactured by Shin-Nakamura Chemical Co., Ltd.)
A-2: Radically polymerizable compound (Kayarad DPHA (a mixture of dipentaerythritol penta and hexaacrylate) manufactured by Nippon Kayaku Co., Ltd.)
B-1: IRGACURE 907 manufactured by BASF (radical polymerization initiator)
C-1: Shine Chemical Industry Co., Ltd. silane coupling agent KBE-403
D-1: 2-butanone (solvent)
E-1: Compound represented by the following formula (1) (antioxidant)
F-1: Compound I-1-161 (Compound I-1)

The curability and heat resistance of the compositions of the obtained Example 2 and Comparative Examples 1 and 2 were evaluated by the following methods.

[Curable]
The compositions of Example 2 and Comparative Examples 1 and 2 were each applied to a PET film with a bar coater to a thickness of about 3 μm. Next, after prebaking at 80 ° C. for 3 minutes, exposure was performed (20 mW / cm ² ) using an ultra-high pressure mercury lamp (UL 750) as a light source. The exposure was performed so that the exposure light amount was 500 mJ / cm ² . Under the present circumstances, the negative film made so that light transmittance might be decreased in steps in order to measure a photosensitivity (The optical density 0.05 is made into the 1st step, The optical density is 0.15 at a time for every step. An increasing step tablet was used. Then, development was carried out by washing with isopropanol (IPA) for 10 seconds in an environment of 25 ° C., followed by drying at 80 ° C. for 30 minutes. And the photosensitivity was evaluated by measuring the number of steps of the step tablet of the hardened | cured material formed on PET film. The results are shown in Table 4 below. The higher the number of steps of the step tablet, the higher the light sensitivity.

[Heat-resistant]
The compositions of Example 2 and Comparative Examples 1 and 2 were each applied to a glass substrate by a spin coater. Next, after prebaking at 80 ° C. for 3 minutes, exposure was performed (20 mW / cm ² ) using an ultra-high pressure mercury lamp (UL 750) as a light source. The exposure was performed such that the exposure light amount was 100 mJ / cm ² . Furthermore, 3000 mJ / cm < ² > irradiation was carried out and the sample for heat resistance evaluation was produced. Then, using an oven, a heat resistance test was performed in which the evaluation sample was heat-treated at 200 ° C. for 2 hours.
The difference in transmittance (%) at a wavelength of 430 nm before and after the heat resistance test of the evaluation sample ((Transmittance (% before heat resistance test-transmittance (%) before heat resistance test) was measured, The heat resistance was evaluated on the basis of the standard, and the results are shown in Table 3 below.
Good: The transmittance difference (%) is less than 1% with respect to the transmittance before the heat resistance test.
X: The difference in transmittance (%) is 1% or more with respect to the transmittance before the heat resistance test.

A cured product shows that it is excellent in heat resistance in heat resistance evaluation being "O".

From Table 3, the composition of Example 2 containing Compound I-1 has better heat resistance than the composition of Comparative Example 1 containing no antioxidant. In addition, the composition of Example 2 has better curability than the composition of Comparative Example 2 containing an antioxidant. From this, it can be seen that according to the present invention, a composition having less curing inhibition and having excellent antioxidant performance can be obtained.

According to the compound of the present invention, it is possible to provide a compound which has less inhibition of curing and which can easily impart an antioxidant ability and the like to a cured product.
According to the latent antioxidant of the present invention, the curing inhibition is small, and the cured product can be easily imparted with the antioxidant ability and the like.
According to the composition of the present invention, it is possible to provide, for example, a composition capable of obtaining a cured product having excellent anti-oxidation ability with less curing inhibition.
According to the cured product of the present invention, a cured product having excellent antioxidant performance can be provided.
According to the production method of the present invention, a cured product having excellent antioxidant performance can be produced without causing inhibition of curing.
According to the second composition of the present invention, it is possible to provide a composition from which a cured product having excellent antioxidant performance can be obtained without causing curing inhibition.

Claims

The compound represented by the following general formula (I-1).

(Wherein, A represents a group having an antioxidant ability, B represents a photoleaving group, and k represents an integer of 1 to 10).
In the general formula (I-1), B is a group represented by the following general formula (B-1), (B-2), (B-3), (B-4), (B-5), (B-6) The compound according to claim 1, comprising at least one group of the groups represented by (B-7), (B-8), (B-9) and (B-10).

(Wherein, R 11 , R 13 , R 16 , R 18 , R 19 , R 20 , R 23 , R 26 and R 28 each independently represent a halogen atom, a cyano group, a hydroxyl group, a nitro group, a carboxyl group, An alkyl group having 1 to 40 carbon atoms, an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, or a heterocycle-containing group having 2 to 20 carbon atoms,
R 12, R 14, R 17 , R 21, R 22, R 24, R 25, R 27, R 29 and R 30 each independently represent a hydrogen atom, a halogen atom, a cyano group, a hydroxyl group, a nitro group, a carboxyl A group, an alkyl group having 1 to 40 carbon atoms, an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms or a heterocycle-containing group having 2 to 20 carbon atoms,
R 15 represents an alkyl group having 1 to 40 carbon atoms, an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms or a heterocycle-containing group having 2 to 20 carbon atoms,
R 11, R 12, R 13 , R 14, R 15, R 16, R 17, R 18, R 19, R 20, R 21, R 22, R 23, R 24, R 25, R 26, R 27 And the methylene group in the alkyl group and arylalkyl group represented by R 28 , R 29 and R 30 is a carbon-carbon double bond, -O-, -S-, -CO-, -O-CO-, -CO-O-, -O-CO-O-, -O-CO-O-, -S-CO-, -CO-S-, -S-CO-O-, -O-CO-S-, -CO-NH-, -NH-CO-, -NH-CO-O-, -NR'-,> P = O, -S-S-, -SO 2 -or a combination thereof, Yes,
The alkyl group, aryl group, arylalkyl group and heterocycle-containing group may have a substituent,
R ′ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms,
Multiple R 11 each other, multiple R 13 each other, multiple R 16 each other, multiple R 18 each other, multiple R 19 each other, multiple R 20 each other, multiple R 23 each other, multiple R 26 each other and multiple R 28 may be bonded to each other to form a benzene ring or a naphthalene ring,
Plural R 11 , R 12 , R 13 , R 14 , R 16 , R 17 , R 18 , R 19 , R 20 , R 23 , R 25 , R 26 , R 27 , R 28 , R 29 and R 30 , Each may be the same, may be different,
b1, b2, b3, b6, b7, b8 and b9 each independently represent an integer of 0 to 4;
b4 and b5 each independently represent an integer of 0 to 5;
** represents the bonding position with the AO-. )

(Wherein, each of R 31 and R 40 independently represents a halogen atom, a cyano group, a hydroxyl group, a nitro group, a carboxyl group, an alkyl group having 1 to 40 carbon atoms, an aryl group having 6 to 20 carbon atoms, carbon Represents an arylalkyl group having 7 to 20 atoms or a heterocycle-containing group having 2 to 20 carbon atoms,
R 32 , R 33 , R 41 , R 42 , R 43 and R 44 are each independently a hydrogen atom, a halogen atom, a cyano group, a hydroxyl group, a nitro group, a carboxyl group, an alkyl group having 1 to 40 carbon atoms, An aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, or a heterocycle-containing group having 2 to 20 carbon atoms,
The methylene group in the alkyl group and arylalkyl group represented by R 31 , R 32 , R 33 , R 40 , R 41 , R 42 , R 43 and R 44 is a carbon-carbon double bond, -O-, -S-, -CO-, -O-CO-, -CO-O-, -O-CO-O-, -O-CO-O-, -S-CO-, -CO-S-, -S -CO-O-, -O-CO-S-, -CO-NH-, -NH-CO-, -NH-CO-O-, -NR'-,> P = O, -SS-, -SO 2 -or a combination of these may be substituted,
The alkyl group, aryl group, arylalkyl group and heterocycle-containing group may have a substituent,
c1 represents an integer of 0 to 5;
c2 represents an integer of 0 to 4;
** represents the bonding position with the AO-. )
The compound represented by the above general formula (I-1) is a compound represented by the following general formula (A-1), (A-2) or (A-3),
The photoleaving group B includes the following general formula (B-1-a):
A compound according to claim 2.

(Wherein, R 1 represents a halogen atom, a cyano group, a hydroxyl group, a nitro group, a carboxyl group, an alkyl group having 1 to 40 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryl having 7 to 20 carbon atoms Represents an alkyl group or a heterocycle-containing group having 2 to 20 carbon atoms,
R 2 , R 3 and R 4 each independently represent an alkyl group having 1 to 40 carbon atoms, an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms or 2 to 6 carbon atoms Represents 20 heterocyclic containing groups,
The methylene group in the alkyl group and arylalkyl group used for R 1 , R 2 , R 3 and R 4 is a carbon-carbon double bond, -O-, -S-, -CO-, -O-CO- , -CO-O-, -O-CO-O-, -O-CO-O-, -S-CO-, -CO-S-, -S-CO-O-, -O-CO-S- When substituted by -CO-NH-, -NH-CO-, -NH-CO-O-, -NR'-,> P = O, -S-S-, -SO 2 -or a combination thereof There is
The alkyl group, aryl group, arylalkyl group and heterocycle-containing group may have a substituent,
R ′ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms,
Several R 1 may be combined to form a benzene ring or a naphthalene ring,
Several R 1 may be the same or different.
m represents an integer of 1 to 10,
n represents an integer of 2 to 10,
a represents an integer of 0 to 2;
X 1 represents an m-valent linking group,
X 2 represents an n-valent bonding group. )

(Wherein, R 11 represents a halogen atom, a cyano group, a hydroxyl group, a nitro group, a carboxyl group, an alkyl group having 1 to 40 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryl having 7 to 20 carbon atoms Represents an alkyl group or a heterocycle-containing group having 2 to 20 carbon atoms,
R 12 each independently represents a hydrogen atom, a halogen atom, a cyano group, a hydroxyl group, a nitro group, a carboxyl group, an alkyl group having 1 to 40 carbon atoms, an aryl group having 6 to 20 carbon atoms, or 7 to carbon atoms 20 arylalkyl groups or heterocyclic groups containing 2 to 20 carbon atoms,
The methylene group in the alkyl group and arylalkyl group represented by R 11 and R 12 is a carbon-carbon double bond, -O-, -S-, -CO-, -O-CO-, -CO-O -, -O-CO-O-, -O-CO-O-, -S-CO-, -CO-S-, -S-CO-O-, -O-CO-S-, -CO-NH -, -NH-CO-, -NH-CO-O-, -NR'-,> P = O, -S-S-, -SO 2 -or a combination thereof may be substituted,
The alkyl group, aryl group, arylalkyl group and heterocycle-containing group may have a substituent,
R ′ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms,
Several R 11 may be combined to form a benzene ring or a naphthalene ring,
Plural R 11 and R 12 may be the same or different.
b1 represents an integer of 0 to 4;
** represents the bonding position with the AO-. )
A latent antioxidant comprising a compound according to any one of claims 1 to 3.
A composition comprising a compound according to any one of claims 1 to 3.
A cured product of a composition comprising the compound according to any one of claims 1 to 3 and a polymerizable compound.
Curing the composition containing the compound according to any one of claims 1 to 3 and a polymerizable compound to form a cured product;
Irradiating the cured product with light to release a photoleaving group contained in the compound;
A method of producing a cured product having:
A composition comprising a compound represented by the following general formula (I-2), and a leaving substance derived from a photoleaving group.

(Wherein, A represents a group having an antioxidant ability, and k represents an integer of 1 to 10).