CN110869343A

CN110869343A - Compound, latent antioxidant, composition, cured product, and method for producing cured product

Info

Publication number: CN110869343A
Application number: CN201880045833.6A
Authority: CN
Inventors: 金原有希子; 冈田光裕; 中屋敷哲千
Original assignee: Adeka Corp
Current assignee: Adeka Corp
Priority date: 2017-10-05
Filing date: 2018-10-02
Publication date: 2020-03-06
Also published as: KR20200058327A; TW201922684A; WO2019069961A1; JPWO2019069961A1; KR102587531B1; TWI788428B; JP7293119B2

Abstract

A compound represented by the following general formula (I-1). 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 an atomic group having antioxidant ability, B represents a photodissociable group, and k represents an integer of 1 to 10.)

Description

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

Technical Field

The present invention relates to a compound which is less likely to cause curing inhibition and can easily impart antioxidant ability to a cured product.

Background

In order to improve the antioxidant ability and heat resistance of the curable composition, a method of adding an ultraviolet absorber and an antioxidant to a curing inhibitor to stabilize the same is known (patent documents 1 to 3).

Documents of the prior art

Patent document

Patent document 1: japanese patent laid-open publication No. 2011-048382

Patent document 2: US2016016919a1

Patent document 3: japanese laid-open patent publication No. 2015-108649

Disclosure of Invention

However, the antioxidants described in patent documents 1 to 3 have a problem that they sometimes inhibit curing of the curable composition.

To solve the above problems, the present inventors have found that: the phenolic antioxidant has an effect of trapping radicals which have a great influence on the deterioration of the polymer; when a phenol antioxidant is added to the polymerization system in order to have such an effect, the phenol antioxidant generally functions as a so-called polymerization inhibitor, and may inhibit curing.

As a means for solving the above problems, a latent additive is known which is inactivated to absorb light in a polymerization system and activated after curing.

On the other hand, a latent additive which can be activated after curing may require high-temperature heating or the like for activation, and there is a demand for a latent additive which can be more easily activated.

The present invention has been made in view of the above problems, and a main object thereof is to provide a compound which is less in curing inhibition and can easily impart antioxidant ability and the like to a cured product.

The present inventors have conducted intensive studies to solve the above problems, and as a result, have found that the above problems can be solved by using a photodetachment group as a protecting group and protecting a phenolic hydroxyl group contained in an antioxidant with the photodetachment group, thereby facilitating the adjustment of the timing at which the antioxidant ability is exhibited, and have completed the present invention.

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

[ chemical formula 1]

(wherein A represents an antioxidant radical, B represents a photodissociable group, and k represents an integer of 1 to 10.)

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

Further, the present invention 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 containing a compound represented by the above general formula (I-1) and a polymerizable compound.

The present invention also provides a method for producing a cured product, comprising the steps of: a step of curing a composition containing a compound represented by the general formula (I-1) and a polymerizable compound to form a cured product; and a step of irradiating the cured product with light to remove a light-releasing group contained in the compound represented by the general formula (I-1).

The present invention also provides a composition (hereinafter, sometimes referred to as "composition 2") comprising a compound represented by the following general formula (I-2) (hereinafter, sometimes referred to as "compound I-2") and a desorbed product derived from a photodissociable group (hereinafter, sometimes referred to as "compound B'").

[ chemical formula 2]

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

Detailed Description

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

A. Compound (I)

First, the compound of the present invention will be explained.

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).

[ chemical formula 3]

The radical A of the compound I-1 of the present invention has antioxidant ability. The compound I-1 of the present invention has low antioxidant ability before the elimination of the photodissociable group B, but shows excellent antioxidant ability based on the radical A after the elimination of the photodissociable group B.

Therefore, when the compound I-1 before the photodissociation group B is dissociated is added to, for example, a polymerization system, the compound I-1 has a low ability to trap radicals generated by polymerization, and it is difficult to inhibit the curing of the polymerization system.

In addition, compound I-1 of the present invention shows excellent antioxidant ability by the photoradical elimination by irradiation with light. Therefore, by irradiating a cured product containing the compound I-1 with light, the oxidation resistance can be easily imparted to the cured product. Since the compound I-1 does not require heat treatment for exhibiting its antioxidant ability, it has an advantage that it is difficult to cause damage to peripheral members such as a cured product and a substrate due to heating.

For the above reasons, the compound I-1 has little curing inhibition and can easily impart antioxidant ability to a cured product.

Further, the compound I-1 having the photo-releasing group B can easily adjust the dispersion stability in the composition, for example.

By selecting the photo-cleavable group B so that the compound I-1 has an improved affinity with other components contained in the composition, it is possible to impart excellent dispersibility to the composition.

Therefore, the compound I-1 can impart an excellent antioxidant ability 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-cleavable group B

The compound I-1 of the present invention has a photoreleasing group B.

The photocleavable group in the present invention may be a group which can be cleaved from the compound I-1 by irradiation with light of a specific wavelength. When the compound I-1 is irradiated with light of a specific wavelength, the photodissociable group B dissociates from the compound I-1 to produce a compound having a hydroxyl group and an antioxidant radical A represented by the general formula (I-2).

[ chemical formula 4]

The wavelength of light with which the light-releasing group B is released from the compound I-1 is, for example, in the wavelength region of ultraviolet rays or visible rays. Specifically, light having a wavelength of 365nm, more specifically, light having a wavelength of 250nm or more and 450nm or less, and preferably light having a wavelength of 280nm or more and 380nm or less may be used.

The cumulative quantity of light irradiated to dissociate the photolytic group B from the compound I-1 may be set to, for example, 1000mJ/cm²10000mJ/cm or more²Hereinafter, the concentration is preferably 1000mJ/cm²Above 5000mJ/cm²Hereinafter, more preferably 2000mJ/cm²Above 4000mJ/cm²The following. The cumulative amount of light irradiated for curing a composition containing a polymerizable compound or the like may be usually less than 1000mJ/cm². Therefore, the light quantity is integrated to the above rangeFor example, it can be easily applied to a photocurable composition.

The light-releasing group B may be a group having a desired antioxidant ability, and the releasing rate of the light-releasing group may be 50% or more, and particularly preferably 80% or more.

On the other hand, the cumulative amount of light for suppressing the light release of the compound I-1 may be set to less than 1000mJ/cm as long as the desired effect of suppressing the curing inhibition can be obtained². This is because it is easily applied to a photocurable composition.

The light release is suppressed as long as the desired effect of suppressing the curing inhibition can be obtained, and for example, the release rate of the light-releasing group B may be less than 50%, and particularly preferably 20% or less. This is because it is easily applied to a photocurable composition.

The cumulative amount of light can be measured by preparing a 0.01 mass% acetonitrile solution of compound I-1 and using the same method as the method for measuring the desorption rate described in the examples.

Specific examples of the photo-cleavable group B satisfying the above requirements include groups represented by the following general formulae (B-1), (B-2), (B-3), (B-4), (B-5), (B-6), (B-7) and (B-8). Particularly preferred are groups represented by the following general formulae (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), and preferred is a group represented by the following general formula (B-1-a). This is because the use of these photo-dissociable groups makes it possible to easily dissociate from the compound I-1 and easily impart antioxidant ability and the like to the cured product. Specific examples of the photo-cleavable group B satisfying the above requirements include groups represented by the following general formulae (B-9) and (B-10).

[ chemical formula 5]

[ chemical formula 6]

(in the formula, R¹¹、R¹³、R¹⁶、R¹⁸、R¹⁹、R²⁰、R²³、R²⁶And R²⁸Each 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, an arylalkyl group having 7 to 20 carbon atoms or a heterocyclic group having 2 to 20 carbon atoms,

R¹²、R¹⁴、R¹⁷、R²¹、R²²、R²⁴、R²⁵、R²⁷、R²⁹and R³⁰Each 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, an arylalkyl group having 7 to 20 carbon atoms or a heterocyclic group having 2 to 20 carbon atoms,

R¹⁵represents 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 group having 2 to 20 carbon atoms,

R¹¹、R¹²、R¹³、R¹⁴、R¹⁵、R¹⁶、R¹⁷、R¹⁸、R¹⁹、R²⁰、R²¹、R²²、R²³、R²⁴、R²⁵、R²⁶、R²⁷、R²⁸、R²⁹and R³⁰Methylene groups in the alkyl and arylalkyl groups may be replaced by carbon-carbon double bonds, -O-, -S-, -CO-, -O-CO-, -CO-O-, -O-CO-O-, -S-CO-, -CO-S-, -S-CO-O-, -O-CO-S-, -CO-NH-, -NH-CO-O-, -NR' -, > P ═ O, -S-, -SO-, -₂-or a combination thereof,

r' represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms,

plural R¹¹Each other, a plurality of R¹³Each other, a plurality of R¹⁶Each other, a plurality of R¹⁸Each other, a plurality of R¹⁹Each other, a plurality of R²⁰Each other, a plurality of R²³Each other, a plurality of R²⁶To each other and a plurality ofR²⁸Are sometimes bonded to each other to form a benzene ring or a naphthalene ring,

plural R¹¹、R¹²、R¹³、R¹⁴、R¹⁶、R¹⁷、R¹⁸、R¹⁹、R²⁰、R²³、R²⁵、R²⁶、R²⁷、R²⁸、R²⁹And R³⁰Sometimes the same, sometimes 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,

indicates the bonding position to the above-mentioned A-O-. )

[ chemical formula 6A ]

(in the formula, R³¹And R⁴⁰Each 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, an arylalkyl group having 7 to 20 carbon atoms or a heterocyclic group having 2 to 20 carbon atoms,

R³²、R³³、R⁴¹、R⁴²、R⁴³、R⁴⁴each 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, an arylalkyl group having 7 to 20 carbon atoms or a heterocyclic group having 2 to 20 carbon atoms,

R³¹、R³²、R³³、R⁴⁰、R⁴¹、R⁴²、R⁴³and R⁴⁴Methylene groups in the alkyl and arylalkyl groups shown are sometimes interrupted by carbon-carbon double bonds, -O-, -S-, -CO-, -O-CO-, -CO-O-, -O-CO-O-, -S-CO-, -CO-S-, -S-CO-O-, -O-CO-S-, -CO-NH-, -NH-CO-O-, -NR' -, > P ═ O, -S-, -SO-, -₂-or a combination thereof,

the above-mentioned alkyl group, aryl group, arylalkyl group and heterocyclic group-containing group may have a substituent,

c1 represents an integer of 0 to 5,

c2 represents an integer of 0 to 4,

indicates the bonding position to the above-mentioned A-O-. )

R is as defined above¹¹、R¹²、R¹³、R¹⁴、R¹⁵、R¹⁶、R¹⁷、R¹⁸、R¹⁹、R²⁰、R²¹、R²²、R²³、R²⁴、R²⁵、R²⁶、R²⁷、R²⁸、R²⁹、R³⁰、R³¹、R³²、R³³、R⁴⁰、R⁴¹、R⁴²、R⁴³And R⁴⁴(hereinafter, these functional groups may be collectively referred to as "R" in some cases¹¹And the like) and alkyl groups having 1 to 40 carbon atoms, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, tert-butyl group, isobutyl group, pentyl group, isopentyl group, tert-pentyl group, cyclopentyl group, hexyl group, 2-hexyl group, 3-hexyl group, cyclohexyl group, 4-methylcyclohexyl group, heptyl group, 2-heptyl group, 3-heptyl group, isoheptyl group, tert-heptyl group, 1-octyl group, isooctyl group, tert-octyl group, adamantyl group and the like.

As the above-mentioned R¹¹Examples of the aryl group having 6 to 20 carbon atoms include phenyl, naphthyl and anthracenyl.

As the above-mentioned R¹¹Examples of the arylalkyl group having 7 to 20 carbon atoms include benzyl, fluorenyl, indenyl, and 9-fluorenylmethyl.

As the above-mentioned R¹¹Examples of the heterocyclic group having 2 to 20 carbon atoms include pyridyl, pyrimidyl, pyridazinyl, piperidyl, pyranyl, pyrazolyl, triazinyl, pyrrolyl, quinolyl, isoquinolyl, imidazolyl, benzimidazolyl, triazolyl, furyl (furyl), benzofuryl, thienyl, thiophenyl, benzothienyl, thiadiazolyl, thiazolyl, benzothiazolyl, oxazolyl, benzoxazolyl, isothiazolyl, isoxazolyl, indolyl, 2-pyrrolidone-1-yl, 2-piperidone-1-yl, 2, 4-dioxyImidazolidin-3-yl and 2, 4-dioxooxazolidin-3-yl.

Examples of the alkyl group having 1 to 8 carbon atoms represented by R' include R¹¹Examples of the alkyl group include alkyl groups having 1 to 8 carbon atoms.

The above-mentioned alkyl group, aryl group, arylalkyl group and heterocyclic group-containing group may have a substituent. Unless otherwise specified, the compound I-1 of the present invention includes compounds having no substituent and compounds having a substituent.

Examples of the substituent which may be substituted with a hydrogen atom such as an alkyl group, an aryl group, an arylalkyl group, and a heterocyclic group include an ethylenically unsaturated group such as a vinyl group, an allyl group, an acrylic group, and a methacrylic group; halogen atoms such as fluorine, chlorine, bromine and iodine; acyl groups such as acetyl, 2-chloroacetyl, propionyl, octanoyl, acryloyl, methacryloyl, phenylcarbonyl (benzoyl), phthaloyl, 4-trifluoromethylbenzoyl, pivaloyl, salicyloyl, oxalyl, stearoyl, methoxycarbonyl, ethoxycarbonyl, tert-butoxycarbonyl, n-octadecyloxycarbonyl, and carbamoyl; acyloxy groups such as acetoxy and benzoyloxy; amino, ethylamino, dimethylamino, diethylamino, butylamino, cyclopentylamino, 2-ethylhexylamino, dodecylamino, anilino, chlorophenylamino, toluidino, anisylamino, N-methyl-anilino, diphenylamino, naphthylamino, 2-pyridylamino, methoxycarbonylamino, phenoxycarbonylamino, acetylamino, benzoylamino, formylamino, pivaloylamino, lauroylamino, carbamoylamino, N-dimethylaminocarbonylamino, N-diethylaminocarbonylamino, morpholinocarbonylamino, methoxycarbonylamino, ethoxycarbonylamino, tert-butoxycarbonylamino, N-octadecyloxycarbonylamino, N-methyl-methoxycarbonylamino, phenoxycarbonylamino, cyclopentyloxycarbonylamino, N-methyl-anilino, N-methylaminocarbonyl, N-diethylaminocarbonylamino, morpholinocarbonylamino, methoxycarbonylamino, ethoxycarbonylamino, tert-butoxycarbonylamino, N-octadecyloxycarbonylamino, N-methyl-methoxycarbonylamino, phenoxy, Substituted amino groups such as sulfamoylamino, N-dimethylaminosulfonylamino, methylsulfonylamino, butylsulfonylamino, and phenylsulfonylamino; sulfonamide, sulfonyl, carboxyl, cyano, sulfo, hydroxyl, nitro, sulfhydryl, imide, carbamoyl, sulfonamide, phosphonate, phosphate, or salts of carboxyl, sulfo, phosphonate, phosphate, and the like.

In the present invention, when a hydrogen atom in a group is substituted with a substituent, the number of carbon atoms in the group is defined as the number of carbon atoms in the group after the substitution. For example, when the alkyl group having 1 to 40 carbon atoms has a hydrogen atom substituted, the carbon number of 1 to 40 means the number of carbon atoms after the hydrogen atom has been substituted, and does not mean the number of carbon atoms before the hydrogen atom has been substituted.

In the present invention, when a methylene group in a group is replaced with the above-mentioned 2-valent group, the number of carbon atoms in the group is defined as the number of carbon atoms in 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 with the above-mentioned group having a valence of 2, "1 to 40 carbon atoms" refers to the number of carbon atoms after the methylene group is replaced and does not refer to the number of carbon atoms before the methylene group is replaced. Thus, "-O-C₄₀H₈₁"corresponds to" an alkyl group having 40 carbon atoms (i.e., an alkoxy group having 40 carbon atoms) in which a terminal methylene group is replaced with — O- ". Likewise, "-CO-O-C₃₉H₇₉"corresponds to" an alkyl group having 40 carbon atoms in which the terminal methylene group is replaced with-CO-O-.

R¹¹Methylene groups in the alkyl and arylalkyl groups used for the above are sometimes replaced by carbon-carbon double bonds, -O-, -S-, -CO-, -O-CO-, -CO-O-, -O-CO-O-, -S-CO-, -CO-S-, -S-CO-O-, -O-CO-S-, -CO-NH-, -NH-CO-O-, -NR' -, > P ═ O, -S-, -SO-, -₂-or a combination thereof.

The combination of the above methylene groups replaced may be a combination under the condition that oxygen atoms are not adjacent to each other.

From R¹¹And (c) an alkyl group having 1 to 40 carbon atoms represented by (a) or (b) may have a methylene group at the terminal of the base end replaced by an-O-group to form an alkoxy group. Examples of the alkoxy group include alkoxy groups having 1 to 10 carbon atoms. Specifically, there may be mentioned: methoxy, ethoxy, isopropoxy, butoxy, sec-butoxy, tert-butoxy, isobutoxy, pentyloxy, isopentyloxy, pentyloxy, n-hexyloxy,t-pentyloxy, hexyloxy, 2-hexyloxy, 3-hexyloxy, cyclohexyloxy, 4-methylcyclohexyloxy, heptyloxy, 2-heptyloxy, 3-heptyloxy, isoheptyloxy, t-heptyloxy, 1-octyloxy, isooctyloxy, t-butyloxy, and the like.

R is as defined above¹¹、R¹³、R¹⁶、R¹⁸、R¹⁹、R²⁰、R²³、R²⁶And R²⁸Preferably a group other than a hydroxyl group, for example, a halogen atom, a cyano 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, a heterocyclic group having 2 to 20 carbon atoms, or the like. This is because the photocleavable group B becomes a group which is easily cleavable from the compound I-1 by a group other than a hydroxyl group, and the synthesis of the compound I-1 becomes easy.

R is as defined above¹¹And R²³Alkoxy groups are preferred. This is because the photocleavable group B becomes a group which is easily cleavable from the compound I-1, and the synthesis of the compound I-1 becomes easy.

R is as defined above¹³、R¹⁸、R¹⁹、R²⁰、R²⁶And R²⁸Preferably an alkyl group having 1 to 40 carbon atoms. This is because the photocleavable group B becomes a group which is easily cleavable from the compound I-1, and the synthesis of the compound I-1 becomes easy.

Wherein R is as defined above¹⁶Particularly preferably adjacent 2R¹⁶Groups bonded to each other to form a benzene ring. This is because the photocleavable group B becomes a group which is easily cleavable from the compound I-1, and the synthesis of the compound I-1 becomes easy.

R is as defined above¹⁸And R¹⁹When a methylene group in the alkyl group and the arylalkyl group is replaced with-O-, the methylene group-replaced-O-may be contained so that the alkyl group and the arylalkyl group are interrupted, that is, a methylene group other than the terminal of the alkyl group and the arylalkyl group is replaced.

R is as defined above¹²Preferably a hydrogen atom, a carboxyl group, or an alkyl group having 1 to 5 carbon atoms, and particularly preferably a hydrogen atom or a methyl group.

R is as defined above¹⁴、R¹⁷、R²¹、R²⁴、R²⁵、R²⁷、R²⁹And R³⁰Preferably a hydrogen atom or an alkyl group having 1 to 40 carbon atoms, and particularly preferably a hydrogen atom. This is because the photocleavable group B becomes a group which is easily cleavable from the compound I-1, and the synthesis of the compound I-1 becomes easy.

R is as defined above¹⁵And R²²Preferably an alkyl group having 1 to 5 carbon atoms, and particularly preferably a methyl group. This is because a compound which has little inhibition of curing and can easily impart antioxidant ability to a cured product can be provided.

Each of b1, b2, b3, b6, b7, b8, and b9 is independently an integer of 0 to 4, and from the viewpoint of ease of synthesis, an integer of 0 to 3 is preferable, an integer of 0 to 2 is more preferable, an integer of 0 to 1 is further preferable, and 0 is particularly preferable. This is because a compound which has little inhibition of curing and can easily impart antioxidant ability to a cured product can be provided.

Each of b4 and b5 may be independently an integer of 0 to 5, and is preferably an integer of 0 to 3, more preferably an integer of 0 to 2, further preferably 0 to 1, and particularly preferably 0, from the viewpoint of ease of synthesis. This is because a compound which has little inhibition of curing and can easily impart antioxidant ability to a cured product can be provided.

When k is 2 or more, the number of types of the photo-labile groups B contained in the compound I-1 of the present invention is sometimes 1, sometimes 2 or more, but is preferably 1, from the viewpoint of less curing inhibition, easy addition of antioxidant ability to a cured product, and easy synthesis of the compound I-1.

The number k of the photo-releasing group is an integer of 1 to 10, but from the viewpoint of less curing inhibition, easy addition of antioxidant ability to a cured product, and easy synthesis, an integer of 1 to 5 is preferable, an integer of 1 to 4 is more preferable, and an integer of 1 to 3 is particularly preferable.

2. Radical having antioxidant ability

The atomic group A is an atomic group having an antioxidant ability.

When the compound I-1 of the present invention is irradiated with light of a specific wavelength, the photolytic group B is dissociated to produce a compound I-2 having a hydroxyl group. In the present invention, having an antioxidant ability means having a function of preventing or suppressing oxidation of a substance by heat, light, or other energy, and for example, a function of capturing a radical. In the present invention, the radical trapping means that the compound I-2 reacts with an autoxidized chain carrier peroxidation radical to stop the oxidation. In the present invention, the radical having antioxidant ability may be a group having antioxidant ability or an aggregate of atoms having at least one group having antioxidant ability.

The atomic group a may be the same as an atomic group generally used for an antioxidant having a phenolic hydroxyl group.

That is, the compound I-2 may be a compound which is generally used as an antioxidant having a phenolic hydroxyl group.

As the compound I-2, for example, a phenol-based antioxidant described in Japanese patent laid-open Nos. 6-179798, 11-71355, 2002-97224 and the like, an alkyl-substituted phenol-based antioxidant described in Japanese patent laid-open No. 7-109380 and the like can be used.

Specific examples of the radical A having an antioxidant ability include a radical obtained by removing the above-mentioned B-O-from a benzene ring having a protected phenol structure, i.e., a phenolic hydroxyl group protected by the above-mentioned photodissociable group B. More specifically, the group includes an atomic group containing a benzene ring directly bonded with the B-O-, 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 a1 st substituent group which is a heterocyclic group having 2 to 20 carbon atoms. The 1 st substituent is preferably bonded directly to the benzene ring, and the bonding position of the 1 st substituent on the benzene ring is more preferably ortho to the bonding position of the B-O-. The atomic group A is preferably an atomic group in which a2 nd substituent represented by 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 group having 2 to 20 carbon atoms is further directly bonded to the benzene ring to which the 1 st substituent is directly bonded, and the bonding position of the 2 nd substituent on the benzene ring is more preferably an ortho position with respect to the bonding position of the B-O-. That is, it is particularly preferable that the radical A has a1 st substituent bonded to one ortho position and a2 nd substituent bonded to the other ortho position with respect to the bonding position of B-O-. This is because a compound which has little inhibition of curing and can easily impart antioxidant ability to a cured product can be easily produced.

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

[ chemical formula 7]

(in the formula, R¹Represents 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 heterocyclic group having 2 to 20 carbon atoms,

R²、R³and R⁴Each independently 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 heterocyclic group having 2 to 20 carbon atoms,

R¹、R²、R³and R⁴The methylene group in the alkyl group and arylalkyl group used in (1) may be replaced by a carbon-carbon double bond, -O-, -S-, -CO-, -O-CO-, -CO-O-, -O-CO-O-, -S-CO-, -CO-S-, -S-CO-O-, -O-CO-S-, -CO-NH-, -NH-CO-O-, -NR' -, > P ═ O, -S-, -SO₂-or a combination thereof,

r' represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms,

plural R¹Sometimes bonded to each other to form a benzene ring or a naphthalene ring,

plural R¹Are sometimes the same, sometimes 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,

X¹represents a bonding group having a valence of m,

X²represents a bonding group having a valence of n. )

As the above-mentioned R¹、R²、R³And R⁴Examples of the C1-40 alkyl group, C6-20 aryl group, C7-20 arylalkyl group, C2-20 heterocyclic group-containing group and C1-8 alkyl group used for R' include those described in the above item "1. Photocleavable group" as R¹¹And R' are exemplified as the above groups.

R is as defined above¹Preferably 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 group having 2 to 20 carbon atoms, particularly preferably an alkyl group having 1 to 40 carbon atoms, and particularly preferably an alkyl group having 1 to 5 carbon atoms. This is because the compound I-1 exerts an excellent antioxidant ability after the elimination of the photodissociable group B.

R is as defined above²、R³And R⁴The alkyl group is 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, and particularly preferably a methyl group or a tert-butyl group. This is because the compound I-1 exerts an excellent antioxidant ability after the elimination of the photodissociable group B.

The m is an integer of 1 to 10, preferably an integer of 1 to 6, particularly preferably an integer of 1 to 5, and particularly preferably an integer of 1 to 4, from the viewpoint of ease of synthesis. This is because the compound I-1 exerts an excellent antioxidant ability after the elimination of the photodissociable group B.

The n is an integer of 2 to 10, preferably an integer of 2 to 6, particularly preferably an integer of 2 to 5, particularly preferably an integer of 2 to 4, and preferably an integer of 2 to 3, from the viewpoint of ease of synthesis. This is because the compound I-1 exerts an excellent antioxidant ability after the elimination of the photodissociable group B.

The a is an integer of 0 to 2, and is preferably 0 to 1 from the viewpoint that the compound I-1 exhibits excellent antioxidant ability after the removal of the photo-cleavable group B and further is easy to synthesize.

Represented by the above general formula (A-1)Compound I-1 of (a) has X¹The structure is formed by bonding m-valent specific atoms and m specific groups. The m specific groups may be the same as or different from each other.

X is above¹Represents a m-valent bonding group.

As the above-mentioned bonding group X¹Specifically, it represents 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, > NR⁵³、-OR⁵³、-SR⁵³、-NR⁵³R⁵⁴Or an aliphatic hydrocarbon group having 1 to 120 carbon atoms, an aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms, or a heterocyclic group having 2 to 35 carbon atoms, which have the same number of valences as m. R is as defined above⁵³And R⁵⁴Represents 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, aromatic ring-containing hydrocarbon group and heterocyclic group-containing hydrocarbon group may be further substituted by-O-, -S-, -CO-, -O-CO-, -CO-O-, -O-CO-O-, -S-CO-, -CO-S-, -S-CO-O-, -O-CO-S-, -CO-NH-, -NH-CO-O-, -NR' -, -S-, -SO₂Nitrogen atom or a combination thereof, and the above aromatic ring or heterocyclic ring is sometimes fused with other rings.

However, in X¹In the case of a nitrogen atom, a phosphorus atom or a bonding group represented by the following (II-a) or (II-b), m is 3, X¹Is an oxygen or sulfur atom, > C ═ O, -NH-CO-, -CO-NH-or > NR⁵³In the case of (A), m is 2, at X¹is-OR⁵³、-SR⁵³or-NR⁵³R⁵⁴In the case of (2), m is 1, and X1 may form a ring together with a benzene ring.

[ chemical formula 8]

(. means bonding to an adjacent group at the site.)

With respect to the above-mentioned bonding group X¹Shown as having valences equal to the number mExamples of the aliphatic hydrocarbon group having 1 to 120 carbon atoms of (a) include alkyl groups having a valence of 1m, such as methyl, ethyl, propyl, isopropyl, cyclopropyl, butyl, sec-butyl, tert-butyl, isobutyl, pentyl, isopentyl, tert-pentyl, cyclopentyl, hexyl, 2-hexyl, 3-hexyl, cyclohexyl, bicyclohexyl, 1-methylcyclohexyl, heptyl, 2-heptyl, 3-heptyl, isoheptyl, tert-heptyl, n-octyl, isooctyl, tert-octyl, 2-ethylhexyl, nonyl, isononyl and decyl groups; alkoxy groups such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, sec-butoxy, tert-butoxy, isobutoxy, pentyloxy, isopentyloxy, tert-pentyloxy, hexyloxy, cyclohexyloxy, heptyloxy, isoheptyloxy, tert-heptyloxy, n-octyloxy, isooctyloxy, tert-octyloxy, 2-ethylhexyloxy, nonyloxy, and decyloxy; alkylthio groups such as methylthio, ethylthio, propylthio, isopropylthio, butylthio, sec-butylthio, tert-butylthio, isobutylthio, pentylthio, isopentylthio, tert-pentylthio, hexylthio, cyclohexylthio, heptylthio, isoheptylthio, tert-heptylthio, n-octylthio, isooctylthio, tert-octylthio and 2-ethylhexylthio; alkenyl groups such as vinyl, 1-methylvinyl, 2-propenyl, 1-methyl-3-propenyl, 3-butenyl, 1-methyl-3-butenyl, isobutenyl, 3-pentenyl, 4-hexenyl, cyclohexenyl, bicyclohexenyl, heptenyl, octenyl, decenyl, pentadecenyl, eicosenyl and tricosenyl; and those substituted with a substituent described later.

With respect to the above-mentioned bonding group X¹The aliphatic hydrocarbon group having 1 to 120 carbon atoms and having the same number of valences as m, and examples of the group having a valency of 2 include alkylene groups such as methylene, ethylene, propylene, butylene, and butylene; a group wherein the methylene chain of the alkylene group is replaced by-O-, -S-, -CO-O-, -O-CO-; residues of diol groups such as ethylene glycol, propylene glycol, butylene glycol, pentylene glycol, and hexylene glycol; residues of dithiol groups such as ethanedithiol, propanedithiol, butanedithiol, pentanethiol, and hexanedithiol, and those groups substituted with substituents described later, and the like.

With respect to the above-mentioned bonding group X¹The aliphatic hydrocarbon group having 1 to 120 carbon atoms and having the same number of valences as m, and examples of the group in which m is a valency of 3 include an alkylidene group such as propylidene and 1, 1, 3-butylidene propylidene; and those in which these groups are substituted with the substituents described later.

With respect to the above-mentioned bonding group X¹The aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms and having the same number of valences as m includes an arylalkyl group such as a benzyl group, a phenethyl group, a diphenylmethyl group, a triphenylmethyl group, a styryl group, or a cinnamyl group, as the group in which m has a valency of 1; aryl groups such as phenyl and naphthyl; aryloxy groups such as phenoxy and naphthoxy; arylthio groups such as phenylthio and naphthylthio; and those substituted with a substituent described later.

With respect to the above-mentioned bonding group X¹The aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms and having the same number of valences as m, wherein m is a group having a valency of 2, and examples thereof include arylene groups such as phenylene and naphthylene; a residue of a bifunctional phenol group such as a catechol group or a bisphenol group; 2, 4, 8, 10-tetraoxaspiro [5, 5]]An undecyl group; and those in which these groups are substituted with the substituents described later.

With respect to the above-mentioned bonding group X¹The aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms and having the same number of valences as m includes, as the group in which m is a valency of 3, phenyl-1, 3, 5-trimethylene group and a group in which the group is substituted with a substituent described later.

With respect to the above-mentioned bonding group X¹Examples of the heterocyclic group having 2 to 35 carbon atoms and having the same number of valences as m include pyridyl, pyrimidinyl, pyridazinyl, piperidyl, pyranyl, pyrazolyl, triazinyl, pyrrolyl, quinolyl, isoquinolyl, imidazolyl, benzimidazolyl, triazolyl, furyl (furyl), benzofuryl, thienyl, thiophenyl, benzothienyl, thiadiazolyl, thiazolyl, benzothiazolyl, oxazolyl, benzoxazolyl, isothiazolyl, isoxazolyl, indolyl, 2-pyrrolidone-1-yl, 2-piperidone-1-yl, 2, 4-dioxoimidazolidinyl, and groups in which m has a valency of 1A-3-yl group, a2, 4-dioxooxazolidin-3-yl group, a benzotriazolyl group and the like, and a group obtained by substituting these groups with a substituent described later.

With respect to the above-mentioned bonding group X¹Examples of the heterocyclic group having 2 to 35 carbon atoms and having the same number of valences as m include groups having valences 2 as m, such as groups having valences 2, including pyridine rings, pyrimidine rings, piperidine rings, piperazine rings, triazine rings, furan rings, thiophene rings, and indole rings, and groups in which these groups are substituted with substituents described later.

As R⁵³And R⁵⁴The aliphatic hydrocarbon group having 1 to 35 carbon atoms used in the above-mentioned step (A) includes the above-mentioned X¹The aliphatic hydrocarbon group having 1 to 120 carbon atoms used in (1) or the group in which the aliphatic hydrocarbon group is substituted with a substituent described later has 1 to 35 carbon atoms.

As R⁵³And R⁵⁴The aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms or the heterocyclic group having 2 to 35 carbon atoms includes X¹The aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms, the heterocyclic group having 2 to 35 carbon atoms, or a group obtained by substituting these groups with a substituent described later.

The functional groups such as the aliphatic hydrocarbon group, the aromatic ring-containing hydrocarbon group, and the heterocyclic group may have a substituent, and the compound I-1 of the present invention includes compounds having no substituent and compounds having a substituent unless otherwise specified.

Examples of the substituent such as the aliphatic hydrocarbon group, the aromatic ring-containing hydrocarbon group and the heterocyclic group include¹¹The same ones as those mentioned above for the substituents substituted with hydrogen atoms such as alkyl groups.

When m is 2, the above-mentioned X¹A group represented by the following general formula (1) can be used.

When m is 3, the above-mentioned X¹A group represented by the following general formula (2) can be used.

When m is 4, the above-mentioned X¹A group represented by the following general formula (3) can be used.

When m is 5, the above-mentioned X¹A group represented by the following general formula (4) can be usedAnd (4) clustering.

When m is 6, the above-mentioned X¹A group represented by the following general formula (5) can be used.

[ chemical formula 9]

＊－Ｚ^1-Y¹-Z²-＊ (1)

(in the above general formula (1), Y¹Represents a single bond, -CR⁵⁵R⁵⁶-、-NR⁵⁷A divalent aliphatic hydrocarbon group having 1 to 35 carbon atoms, an aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms, a heterocyclic group having 2 to 35 carbon atoms, or any of the substituents represented by the following (1-1) to (1-3), wherein 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 are optionally substituted with a bonding group of-O-, -S-, -CO-, -COO-, -OCO-, or-NH-or a combination thereof,

R⁵⁵and R⁵⁶Represents 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,

Z¹and Z²Each independently represents a direct bond, -O-, -S-, > CO, -CO-O-, -O-CO-, -SO₂-、-SS-、-SO-、＞NR⁵⁸Or > PR⁵⁸，

R⁵⁷And R⁵⁸Represents 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,

refers to bonding to an adjacent group at the moiety. )

[ chemical formula 10]

(in the above formula, R⁵⁹Represents a hydrogen atom, a phenyl group which may have a substituent, or a cycloalkyl group having 3 to 10 carbon atoms,

R⁶⁰c1 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, the alkyl group, alkoxy group and alkenyl group may have a substituentAn integer of 0 to 5, which means that the bonding to the adjacent group is at the moiety. )

[ chemical formula 11]

(. means bonding to an adjacent group at the site.)

[ chemical formula 12]

(in the above formula, R⁶¹And R⁶²Each independently represents 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, an arylthio group having 6 to 20 carbon atoms, an arylalkenyl 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 or a halogen atom, and a methylene group in the alkyl group and the arylalkyl group may be replaced by an unsaturated bond, -O-or-S-,

R⁶¹also present through adjacent R⁶¹In the case of forming a loop with each other,

c2 represents a number of 0 to 4,

c3 represents a number of 0 to 8,

c4 represents a number of 0 to 4,

c5 represents a number of 0 to 4,

the sum of the numbers of c4 and c5 is 2 to 4,

refers to bonding to an adjacent group at the moiety. )

[ chemical formula 13]

(in the above general formula (2), Y¹¹Represents a trivalent aliphatic hydrocarbon group having 3 to 35 carbon atoms, an alicyclic hydrocarbon group having 3 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,

Z¹、Z²and Z³Each independently represents a direct bond, -O-, -S-, > CO, -CO-O-, -O-CO-, -SO₂-、-SS-、-SO-、＞NR⁶²、PR⁶²An 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,

R⁶²represents 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,

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 may be substituted with a carbon-carbon double bond, -O-, -CO-, -O-CO-, -CO-O-, or-SO₂-substitution. )

[ chemical formula 14]

(in the above general formula (3), Y¹²Represents a C1-35 aliphatic hydrocarbon group, a C6-35 aromatic ring-containing hydrocarbon group or a C2-35 heterocyclic group, the aliphatic hydrocarbon group, the C6-35 aromatic ring-containing hydrocarbon group or the C2-35 heterocyclic group may be substituted by-COO-, -O-, -OCO-, -NHCO-, -NH-or-CONH-, Z¹～Z⁴Each independently of the other, is the same as Z in the above general formula (2)¹～Z³The groups shown are in the same range of groups. )

[ chemical formula 15]

(in the above general formula (4), Y¹³Represents a pentavalent aliphatic hydrocarbon group having 2 to 35 carbon atoms, a hydrocarbon group having 6 to 30 carbon atoms and containing an aromatic ring, or a heterocyclic group having 2 to 30 carbon atoms, wherein the aliphatic hydrocarbon group, the hydrocarbon group having 6 to 35 carbon atoms and containing an aromatic ring, and the heterocyclic group having 2 to 35 carbon atoms are optionally substituted by-COO-, -O-, -OCO-, -NHCO-, -NH-, or-CONH-, and Z¹～Z⁵Each is independentThe vertical position is the same as Z in the general formula (2)¹～Z³The groups shown are in the same range of groups. )

[ chemical formula 16]

(in the above general formula (5), Y¹⁴Represents a single bond, hexavalent aliphatic hydrocarbon group having 2 to 35 carbon atoms, aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms or heterocyclic group having 2 to 35 carbon atoms, wherein the aliphatic hydrocarbon group, aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms or heterocyclic group having 2 to 35 carbon atoms is optionally substituted with-COO-, -O-, -OCO-, -NHCO-, -NH-or-CONH-, and Z¹～Z⁶Each independently of the other, is the same as Z in the above general formula (7)¹～Z³The groups shown are in the same range of groups. )

Y as in the group represented by the above general formula (1)¹Examples of the divalent aliphatic hydrocarbon group having 1 to 35 carbon atoms include a divalent aliphatic hydrocarbon group having Z-bond such as methane, ethane, propane, isopropane, butane, sec-butyl, tert-butyl, isobutane, hexane, 2-methylhexane, 3-methylhexane, heptane, 2-methylheptane, 3-methylheptane, isoheptane, tert-heptane, 1-methyloctane, isooctane, tert-octane, cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, 2, 4-dimethylcyclobutane, 4-methylcyclohexane and the like¹And Z²A substituted divalent group. These groups are sometimes interrupted by-O-, -S-, -CO-, -COO-, -OCO-, -NH-or a combination thereof.

Y as in the group represented by the above general formula (1)¹Examples of the divalent aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms include a group represented by Z such as phenylene, naphthylene and biphenyl¹And Z²Substituted divalent groups, and the like.

Y as in the group represented by the above general formula (1)¹Examples of the divalent heterocyclic group having 2 to 35 carbon atoms include pyridine, pyrazine, piperidine, piperazine, pyrimidine, pyridazine, triazine, hexahydrotriazine, furan, tetrahydrofuran, chroman, xanthene, thiophene, and the like,Quilt Z of tetrahydrothiophene or the like¹And Z²A substituted divalent group.

Y in the group represented by the above general formula (1)¹The aliphatic hydrocarbon group, aromatic ring-containing hydrocarbon group and heterocyclic group may be further substituted with a halogen atom, a cyano group, a nitro group or an alkoxy group having 1 to 8 carbon atoms.

Each functional group such as the aliphatic hydrocarbon group, the aromatic ring-containing hydrocarbon group, and the heterocyclic group may have a substituent, and unless otherwise specified, the functional group may be an unsubstituted or substituted group having no substituent.

Examples of the substituent for such an aliphatic hydrocarbon group, aromatic ring-containing hydrocarbon group, heterocyclic group-containing hydrocarbon group and the like include¹¹The same ones as those mentioned above for the substituents substituted with hydrogen atoms such as alkyl groups.

R as in the group represented by the above general formula (1)⁵⁵And R⁵⁶Examples of the alkyl group having 1 to 8 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert-butyl group, an isobutyl group, a pentyl group, an isopentyl group, a tert-pentyl group, a hexyl group, a 2-hexyl group, a 3-hexyl group, a cyclohexyl group, a 4-methylcyclohexyl group, a heptyl group, a 2-heptyl group, a 3-heptyl group, an isoheptyl group, a tert-heptyl group, a 1-octyl group, an isooctyl group, and a tert-.

R as in the group represented by the above general formula (1)⁵⁵And R⁵⁶Examples of the arylalkyl group having 7 to 20 carbon atoms include a benzyl group, a phenethyl group, a 2-phenylpropan-2-yl group, a diphenylmethyl group, a triphenylmethyl group, a styryl group, and a cinnamyl group.

R in the group represented by the above general formula (1)⁵⁷And R⁵⁸The aliphatic hydrocarbon group having 1 to 35 carbon atoms, the aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms or the heterocyclic group having 2 to 35 carbon atoms is represented by R⁵³And R⁵⁴And the exemplified groups are the same.

R as in the group represented by the above general formula (1-1)⁵⁹Examples of the cycloalkyl group having 3 to 10 carbon atoms include cyclopropyl, cyclobutyl, cyclopentyl, cycloheptyl, cyclooctyl and the like, and an alkyl group having 1 to 10 carbon atoms or a carbon-containing alkyl groupAlkoxy groups having 1 to 10 atoms, and the like.

R as in the group represented by the above general formula (1-1)⁶⁰Examples of the alkyl group having 1 to 10 carbon atoms include R in the above-mentioned "1. Photocleavable group B¹¹And alkyl groups having 1 to 10 carbon atoms are exemplified as the alkyl groups represented by the following formulae.

R as in the group represented by the above general formula (1-1)⁶⁰The alkoxy group having 1 to 10 carbon atoms is represented by the formula R in the above-mentioned "1. Photocleavable group B¹¹And alkoxy groups having 1 to 10 carbon atoms, which are exemplified as the alkoxy groups represented by the above general formula (I).

Examples of the alkenyl group having 2 to 10 carbon atoms in the group represented by the general formula (1-1) include vinyl, allyl, 1-propenyl, isopropenyl, 2-butenyl, 1, 3-butadienyl, 2-pentenyl, and 2-octenyl.

The phenyl group, alkyl group, alkoxy group and alkenyl group in the general formula (1-1) may have a substituent. Examples of such a substituent include R¹Examples of the substituent include the same ones as those exemplified for the substituent substituted with a hydrogen atom such as an alkyl group used in the above description.

R is as defined above⁶⁰The alkyl group, alkoxy group and alkenyl group in (1) may be substituted with a halogen atom, and the substitution position is not limited.

R as in the group represented by the above general formula (1-3)⁶¹And R⁶²Examples of the alkyl group having 1 to 10 carbon atoms, the aryl group having 6 to 20 carbon atoms, and the arylalkyl group having 7 to 20 carbon atoms include R in the above-mentioned "1. Photocleavable group B¹¹And the like, and those satisfying a predetermined number of carbon atoms in the examples.

R as in the group represented by the above general formula (1-3)⁶¹And R⁶²Examples of the aryloxy group having 6 to 20 carbon atoms include a phenoxy group, a naphthoxy group, a 2-methylphenyloxy group, a 3-methylphenyloxy group, a 4-vinylphenyloxy group, a 3-isopropylphenyloxy group, a 4-butylphenyloxy group, a 4-tert-butylphenyloxy group, a 4-hexylphenyloxy group, a,4-cyclohexylphenyloxy, 4-octylphenyloxy, 4- (2-ethylhexyl) phenyloxy, 2, 3-dimethylphenyloxy, 2, 4-dimethylphenyloxy, 2, 5-dimethylphenyloxy, 2, 6-dimethylphenyloxy, 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-pentylphenyloxy, 4-cyclohexylphenyloxy, 2, 4, 5-trimethylphenyloxy and ferrocenyloxy, and groups thereof which are obtained by substituting these groups with halogen atoms.

R as in the group represented by the above general formula (1-3)⁶¹And R⁶²Examples of the arylthio group having 6 to 20 carbon atoms include groups obtained by substituting an oxygen atom of an aryloxy group having 6 to 20 carbon atoms, which may be substituted with the above-mentioned halogen atom, with a sulfur atom.

R as in the group represented by the above general formula (1-3)⁶¹And R⁶²Examples of the arylalkenyl group having 8 to 20 carbon atoms include groups obtained by replacing an oxygen atom of an aryloxy group having 6 to 20 carbon atoms, which may be substituted with the above-mentioned halogen atom, with an alkenyl group such as a vinyl group, an allyl group, a 1-propenyl group, an isopropenyl group, a 2-butenyl group, a1, 3-butadienyl group, a 2-pentenyl group, or a 2-octenyl group.

R as in the group represented by the above general formula (1-3)⁶¹And R⁶²Examples of the heterocyclic group having 2 to 20 carbon atoms include pyridyl, pyrazinyl, piperidyl, piperazinyl, pyrimidinyl, pyridazinyl, triazinyl, hexahydrotriazinyl, furyl, tetrahydrofuryl, chromanyl, xanthenyl, thienyl and thiofuryl groups, and groups in which these groups are substituted with a halogen atom.

R in the group represented by the above general formula (1-3)⁶¹And R⁶²Each functional group such as an aryloxy group, an arylthio group, an arylalkenyl group, and a heterocyclic group may have a substituent, and unless otherwise specified, the functional group may be an unsubstituted group having no substituent or a group having a substituent.

As a heterocyclic ring containing aryloxy, arylthio, arylalkenylA substituent substituted with a hydrogen atom such as R¹¹The same applies to the substituent substituted with a hydrogen atom such as an alkyl group.

Y as a group represented by the above general formula (2)¹¹The trivalent aliphatic hydrocarbon group having 3 to 35 carbon atoms is represented by X in the general formula (1)¹The aliphatic hydrocarbon group exemplified in the description of (1) is represented by Z¹、Z²And Z³Substituted trivalent radicals, these radicals sometimes being substituted by-O-, -S-, -CO-O-, -O-CO-, -SO₂-, -NH-or a combination thereof.

Y as a group represented by the above general formula (2)¹¹The trivalent aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms is represented by X in the general formula (1)¹The aromatic ring-containing hydrocarbon group exemplified in the description of (1) is represented by Z¹、Z²And Z³Substituted trivalent groups.

Y as a group represented by the above general formula (2)¹¹The trivalent heterocyclic group having 2 to 35 carbon atoms is represented by X in the general formula (1)¹The heterocyclic group-containing group exemplified in the description of (1) is represented by Z¹、Z²And Z³Substituted trivalent groups.

Z in the group represented by the above general formula (2)¹、Z²And Z³And R⁶²The aliphatic hydrocarbon group having 1 to 35 carbon atoms, the aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms or the heterocyclic group having 2 to 35 carbon atoms as R⁵³And R⁵⁴The same applies to the examples.

Y as in the group represented by the above general formula (3)¹²The tetravalent aliphatic hydrocarbon group having 1 to 35 carbon atoms is X in the general formula (1)¹The aliphatic hydrocarbon group exemplified in the description of (1) is represented by Z¹、Z²、Z³And Z⁴Substituted tetravalent groups, which are sometimes substituted with-O-, -S-, -CO-, -COO-, -OCO-, -NH-or combinations thereof.

Y as a group represented by the above general formula (3)¹²The tetravalent aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms represented by the formula (1) includes X¹The aromatic ring-containing hydrocarbon group exemplified in the description of (1) is represented by Z¹、Z²、Z³And Z⁴A substituted tetravalent group.

Y as a group represented by the above general formula (3)¹²The tetravalent heterocyclic group having 2 to 35 carbon atoms is represented by X in the general formula (1)¹The heterocyclic group-containing group exemplified in the description of (1) is represented by Z¹、Z²、Z³And Z⁴A substituted tetravalent group.

Y as in the group represented by the above general formula (4)¹³The pentavalent aliphatic hydrocarbon group having 2 to 35 carbon atoms used in the above formula (1) includes X¹The aliphatic hydrocarbon group exemplified in the description of (1) is represented by Z¹、Z²、Z³、Z⁴And Z⁵Substituted pentavalent radicals, these radicals sometimes being substituted by-O-, -S-, -CO-O-, -O-CO-, -SO₂-, -NH-or a combination thereof.

The aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms and a pentavalent carbon atom in the group represented by the general formula (4) includes X in the general formula (1)¹The aromatic ring-containing hydrocarbon group exemplified in the description of (1) is represented by Z¹、Z²、Z³、Z⁴And Z⁵Substituted pentavalent groups.

Examples of the heterocyclic group having 2 to 35 carbon atoms and having a pentavalent carbon atom in the group represented by the general formula (4) include X in the general formula (1)¹The heterocyclic group-containing group exemplified in the description of (1) is represented by Z¹、Z²、Z³、Z⁴And Z⁵Substituted pentavalent groups.

As Y in the above general formula (5)¹⁴The hexavalent aliphatic hydrocarbon group having 2 to 35 carbon atoms includes X in the general formula (1)¹The aliphatic hydrocarbon group exemplified in the description of (1) is represented by Z¹、Z²、Z³、Z⁴、Z⁵And Z⁶Substituted hexavalent radicals, these radicals sometimes being substituted by-O-, -S-, -CO-, -COO-, -OCO-, -SO₂-, -NH-or a combination thereof.

As Y in the above general formula (5)¹⁴Examples of the hexavalent aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms include X in the general formula (1)¹The aromatic ring-containing hydrocarbon group exemplified in the description of (1) is represented by Z¹、Z²、Z³、Z⁴、Z⁵And Z⁶A substituted hexavalent group.

As Y in the above general formula (5)¹⁴Examples of the hexavalent heterocyclic group having 2 to 35 carbon atoms include X in the general formula (1)¹The heterocyclic group-containing group exemplified in the description of (1) is represented by Z¹、Z²、Z³、Z⁴、Z⁵And Z⁶A substituted hexavalent group.

The above-mentioned bonding group X¹When m is 2, it is preferably any of the substituents represented by the following general formulae (1-4), (1-5) and (1-6-a) to (1-6-e).

The above-mentioned bonding group X¹In the case where m is 3, a group selected from the following group 1 is preferable.

The above-mentioned bonding group X¹In the case where m is 4, a group selected from the following group 2 is preferable.

The above-mentioned bonding group X¹In the case where m is 5, a group selected from the following group 3 is preferable.

The above-mentioned bonding group X¹In the case where m is 6, a group selected from the following group 4 is preferable.

These substituents are groups which exhibit excellent antioxidant ability after the photodissociation of the group B in the compound I-1, and are easy to obtain and produce raw materials.

[ chemical formula 17]

(in the above general formula (1-4), Y¹And Y⁵Each independently represents an alkylene group having 1 to 4 carbon atoms, Y²And Y⁴Each independently represents an oxygen atom or-NR¹¹³-，R¹¹³Y represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 20 carbon atoms³represents-CR¹¹⁴R¹¹⁵-、-NR¹¹⁶A divalent aliphatic hydrocarbon group having 1 to 35 carbon atoms, an aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms, or a substituent represented by the following general formula (1-7), wherein the aliphatic hydrocarbon group, the aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms, and the heterocyclic group having 6 to 35 carbon atoms are optionally substituted with-COO-, -O-, -OCO-, -NHCO-, -NH-, or-CONH-, R¹¹⁴And R¹¹⁵Each independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 20 carbon atoms or an arylalkyl group having 7 to 20 carbon atoms, R¹¹⁶Represents 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. )

[ chemical formula 18]

(in the above general formula (1-5), Y⁶And Y⁸Each independently represents-NR¹¹⁷Or alkylene having 1 to 4 carbon atoms which may be substituted with oxygen atom, Y⁷Denotes direct bonding, -O-, -S-, -SO₂-、-CR¹¹⁸R¹¹⁹Or any of the substituents represented by the above general formulae (1-1) to (1-3), R¹¹⁷R represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 20 carbon atoms¹¹⁸And R¹¹⁹Each independently represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms which may be substituted with a halogen atom. )

[ chemical formula 19]

(in the above general formulae (1-6-a) to (1-6-e), R³¹Represents 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. )

[ chemical formula 20]

(in the above general formula (1-7), Y⁹And Y¹⁰Each independently represents an alkylene group having 1 to 4 carbon atoms. )

[ chemical formula 21]

< group 1>

(in the formula, R³²Is the same as R in the above general formula (2)⁶²The same or different groups in the case where there are 2 or more groups in the same group, Z¹¹Is represented by the formula Z¹～Z³The groups shown are in the same range of groups. )

[ chemical formula 22]

< group 2>

(in the above formula, R³²Is the same as R in the above general formula (2)⁶²The same or different groups in the case where there are 2 or more groups in the same group, Z¹¹Is represented by the formula Z¹～Z³The groups shown are in the same range of groups. )

[ chemical formula 23]

< group 3>

(in the above formula, Z¹⁰、Z¹¹、Z¹²、Z¹³And Z¹⁴Is represented by the formula Z¹～Z³The groups shown are in the same range of groups. )

[ chemical formula 24]

< group 4>

Y used as a substituent in the above general formulae (1-4) to (1-7)¹、Y⁵、Y⁶、Y⁸、Y⁹And Y¹⁰Examples of the alkylene group having 1 to 4 carbon atoms to be used include a methylene group, an ethylene group, a propylene group, an isopropylene group, and a butylene group.

As the above-mentioned R¹¹³And R¹¹⁷The aliphatic hydrocarbon group having 1 to 20 carbon atoms used in the above-mentioned step (A) includes the above-mentioned bonding group X¹The aliphatic hydrocarbon group having 1 to 120 carbon atoms used in the above (1) is a group having m as a valence of 1 and satisfying a predetermined number of carbon atoms.

As a result of Y mentioned above³The 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 the formula (I) may be used in combination with the above-mentioned Y¹The same applies to the examples.

As the above-mentioned R¹¹⁴、R¹¹⁵、R¹¹⁸And R¹¹⁹Alkyl group having 1 to 8 carbon atoms and R used in the above¹¹⁴And R¹¹⁵The aryl group having 6 to 20 carbon atoms and arylalkyl group having 7 to 20 carbon atoms used in the above formula may be used together with the above-mentioned R⁵⁵And R⁵⁶The same applies to the examples.

As the above-mentioned R¹¹⁶And R³¹The aliphatic hydrocarbon group having 1 to 35 carbon atoms, the aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms and the heterocyclic group having 2 to 35 carbon atoms to be used may be used together with the above-mentioned R⁵³And R⁵⁴The same applies to the examples.

The functional groups such as the aliphatic hydrocarbon group, the aromatic ring-containing hydrocarbon group, and the heterocyclic group may have a substituent, and unless otherwise specified, the functional groups are unsubstituted or substituted groups having no substituent.

As suchThe substituent(s) such as the aliphatic hydrocarbon group, aromatic ring-containing hydrocarbon group and heterocyclic group of (A) may be represented by¹¹The same applies to the substituent substituted with a hydrogen atom such as an alkyl group.

Further, the above-mentioned bonding group X¹When m is 2, an aliphatic hydrocarbon group having 1 to 10 carbon atoms may be preferably used, and an aliphatic hydrocarbon group having 1 to 6 carbon atoms is particularly preferable. This is because a compound which has less curing inhibition and can easily impart antioxidant ability to a cured product, and the compound I-1 can be easily produced.

When m is 1, the bonding group X is preferably a hydrogen atom or an aliphatic hydrocarbon group having 1 to 120 carbon atoms, and more preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. This is because the compound I-1 exerts an excellent antioxidant ability after the removal of the photocleavable group B, and the compound I-1 is easily produced.

As the above-mentioned bonding group X¹The bonding position to the benzene ring may be any position that can be bonded in the benzene ring, and for example, the bonding position to the above-mentioned B-O-may be an ortho-position or a para-position, and may be a para-position. This is because the compound I-1 exerts an excellent antioxidant ability after the elimination of the photodissociable group B.

X is above¹When m is 1, it is preferably a hydrogen atom or a group with R¹The same groups.

The compound I-1 represented by the above general formula (A-2) or (A-3) has X bonded thereto²The structure of n-valent specific atoms and n specific groups is shown. The n specific groups may be the same as or different from each other.

X is above²Can be reacted with the above X¹The same applies to the bonding group used in (1) wherein m is 2 or more.

As the above-mentioned bonding group X²The bonding position with the benzene ring may be set to the above-mentioned X¹The same is true.

X is above²When n is 1, it is preferably a hydrogen atom or a group with R¹The same groups.

The above-mentioned atomic group A may contain a phenolic hydroxyl group, that is, the compound I-1 may contain a phenolic hydroxyl group which is not protected by the photo-cleavable group B, and the number of phenolic hydroxyl groups is preferably 2 or less, more preferably 0. This is because the compound I-1 is a compound which hardly inhibits curing.

3. Compound (I)

The compound of the present invention may be a compound represented by the above general formula (I-1), but is preferably a compound represented by the above general formula (A-1), general formula (A-2) or (A-3), and the photo-cleavable group B preferably contains a group represented by the above general formula (B-1-a). This is because synthesis is easy and light extraction is easy. This is because oxidation resistance and the like can be easily imparted to the cured product. Further, since the compound I-1 is represented by the above general formula (A-1), (A-2) or (A-3), it is possible to stably trap a radical or the like by elimination of the photo-cleavable group B.

Specific examples of the compound I-1 include the following compounds.

[ chemical formula 25]

[ chemical formula 26]

[ chemical formula 27]

[ chemical formula 28]

[ chemical formula 29]

[ chemical formula 30]

[ chemical formula 31]

[ chemical formula 32]

[ chemical formula 33]

[ chemical formula 34]

[ chemical formula 35]

[ chemical formula 36]

[ chemical formula 37]

[ chemical formula 38]

[ chemical formula 39]

[ chemical formula 40]

The molecular weight of the compound I-1 can be set in accordance with the use of the compound I-1, for example.

The molecular weight may be, for example, 250 to 5000, 300 to 2500, 350 to 1500.

When the compound I-1 is a polymer having a repeating structure as its structure, the molecular weight may be a molecular weight represented by a weight average molecular weight (Mw).

Hereinafter, the weight average molecular weight (Mw) can be determined as a standard polystyrene equivalent by Gel Permeation Chromatography (GPC).

The weight average molecular weight Mw is measured, for example, using HLC-8120GPC manufactured by TOSOH corporation, N-methylpyrrolidone to which 0.01 mol/L of lithium bromide is added as an eluting solvent, Mw377400, 210500, 96000, 50400, 20650, 10850, 5460, 2930, 1300, 580 (the above are Easi PS-2 series manufactured by Polymer laboratories) and Mw1090000 (manufactured by TOSOH corporation) as calibration curves using polystyrene standards, and TSK-GEL ALPHA-M.times.2 (manufactured by TOSOH corporation) as a measuring column. The measurement temperature was set to 40 ℃ and the flow rate was set to 1.0 mL/min.

The method for producing the compound I-1 is not particularly limited as long as it is a method capable of obtaining a desired structure, and for example, a method in which a phenolic compound produced by the method described in each of Japanese patent laid-open Nos. 57-111375, 3-173843, 6-128195, 7-206771, 7-252191 and 2004-501128 is reacted with an alkyl halide or the like can be used.

The compound I-1 is inactive before light irradiation, and a photocleavable group is cleaved by light irradiation to produce a compound I-2 having a hydroxyl group. The compound I-2 exerts antioxidant ability.

The compound I-1 is preferably used in applications requiring the antioxidant ability by light irradiation, and examples thereof include antioxidants added to compositions.

Further, the compound I-1 is irradiated with light to produce a compound I-2 having a hydroxyl group. Examples of the use of the compound I-1 include antioxidants which require high dispersion stability.

B. Latent antioxidants

Next, the latent antioxidant of the present invention will be described.

The latent antioxidant of the present invention comprises the compound I-1 of the present invention.

The latent antioxidant according to the present invention is less likely to inhibit curing, and can easily impart antioxidant ability to a cured product.

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 may be one comprising 100 parts by mass of the compound I-1 in 100 parts by mass of the latent antioxidant, that is, the latent antioxidant is composed of only the compound I-1.

The latent antioxidant of the present invention may contain other components in addition to the compound I-1. When the latent antioxidant of the present invention contains other components, the content of the compound I-1 may be set to, for example, more than 20 parts by mass and 99 parts by mass or less, preferably 25 parts by mass and 99 parts by mass or less, more preferably 50 parts by mass and 99 parts by mass or less, and particularly preferably 80 parts by mass and 99 parts by mass or less, per 100 parts by mass of the latent antioxidant. This is because the effects such as less curing inhibition can be more effectively exhibited.

The number of the types of the compound I-1 contained in the latent antioxidant may be only 1, and may be 2 or more. When the latent antioxidant contains a plurality of compounds I-1, the number of the compounds may be, for example, 2 or more and 5 or less.

The compound I-1 may be the same as that described in the section "compound a", and therefore, the description thereof will be omitted.

The other component may be, for example, the one described in "2. other component" of "c. composition" described later.

The latent antioxidant may be a resin component containing a polymer having no polymerizable group or the like as another component.

The latent antioxidant may be in the form of a powder or a granule.

In the case of the granular form, as a method for producing the latent antioxidant, for example, the following method can be used: the compound I-1 and the resin component are mixed by an extruder or the like and molded into pellets.

C. Composition comprising a metal oxide and a metal oxide

Next, the composition of the present invention will be described.

The composition of the present invention comprises the compound I-1 of the present invention.

According to the composition of the present invention, for example, a cured product having little curing inhibition and excellent oxidation resistance can be obtained. In addition, the composition of the present invention can easily impart photosensitivity, and can easily impart antioxidant ability to a cured product. Hereinafter, each component contained in the composition of the present invention will be described.

1. Compound (I)

The content of the compound I-1 in the composition of the present invention is not particularly limited as long as it can impart a desired antioxidant ability or the like to the composition.

The content may be, for example, 0.01 to 20 parts by mass, preferably 0.05 to 5 parts by mass, based on 100 parts by mass of the solid content of the composition. This is because a composition which has little curing inhibition and can easily impart antioxidant ability to a cured product can be easily produced.

The solid component means a component containing all components except the solvent.

In the present invention, the content is based on mass unless otherwise specified.

The content of the compound I-1 varies depending on the content of the solvent and the like, and may be, for example, 0.001 part by mass or more and 20 parts by mass or less, and particularly preferably 0.005 part by mass or more and 10 parts by mass or less, per 100 parts by mass of the composition. This is because a composition which has little curing inhibition and can easily impart antioxidant ability to a cured product can be easily produced.

The number of the compounds I-1 contained in the composition may be only 1, or may be 2 or more. The types of the above-mentioned substances may be set to 2 or more and 5 or less, for example.

2. Other ingredients

The composition may contain other components than the compound I-1 depending on the use thereof.

Examples of the other component include a resin component.

This is because, for example, the composition can be easily provided with, for example, curability by containing the resin component.

In addition, as the other component, it is preferable to contain a polymerization initiator together with the resin component. This is because the composition can be easily provided with, for example, curability by containing a resin component, a polymerization initiator, and the like as other components.

(1) Resin component

The resin component may be a component capable of holding the compound I-1, and may be suitably set according to the use of the composition, and examples thereof include polymerizable compounds having a polymerizable group, polymers having no polymerizable group, and the like.

When a polymerizable compound is contained as the resin component, the composition can be used as, for example, a photocurable composition, a thermosetting composition, or the like.

(a) Polymerizable compound

The polymerizable compound is a compound having a polymerizable group.

In addition, a polymerizable compound is generally used together with a polymerization initiator.

Such polymerizable compounds vary depending on the type of polymerizable group, i.e., the type of polymerization reaction, and examples thereof include radical polymerizable compounds, cationic polymerizable compounds, and anionic polymerizable compounds.

The polymerizable compound preferably contains a radical polymerizable compound from the viewpoint of effectively exhibiting the effect of reducing the curing inhibition.

(i) Radical polymerizable compound

The radical polymerizable compound may have 1 or more radical polymerizable groups, and may include 2 or more radical polymerizable groups.

The radical polymerizable compound is usually used together with a radical polymerization initiator.

Examples of the radical polymerizable group include an ethylenically unsaturated double bond group such as a (meth) acryloyl group and a vinyl group.

The term (meth) acryloyl is used to mean that it includes both acryloyl and methacryloyl groups. In addition, (meth) acrylates are used in the meaning of including acrylates and methacrylates.

The radical polymerizable compound may be a compound having an acid value or a compound having no acid value.

Examples of the compound having an acid value include a compound having a carboxyl group.

In the above composition, the compound having an acid value is contained as a radical polymerizable compound, so that the solubility of the light irradiation site in an alkali developing solution is lowered. Therefore, the composition can be used as a photosensitive composition whose solubility in a solvent such as an alkali developing solution changes before and after light irradiation. More specifically, the composition can be used as a negative composition by containing a compound having an acid value.

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

Examples of the radical polymerizable compound include a compound having an ethylenically unsaturated double bond group and an acid value, for example, a mono (meth) acrylate of a polymer having a carboxyl group and a hydroxyl group at both ends, such as (meth) acrylic acid, α -chloroacrylic acid, itaconic acid, maleic acid, citraconic acid, fumaric acid, nadic acid, crotonic acid, isocrotonic acid, vinylacetic acid, allylacetic acid, cinnamic acid, sorbic acid, mesaconic acid, succinic acid mono [2- (meth) acryloyloxyethyl ester ], phthalic acid mono [2- (meth) acryloyloxyethyl ester ] and ω -carboxy polycaprolactone mono (meth) acrylate, a phenol and/or cresol novolac epoxy resin, a novolac epoxy resin having a biphenyl skeleton, a naphthalene skeleton, a bisphenol a novolac epoxy compound, a dicyclopentadiene novolac epoxy compound, a compound having a hydroxyl group, a multifunctional (meth) acrylate having a carboxyl group and 2 or more (meth) acryloyl group, a polyhydric epoxy anhydride having a hydroxyl group, a pentaerythritol epoxy group, and a pentaerythritol-containing epoxy group, and further, and the above-unsaturated epoxy resin such as a pentaerythritol-containing epoxy anhydride.

[ chemical formula 41]

(in the formula, X⁴¹Represents a direct bond, an alkylidene group having 1 to 4 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, -O-, -S-, -SO₂-, -SS-, -SO-, -CO-, -OCO-, or the substituents represented by the above-mentioned (1-1) to (1-3),

R⁴¹、R⁴²、R⁴³and R⁴⁴Each independently represents 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 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 R in the item "A. Compound" mentioned above¹¹And the like, which satisfy a predetermined number of carbon atoms.

Examples of the alkylidene group having 1 to 4 carbon atoms include a methylidene group, an ethylidene group, a propylidene group, and a butylidene group.

Examples of the alicyclic hydrocarbon group include cyclopropyl, cyclopentyl, cyclohexyl, and cycloheptyl.

The alkyl group, alkoxy group, alkenyl group, alkylidene group, alicyclic hydrocarbon group, and the like may have a substituent, and unless otherwise specified, the group may be unsubstituted or substituted.

The substituent for substituting a hydrogen atom of such an alkyl group, alkoxy group, alkenyl group, alkylidene group, alicyclic hydrocarbon group or the like may be the same as that for R¹¹The same applies to the substituent substituted with a hydrogen atom such as an alkyl group.

Examples of the radical polymerizable compound include compounds having an ethylenically unsaturated double bond and no acid value, such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, glycidyl (meth) acrylate, methyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, cyclohexyl (meth) acrylate, N-octyl (meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, methoxyethyl (meth) acrylate, dimethylaminomethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, aminopropyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, ethoxyethyl (meth) acrylate, polyethoxy (meth) acrylate, butoxyethoxyethyl (meth) acrylate, ethylhexyl (meth) acrylate, phenoxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, vinyl (meth) acrylate, benzyl (meth) acrylate, ethylene glycol di (meth) acrylate, 4-vinyl methacrylate, a copolymer containing a vinyl methacrylate, a maleic anhydride, a vinyl methacrylate, a maleic anhydride, a methacrylic anhydride, a maleic anhydride, a methacrylic anhydride, a maleic anhydride, a methyl methacrylate, a maleic anhydride, a methyl methacrylate, a maleic anhydride, a methyl methacrylate, a maleic anhydride, a methyl methacrylate, a maleic anhydride, a methyl methacrylate, a maleic anhydride, a methyl methacrylate, a maleic anhydride, a methyl methacrylate, a maleic anhydride, a methyl methacrylate, a maleic anhydride, a methyl methacrylate, a maleic anhydride, a methyl methacrylate, a maleic anhydride, a methyl methacrylate, a maleic anhydride, a methyl methacrylate, a maleic anhydride, a methyl methacrylate.

[ chemical formula 42]

Compound No. A1

[ chemical formula 43]

Compound No. A2

[ chemical formula 44]

Compound No. A3

[ chemical formula 45]

Compound No. A4

The radical polymerizable compounds can be used alone or in combination of 2 or more. The radical polymerizable compound may be a compound having an ethylenically unsaturated double bond group and an acid value, or a compound having an ethylenically unsaturated double bond group and no acid value.

When 2 or more kinds of radical polymerizable compounds are mixed and used, they may be copolymerized in advance and used as a copolymer.

The content of the radical polymerizable compound may be appropriately set according to the use of the composition, and for example, may be set to 1 part by mass or more and 99 parts by mass or less, preferably 10 parts by mass or more and 90 parts by mass or less, and particularly preferably 40 parts by mass or more and 80 parts by mass or less in 100 parts by mass of the composition. This is because, when the content is in the above range, the composition can be used as a negative composition having excellent sensitivity, for example. This is because a composition which has less curing inhibition and can easily impart antioxidant ability to a cured product can be provided.

The content of the polymerizable compound may be any content as long as the composition can be used as a curable composition, but is preferably 1 part by mass or more and 99 parts by mass or less, preferably 50 parts by mass or more and 99.9 parts by mass or less, particularly preferably 80 parts by mass or more and 99.7 parts by mass or less, and more preferably 90 parts by mass or more and 99.5 parts by mass or less, of the total 100 parts by mass of the compound I-1 and the polymerizable compound. This is because, when the content is in the above range, the curing inhibition of the composition is small, and a composition capable of easily providing a cured product with oxidation resistance and the like can be provided.

The content of the compound I-1 and the radical polymerizable compound may be appropriately set according to the use of the composition, and for example, may be set to 1 part by mass or more and 99 parts by mass or less, preferably 10 parts by mass or more and 90 parts by mass or less, and particularly preferably 40 parts by mass or more and 80 parts by mass or less in 100 parts by mass of the composition. This is because, when the content is in the above range, the composition can be used as a negative composition having excellent sensitivity, for example. This is because a composition which has less curing inhibition and can easily impart antioxidant ability to a cured product can be provided.

(ii) Cationically polymerizable compound and anionically polymerizable compound

The cationically polymerizable compound may have 1 or more polymerizable groups capable of cationic polymerization.

The cationic polymerizable compound is usually used together with a cationic polymerization initiator.

Examples of the polymerizable group capable of cationic polymerization include a cyclic ether group such as an epoxy group and an oxetane group, and a vinyl ether group.

That is, examples of the cationically polymerizable compound include cyclic ether compounds such as epoxy compounds and oxetane compounds, and vinyl ether compounds.

Examples of the epoxy compound include methyl glycidyl ether, 2-ethylhexyl glycidyl ether, butyl glycidyl ether, decyl glycidyl ether, C12-13 mixed alkyl glycidyl ethers, phenyl-2-methyl glycidyl ether, hexadecyl 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, tolyl glycidyl ether, dibromotolyl glycidyl ether, decyl glycidyl ether, methoxypolyethylene glycol monoglycidyl ether, ethoxypolyethylene glycol monoglycidyl ether, butoxypolyethylene glycol monoglycidyl ether, phenoxypolyethylene glycol monoglycidyl ether, dibromophenyl glycidyl ether, 1, 4-butanediol diglycidyl ether, 1, 5-pentanediol diglycidyl ether, 1, 6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, 1, 2-epoxycyclohexane, 1, 4-epoxycyclohexane, 3-epoxycyclohexane, 3-4- (3, 3-methylcyclohexyl) oxide, 3-epoxycyclohexane oxide, 3-4-epoxycyclohexane oxide, 3-epoxycyclohexane oxide (3-methylcyclohexyl) carboxylate, 3-epoxycyclohexane oxide, 3-4-epoxycyclohexane oxide, 3-epoxycyclohexane carboxylate, 4-epoxycyclohexane oxide, 3-epoxycyclohexane carboxylate, 3-epoxycyclohexane oxide, 3-epoxycyclohexane carboxylate, 4-epoxycyclohexane carboxylate, 3-epoxycyclohexane carboxylate, 4-epoxycyclohexane carboxylate.

Ethylene, an α -olefin having 3 to 20 carbon atoms, an epoxy group-containing monomer, and optionally other monomers may be copolymerized by any of a copolymerization method and a grafting method, ethylene, a α -olefin having 3 to 20 carbon atoms, an epoxy group-containing monomer, and other monomers may be polymerized individually or in plurality with other monomers, ethylene, a monomer having a hydroxyl group at the end of a nonconjugated polybutadiene may be epoxidized by a peracetic acid method, a substance having a hydroxyl group in the molecule may be used, a hydroxyl group may be carbamated with an isocyanate, and an epoxy group may be introduced by reacting an epoxy compound containing a primary hydroxyl group therein.

Examples of the ethylene or α -olefin having 3 to 20 carbon atoms include ethylene, propylene, butene, 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.

Examples of the epoxy group-containing monomer include α -glycidyl ester of unsaturated acid, vinylbenzyl glycidyl ether, and allyl glycidyl ether, and specific examples of the α -glycidyl ester of unsaturated acid include glycidyl acrylate, glycidyl methacrylate, and glycidyl ethacrylate, and glycidyl methacrylate is particularly preferable.

Examples of the other monomers include unsaturated aliphatic hydrocarbons such as vinyl chloride, vinylidene fluoride and tetrafluoroethylene, mono (meth) acrylic acid, α -chloroacrylic acid, itaconic acid, maleic acid, citraconic acid, fumaric acid, nadic acid, crotonic acid, isocrotonic acid, vinyl acetic acid, allyl acetic acid, cinnamic acid, sorbic acid, mesaconic acid, succinic acid mono [2- (meth) acryloyloxyethyl ester ], phthalic acid mono [2- (meth) acryloyloxyethyl ester, omega-carboxypolycaprolactone mono (meth) acrylate, mono (meth) acrylic acid esters of polymers having carboxyl and hydroxyl groups at both ends, hydroxyethyl (meth) acrylate maleic acid esters, hydroxypropyl (meth) acrylate maleic acid esters, dicyclopentadiene maleic acid esters, polyfunctional (meth) acrylate having 1 carboxyl group and 2 or more (meth) acryloyl groups, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, methyl (meth) acrylate, butyl (meth) acrylate, tert-butyl (meth) acrylate, (meth) acrylate, N-cyclohexyl) acrylate, N-vinyl chloride, N-allyl methacrylate, maleic anhydride.

As the epoxidized polyolefin, commercially available products such as EPOLEAD PB3600 and EPOLEAD PB4700 (manufactured by Daicel corporation); BF-1000, FC-3000 (manufactured by ADEKA Co., Ltd.); BONDFAST 2C, BONDFAST E, BONDFAST CG5001, BONDFAST CG5004, BONDFAST 2B, BONDFAST 7B, BONDFAST7L, BONDFAST 7M, BONDFAST VC40 (manufactured by Sumitomo chemical Co., Ltd.); JP-100 and JP-200 (manufactured by Nippon Caoda Co., Ltd.); poly bd R-45HT, Poly bd R-15HT (manufactured by Shixinghe Co., Ltd.), and Ricon657 (manufactured by Arkema Co., Ltd.).

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

Examples of the oxetane compound include: 3, 7-bis (3-oxetanyl) -5-oxo-nonane, 1, 4-bis [ (3-ethyl-3-oxetanylmethoxy) methyl ] benzene, 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-oxetanylmeth) ether, 1, 4-bis (3-ethyl-3-oxetanylmethoxy) butane, 1, 3-bis (3-oxetanylmethoxy) ethane, 1, 3-bis [ (3-ethyl-3-oxetanylmethoxy) methyl ] ethane, 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, etc.

Examples of the vinyl ether compound 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-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, 1, 6-cyclohexanedimethanol monovinyl ether, ethylene glycol divinyl ether, 1, 4-butanediol divinyl ether, 1, 6-cyclohexanedimethanol divinyl ether, and the like.

The anionic polymerizable compound may have 1 or more polymerizable groups capable of anionic polymerization.

The anionic polymerizable compound is usually used together with an anionic polymerization initiator.

Examples of the polymerizable group capable of anionic polymerization include an epoxy group, a lactone group, and a (meth) acryloyl group.

That is, examples of the anionic polymerizable compound include an epoxy compound, a lactone compound, a compound having a (meth) acryloyl group, and the like.

Examples of the lactone compound include β -propiolactone and epsilon-caprolactone.

As the epoxy compound, the epoxy compounds exemplified as the above cationically polymerizable compound can be used. As the compound having a (meth) acryloyl group, the compounds exemplified as the above radical polymerizable compounds can be used.

The cationic polymerizable compound and the anionic polymerizable compound may be used alone or in combination of 2 or more.

(b) Polymer and method of making same

The weight average molecular weight (Mw) of the polymer may be appropriately set according to the use of the composition, and may be, for example, 1500 or more, and may be 1500 or more and 300000 or less.

The polymer has no polymerizable group.

Such a polymer may contain a repeating structure, and examples thereof include a photosensitive resin having photosensitivity, a non-photosensitive resin having no photosensitivity, and the like.

The composition can be used as a photosensitive composition by containing a photosensitive resin as a resin component, for example.

(i) Photosensitive resin

The photosensitive resin has photosensitivity, and examples thereof include: a normal resin used together with an acid generator, which changes its solubility in a developer in a direction of increasing the solubility in the developer by cutting chemical bonds such as ester groups and acetal groups by the action of an acid.

The composition contains a normal resin as a resin component, and thus the solubility of the light-irradiated site in an alkali developing solution is increased.

Therefore, the composition can be used as a photosensitive composition whose solubility in a solvent such as an alkali developer changes before and after light irradiation, and more specifically, as a positive type composition.

As the positive type resin, a resin in which a high molecular polymer is partially substituted with an acid-labile group having an alkali dissolution controlling ability can be used.

Examples of the polymer include polyhydroxystyrene and derivatives thereof; polyacrylic acid and derivatives thereof; polymethacrylic acid and derivatives thereof; 2 or more copolymers selected from hydroxystyrene, acrylic acid, methacrylic acid and derivatives thereof; 2 or more copolymers selected from hydroxystyrene, styrene and derivatives thereof; a copolymer of 3 or more selected from the group consisting of cycloolefin and its derivative, maleic anhydride, and acrylic acid and its derivative; a copolymer of 3 or more selected from the group consisting of cycloolefins and derivatives thereof, maleimides, and acrylic acid and derivatives thereof; polynorbornene; and 1 or more kinds of high-molecular polymers selected from the group consisting of metathesis ring-opening polymers.

Examples of the acid-labile group introduced into the polymer include: tertiary alkyl groups, trialkylsilyl groups, oxoalkyl groups, aryl-substituted alkyl groups, heterocyclic groups such as tetrahydropyran-2-yl groups, tertiary alkylcarbonyl groups, tertiary alkylcarbonylalkyl groups, alkoxycarbonyl groups, and the like.

Specific examples of the positive resin may be the same as those described in, for example, Japanese patent application laid-open Nos. 2003-192665, 2004-323704, claim 3, and 10-10733.

As the acid generator used together with the normal resin, a known acid generator can be used. Specific examples of the acid generator include a photo cation polymerization initiator and a thermal cation polymerization initiator, which will be described later.

(ii) Non-photosensitive resin

The non-photosensitive resin may be any resin as long as it does not have photosensitivity, and examples thereof include polystyrene, polymethyl methacrylate, a methyl methacrylate-ethyl acrylate copolymer, poly (meth) acrylic acid, a styrene- (meth) acrylic acid copolymer, a (meth) acrylic acid-methyl methacrylate copolymer, an ethylene-vinyl chloride copolymer, an ethylene-vinyl copolymer, a polyvinyl chloride resin, an ABS resin, nylon 6, nylon 66, nylon 12, a urethane resin, a polycarbonate polyvinyl butyral, a cellulose ester, a polyacrylamide, a saturated polyester, a phenol resin, a phenoxy resin, a polyamideimide resin, a polyamic acid resin, and an epoxy resin.

The non-photosensitive resin may be a polymer of the polymerizable compound.

(iii) Polymer and method of making same

(c) Resin component

The content of the resin component may be appropriately set according to the use of the composition, and for example, may be 1 to 99 parts by mass, preferably 10 to 90 parts by mass, and particularly preferably 20 to 80 parts by mass, based on 100 parts by mass of the solid content of the composition. This is because, for example, the composition can stably retain the compound I-1 by setting the content to the above range.

The content of the resin component may be appropriately set according to the use of the composition, and for example, may be 1 part by mass or more and 99 parts by mass or less, preferably 10 parts by mass or more and 90 parts by mass or less, and particularly preferably 40 parts by mass or more and 80 parts by mass or less in 100 parts by mass of the composition. This is because, when the content is in the above range, the composition can be used as a negative composition having excellent sensitivity, for example. This is because a composition which has less curing inhibition and can easily impart antioxidant ability to a cured product can be provided.

The content of the resin component varies depending on the use of the composition and the like, but is preferably 1 part by mass or more and 99.9 parts by mass or less, preferably 50 parts by mass or more and 99.7 parts by mass or less, particularly preferably 80 parts by mass or more and 99.5 parts by mass or less, and more preferably 90 parts by mass or more and 98 parts by mass or less, in total 100 parts by mass of the compound I-1 and the resin component. This is because, when the content is in the above range, the composition can provide a composition which can easily impart antioxidant ability and the like to a cured product.

The content of the compound I-1 and the resin component may be appropriately set according to the use of the composition, and for example, may be 1 part by mass or more and 99 parts by mass or less, preferably 10 parts by mass or more and 90 parts by mass or less, and particularly preferably 40 parts by mass or more and 80 parts by mass or less in 100 parts by mass of the composition. This is because, when the content is in the above range, the composition can be used as a negative composition having excellent sensitivity, for example. This is because a composition which has less curing inhibition and can easily impart antioxidant ability to a cured product can be provided.

The kind of the resin component may be only 1 kind, or may be a combination of 2 or more kinds.

The resin component may be a resin component containing only one of the polymerizable compound and the polymer or a resin component containing both of them.

When the resin component contains both a polymerizable compound and a polymer, the content of the polymerizable compound may be appropriately set according to the use of the composition, and for example, may be 1 part by mass or more and 99 parts by mass or less based on 100 parts by mass of the total of the polymerizable compound and the polymer.

(2) Polymerization initiator

The polymerization initiator is contained as a curable component, and is usually used together with a polymerizable compound and the like.

The polymerization initiator may be any polymerization initiator capable of polymerizing the polymerizable compound, and examples thereof include a photopolymerization initiator capable of polymerizing the polymerizable compound by being irradiated with light, and a thermal polymerization initiator capable of polymerizing the polymerizable compound by being heated.

(a) Photopolymerization initiator

The photopolymerization initiator may be any photopolymerization initiator that can polymerize the polymerizable compound by irradiation with light, and examples thereof include a radical photopolymerization initiator, a cationic photopolymerization initiator, and an anionic photopolymerization initiator.

The photopolymerization initiator preferably contains a photo radical polymerization initiator from the viewpoint of effectively exerting the effect that the composition becomes a substance with little curing inhibition.

The photo radical polymerization initiator is not particularly limited as long as it is a photo radical polymerization initiator that generates radicals by light irradiation, and conventionally known compounds can be used.

Examples of the photo radical polymerization initiator include acetophenone compounds, benzil compounds, benzophenone compounds, thioxanthone compounds, and oxime ester compounds, which are preferable photo radical polymerization initiators.

Examples of the acetophenone-based compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 4' -isopropyl-2-hydroxy-2-methylpropiophenone, 2-hydroxymethyl-2-methylpropiophenone, 2-dimethoxy-1, 2-diphenylethan-1-one, p-dimethylaminoacetophenone, p-tert-butyldichloroacetophenone, p-tert-butyltrichloroacetophenone, p-azidobenzylideneacetophenone, 1-hydroxycyclohexylphenylketone, 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinoacetone-1, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, and, Benzoin, 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-propan-1-one.

Examples of the benzil compound include benzil and the like.

Examples of the benzophenone-based compound include benzophenone, methyl benzoylbenzoate, michler's ketone, 4' -bisdiethylaminobenzophenone, 4 '-dichlorobenzophenone, and 4-benzoyl-4' -methyldiphenyl sulfide.

Examples of the thioxanthone compound include thioxanthone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, and 2, 4-diethylthioxanthone.

Examples of the oxime compound include compounds represented by the following general formula (IV).

[ chemical formula 46]

(in the formula, R⁷¹And R⁷²Each independently represents a hydrogen atom, a cyano group, 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 heterocyclic group having 2 to 20 carbon atoms,

R⁷³and R⁷⁴Each independently represents a halogen atom, a nitro group, a cyano group, a hydroxyl group, a carboxyl group, R⁷⁵、OR⁷⁶、SR⁷⁷、NR⁷⁸R⁷⁹、COR⁸⁰、SOR⁸¹、SO₂R⁸²Or CONR⁸³R⁸⁴，R⁷³And R⁷⁴Sometimes bonded to each other to form a ring,

R⁷⁵、R⁷⁶、R⁷⁷、R⁷⁸、R⁷⁹、R⁸⁰、R⁸¹、R⁸²、R⁸³and R⁸⁴Each independently represents a carbon atomAn 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 heterocyclic group having 2 to 20 carbon atoms,

X³represents an oxygen atom, a sulfur atom, a selenium atom, CR⁸⁵R⁸⁶、CO、NR⁸⁷Or PR⁸⁸，

X⁴Represents a single bond or CO, or a salt thereof,

R⁸⁵、R⁸⁶、R⁸⁷and R⁸⁸Each independently represents 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 a 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, or may be substituted with-O-,

R⁷³and R⁷⁴Or each independently form a ring together with any of the adjacent benzene rings,

e1 represents an integer of 0 to 4,

e2 represents an integer of 0 to 5. )

As R in the above general formula (IV)⁷¹、R⁷²、R⁷⁵、R⁷⁶、R⁷⁷、R⁷⁸、R⁷⁹、R⁸⁰、R⁸⁵、R⁸⁶、R⁸⁷And R⁸⁸The alkyl group having 1 to 20 carbon atoms, aryl group having 6 to 30 carbon atoms, arylalkyl group having 7 to 30 carbon atoms, heterocyclic group having 2 to 20 carbon atoms and substituents thereof used in the above-mentioned step include the R group in the above-mentioned "1. Photoreleasable group B¹¹And the like, which satisfy a predetermined number of carbon atoms in the exemplified contents.

Examples of the oxime 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-octane-1-ketoxime-O-acetate, 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -ethane-1-ketoxime-O-benzoate, and 1- [ 9-n-butyl-6- (2-ethylbenzoyl) -9H-carbazol-3-yl ] -ethane-1- ketoxime-O-benzoate, ethanone-1- [ 9-ethyl-6- (2-methyl-4-tetrahydrofurylbenzoyl) -9H-carbazol-3-yl ] -1- (O-acetyloxime), ethanone-1- [ 9-ethyl-6- (2-methyl-4-tetrahydropyranoylbenzoyl) -9H-carbazol-3-yl ] -1- (O-acetyloxime), ethanone-1- [ 9-ethyl-6- (2-methyl-5-tetrahydrofurylbenzoyl) -9H-carbazol-3-yl ] -1- (O-acetyloxime), Carbazole oxime ester compounds having a carbazole structure such as ethanone-1- [ 9-ethyl-6- { 2-methyl-4- (2, 2-dimethyl-1, 3-dioxolanyl) methoxybenzoyl } -9H-carbazol-3-yl ] -1- (O-acetyloxime), and ethanone-1- [ 9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxybenzoyl) -9H-carbazol-3-yl ] -1- (O-acetyloxime).

As the oxime compound, for example, an indole oxime ester compound having an indole structure can be used.

Examples of indole oxime ester compounds include an oxime ester compound represented by the following general formula (V) described in international publication No. 2017/051680.

[ chemical formula 47]

(in the formula, R²⁰¹And R²⁰²Each independently represents R²¹¹、OR²¹¹、COR²¹¹、SR²¹¹、CONR²¹²R²¹³Or the CN group is selected from the group consisting of,

R²¹¹、R²¹²and R²¹³Each independently 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 heterocyclic group having 2 to 20 carbon atoms,

R²¹¹、R²¹²and R²¹³The hydrogen atoms of the radicals indicated are sometimes further substituted by R²²¹、OR²²¹、COR²²¹、SR²²¹、NR²²²R²²³、CONR²²²R²²³、NR²²²OR²²³、NCOR²²²OCOR²²³、NR²²²COR²²¹、OCOR²²¹、COOR²²¹、SCOR²²¹、OCSR²²¹、COSR²²¹、CSOR²²¹Hydroxy, nitro, CN, halogen atomA seed, or COOR²²¹The substitution is carried out by the following steps,

R²²¹、R²²²and R²²³Each independently 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 heterocyclic group having 2 to 20 carbon atoms,

R²²¹、R²²²and R²²³The hydrogen atom of the group shown is sometimes further substituted by a hydroxyl group, a nitro group, CN, a halogen atom, a hydroxyl group or a carboxyl group,

R²¹¹、R²¹²、R²¹³、R²²¹、R²²²and R²²³Methylene groups of the alkylene portion of the groups shown are sometimes replaced by-O-, -S-, -COO-, -OCO-, -OCOO-, -CONR²²⁴-、-NR²²⁴-、-NR²²⁴CO-、-NR²²⁴COO-、-OCONR²²⁴-, -SCO-, -COS-, -OCS-or-SCOO-substitution,

R²²⁴represents 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 heterocyclic group having 2 to 20 carbon atoms,

R²¹¹、R²¹²、R²¹³、R²²¹、R²²²、R²²³and R²²⁴The alkyl portion of the groups shown may have a branched side chain, and may be a cyclic alkyl group,

R²⁰³represents 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 heterocyclic group having 2 to 20 carbon atoms, R²⁰³The alkyl moiety of the group shown may have a branched side chain, may be a cyclic alkyl group, and R may be²⁰³And R²⁰⁷And R²⁰³And R²⁰⁸Sometimes together form a ring respectively,

R²⁰³the hydrogen atoms of the radicals indicated are sometimes further substituted by R²²¹、OR²²¹、COR²²¹、SR²²¹、NR²²²R²²³、CONR²²²R²²³、NR²²²OR²²³、NCOR²²²OCOR²²³、NR²²²COR²²¹、OCOR²²¹、COOR²²¹、SCOR²²¹、OCSR²²¹、COSR²²¹、CSOR²²¹A hydroxyl group, a nitro group, CN, a halogen atom, or COOR²²¹The substitution is carried out by the following steps,

R²⁰⁴、R²⁰⁵、R²⁰⁶and R²⁰⁷Each independently represents R²¹¹、OR²¹¹、SR²¹¹、COR²¹⁴、CONR²¹⁵R²¹⁶、NR²¹²COR²¹¹、OCOR²¹¹、COOR²¹⁴、SCOR²¹¹、OCSR²¹¹、COSR²¹⁴、CSOR²¹¹A hydroxyl group, CN or halogen atom, R²⁰⁴And R²⁰⁵、R²⁰⁵And R²⁰⁶And R²⁰⁶And R²⁰⁷Sometimes together form a ring respectively,

R²⁰⁴、R²⁰⁵、R²⁰⁶and R²⁰⁷The hydrogen atoms of the radicals indicated are sometimes further substituted by R²²¹、OR²²¹、COR²²¹、SR²²¹、NR²²²R²²³、CONR²²²R²²³、NR²²²OR²²³、NCOR²²²OCOR²²³、NR²²²COR²²¹、OCOR²²¹、COOR²²¹、SCOR²²¹、OCSR²²¹、COSR²²¹、CSOR²²¹Hydroxy, nitro, CN, halogen atom or COOR²²¹The substitution is carried out by the following steps,

R²¹⁴、R²¹⁵and R²¹⁶Represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms,

R²¹⁴、R²¹⁵and R²¹⁶The alkyl portion of the groups shown may have a branched side chain, and may be a cyclic alkyl group,

R²⁰⁸represents R²¹¹、OR²¹¹、SR²¹¹、COR²¹¹、CONR²¹²R²¹³、NR²¹²COR²¹¹、OCOR²¹¹、COOR²¹¹、SCOR²¹¹、OCSR²¹¹、COSR²¹¹、CSOR²¹¹A hydroxyl group, CN or a halogen atom,

n1 represents 0 or 1. )

As R in the above general formula (V)²⁰³、R²¹¹、R²¹²、R²¹³、R²¹⁴、R²¹⁵、R²¹⁶、R²²¹、R²²²、R²²³And R²²⁴The alkyl group having 1 to 20 carbon atoms, the aryl group having 6 to 30 carbon atoms, the arylalkyl group having 7 to 30 carbon atoms or the heterocyclic group having 2 to 20 carbon atoms used in the above-mentioned step include the R group in the item "1. Photoreleasable group B¹¹And the like, which satisfy a predetermined number of carbon atoms in the exemplified contents.

Examples of the other radical polymerization initiator include phosphine oxide compounds such as 2, 4, 6-trimethylbenzoyldiphenylphosphine oxide and titanocene compounds such as bis (cyclopentadienyl) -bis [2, 6-difluoro-3- (pyrrolyl-1-yl) ] titanium.

Examples of commercially available radical polymerization initiators include Adeka optomer N-1414, N-1717, N-1919, Adeka arkls NCI-831, NCI-930 (manufactured by ADEKA Co., Ltd.), IRGACURE184, IRGACURE369, IRGACURE651, IRGACURE907, IRGACURE OXE 01, IRGACURE OXE 02, OXE 03, OXE 04, IRGACURE784 (manufactured by BASF Co., Ltd.), TR-PBG-304, TR-PBG-305, TR-PBG-309, TR-PBG-314, and TR-PBG-327 (manufactured by Tronly Co., Ltd.).

These photo radical polymerization initiators may be used in combination of 1 or 2 or more depending on the desired properties.

The content of the photo radical polymerization initiator may be, for example, 0.001 to 20 parts by mass, preferably 0.1 to 30 parts by mass, and preferably 0.5 to 10 parts by mass, based on 100 parts by mass of the polymerizable compound, as long as the desired curability and photosensitivity can be imparted. This is because the above content provides a composition having excellent curability and dispersibility.

The photo cation polymerization initiator is not particularly limited as long as it is a compound capable of releasing a substance that initiates cation polymerization by irradiation with light, and a conventional compound may be used, and is preferably an onium salt that releases a lewis acid by irradiation with an energy ray, that is, a double salt or a derivative thereof. Typical examples of the compound include salts of cations and anions represented by the following general formula.

[A1]^r+[B1]^r-

The above cation [ A1]^r+Preferably, the onium salt has a structure represented by the following general formula.

[(R¹⁰¹)_f1Q]^r+

Further, here, R¹⁰¹An organic group having 1 to 60 carbon atoms and sometimes containing several atoms other than carbon atoms. f1 is an integer of 1 to 5. e number of R⁵⁸Each is independent, may be the same or different. In addition, R¹⁰¹At least 1 of them is preferably an organic group having an aromatic ring as described above. For example, there may be mentioned a phenyl group which may be substituted with an alkyl group, an alkoxy group, a hydroxyl group, a hydroxyalkoxy group, a halogen atom, a benzyl group, a thiophenoxy group, a 4-benzoylphenylthio group, a 2-chloro-4-benzoylphenylthio group or the like. Q is an atom or group of atoms selected from the group consisting of S, N, Se, Te, P, As, Sb, Bi, O, I, Br, Cl, F, N ═ N. In addition, the cation [ A1 ]]^r+When the valence of Q in (2) is Q, it is necessary that r ═ f1-Q be satisfied (where N ═ N is treated as valence 0).

In addition, an anion [ B1 ]]^r-Preferably a halide complex, the structure of which may be represented by the following general formula [ LX_f2]^r-And (4) showing.

Here, L is a metal or semimetal (metaloid) As a central atom of the halide complex, and B, P, As, Sb, Fe, Sn, Bi, Al, Ca, In, Ti, Zn, Sc, V, Cr, Mn, Co, and the like.

X_f2Is a halogen atom or a phenyl group which may be substituted with a halogen atom, an alkoxy group or the like. f2 is an integer of 3 to 7.

In addition, an anion [ B1 ]]^r-When the valence of L in (b) is p, r ═ f2-p must be satisfied.

As anions of the above formula [ LX_f2]^r-Tool (A)Specific examples thereof include tetrakis (pentafluorophenyl) borate, tetrakis (3, 5-difluoro-4-methoxyphenyl) borate, and tetrafluoroborate (BF)₄)^-Hexafluorophosphate radical (PF)₆)^-Hexafluoroantimonate (SbF)₆)^-Hexafluoroarsenate (AsF)₆)^-And hexachloroantimonate (SbCl)₆)^-And the like.

In addition, an anion [ B1 ]]^r-Anions of the structure represented by the following general formula can also be preferably used.

[LX_f2-1(OH)]^r-

L, X, f2 are the same as described above. Examples of other anions that can be used include perchlorate ion (ClO)₄)^-Trifluoromethyl sulfite ion (CF)₃SO₃)^-Fluorosulfonate ion (FSO)₃)^-Tosylate anion, trinitrobenzene sulfonate anion, camphorsulfonate, nonafluorobutanesulfonate, hexadecafluorooctansulfonate, tetraarylborate, tetrakis (pentafluorophenyl) borate, and the like.

In the present invention, among such onium salts, the use of the following aromatic onium salts (M) to (O) is particularly effective and preferable. Of these, 1 kind may be used alone, or 2 or more kinds may be used in combination.

(M) aryldiazonium salts such as phenyldiazonium hexafluorophosphate, 4-methoxybenzylazonylammonium hexafluoroantimonate and 4-methylbenzylazonylammonium hexafluorophosphate.

Diaryliodonium salts such as (N) diphenyliodonium hexafluoroantimonate, bis (4-methylphenyl) iodonium hexafluorophosphate, bis (4-tert-butylphenyl) iodonium hexafluorophosphate, and tricumyliodionium tetrakis (pentafluorophenyl) borate.

(O) a sulfonium salt of a sulfonium cation represented by the following group I or group II with hexafluoroantimonate ion, tetrakis (pentafluorophenyl) borate ion, or the like.

[ chemical formula 48]

< group I >

[ chemical formula 49]

< group II >

Further, as other preferable substances, there may be mentioned iron-arene complexes such as (η 5-2, 4-cyclopentadien-1-yl) [ (1, 2, 3, 4, 5, 6- η) - (1-methylethyl) benzene ] -iron-hexafluorophosphate, aluminum complexes such as tris (acetylacetonate) aluminum, tris (ethylacetonoacetate) aluminum, tris (salicylaldehyde) aluminum, and mixtures of silanols such as triphenylsilanol.

As the above-mentioned photo cation polymerization initiator, commercially available products can be used, and examples thereof include IRUGACURE261 (manufactured by BASF corporation), Adeka optomer SP-150, SP-151, SP-152, SP-170, SP-171, SP-172 (manufactured by ADEKA corporation), UVE-1014 (manufactured by General Electronics), CD-1012 (manufactured by Sartomer corporation), CI-2064, CI-2481 (manufactured by Nippon Cauda corporation), Uvacure1590, 1591(Daicel UCB), RACCYURE I-6990 (manufactured by UnionCardide corporation), BBI-103, MPI-103, TPS-103, MDS-103, DTS-103, NAT-103, and NDS-103 (manufactured by Midori chemical Co., Ltd.).

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

As the photo-anionic polymerization initiator, an initiator that generates a base by light can be used, and as the photo-anionic polymerization initiator, a known initiator can be used.

Examples of the photo-anionic polymerization initiator include acetophenone O-aroyl oxime (acetophenoneO) and nifedipine (nifedipine).

(b) Thermal polymerization initiator

The thermal polymerization initiator may be any thermal polymerization initiator capable of polymerizing the polymerizable compound by heating, and examples thereof include a thermal radical polymerization initiator, a thermal cationic polymerization initiator, and a thermal anionic polymerization initiator.

The thermal polymerization initiator preferably contains a thermal radical polymerization initiator from the viewpoint of effectively exerting the effect of suppressing the curing decrease.

As the thermal radical polymerization initiator, an initiator that generates radicals by heating may be used, and as the thermal radical polymerization initiator, a known initiator may be used.

Examples of the thermal radical polymerization initiator include azo compounds, peroxides, persulfates, and the like, which are preferable initiators.

Examples of the azo compound include 2, 2 '-azobisisobutyronitrile, 2' -azobis (methyl isobutyronitrile), 2 '-azobis-2, 4-dimethylvaleronitrile, and 1, 1' -azobis (1-acetoxy-1-phenylethane).

Examples of the peroxide include benzoyl peroxide, di-t-butylbenzoyl peroxide, t-butyl peroxypivalate, di (4-t-butylcyclohexyl) peroxydicarbonate, and the like.

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

As the thermal cationic polymerization initiator, an initiator that generates a cationic species or a lewis acid by heating may be used, and as the thermal cationic polymerization initiator, a known initiator may be used.

Specific examples of the thermal cationic polymerization initiator include salts such as sulfonium salts, thiophenium salts, tetrahydrothiophenium salts, benzylammonium, pyridinium salts, and hydrazinium salts; polyalkylpolyamines such as diethylenetriamine, triethylenetriamine and tetraethylenepentamine; alicyclic polyamines such as 1, 2-diaminocyclohexane, 1, 4-diamino-3, 6-diethylcyclohexane, and isophoronediamine; aromatic polyamines such as m-xylylenediamine, diaminodiphenylmethane and diaminodiphenylsulfone; a modified polyepoxy adduct produced by reacting the above polyamine with various epoxy resins such as glycidyl ethers such as phenyl glycidyl ether, butyl glycidyl ether, bisphenol a-diglycidyl ether and bisphenol F-diglycidyl ether, or glycidyl esters of carboxylic acids by a conventional method; amidated modified products produced by reacting the above-mentioned organic polyamines with carboxylic acids such as phthalic acid, isophthalic acid and dimer acid by a conventional method; a mannich-modified product produced by reacting the polyamine with an aldehyde such as formaldehyde and a phenol having at least 1 hydroformylation-reactive site in the core such as phenol, cresol, xylenol, tert-butylphenol, and resorcinol by a conventional method; an acid anhydride of a polycarboxylic acid (e.g., aliphatic dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, 2-methylsuccinic acid, 2-methyladipic acid, 3-methylglutaric acid, 2-methylsuberic acid, 3, 8-dimethyldecanedioic acid, 3, 7-dimethyldecanedioic acid, hydrogenated dimer acid and dimer acid; aromatic dicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid and naphthalenedicarboxylic acid; alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid; tricarboxylic acids such as trimellitic acid, trimers such as trimers and castor oil fatty acids; tetracarboxylic acids such as pyromellitic acid); dicyandiamide, imidazoles, carboxylic esters, sulfonic esters, and aminimides.

As the thermal cationic polymerization initiator, commercially available ones can be used, and examples thereof include Adeka optionCP-77, Adeka optionCP-66 (manufactured by ADEKA Co., Ltd.), CI-2639, CI-2624 (manufactured by Nippon Cauda Co., Ltd.), Saneid SI-60L, Saneid SI-80L, and Saneid SI-100L (manufactured by Sanxin chemical industries Co., Ltd.).

As the thermal anionic polymerization initiator, an initiator which generates a base by heat can be used, and as the thermal anionic polymerization initiator, a known 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, polythiol compounds, boron trifluoride-amine complexes, dicyanamide, and organic acid hydrazide.

(c) Content of polymerization initiator

The content of the polymerization initiator may be, for example, 0.1 part by mass or more and 30 parts by mass or less, and preferably 0.5 part by mass or more and 10 parts by mass or less, per 100 parts by mass of the solid content, as long as the desired curability and photosensitivity can be imparted. This is because the above content provides a composition having excellent curability and dispersibility.

The content of the polymerization initiator may be, for example, 0.001 to 20 parts by mass, preferably 0.1 to 30 parts by mass, and preferably 0.5 to 10 parts by mass, based on 100 parts by mass of the polymerizable compound, as long as the desired curability and photosensitivity can be imparted. This is because the above content provides a composition having excellent curability and dispersibility.

(3) Others

The other components may contain, in addition to the resin component and the polymerization initiator, a colorant, a solvent, a chain transfer agent, a sensitizer, a surfactant, a silane coupling agent, a melamine compound, and the like as needed.

In addition to these, as the other components, a thermal polymerization inhibitor such as hydroquinone, catechol, t-butyl catechol, phenothiazine, or the like; a plasticizer; an adhesion promoter; a filler; defoaming agents; leveling agent; a surface conditioner; antioxidants such as phenol antioxidants, phosphite antioxidants and thioether antioxidants other than the compounds represented by the above-mentioned compound I-1; an ultraviolet absorber; a dispersing aid; an anti-agglomerating agent; a catalyst; an effect-promoting agent; a crosslinking agent; thickeners and the like.

(a) Coloring agent

The colorant may be, for example, a dye or a pigment as long as it can impart a desired coloring to the composition or a cured product thereof.

As the dye, a compound having an absorption at 380 to 1200nm can be used, and examples thereof include: azo compounds, anthraquinone compounds, indigoid compounds, triarylmethane compounds, xanthene compounds, alizarin compounds, acridine compounds, stilbene compounds, thiazole compounds, naphthol compounds, quinoline compounds, nitro compounds, indamine compounds, oxazine compounds, phthalocyanine compounds, cyanine compounds, diimmonium compounds, cyanovinyl compounds, dicyanostyrene compounds, rhodamine compounds, perylene compounds, polyene lactam (polyene naphthaloctam) compounds, coumarin compounds, squarylium compounds, croconium compounds, spiropyran compounds, spirooxazine compounds, merocyanine compounds, oxonol compounds, styryl compounds, pyrylium compounds, rhodanine compounds, oxazolone compounds, phthalimide compounds, cinnoline compounds, naphthoquinone compounds, azaanthraquinone compounds, Dyes such as porphyrin compounds, azaporphyrin compounds, pyrromethene compounds, quinacridone compounds, diketopyrrolopyrrole compounds, indigo compounds, acridine compounds, azine compounds, azomethine compounds, aniline compounds, quinacridone compounds, quinophthalone compounds, quinoneimine compounds, iridium complex compounds, europium complex compounds, and the like, and a plurality of these may be mixed and used.

Examples of the pigment include nitroso compounds, nitro compounds, azo compounds, diazo compounds, xanthene compounds, quinoline compounds, anthraquinone compounds, coumarin compounds, phthalocyanine compounds, isoindolinone compounds, isoindoline compounds, quinacridone compounds, anthanthrone compounds, perinone compounds, perylene compounds, diketopyrrolopyrrole compounds, thioindigo compounds, dioxazine compounds, triphenylmethane compounds, quinophthalone compounds, and naphthalenetetracarboxylic acids; metal complex compounds of azo dyes, cyanine dyes; a lake pigment; carbon black obtained by a furnace method, a tunnel method, a thermal method, or carbon black such as acetylene black, ketjen black, or lamp black; a pigment obtained by adjusting and coating the carbon black with an epoxy resin, a pigment obtained by dispersing the carbon black in a solvent in advance with a resin and adsorbing 20 to 200mg/g of the resin, a pigment obtained by subjecting the carbon black to an acidic or basic surface treatment, a carbon black having an average particle diameter of 8nm or more and a DBP oil absorption of 90ml/100g or less, a carbon black having a DBP oil absorption of 90ml/100g or less, a pigment obtained by volatilizing at 950 ℃CO and CO in the component (A)₂The calculated total oxygen amount is per 100m²Carbon black having a surface area of 9mg or more; graphite, graphitized carbon black, activated carbon, carbon fiber, carbon nanotube, carbon microcoil, carbon nanohorn, carbon aerogel, fullerene; nigrosine, pigment black 7, titanium black; inorganic pigments or organic pigments such as hydrophobic resins, chromium oxide green, milori blue, cobalt green, cobalt blue, manganese-based, ferrocyanide, phosphate ultramarine, prussian blue, ultramarine, chromium green, emerald green, lead sulfate, chrome yellow, zinc yellow, iron oxide red (red iron oxide (III)), cadmium red, synthetic iron black, and umber. These pigments may be used alone or in combination of two or more.

As the inorganic pigment or the organic pigment, commercially available pigments may be used, and for example, pigment red 1,2, 3, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48, 49, 88, 90, 97, 112, 119, 122, 123, 144, 149, 166, 168, 169, 170, 171, 177, 179, 180, 184, 185, 192, 200, 202, 209, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, 254; pigment orange 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, 125, 126, 127, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 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, etc.

The content of the colorant may be 0.01 part by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the solid content of the composition.

The content of the colorant may 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(s)

The solvent may be any solvent as long as it can dissolve or disperse the above components, and examples thereof include ketones such as methyl ethyl ketone, methyl amyl ketone, diethyl ketone, acetone, methyl isopropyl ketone, methyl isobutyl ketone, cyclohexanone, and 2-heptanone; ether solvents such as diethyl ether, dioxane, tetrahydrofuran, 1, 2-dimethoxyethane, 1, 2-diethoxyethane, and dipropylene glycol dimethyl ether; ester-based solvents such as methyl acetate, ethyl acetate, n-propyl acetate, 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 methanol, ethanol, iso-or n-propanol, iso-or n-butanol, pentanol, diacetone alcohol, etc.; ether ester solvents such as ethylene glycol monomethyl acetate, ethylene glycol monoethyl acetate, propylene glycol-1-monomethyl ether-2-acetate (PGMEA), dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, ethoxyethyl propionate, 1-tert-butoxy-2-propanol, 3-methoxybutyl acetate, and cyclohexanol acetate; BTX solvents such as benzene, toluene, and xylene; aliphatic hydrocarbon solvents such as hexane, heptane, octane and cyclohexane; terpene-based hydrocarbon oils such as turpentine, D-limonene and pinene; paraffin solvents such as mineral spirits, Swasol #310(Cosmo Songshan oil Co., Ltd.), Solvesso #100(Exxon chemical Co., Ltd.); halogenated aliphatic hydrocarbon solvents such as carbon tetrachloride, chloroform, trichloroethylene, methylene chloride and 1, 2-dichloroethane; halogenated aromatic hydrocarbon solvents such as chlorobenzene; carbitol solvent, aniline, triethylamine, pyridine, acetic acid, acetonitrile, carbon disulfide, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, water, and the like, and a mixed solvent of 1 or 2 or more of these solvents can be used.

The content of the solvent varies depending on the application of the composition, but may be 1 part by mass or more and 99 parts by mass or less, and preferably 10 parts by mass or more and 70 parts by mass or less, in 100 parts by mass of the composition. This is because the coating property and the like are easily made excellent.

(c) Chain transfer agent and sensitizer

The chain transfer agent and the sensitizer may be those capable of adjusting the sensitivity of the composition, and are generally usedA compound containing a sulfur atom. Examples thereof include: thioglycolic acid, thiomalic acid, thiosalicylic acid, 2-mercaptopropionic acid, 3-mercaptobutyric acid, N- (2-mercaptopropionyl) glycine, 2-mercaptonicotinic acid, and 3- [ N- (2-mercaptoethyl) carbamoyl group]Propionic acid, 3- [ N- (2-mercaptoethyl) amino group]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-mercaptoethylamine, 2-mercaptoimidazole, 2-mercaptobenzimidazole, 2-mercapto-3-pyridinol, 2-mercaptobenzothiazole, mercaptoacetic acid, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), and other mercapto compounds, disulfide compounds obtained by oxidizing the mercapto compounds, and mixtures thereof, Iodinated alkyl compounds such as iodoacetic acid, iodopropionic acid, 2-iodoethanol, 2-iodoethanesulfonic acid, and 3-iodopropanesulfonic acid, aliphatic polyfunctional thiol compounds such as trimethylolpropane tris (3-mercaptoisobutyrate), butanediol bis (3-mercaptoisobutyrate), hexanedithiol, decanedithiol, 1, 4-dimethylmercaptobenzene, butanediol dithiopropionate, butanediol dithioglycolate, ethylene glycol dithioglycolate, trimethylolpropane trithioglycolate, butanediol dithiopropionate, trimethylolpropane trithiopropionate, trimethylolpropane trithioglycolate, pentaerythritol tetrathiopropionate, pentaerythritol tetrathioglycolate, trihydroxyethyl trithiopropionate, the following compounds No. C1, tris (2-hydroxyethyl) isocyanurate of trimercaptopropionic acid, and the like, and mixtures thereof, Karenz MT BD1, PE1, NR manufactured by Showa Denko K.K¹And the like.

[ chemical formula 50]

Compound No. C1

(d) Surface active agent

As the surfactant, a surfactant capable of improving dispersion stability, coating property, and the like of the composition can be used, and a fluorinated surfactant such as perfluoroalkyl phosphate ester and perfluoroalkyl carboxylate, an anionic surfactant such as higher fatty acid alkali salt, alkylsulfonate, and alkylsulfate, a cationic surfactant such as higher amine halide and quaternary ammonium salt, a nonionic surfactant such as polyethylene glycol alkyl ether, polyethylene glycol fatty acid ester, sorbitan fatty acid ester, and fatty acid monoglyceride, an amphoteric surfactant, a silicone surfactant, and the like can be used in combination.

(e) Silane coupling agent

The 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, and a silane coupling agent capable of improving adhesion and the like of a composition or a cured product thereof can be used. As the silane coupling agent, for example, a silane coupling agent manufactured by shin-Etsu chemical Co., Ltd can be used, and among them, silane coupling agents having an isocyanate group, a methacryloyl group, and an epoxy group such as KBE-9007, KBM-502, and KBE-403 can be preferably used.

(f) Melamine compound

As the melamine compound, compounds capable of improving curability can be used, and examples thereof include active methylol groups (CH) in nitrogen compounds such as (poly) methylolmelamine, (poly) methylolglycoluril, (poly) methylolbenzoguanamine, and (poly) methylolurea₂OH groups) or a part (at least 2) of them by alkyl etherification. Here, examples of the alkyl group constituting the alkyl ether include a methyl group, an ethyl group and a butyl group, and they may be the same as each other or different from each other. In addition, a methylol group not subjected to alkyl etherification may be self-condensed in one molecule or may be condensed between two molecules, resulting in formation of an oligomer component. Specifically, hexamethoxymethylmelamine, hexabutoxymethylmelamine, tetramethoxymethylglycoluril, tetrabutoxymethylglycoluril, or the like can be used. Among them, alkyl-etherified melamines such as hexamethoxy methyl melamine and hexabutoxy methyl melamine are preferable.

3. Composition comprising a metal oxide and a metal oxide

The viscosity of the composition may be, for example, 200mPa · s or less, or 1mPa · s or more and 200mPa · s or less, from the viewpoint of forming a composition having coatability. This is because the composition is excellent in coatability.

The above viscosity means a viscosity according to JIS Z8803: 2011A rotational viscometer (e.g., Physica MCR manufactured by Anton Paar Co., Ltd.) is used³01, etc.) of the measurement. In the present specification, the treatment and measurement without specifying the temperature may be performed at 25 ℃.

The method for producing the composition may be any method as long as the components can be mixed in a desired content, and the components may be added and mixed at the same time or sequentially.

The composition can be used in thermosetting paint, photocurable paint or varnish, thermosetting adhesive, photocurable adhesive, printed circuit board, color filter in color display liquid crystal display panel such as color television, PC monitor, portable information terminal, digital camera, etc., color filter of CCD image sensor, photo spacer, black column spacer, electrode material for plasma display panel, touch sensor, powder coating, printing ink, printing plate, adhesive, dental composition, resin for stereolithography, gel coat, photoresist for electronic engineering, plating resist, etching resist, both liquid and dry film, solder resist, resist for manufacturing color filter for various display applications or resist for forming structure in manufacturing process of plasma display panel, electroluminescence display device and LCD, manufacturing method of liquid crystal display panel, liquid crystal display device and LCD, liquid crystal display device, liquid crystal, The composition for encapsulating electric and electronic components, solder resist, magnetic recording material, micromachine component, waveguide, optical switch, plating mask, etching mask, color test system, glass fiber cable coating, stencil for screen printing, material for producing three-dimensional object by stereolithography, hologram recording material, image recording material, fine electronic circuit, decoloring material for image recording material using microcapsule, photoresist material for printed wiring board, photoresist material for UV and visible laser direct image system, photoresist material used in dielectric layer formation in successive lamination of printed circuit board, photoresist material for 3D mounting, protective film and the like, and the use thereof is not particularly limited.

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 contains the compound and a polymerizable compound.

According to the present invention, the composition is used, and therefore, the composition is easily cured and can easily impart antioxidant ability and the like.

The cured product of the present invention uses the above composition.

The cured product of the present invention will be described in detail below.

The composition contains the compound I-1 and a polymerizable compound.

The composition may contain components other than the compound I-1 and the polymerizable compound.

The contents of the components of such a composition may be the same as those described in the section "2. other components" of the above "c.

The compound I-1 contained in the composition may be either before or after the removal of the photocleavable group B in the cured product, but is preferably after the removal. This is because the cured product has excellent oxidation resistance.

The cured product usually contains a polymer of a polymerizable compound.

The residual amount of the polymerizable compound contained in the cured product is appropriately set according to the use of the cured product, and is, for example, 10 parts by mass or less, preferably 1 part by mass or less, based on 100 parts by mass of the cured product.

The cured product may be a cured product substantially free of a solvent.

The content of the solvent contained in the cured product may be, for example, 1 part by mass or less and 0.5 part by mass or less with respect to 100 parts by mass of the cured product.

The modulus of elasticity of the cured product is usually higher than that of the composition, and may be set to 10, for example^-3M is 10MPa or more. This is because the cured product can stably hold the compound I-1 or the like by the elastic modulus.

The upper limit of the elastic modulus may be appropriately set according to the use of the cured product, and may be, for example, 10⁶MPa or less.

Hereinafter, the elastic modulus means a compression elastic modulus, and can be measured at 23 ℃ in accordance with JIS K7181.

For example, a test piece of a cube having a side length of 6mm may be prepared or cut out, and the measurement may be performed at a test speed of 1. + -. 0.2 mm/min in accordance with JIS K7181.

The method for producing the cured product may be any method as long as the composition can be cured, and may be, for example, the same as the method described in "method for producing cured product" described later.

The use of the cured product can be the same as that described in the section "c composition".

E. Composition comprising a metal oxide and a metal oxide

Next, the composition of the invention 2 will be described.

The composition 2 of the present invention is characterized by comprising a compound represented by the following general formula (I-2) and a desorbed product derived from a photodissociable group.

[ chemical formula 51]

According to the present invention, the composition of the 2 nd above can be easily formed using the above composition, for example. In addition, the composition of item 2 can easily impart antioxidant ability and the like.

The composition 2 of the present invention has the compound I-2 and the compound B'.

The composition 2 of the present invention will be described in detail below.

1. Compound I-2

The compound I-2 exerts antioxidant ability.

The above-mentioned compound I-2 is a compound wherein the above-mentioned B-O-is substituted with an-OH group in the above-mentioned compound I-1.

The contents of the compound I-1 may be the same as those described in the section "A. Compound", and therefore, the description thereof will be omitted.

The content of the compound I-2 in the composition may be the same as that of the solid component of the compound I-1 described in the section "C.

2. Compound B'

The compound B' is a desorbed product derived from a photodissociable group.

The photodetachment group may be any group capable of bonding to a phenolic hydroxyl group as a protective group, and may be the same as described in "1. photodetachment group B" of the above "a. compound".

The compound B' may be any compound that can be obtained by removing the photocleavable group from the phenolic hydroxyl group.

The photocleavable group B after cleavage from the phenolic hydroxyl group is generally highly reactive and can have various structures.

When the photo-dissociable group B is a group represented by the general formula (B-1-a), (B-2), (B-3), (B-4), (B-5), (B-6), (B-7), etc., the compound B' may include, for example, compounds represented by the following general formulae (B-111-a), (B-112), (B-113), (B-114), (B-115), (B-116), (B-117), etc.

[ chemical formula 52]

With respect to R contained in the above-mentioned compound B¹¹、R¹²、R¹³、R¹⁴、R¹⁵、R¹⁶、R¹⁷、R¹⁸、R¹⁹、R²⁰、R²¹、R²²、R²³、R²⁴、R²⁵、R²⁶And R²⁷And b1, b2, b3, b4, b5, b6, b7, and b8 may be the same as those described in the above "compound a" item, and therefore, the description thereof is omitted here.

The kinds of the above-mentioned compounds B' may be only 1 kind, or may be a combination of 2 or more kinds.

The compound B' may contain 1 kind of the source of the light-releasing group B, or may contain 2 or more kinds of the source of the light-releasing group B.

3. Others

The composition 2 contains the compound I-2 and the compound B', but usually contains other components.

Examples of such other components include those described in the section "2. other components" of the above "c.

The other component particularly preferably contains a resin component, and particularly preferably contains a polymer having no polymerizable group such as a polymer containing a polymerizable compound. This is because the composition 2 can effectively exhibit an effect of easily imparting antioxidant ability and the like to a cured product, for example.

The kind of the resin component may be only 1 kind, or 2 or more kinds may be used in combination.

The composition 2 may be a composition having coatability and containing a solvent, a polymerizable compound, or the like, and the viscosity in this case may be the same as that described in the above "c.

When the composition 2 is a cured product of a polymer containing a polymerizable compound, the elastic modulus of the composition 2 may be the same as that described in the section "d cured product".

The use of the composition 2 can be the same as that described in the section "D cured product".

The method for producing the composition 2 may be any method as long as it is capable of producing a composition containing the above-mentioned components, and for example, a method of irradiating a cured product of a composition containing the compound I-1 or a composition thereof with light may be used.

As for the method for producing a cured product of the composition, the method for irradiating light, and the like, the same methods as those described in the section "method for producing a cured product" to be described later can be used.

F. Method for producing cured product

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

The method for producing a cured product of the present invention comprises a step of curing a composition containing the compound I-1 of the present invention and a polymerizable compound to form a cured product, and a step of irradiating the cured product with light to remove the photocleavable 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 oxidation resistance and the like can be easily produced.

The production method of the present invention includes a step of forming a cured product and a step of releasing the cured product. Hereinafter, each step will be described in detail.

1. Step of Forming cured product

The step of forming the cured product is a step of forming a cured product of the composition.

The method of forming a cured product of the composition in this step may be any method that can form a cured product having a desired hardness, and may vary depending on the components contained in the composition.

As the curing method, for example, in the case where the composition contains a polymerizable compound and a photopolymerization initiator as a polymerization initiator, a method of irradiating the composition with light to polymerize the polymerizable compounds with each other can be used.

The light to be irradiated to the composition may include light having a wavelength of 300nm to 450 nm.

Examples of the light source for the light irradiation include ultrahigh-pressure mercury, mercury vapor arc, carbon arc, and xenon arc.

As the light to be irradiated, laser light may be used. The laser light may be a laser light including light having a wavelength of 340 to 430 nm.

As the light source of the laser, a light source emitting light in the visible to infrared region, such as an argon ion laser, a helium neon laser, a YAG laser, or a semiconductor laser, may be used.

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

The total amount of the irradiated light is preferably an amount of light capable of suppressing the desorption of the photodetachment group B, and may be set to less than 1000mJ/cm, for example²Can be set to 800mJ/cm²The thickness is set to 500mJ/cm²The following.

As the curing method, for example, in the case where the composition contains a polymerizable compound and a thermal polymerization initiator as a polymerization initiator, a method of polymerizing the polymerizable compounds with each other by heating the composition can be used.

The heating temperature is not particularly limited as long as it is a heating temperature at which the composition can be stably cured, and may be 60 ℃ or higher, and preferably 100 ℃ or higher and 300 ℃ or lower.

The heating temperature may be the temperature of the coating film surface of the composition.

The heating time may be about 10 seconds to 3 hours.

The curing method may be of a type including only 1 kind, or may include 2 or more kinds.

The composition used in this step comprises the above-mentioned compound I-1 and a polymerizable compound.

The composition may contain other components than the compound I-1 and the polymerizable compound.

The contents of the components of such a composition may be the same as those described in the above "c. composition" item "2. other components", and therefore, the description thereof will be omitted.

2. Step of detachment

The step of removing is a step of removing the photodissociable group B contained in the compound I-1.

The method for removing the photo-cleavable group B contained in the compound I-1 may be any method as long as the cured product is irradiated with light.

The amount of light and the total amount of light to be irradiated to the cured product are not particularly limited as long as the light and the total amount of light are capable of releasing the light-releasing group B, and may be the same as those described in the above item "1. light-releasing group B".

The light source for light irradiation may be appropriately selected according to the wavelength of light to be irradiated, and may be, for example, the same as described in the above section "1. step of forming cured product".

The temperature of the cured product in this step may be appropriately set according to the heat resistance of the cured product or the substrate supporting the cured product, and is, for example, preferably 200 ℃ or lower, preferably 0 ℃ or higher and 150 ℃ or lower, and particularly preferably 0 ℃ or higher and 100 ℃ or lower. This is because the above temperature is in the above range, so that the light-leaving group B can be easily removed. As a result, for example, damage to the cured product, the peripheral members such as the base material, and the like due to heating can be reduced.

The temperature of the cured product may be the temperature of the surface of the cured product.

3. Other procedures

The above-mentioned production method includes a step of forming a cured product and a step of releasing the cured product, but may include other steps as necessary.

Examples of the other step include a step of applying the composition to a substrate.

As a method for coating the composition, known methods such as a spin coater, roll coater, bar coater, die coater, curtain coater, various printing, dipping, and the like can be used.

The base material may be appropriately set according to the use of the cured product, and examples thereof include soda glass, quartz glass, semiconductor substrates, metals, paper, and plastics.

The cured product may be used after being peeled from a substrate after being formed on the substrate, or may be used after being transferred from the substrate to another adherend.

4. Others

The cured product produced by the above production method, the use thereof, and the like may be the same as those described in the above "d.

The present invention is not limited to the above embodiments. The above-described embodiments are illustrative, and any embodiments having substantially the same configuration as the technical idea described in the claims of the present invention and having the same operational effects are included in the technical scope of the present invention.

Examples

The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

The various measurements were carried out according to the following methods.

[ example 1]

0.003mol of a phenol compound in the following scheme 1, 0.0062mol of potassium carbonate and DMF10g were mixed, 0.0075mol of o-nitrobenzyl chloride was added dropwise at room temperature under a nitrogen atmosphere, and stirred for 10 hours to obtain a compound I-1-161 represented by the following general formula (I-1-161) corresponding to the compound I-1 by the following reaction. 50g of ethyl acetate and 50g of ion-exchanged water were added to the reaction mixture to conduct oil-water separation. After the organic layer was dried over anhydrous sodium sulfate, the solvent was distilled off, and the residue was separated by a silica column (hexane: ethyl acetate 9: 1). After separation, the solid was washed with methanol, and the obtained white solid was dried at 40 ℃ under reduced pressure for 2 hours to obtain the objective compound. The obtained white solid was confirmed by H-NMR to be the objective substance.

[ chemical formula 53]

Scheme 1

TABLE 1

[ evaluation ]

A0.01 mass% acetonitrile solution of the compound I-1 (the compound I-1-161) was prepared and placed in a 1cm square quartz cell. The ultra-high pressure mercury lamp UL750 (manufactured by HOYA) was adjusted to 20mW/cm²Irradiating the solution-filled quartz cell with a radiation of 100mJ/cm²、3000mJ/cm²、10000mJ/cm²The amount of light of (c).

The irradiated liquid was analyzed by High Performance Liquid Chromatography (HPLC), and the desorption ratio was calculated from the following equation. The results are shown in table 2 below.

In the HPLC analysis, when all of the 230nm peak derived from Compound I-1 disappeared, the calculation was performed assuming 100% dissociation.

Separation rate (%) ═ phenol compound (compound I-2)/phenol compound (compound I-2) + compound I-1) × 100

TABLE 2

Exposure (mJ/cm)²)	Separation Rate (%)
		100	4.4
3000	84.6
		10000	100

As can be seen from Table 2, compound I-1 was irradiated with light to release the photodefinable group B.

As a result, it was confirmed that the compound I-1 can impart antioxidant ability to a cured product by light irradiation.

Further, it was confirmed that the phenolic hydroxyl group of the compound I-1 was protected by the photodetachment group B before the light irradiation, and the curing inhibition could be suppressed.

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 represent the following compounds. The numerical values in the table represent parts by mass.

A-1: radical polymerizable Compound (NKoligo EA-1020 (bisphenol A epoxy acrylate) manufactured by Ningmura chemical industries, Ltd.)

A-2: radically polymerizable Compound (KAYARAD DPHA (mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate, manufactured by Nippon Chemicals Co., Ltd.))

B-1: IRGACURE907 (radical polymerization initiator) manufactured by BASF corporation

C-1: silane coupling agent KBE-403 manufactured by shin-Etsu chemical industries Ltd

D-1: 2-butanone (solvent)

E-1: a compound represented by the following formula (1) (antioxidant)

F-1: compound I-1-161 (Compound I-1)

[ chemical formula 54]

The obtained compositions of example 2 and comparative examples 1 and 2 were evaluated for curability and heat resistance by the following methods.

[ curability ]

The compositions of example 2 and comparative examples 1 and 2 were applied to a thickness of about 3 μm using a bar coaterOn a PET film. Next, after prebaking at 80 ℃ for 3 minutes, exposure was carried out using an ultra-high pressure mercury lamp (UL750) as a light source (20 mW/cm)²). The exposure light amount was 500mJ/cm²Is carried out in the manner of (1). In this case, in order to measure the light sensitivity, a negative film (step table) in which the optical density is set to 1 st and the optical density is increased by 0.15 for each 1 st stage) was used, which was prepared so that the light transmittance was decreased stepwise. Subsequently, the resultant was washed with isopropyl alcohol (IPA) at 25 ℃ for 10 seconds to develop a film, and then dried at 80 ℃ for 30 minutes. Then, the photosensitivity was evaluated by measuring the number of stages in the stepwise exposure table of the cured product formed on the PET film. The results are shown in table 4 below. The higher the number of stages in the stepwise exposure table, the higher the light sensitivity.

[ Heat resistance ]

The compositions of example 2 and comparative examples 1 and 2 were coated on a glass substrate using a spin coater, respectively. Next, after prebaking at 80 ℃ for 3 minutes, exposure was carried out using an ultra-high pressure mercury lamp (UL750) as a light source (20 mW/cm)²). The exposure light amount was 100mJ/cm²Is carried out in the manner of (1). Further irradiating at 3000mJ/cm²Samples for heat resistance evaluation were prepared. Subsequently, a heat resistance test was performed by heat-treating the sample for evaluation at 200 ℃ for 2 hours using an oven.

The difference in transmittance (%) at a wavelength of 430nm between before and after the heat resistance test of the sample for evaluation (transmittance (%) before the heat resistance test-transmittance (%) before the heat resistance test) was measured, and the heat resistance evaluation was performed according to the following criteria, and the results are shown in table 3 below.

○ the difference (%) in transmittance was less than 1% with respect to the transmittance before the heat resistance test.

X: the transmittance difference (%) was 1% or more with respect to the transmittance before the heat resistance test.

If the heat resistance evaluation of "○", show that the cured product of excellent heat resistance.

TABLE 3

	Example 2	Comparative example 1	Comparative example 2
				A-1	50	50	50
A-2	50	50	50
				B-1	5	5	5
C-1	1	1	1
				D-1	50	50	50
E-1			1
				F-1	1
Curing Properties	18	18	14
				Heat resistance	○	×	○

As is clear 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. The composition of example 2 was better in curability than the composition of comparative example 2 containing an antioxidant. Thus, it was found that the present invention provides a composition having less inhibition of curing and excellent antioxidant ability.

Industrial applicability

The compound of the present invention can provide a compound which is less likely to cause curing inhibition and can easily impart antioxidant ability to a cured product.

The latent antioxidant according to the present invention has less curing inhibition, and can easily impart antioxidant ability to a cured product.

The composition of the present invention can provide a composition which has little inhibition of curing and can give a cured product having excellent antioxidant ability.

According to the cured product of the present invention, a cured product having excellent antioxidant ability can be provided.

According to the production method of the present invention, a cured product having excellent oxidation resistance can be produced without causing curing inhibition.

The composition of claim 2 can provide a composition which does not cause curing inhibition and can give a cured product having excellent antioxidant ability.

Claims

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

wherein A represents an atomic group having an antioxidant ability, B represents a photo-dissociable group, and k represents an integer of 1 to 10.

2. The compound of claim 1, wherein,

b in the general formula (I-1) comprises at least 1 group in the groups shown in the following general formula (B-1), (B-2), (B-3), (B-4), (B-5), (B-6), (B-7), (B-8), (B-9) and (B-10),

in the formula, R¹¹、R¹³、R¹⁶、R¹⁸、R¹⁹、R²⁰、R²³、R²⁶And R²⁸Each 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, an arylalkyl group having 7 to 20 carbon atoms or a heterocyclic group having 2 to 20 carbon atoms,

R¹²、R¹⁴、R¹⁷、R²¹、R²²、R²⁴、R²⁵、R²⁷、R²⁹and R³⁰Each 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, an arylalkyl group having 7 to 20 carbon atoms or a heterocyclic group having 2 to 20 carbon atoms,

R¹¹、R¹²、R¹³、R¹⁴、R¹⁵、R¹⁶、R¹⁷、R¹⁸、R¹⁹、R²⁰、R²¹、R²²、R²³、R²⁴、R²⁵、R²⁶、R²⁷、R²⁸、R²⁹and R³⁰The methylene groups in the alkyl and arylalkyl groups shown may be interrupted by carbon-carbon double bonds, -O-, -S-, -CO-, -O-CO-, -CO-O-, -O-CO-O-, -S-CO-, -CO-S-, -S-CO-O-, -O-CO-S-, -CO-NH-, -NH-CO-O-, -NR' -, > P ═ O, -S-, -SO-, -₂-or a combination thereof,

the alkyl group, the aryl group, the arylalkyl group and the heterocyclic group may have a substituent,

r' represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms,

plural R¹¹Each other, a plurality of R¹³Each other, a plurality of R¹⁶Each other, a plurality of R¹⁸Each other, a plurality of R¹⁹Each other, a plurality of R²⁰Each other, a plurality of R²³Each other, a plurality of R²⁶Each and a plurality of R²⁸May be bonded to each other to form a benzene ring or a naphthalene ring,

plural R¹¹、R¹²、R¹³、R¹⁴、R¹⁶、R¹⁷、R¹⁸、R¹⁹、R²⁰、R²³、R²⁵、R²⁶、R²⁷、R²⁸、R²⁹And R³⁰May be the same or different from each other,

b4 and b5 each independently represent an integer of 0 to 5,

indicates a bonding position to the A-O-,

in the formula, R³¹And R⁴⁰Each 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, an arylalkyl group having 7 to 20 carbon atoms or a heterocyclic group having 2 to 20 carbon atoms,

R³¹、R³²、R³³、R⁴⁰、R⁴¹、R⁴²、R⁴³and R⁴⁴The methylene groups in the alkyl and arylalkyl groups shown may be interrupted by carbon-carbon double bonds, -O-, -S-, -CO-, -O-CO-, -CO-O-, -O-CO-O-, -S-CO-, -CO-S-, -S-CO-O-, -O-CO-S-, -CO-NH-, -NH-CO-O-, -NR' -, > P ═ O, -S-, -SO-, -₂-or a combination thereof,

c1 represents an integer of 0 to 5,

c2 represents an integer of 0 to 4,

indicates the bonding position to said a-O-.

3. The compound of claim 2, wherein,

the compound shown in the general formula (I-1) is a compound shown in the following general formula (A-1), general formula (A-2) or (A-3),

the photo-cleavable group B includes a group represented by the following general formula (B-1-a),

in the formula, R¹Represents 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 heterocyclic group having 2 to 20 carbon atoms,

R¹、R²、R³and R⁴The methylene group in the alkyl and arylalkyl groups used in (A) may be replaced by a carbon-carbon double bond, -O-, -S-, -CO-, -O-CO-, -CO-O-, -O-CO-O-, -S-CO-, -CO-S-, -S-CO-O-, -O-CO-S-, -CO-NH-, -NH-CO-O-, -NR' -, > P ═ O, -S-, -SO₂-or a combination thereof,

r' represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms,

plural R¹May be bonded to each other to form a benzene ring or a naphthalene ring,

plural R¹May be the same or different from each other,

m represents an integer of 1 to 10,

n represents an integer of 2 to 10,

a represents an integer of 0 to 2,

X¹represents a bonding group having a valence of m,

X²represents a bonding group of n-valent type,

in the formula, R¹¹Represents 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 carbon atomA heterocyclic group having a sub-number of 2 to 20,

R¹²each 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, an arylalkyl group having 7 to 20 carbon atoms or a heterocyclic group having 2 to 20 carbon atoms,

R¹¹and R¹²The methylene groups in the alkyl and arylalkyl groups shown may be interrupted by carbon-carbon double bonds, -O-, -S-, -CO-, -O-CO-, -CO-O-, -O-CO-O-, -S-CO-, -CO-S-, -S-CO-O-, -O-CO-S-, -CO-NH-, -NH-CO-O-, -NR' -, > P ═ O, -S-, -SO-, -₂-or a combination thereof,

r' represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms,

plural R¹¹May be bonded to each other to form a benzene ring or a naphthalene ring,

plural R¹¹And R¹²May be the same or different from each other,

b1 represents an integer of 0 to 4,

indicates the bonding position to said a-O-.

4. A latent antioxidant comprising a compound of any one of claims 1 to 3.

5. A composition comprising a compound of any one of claims 1-3.

6. A cured product of a composition comprising the compound according to any one of claims 1 to 3 and a polymerizable compound.

7. A method for producing a cured product, comprising the steps of:

a step of curing a composition containing the compound according to any one of claims 1 to 3 and a polymerizable compound to form a cured product; and

and irradiating the cured product with light to remove a light-releasing group contained in the compound.

8. 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 an atomic group having an antioxidant ability, and k represents an integer of 1 to 10.