CN111094256A

CN111094256A - Compound, latent ultraviolet absorber, composition, cured product, and method for producing cured product

Info

Publication number: CN111094256A
Application number: CN201880046837.6A
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: 2020-05-01
Also published as: KR20200064029A; TW202325698A; TW201922717A; JPWO2019069960A1; JP7393205B2; WO2019069960A1

Abstract

The present invention relates to a compound represented by the following general formula (I-1). (wherein A represents an atomic group having ultraviolet absorption ability, B represents a photo-leaving group, and k represents an integer of 1 to 10.) the present invention relates to a composition comprising a compound represented by the following general formula (I-2) and a leaving material derived from the photo-leaving group. (wherein A represents an atomic group having ultraviolet absorptivity, and k represents an integer of 1 to 10.)

Description

Compound, latent ultraviolet absorber, composition, cured product, and method for producing cured product

Technical Field

The present invention relates to a compound which is less inhibited from curing and can easily impart ultraviolet absorption ability or the like to a cured product.

Background

In order to improve the ultraviolet absorption ability or heat resistance of a curable composition, a method of adding an ultraviolet absorber or an ultraviolet absorber to a curable composition to stabilize the composition 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 ultraviolet absorbers described in patent documents 1 to 3 have a problem that curing of the curable composition may be inhibited.

In view of such problems, the present inventors have found that: the ultraviolet absorber has an action of absorbing light irradiated for curing the curable composition, and because of this action, when the ultraviolet absorber is added to a polymerization system, curing inhibition may occur.

As a means for solving the above problems, a latent additive is known which can activate the above-described action of absorbing light after curing without activating it in a polymerization system.

However, for activation of a latent additive capable of being activated after curing, heating or the like is sometimes required, and as a result, easier activation is sometimes required.

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 ultraviolet absorption ability and the like to a cured product.

As a result of earnest study to solve the above-mentioned problems, the present inventors have found that the above-mentioned problems can be solved by using a photo-leaving group as a protecting group and protecting a phenolic hydroxyl group contained in an ultraviolet absorbent with the photo-leaving group to easily adjust the timing of exhibiting ultraviolet absorbability, and have completed the present invention.

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

(wherein A represents an atomic group having ultraviolet absorption ability, B represents a photo-leaving group, and k represents an integer of 1 to 10.)

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

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

The present invention also provides a cured product of the composition containing the 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 photo-leaving 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 leaving compound derived from a photoleaving group (hereinafter, sometimes referred to as "compound B'").

(wherein A is an atomic group having ultraviolet absorptivity, and k is an integer of 1-10.)

Detailed Description

The present invention relates to a compound, and an ultraviolet absorber composition each using the same, a cured product thereof, a method for producing the cured product, and a composition No. 2. 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).

(wherein A is an atomic group having ultraviolet absorptivity, B is a photo-leaving group, and k is an integer of 1 to 10.)

The compound I-1 of the present invention is a compound having an ultraviolet-absorbing ability of the atomic group A. The compound I-1 of the present invention has a low ultraviolet absorption ability before leaving the photo-leaving group B, but exhibits an excellent ultraviolet absorption ability based on the atomic group A after leaving the photo-leaving group B.

Therefore, when the compound I-1 before leaving the leaving group B is added to a polymerization system, for example, the compound I-1 has low ultraviolet absorptivity, and therefore, the absorptivity of light irradiated for polymerization is low, and curing of the polymerization system is not easily inhibited.

On the other hand, the compound I-1 of the present invention exhibits excellent ultraviolet absorbability by irradiation of light with the leaving group of light being removed. Therefore, by irradiating a cured product containing the compound I-1 with light, the cured product can be easily imparted with ultraviolet absorbing ability. Since the compound I-1 does not need to be subjected to heat treatment for exhibiting its ultraviolet absorbing ability, it has an advantage that it is less likely to cause damage by heating to the cured product, the substrate, and other peripheral members.

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

Further, the compound I-1 of the present invention has low absorption ability of light irradiated for developing photosensitivity before leaving the leaving group B. Therefore, when the compound I-1 is added to a photosensitive composition in which the solubility in an alkaline developer changes by light irradiation, the photosensitivity can be stably expressed. Further, the compound I-1 can be easily imparted with ultraviolet absorbability or the like by irradiating the photosensitive composition with light capable of leaving a leaving group.

Thus, the compound I-1 has less inhibition of the expression of photosensitivity to the photosensitive composition, and can easily impart ultraviolet absorbability to the photosensitive composition.

Further, the compound I-1 of the present invention having the photo-leaving group B can easily adjust, for example, dispersion or dissolution stability in the composition.

By selecting the photo-leaving group B so as to improve the affinity with other components contained in the composition, the compound I-1 can impart excellent dispersibility in the composition.

Therefore, the compound I-1 can impart an excellent ultraviolet absorbing ability to the composition and also can impart excellent dispersion stability during storage before use.

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

1. Photo-leaving group B

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

The photo-leaving group in the present invention may be a group which can be removed 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 photo-leaving group B is removed from the compound I-1 to produce a compound containing a hydroxyl group and an atomic group A having ultraviolet absorbability represented by the following general formula (I-2).

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

The wavelength of light leaving the leaving group B from the compound I-1 is, for example, in the wavelength region of ultraviolet rays or visible rays. Specifically, the region may include 365nm, more specifically, 250nm to 450nm wavelength light, and preferably 280nm to 380nm wavelength light.

The cumulative quantity of light irradiated to remove the photo-leaving 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 the composition containing the polymerizable compound or the like may be usually less than 1000mJ/cm². Therefore, the cumulative light amount is within the above range, and thus, application to a photocurable composition, for example, is facilitated.

The leaving of the photoleaving group B may be any leaving that can impart a desired ultraviolet absorbing ability, and for example, the leaving ratio of the photoleaving group may be 50% or more, and particularly preferably 80% or more. This is because the application to the photocurable composition becomes easy.

On the other hand, the cumulative amount of light for inhibiting light leaving in the above-mentioned compound I-1 may be set to less than 1000mJ/cm as long as the desired effect of inhibiting curing inhibition can be obtained². This is because the application to the photocurable composition becomes easy.

The light-leaving inhibition is not particularly limited as long as a desired curing inhibition effect can be obtained, and for example, the leaving ratio of the light-leaving group B may be less than 50%, and particularly preferably 20% or less. This is because the application to the photocurable composition becomes easy.

The cumulative amount of light was measured by the same method as that for the leaving ratio described in examples, except that a 0.01 mass% acetonitrile solution of the compound I-1 was prepared.

Specific examples of the photo-leaving 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-leaving groups makes it possible to easily leave the compound I-1 and easily impart ultraviolet absorbability and the like to the cured product. As the photo-leaving group B satisfying the above requirements, specifically, there can be mentioned groups represented by the following general formulae (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 aralkyl 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 aralkyl 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 aralkyl 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 group in the alkyl group and the aralkyl group represented by the formula is sometimes represented 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-S-、-SO₂-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 R²⁶Each and a plurality of R²⁸Are 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 said 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 aralkyl group having 7 to 20 carbon atomsOr a heterocyclic group having 2 to 20 carbon atoms,

R³²、R³³、R⁴¹、R⁴²、R⁴³and 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 aralkyl 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 group in the alkyl group and the aralkyl group represented by the formula is sometimes represented 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-S-、-SO₂-or a combination thereof,

the alkyl group, the aryl group, the aralkyl group and the 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 said a-O-. )

As the above-mentioned R¹¹、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 cases¹¹Etc.) of 1 to 40 carbon atoms, and examples thereof include 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 groupAnd an isooctyl group, a tert-octyl group, an 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 aralkyl 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, pyrimidinyl, pyridazinyl, piperidyl, pyranyl, pyrazolyl, triazinyl, pyrrolyl, quinolyl, isoquinolyl, imidazolyl, benzimidazolyl, triazolyl, furyl (furyl), benzofuryl, thienyl, thiophenyl, benzothiophenyl, thiadiazolyl, thiazolyl, benzothiazolyl, oxazolyl, benzoxazolyl, isothiazolyl, isoxazolyl, indolyl, 2-pyrrolidone-1-yl, 2-piperidone-1-yl, 2, 4-dioxyimidazolidin-3-yl, and 2, 4-dioxyoxazolidin-3-yl groups.

Examples of the alkyl group having 1 to 8 carbon atoms represented by R' include R¹¹And the number of carbon atoms in the group exemplified by alkyl groups represented by the following formulae is 1 to 8.

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

Examples of the substituent which may be substituted for a hydrogen atom in an alkyl group, an aryl group, an aralkyl group, a heterocyclic group, and the like include: ethylenically unsaturated groups such as vinyl, allyl, acrylic and methacrylic groups; 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, o-hydroxybenzoyl, oxalyl, stearoyl, methoxycarbonyl, ethoxycarbonyl, t-butoxycarbonyl, n-octadecyloxycarbonyl, and carbamoyl; acyloxy groups such as acetoxy and benzoyloxy; amino, ethylamino, dimethylamino, diethylamino, butylamino, cyclopentylamino, 2-ethylhexylamino, dodecylamino, anilino, chlorophenylamino, toluidino, methoxyanilino, 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, 2-ethylhexylamino, dodecylamino, anilino, chlorophenylamino, tolylamino, tolylcarbonylamino, tolylamino, substituted amino groups such as sulfamoylamino, N-dimethylaminosulfonylamino, methanesulfonylamino, butanesulfonylamino, and benzenesulfonylamino; 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, the number of carbon atoms of a group is defined as the number of carbon atoms of the group after substitution when a hydrogen atom in the group is substituted with a substituent. For example, when the alkyl group having 1 to 40 carbon atoms is substituted with a hydrogen atom, the carbon number of 1 to 40 means the number of carbon atoms after the hydrogen atom is substituted, and does not mean the number of carbon atoms before the hydrogen atom is substituted.

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

R¹¹The methylene group in the alkyl group and aralkyl group used in the above-mentioned publication 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' -, or by a halogen atom,>P＝O、-S-S-、-SO₂-or a combination thereof.

In addition, a combination in which the methylene groups are substituted may be a combination under the condition that oxygen atoms are not adjacent.

R¹¹And the alkyl group having 1 to 40 carbon atoms represented by (a) or (b) may have a methylene group at the end of the base end substituted with-O-, thereby forming an alkoxy group. Examples of such an alkoxy group include alkoxy groups having 1 to 10 carbon atoms. Specific examples thereof include methoxy group, ethoxy group, isopropoxy group, butoxy group, sec-butoxy group, tert-butoxy group, isobutoxy group, pentyloxy group, isopentyloxy group, tert-pentyloxy group, hexyloxy group, 2-hexyloxy group, 3-hexyloxy group, cyclohexyloxy group, 4-methylcyclohexyloxy group, heptyloxy group, 2-heptyloxy group, 3-heptyloxy group, isoheptyloxy group, tert-heptyloxy group, 1-octyloxy group, isooctyloxy group and tert-octyloxy group.

R is as defined above¹¹、R¹³、R¹⁶、R¹⁸、R¹⁹、R²⁰、R²³、R²⁶And R²⁸Preferably a group other than a hydroxyl group, preferably 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 aralkyl group having 7 to 20 carbon atoms, a heterocyclic group having 2 to 20 carbon atoms, or the like. This is because, by setting the group to be other than a hydroxyl group, the photo-leaving group B becomes easy to leave from the compound I-1, and the synthesis of the compound I-1 becomes easy.

R is as defined above¹¹And R²³Particularly preferred are an alkoxy group having 1 to 10 carbon atoms such as a nitro group or a methoxy group, an alkyl group having 1 to 40 carbon atoms such as a methyl group, a halogen atom, and the like. This is because the photo-leaving group B becomes easy to leave from the compound I-1, and the synthesis of the compound I-1 becomes easy.

R is as defined above¹¹Preferably an alkoxy group having 1 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms or a halogen atom, more preferably an alkoxy group having 1 to 5 carbon atoms, an alkyl group having 1 to 5 carbon atoms or a halogen atom, still more preferably an alkoxy group having 1 to 5 carbon atoms or a halogen atom, and particularly preferably an alkoxy group having 1 to 3 carbon atoms, a chlorine atom or a bromine atom. This is because the photo-leaving group B becomes easy to leave 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 photo-leaving group B becomes easy to leave from the compound I-1, and the synthesis of the compound I-1 becomes easy.

R is as defined above¹⁶Preferably adjacent 2R¹⁶Are bonded to each other to form a benzene ring. This is because the photo-leaving group B becomes easy to leave from the compound I-1, and the synthesis of the compound I-1 becomes easy.

R is as defined above³¹And R⁴⁰Preferably a group other than a hydroxyl group, preferably a halogen atom, a cyano group, a carboxyl group, an alkyl group having 1 to 40 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, a heterocyclic group having 2 to 20 carbon atoms, or the like. This is because, by setting the group to be other than a hydroxyl group, the photo-leaving group B becomes easy to leave from the compound I-1, and the synthesis of the compound I-1 becomes easy.

R is as defined above³¹Preferably an alkyl group having 1 to 40 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, still more preferably an alkyl group having 1 to 5 carbon atoms, and particularly preferably an alkyl group having 1 to 3 carbon atoms.

R is as defined above¹⁸And R¹⁹When a methylene group in the alkyl group and the aralkyl group represented by the above is substituted with-O-, the methylene group may be substituted with-O-, that is, a methylene group other than the terminal of the alkyl group and the aralkyl group, so that the alkyl group and the aralkyl group are each interrupted.

R is as defined above¹²Preferably a hydrogen atom, a carboxyl group, a carbon atom1 to 5 alkyl groups, particularly preferably hydrogen atom or methyl group. This is because the photo-leaving group B becomes easy to leave from the compound I-1, and the synthesis of the compound I-1 becomes easy.

R is as defined above¹⁴、R¹⁷、R²¹、R²⁴、R²⁵、R²⁷、R²⁹And R³⁰Particularly preferred is a hydrogen atom or an alkyl group having 1 to 40 carbon atoms, and particularly preferred is a hydrogen atom. This is because the photo-leaving group B becomes easy to leave from the compound I-1, and the synthesis of the compound I-1 becomes easy.

R is as defined above¹⁵And R²²The alkyl group having 1 to 5 carbon atoms is preferable, and the methyl group is particularly preferable. This is because a compound which has little curing inhibition and can easily impart ultraviolet absorption ability to a cured product can be provided.

R is as defined above³²And R³³Each independently is preferably a hydrogen atom, a carboxyl group or an alkyl group having 1 to 5 carbon atoms, more preferably a hydrogen atom or a methyl group, and particularly preferably a hydrogen atom. This is because a compound which has little curing inhibition and can easily impart ultraviolet absorption ability to a cured product can be provided.

R is as defined above⁴¹～R⁴⁴Each independently is preferably a hydrogen atom, a carboxyl group or an alkyl group having 1 to 5 carbon atoms, more preferably a hydrogen atom or a methyl group, and particularly preferably a hydrogen atom. This is because a compound which has little curing inhibition and can easily impart ultraviolet absorption ability to a cured product can be provided.

Each of b1, b2, b3, b6, b7, b8, and b9 may be independently an integer of 0 to 4, but 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 curing inhibition and can easily impart ultraviolet absorption ability to a cured product can be provided.

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

The c1 may be an integer of 0 to 5, but from the viewpoint of ease of synthesis, it is preferably an integer of 0 to 3, more preferably an integer of 0 to 2, still more preferably an integer of 0 to 1, and particularly preferably 1. This is because a compound which has little curing inhibition and can easily impart ultraviolet absorption ability to a cured product can be provided.

The c2 may be an integer of 0 to 4, but is preferably an integer of 0 to 3, more preferably an integer of 0 to 2, even more preferably an integer of 0 to 1, and particularly preferably 0, from the viewpoint of ease of synthesis. This is because a compound which has little curing inhibition and can easily impart ultraviolet absorption ability to a cured product can be provided.

The type of the photo-leaving group B contained in the compound I-1 of the present invention is preferably 1 type in terms of k being 2 or more, 1 type or 2 or more in each compound I-1 in some cases, but it is preferable from the viewpoint of less curing inhibition, easily imparting ultraviolet absorption ability to a cured product, and the like, and facilitating the synthesis of the compound I-1.

The number k of the light leaving groups is an integer of 1 to 10, but from the viewpoint of less curing inhibition, easy ultraviolet absorption ability to the cured product, and the like, and easy synthesis, the number k is preferably an integer of 1 to 5, more preferably an integer of 1 to 4, and particularly preferably an integer of 1 to 3.

2. Radical A having ultraviolet-absorbing ability

The radical A is a radical having ultraviolet-absorbing ability.

When the compound I-1 of the present invention is irradiated with light of a specific wavelength, the photo-leaving group B is removed, and a compound I-2 having a hydroxyl group is produced. Further, compound I-2 exerts ultraviolet absorbing ability by the fact that the radical A has ultraviolet absorbing ability.

The term "having ultraviolet absorbability" means that, for example, a compound having ultraviolet absorbability, specifically, compound I-1 after leaving the photo-leaving group B, that is, compound I-2 can absorb light having a wavelength in the range of 250nm to 450 nm. The atomic group having ultraviolet absorbability in the present invention may be set to a group having ultraviolet absorbability or an aggregate of atoms containing at least one group having ultraviolet absorbability.

More specifically, compound I-1, i.e., compound I-2 after leaving the photoleaving group B can absorb light having a maximum absorption wavelength of 250nm or more and 400nm or less, preferably 260nm or more and 390nm or less, and particularly preferably 280nm or more and 380nm or less, in a wavelength range of 250nm or more and 600nm or less. This is because a compound which has little curing inhibition and can easily impart ultraviolet absorption ability to a cured product can be provided.

The maximum absorption wavelength of the compound I-1 after leaving the leaving group B, i.e., the compound I-2, can be measured by the following measurement method, for example.

As the sample for evaluation, for example, a compound I-1 after leaving the photo-leaving group B, that is, a compound I-2 was dissolved in a solvent (acetonitrile) to a concentration of 0.01 mass%. The absorbance can be measured by filling a quartz cell (optical path length: 10mm, thickness: 1.25mm) with the sample for evaluation and measuring the absorbance using an absorptiometer (for example, U-3900 (manufactured by Hitachi high-Tech Science Co., Ltd.).

Further, in the case of the compound I-1 of the present invention, when the maximum absorption wavelength of the compound I-1 before the leaving of the photo-leaving group B is compared with the maximum absorption wavelength of the compound I-1 (compound I-2) after the leaving of the photo-leaving group B, it is preferable that the maximum absorption wavelength of the compound I-1 before the leaving of the photo-leaving group B is shorter than the maximum absorption wavelength of the compound I-2 in the range of 250nm or more and 600nm or less. This is because the application to the photocurable composition becomes easy.

The difference in maximum absorption wavelength between the compound I-1 and the compound I-2 after the leaving of the photo-leaving group B is preferably 1nm or more, more preferably 1nm or more and 100nm or less, and particularly preferably 1nm or more and 50nm or less. This is because the application to the photocurable composition becomes easy.

Such a radical a may be the same as a radical generally used in an ultraviolet absorber having a phenolic hydroxyl group. That is, the above-mentioned compound I-2 is a compound which is generally used as an ultraviolet absorber having a phenolic hydroxyl group.

Specifically, as the compound I-2, 2-hydroxybenzophenones, 2- (2' -hydroxyphenyl) benzotriazoles, benzoates and triaryltriazines described in Japanese patent application laid-open No. 2017-008221, benzotriazole-based ultraviolet absorbers and benzophenone-based ultraviolet absorbers described in Japanese patent application laid-open No. 2002-97224, and the like can be used.

Examples of the atomic group a include a phenol structure in which a phenolic hydroxyl group is protected by a photo-leaving group B, that is, a structure containing a benzene ring to which the above-mentioned B — O — is directly bonded. Specifically, there may be mentioned: an atomic group containing a benzene ring and a benzotriazole ring directly bonded with B-O-; a radical containing a B-O-directly bonded benzophenone ring; and an atomic group containing a benzene ring and a triazine ring directly bonded by B-O-. The structure containing at least 1 of the benzotriazolyl, benzophenone and triazine groups directly bonded to the benzene ring contained in the above-mentioned phenol structure is preferable, and the bonding position of at least 1 of the benzotriazolyl, benzophenone and triazine groups on the benzene ring is more preferable to be ortho to the bonding position of the above-mentioned B-O-. This is because a compound which has little curing inhibition and can easily impart ultraviolet absorption ability to a cured product is easily formed.

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

(in the formula, R¹And R²Each independently represents a hydrogen atom, a halogen atom, a cyano group, a hydroxyl group, a nitro group, a carboxyl group, a carbon atom number of 1 to E40 alkyl group, aryl group having 6 to 20 carbon atoms, aralkyl group having 7 to 20 carbon atoms, heterocyclic group having 2 to 20 carbon atoms or the group-O-B,

R¹and R²Is the-O-B group at least one of,

R³、R⁴、R⁵、R⁶、R⁷and R⁸Each 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 aralkyl group having 7 to 20 carbon atoms or a heterocyclic group having 2 to 20 carbon atoms,

R¹、R²、R³、R⁴、R⁵、R⁶、R⁷and R⁸The methylene group in the alkyl or aralkyl group represented by the above-mentioned formula is sometimes 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' - ], or,>P＝O、-S-S-、-SO₂-or a combination thereof,

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

plural R³Each other, a plurality of R⁴Each other, a plurality of R⁵Each other, a plurality of R⁶Each and a plurality of R⁷Are sometimes bonded to each other to form a benzene ring or a naphthalene ring,

plural R³、R⁴、R⁵、R⁶、R⁷And R⁸Sometimes the same, sometimes different,

m1 and m2 each independently represent an integer of 1 to 10,

n represents an integer of 1 to 3,

a1 represents an integer of 0 to 4,

a2 represents an integer of 0 to 2,

a3 represents an integer of 0 to 4,

a4 represents an integer of 0 to 3,

a5 represents an integer of 0 to 3,

a6 represents an integer of 0 to 3-n,

X¹and X²Respectively represent bonding groups with m1 valence and m2 valence. )

As the above-mentioned R¹、R²、R³、R⁴、R⁵、R⁶、R⁷And R⁸Examples of the alkyl group having 1 to 40 carbon atoms, the aryl group having 6 to 20 carbon atoms, the aralkyl group having 7 to 20 carbon atoms, the heterocyclic group having 2 to 20 carbon atoms and the alkyl group having 1 to 8 carbon atoms represented by R' include R described in the above item "1. light leaving group B¹¹And R' are exemplified.

R is as defined above¹And R²At least one of (a) and (B) is the above-mentioned-O-B.

From the viewpoint of ease of synthesis, the above-mentioned R is preferred¹And R²Is the above-mentioned-O-B.

R is as defined above¹And R²From the viewpoint of making the change in ultraviolet absorption ability large, R is preferable¹And R²Both are-O-B as described above.

R is as defined above¹And R²When only one is the above-mentioned-O-B, the other is preferably a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 40 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms or a heterocyclic group having 2 to 20 carbon atoms, and more preferably a hydrogen atom or an alkyl group having 1 to 40 carbon atoms. This is because the above-mentioned R is substituted by¹And R²The other is the above functional group, and the compound I-1 is a compound having a large change in ultraviolet absorptivity. Further, the compound I-1 is a compound which is less likely to cause inhibition of curing.

Further, as the alkyl group, aralkyl group and the like, those having methylene groups interrupted by-O-, -CO-, and the like can also be preferably used.

R is as defined above³、R⁴、R⁵、R⁶、R⁷And R⁸Preferably a cyano group, a hydroxyl group, an alkyl group having 1 to 40 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms, more preferably a cyano group, a hydroxyl group, or a carbon atomAn alkyl group having 1 to 20 carbon atoms or an aralkyl group having 7 to 10 carbon atoms, more preferably an alkyl group having 3 to 20 carbon atoms, and still more preferably an alkyl group having 3 to 10 carbon atoms. This is because the synthesis of the compound I-1 of the present invention becomes easy, and the compound I-1 exerts an excellent ultraviolet absorbing ability after the leaving of the photo-leaving group B.

In addition, from the viewpoint of exhibiting excellent ultraviolet absorbability after leaving the light leaving group B, R⁴The alkyl group having a branched structure is preferably an alkyl group having 3 to 15 carbon atoms, more preferably an alkyl group having a branched structure having 5 to 12 carbon atoms, still more preferably an alkyl group having a branched structure having 6 to 11 carbon atoms, and particularly preferably an alkyl group having a branched structure having 7 to 10 carbon atoms.

As R⁴The bonding position in the benzene ring may be bonded to any position capable of bonding, but is preferably a para position with respect to the bonding position of-O-B. This is because the compound I-1 exerts an excellent ultraviolet absorbing ability after the leaving of the photo-leaving group B.

From the viewpoint of exhibiting excellent ultraviolet absorption ability after leaving the photo-leaving group B, R⁵And R⁶The alkyl group having 1 to 20 carbon atoms, i.e., the alkoxy group having 1 to 20 carbon atoms, in which the methylene group at the terminal of the benzene ring side is substituted with-O-, is preferable, the alkoxy group having 3 to 15 carbon atoms is particularly preferable, and the alkoxy group having 5 to 12 carbon atoms is particularly preferable.

As R⁵And R⁶The bonding position in the benzene ring may be bonded at any position capable of bonding, but is preferably a meta position with respect to the bonding position of-O-B. This is because the compound I-1 exerts an excellent ultraviolet absorbing ability after the leaving of the photo-leaving group B.

From the viewpoint of exhibiting excellent ultraviolet absorption ability after leaving the photo-leaving group B, R⁷Preferably an alkyl group having 1 to 20 carbon atoms in which the methylene group at the end of the benzene ring side is substituted with-O-, that is, an alkoxy group having 1 to 20 carbon atoms, particularly preferably an alkoxy group having 3 to 20 carbon atoms in which the methylene chain other than the end of the benzene ring side is substituted with-O-, -O-CO-, particularly preferably a methylene chain other than the end of the benzene ring sideAn alkoxy group having 3 to 15 carbon atoms which is substituted with-O-, -O-CO-, particularly preferably an alkoxy group having 6 to 15 carbon atoms which is substituted with-O-, -O-CO-for a methylene chain other than the terminal on the benzene ring side, and particularly preferably an alkoxy group having 8 to 13 carbon atoms which is substituted with-O-, -O-CO-for a methylene chain other than the terminal on the benzene ring side.

As R⁷The bonding position in the benzene ring may be bonded at any position capable of bonding, but is preferably a meta position with respect to the bonding position of-O-B. This is because the compound I-1 exerts an excellent ultraviolet absorbing ability after the leaving of the photo-leaving group B.

From the viewpoint of exhibiting excellent ultraviolet absorption ability after leaving the photo-leaving group B, R⁸The aryl group preferably has 6 to 20 carbon atoms, more preferably has 6 to 12 carbon atoms, and particularly preferably has a substituent.

As the alkyl group and the aralkyl group, any of those in which a methylene group is not interrupted and those in which a methylene group is interrupted by-O-, -CO-, or the like can be preferably used.

M1 and m2 each represents an integer of 1 to 10. From the viewpoint of ease of synthesis, each of m1 and m2 is independently preferably an integer of 1 to 6, more preferably an integer of 1 to 4, particularly preferably an integer of 1 to 3, and particularly preferably an integer of 1 to 2. This is because the synthesis of the compound I-1 is easy, and the compound I-1 exhibits excellent ultraviolet absorbability after leaving the photo-leaving group B.

In addition, m2 is preferably an integer of 1 from the viewpoint that compound I-1 exhibits excellent ultraviolet absorbability after leaving the photo-leaving group B.

N represents an integer of 1 to 3. From the viewpoint of the compound I-1 having a large change in the ultraviolet absorption ability, n is preferably an integer of 2 to 3, and particularly preferably 3. From the viewpoint that the compound I-1 exhibits excellent ultraviolet absorptivity after the leaving of the photo-leaving group B, n is preferably an integer of 1 to 2, and particularly preferably 1.

A1 and a3 each independently represent an integer of 0 to 4. From the viewpoint of ease of synthesis, each of a1 and a3 is independently preferably an integer of 0 to 3, more preferably an integer of 0 to 2, and particularly preferably an integer of 0 to 1. This is because the compound I-1 can be formed as a compound which exhibits excellent ultraviolet absorbability after leaving the photo-leaving group B.

A2 represents an integer of 0 to 2. From the viewpoint of solubility, a2 is preferably an integer of 1 to 2. In addition, the above-mentioned a2 is preferably 1 from the viewpoint that the compound I-1 exhibits excellent ultraviolet absorbability after leaving the photoleaving group B.

The a4 and a5 each independently represent an integer of 0 to 3. From the viewpoint of ease of synthesis, the a4 and a5 are preferably integers of 0 to 2, more preferably integers of 1 to 2, and even more preferably integers of 1. This is because the compound I-1 can be formed as a compound which exhibits excellent ultraviolet absorbability after leaving the photo-leaving group B.

A6 represents an integer of 0 to 3-n. The above-mentioned a6 is preferably an integer of 0 to 1, preferably 0, from the viewpoint of the compound I-1 exhibiting excellent ultraviolet absorptivity after the leaving of the photo-leaving group B and the viewpoint of ease of synthesis.

The compounds I-1 represented by the above general formulae (A-1) and (A-2) have the structure represented by the formula¹And X²A structure in which m1 or m2 (hereinafter, sometimes referred to as m) specific groups are bonded to m 1-valent or m 2-valent (hereinafter, sometimes referred to as m-valent) specific atoms or groups (hereinafter, sometimes referred to as X). The m specific groups may be the same as or different from each other.

X represents a bonding group having a valence of m.

The bonding group X specifically 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 and the same number of valence as m, an aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms, or a heterocyclic group having 2 to 35 carbon atoms, R⁵³And R⁵⁴Independently represent a hydrogen atom, an aliphatic hydrocarbon group having 1 to 35 carbon atoms, and an aromatic ring-containing hydrocarbon having 6 to 35 carbon atomsOr a heterocyclic group having 2 to 35 carbon atoms, wherein 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-, -SO-O-, -C-CO-O-, -C-O-, -S-, -SO₂The nitrogen atom or a combination thereof, and the above aromatic ring or heterocyclic ring is also sometimes fused with other rings.

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

(. means bonding to adjacent groups at the site.)

The aliphatic hydrocarbon group having 1 to 120 carbon atoms and having the same number of valences as m as that of the bonding group X, examples of the group in which m is valences 1 include alkyl groups 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, decyl and the like; 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, decyloxy and the like; 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 obtained by substituting these groups with the substituents described later.

The bonding group X has the same number of valence with m of aliphatic hydrocarbon 1-120 carbon atoms, as m for 2 valence group, can be cited, ethylene, propylene, butylene alkylene; a group wherein the methylene chain of the alkylene group is substituted by-O-, -S-, -CO-O-, -O-CO-; residues of diols such as ethylene glycol, propylene glycol, butylene glycol, pentylene glycol, and hexylene glycol; residues of dithiols such as ethanedithiol, propanedithiol, butanedithiol, pentanethiol, and hexanedithiol, and groups obtained by substituting these residues with substituents described later, and the like.

The aliphatic hydrocarbon group having 1 to 120 carbon atoms and having the same number of valences as m as that of the bonding group X, examples of the group in which m is a valency of 3 include an alkylidene group such as propylidene and 1,1, 3-butylidene, and a group obtained by substituting these groups with a substituent described later.

The aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms and having the same number of valences as m as the bonding group X, wherein m is a group having a valence of 1, and examples thereof include aralkyl groups such as benzyl, phenethyl, diphenylmethyl, triphenylmethyl, styryl, and cinnamyl; aryl groups such as phenyl and naphthyl; aryloxy groups such as phenoxy and naphthoxy; arylthio groups such as phenylthio and naphthylthio; and those obtained by substituting these groups with the substituents described later.

The bonding group X has m same number of valence number of 6-35 aromatic ring containing hydrocarbyl, as m for 2 valence group, can give phenylene and naphthylene arylene; a residue of a bifunctional phenol group such as a catechol group or a bisphenol group; 2,4, 8, 10-tetraoxaspiro [5, 5] undecyl and the like; and those obtained by substituting these groups with the substituents described later.

The aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms and having the same number of valences as m as that of the bonding group X includes a group in which m is a valency of 3, such as phenyl-1, 3, 5-trimethylene group and a group obtained by substituting the group with a substituent described later.

The heterocyclic group having 2 to 35 carbon atoms and having the same number of valences as m as the bonding group X is a group in which m is a valency of 1, examples thereof 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-pyrrolidin-1-yl, 2-piperidone-1-yl, 2, 4-dioxoimidazolidin-3-yl, 2, 4-dioxooxazolidin-3-yl, and benzotriazolyl, and those obtained by substituting these groups with substituents described later.

The heterocyclic group having 2 to 35 carbon atoms and having the same number of valences as m as that of the bonding group X includes groups having 2 valences such as a pyridine ring, a pyrimidine ring, a piperidine ring, a piperazine ring, a triazine ring, a furan ring, a thiophene ring, and an indole ring, and groups obtained by substituting these groups with substituents described later.

The heterocyclic group having 2 to 35 carbon atoms and having the same number of valences as m as that of the bonding group X, and examples of the group having a valency of 3 as m include a group having a valency of 3 having a trimeric isocyano ring, a group having a valency of 3 having a triazine ring, and a group obtained by substituting these groups with a substituent described later.

As R⁵³And R⁵⁴The aliphatic hydrocarbon group having 1 to 35 carbon atoms includes the aliphatic hydrocarbon group represented by X or the aliphatic hydrocarbonA group having 1 to 35 carbon atoms, which is obtained by substituting the group with a substituent described later.

As R⁵³And R⁵⁴The C6-35 aromatic ring-containing hydrocarbon group or C2-35 heterocyclic group includes C6-35 aromatic ring-containing hydrocarbon group or C2-35 heterocyclic group represented by X, 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. The compound I-1 of the present invention includes those having no substituent and those having a substituent, unless otherwise specified.

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.

In the above general formulae (A-1) and (A-2), when m is 2, X may represent a group represented by the following general formula (1).

＊-Z¹-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, a divalent aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms, a divalent heterocyclic group having 2 to 35 carbon atoms, or any of the following groups (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 may be interrupted by-O-, -S-, -CO-, -COO-, -OCO-, or-NH-or a combination thereof,

R⁵⁵and R⁵⁶Each 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 aralkyl group having 7 to 20 carbon atoms,

Z¹and Z²Independently represent a direct bond, -O-, -S-, > CO, -CO-O-, -O-CO-, -SO₂-、-SS-、-SO-、＞NR⁵⁷Or > 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 adjacent groups at the moiety. )

(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 which may have a substituent,

R⁶⁰represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms or a halogen atom, and the alkyl group, the alkoxy group and the alkenyl group may have a substituent,

c1 represents an integer of 0 to 5,

refers to bonding to adjacent groups at the moiety. )

(. means bonding to adjacent groups at the site.)

(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-,

R⁶¹or sometimes through adjacent R⁶¹Form a ring 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 adjacent groups at the moiety. )

(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 Z³Independently represent 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-an interrupt. )

(in the above general formula (3), Y¹²Represents a carbon atom, a tetravalent aliphatic hydrocarbon group having 1 to 35 carbon atoms, a tetravalent aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms, or a tetravalent heterocyclic group having 2 to 35 carbon atoms, wherein the aliphatic hydrocarbon group, the aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms, or the heterocyclic group having 2 to 35 carbon atoms may be interrupted by-COO-, -O-, -OCO-, -NHCO-, -NH-, or-CONH-, and Z¹～Z⁴Each independently represents Z in the above general formula (2)¹～Z³The groups represented are the same range of groups. )

(in the above general formula (4), Y¹³Represents a pentavalent aliphatic hydrocarbon group having 2 to 35 carbon atoms, a pentavalent aromatic ring-containing hydrocarbon group having 6 to 30 carbon atoms or a pentavalent heterocyclic group having 2 to 30 carbon atoms, and the aliphatic hydrocarbon group, the aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms or the heterocyclic group having 2 to 35 carbon atoms may be interrupted by-COO-, -O-, -OCO-, -NHCO-, -NH-or-CONH-, Z¹～Z⁵Each independently represents Z in the above general formula (2)¹～Z³The groups represented are the same. )

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

Y in the group represented by the above general formula (1)¹Examples of the divalent aliphatic hydrocarbon group having 1 to 35 carbon atoms include 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 likeQuilt Z¹And Z²A substituted divalent group. These groups are sometimes interrupted by-O-, -S-, -CO-, -COO-, -OCO-, -NH-or a combination thereof.

Y 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 Z²A divalent group obtained by substitution, and the like.

Y 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, tetrahydrothiophene and the like¹And Z²A divalent group obtained by substitution.

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 substituted with a halogen atom, a cyano group, a nitro group or an alkoxy group having 1 to 8 carbon atoms.

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.

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 groups as those used for the substituent substituted with a hydrogen atom such as an alkyl group.

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 R⁵⁶Carbon as shownExamples of the aryl group having 6 to 20 atoms include a phenyl group, a naphthyl group, a 2-methylphenyl group, a 3-methylphenyl group, a 4-vinylphenyl group, a 3-isopropylphenyl group, a 4-butylphenyl group, a 4-isobutylphenyl group, a 4-tert-butylphenyl group, a 4-hexylphenyl group, a 4-cyclohexylphenyl group, a 4-octylphenyl group, a 4- (2-ethylhexyl) phenyl group, a2, 3-dimethylphenyl group, a2, 4-dimethylphenyl group, a2, 5-dimethylphenyl group, a2, 6-dimethylphenyl group, a3, 4-dimethylphenyl group, a3, 5-dimethylphenyl group, a2, 4-di-tert-butylphenyl group, a2, 5-di-tert-butylphenyl group, a2, 6-di-tert-butylphenyl group, 2, 4-di-t-pentylphenyl, 2, 5-di-t-pentylphenyl, 2,4, 5-trimethylphenyl, and the like.

R as in the group represented by the above general formula (1)⁵⁵And R⁵⁶Examples of the aralkyl 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 groups in which these groups are substituted with an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms.

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. light leaving 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. light leaving group B¹¹Alkoxy group having 1 to 10 carbon atoms as exemplified for the alkoxy group represented by the following general formula。

R as in the group represented by the above general formula (1-1)⁶⁰Examples of the alkenyl group having 2 to 10 carbon atoms include vinyl, allyl, 1-propenyl, isopropenyl, 2-butenyl, 1, 3-butadienyl, 2-pentenyl and 2-octenyl.

R is as defined above⁶⁰The alkyl group, alkoxy group and alkenyl group 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 aralkyl group having 7 to 20 carbon atoms include R in the above-mentioned "1. light leaving group B¹¹And the like, and those satisfying a predetermined number of carbon atoms.

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 group, a 4-octylphenyloxy group, a 4- (2-ethylhexyl) phenyloxy group, a2, 3-dimethylphenyloxy group, a2, 4-dimethylphenyloxy group, a2, 5-dimethylphenyloxy group, a2, 6-dimethylphenyloxy group, a3, 4-dimethylphenyloxy group, a3, 5-dimethylphenyloxy group, and a2, 4-di-tert-butylphenyloxy group, 2, 5-di-tert-butylphenyloxy group, 2, 6-di-tert-butylphenyloxy group, 2, 4-di-tert-pentylphenyloxy group, 2, 5-tert-pentylphenyloxy group, 4-cyclohexylphenyloxy group, 2,4, 5-trimethylphenyloxy group, ferrocenyloxy group and groups 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.

AsR 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 the substituent for substituting a hydrogen atom such as aryloxy, arylthio, arylalkenyl, heterocyclic group and the like, R may be the same 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 triA monovalent group.

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 as 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, may be mentioned⁵³And R⁵⁴Examples of the group are the same.

Y as in the group represented by the above general formula (3)¹²The tetravalent aliphatic hydrocarbon group having 1 to 35 carbon atoms is exemplified by the aliphatic hydrocarbon group represented by the formula (1) in the description of X and Z¹、Z²、Z³And Z⁴Substituted tetravalent groups, which are sometimes interrupted by-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 is represented by the aromatic ring-containing hydrocarbon group exemplified in the description of X in the general formula (1) and Z¹、Z²、Z³And Z⁴A substituted tetravalent group.

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

Y as a group represented by the above general formula (4)¹³The pentavalent aliphatic hydrocarbon group having 2 to 35 carbon atoms includes the aliphatic hydrocarbon group exemplified in the description of X in the general formula (1) and Z¹、Z²、Z³、Z⁴And Z⁵Substituted pentavalent radicals, these radicalsThe 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 (4)¹³The pentavalent aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms includes the aromatic ring-containing hydrocarbon group exemplified in the description of X in the general formula (1) and Z¹、Z²、Z³、Z⁴And Z⁵Substituted pentavalent groups.

Y as a group represented by the above general formula (4)¹³The pentavalent heterocyclic group containing 2 to 35 carbon atoms includes the heterocyclic group-containing Z exemplified in the description of X in the general formula (1)¹、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, for example, the aliphatic hydrocarbon group exemplified in the description of X in the general formula (1) and Z¹、Z²、Z³、Z⁴、Z⁵And Z⁶Substituted hexavalent radicals, which radicals are sometimes substituted by-O-, -S-, -CO-, -COO-, -OCO-, -SO₂-, -NH-or a group formed by combining them.

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

As Y in the above general formula (5)¹⁴The hexavalent heterocyclic group containing 2 to 35 carbon atoms includes a heterocyclic group represented by the formula (1) in which X is as defined above¹、Z²、Z³、Z⁴、Z⁵And Z⁶A substituted hexavalent group.

When m is 2, the bonding group X is preferably an aliphatic hydrocarbon group having 1 to 120 carbon atoms, more preferably an alkylene group or a diol residue, preferably an alkylene group having 1 to 10 carbon atoms or a diol residue having 1 to 10 carbon atoms, particularly preferably a diol residue having 1 to 5 carbon atoms such as an alkylene group having 1 to 5 carbon atoms, and particularly preferably an alkylene group having 1 to 3 carbon atoms. This is because a compound which has little curing inhibition and can easily impart ultraviolet absorption ability to a cured product can be formed, and further, the production of compound I-1 is easy.

The bonding position of the bonding group X to the benzene ring may be any position that can be bonded in the benzene ring, and for example, it is preferable that the bonding position is relative to R²Is ortho-position or meta-position. This is because a compound which has little curing inhibition and can easily impart ultraviolet absorption ability to a cured product can be formed.

When m is 1, X is preferably a hydrogen atom or a group with R²The 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 with the photo-leaving group B, but 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 preferably contains a group represented by the above general formula (B-1-a) as the photo-leaving group B. This is because synthesis is easy and light leaving is easy. This is because ultraviolet absorption ability and the like can be easily imparted to the cured product. Further, since the compound I-1 is a compound represented by the general formula (A-1), (A-2) or (A-3), a compound which can stably absorb light in the ultraviolet region by leaving the photo-leaving group B can be produced.

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

The molecular weight of the compound I-1 can be set according to the use of the compound I-1, etc. The molecular weight of the compound I-1 is, for example, preferably 250 to 5000, more preferably 300 to 2500, and particularly preferably 350 to 1500. This is because a compound which has little curing inhibition and can easily impart ultraviolet absorption ability to a cured product can be formed.

When the compound I-1 is a polymer having a repeating structure as its structure, the molecular weight of the compound I-1 is represented by the weight average molecular weight (Mw). 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 can obtain a desired structure, and for example, a phenol compound produced by the method described in JP-A-57-111375, JP-A-3-173843, JP-A-6-128195, JP-A-7-206771, JP-A-7-252191 or JP-A-2004-501128 can be reacted with an alkyl halide.

The compound I-1 is inactive before light irradiation, and a light leaving group is removed by light irradiation to produce a compound I-2 having a phenolic hydroxyl group.

Further, the above-mentioned compound I-2 exerts ultraviolet-absorbing ability.

The compound I-1 is preferably used in applications requiring ultraviolet absorbability by light irradiation, and examples thereof include an ultraviolet absorber added to a composition.

B. Latent ultraviolet absorber

Next, the latent ultraviolet absorber of the present invention will be described.

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

The latent ultraviolet absorber of the present invention contains the compound I-1 of the present invention, and thus, for example, the curing inhibition is small, and ultraviolet absorbing ability and the like can be easily imparted to a cured product.

The content of the compound I-1 in the latent uv absorber of the present invention is not particularly limited, and may be appropriately set according to the use of the latent uv absorber, and the like.

The latent ultraviolet absorber of the present invention may contain 100 parts by mass of the compound I-1 in 100 parts by mass of the latent ultraviolet absorber, that is, the latent ultraviolet absorber may be composed of only the compound I-1.

The latent ultraviolet absorber of the present invention may contain other components in addition to the compound I-1. When the latent ultraviolet absorber 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 or more and 99 parts by mass or less, more preferably 50 parts by mass or more and 99 parts by mass or less, and particularly preferably 80 parts by mass or more and 99 parts by mass or less, in 100 parts by mass of the latent ultraviolet absorber. This is because the latent ultraviolet absorber can effectively exhibit effects such as a small amount of curing inhibition and the ability to easily impart ultraviolet absorption to a cured product.

The number of the types of the compound I-1 contained in the latent ultraviolet absorber may be only 1, and may be 2 or more. When the latent ultraviolet absorber contains a plurality of compounds I-1, the number of species 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.

As the other components contained in the latent ultraviolet absorber, for example, the same components as those described in "2. other components" of "c. composition" described later can be used.

The latent ultraviolet absorber preferably contains a resin component such as a polymer having no polymerizable group as another component. This is because the above-mentioned compound I-1 can be stably maintained.

The latent ultraviolet absorber 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 ultraviolet absorber, 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 compound I-1.

The composition of the present invention can provide a composition that can give a cured product with little curing inhibition and excellent ultraviolet absorption ability, for example. Hereinafter, each component of the above composition 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 ultraviolet absorbing ability or the like to the composition. The content of compound I-1 in the composition of the present invention may be, for example, 0.001 parts by mass or more and 20 parts by mass or less, and preferably 0.005 parts by mass or more and 10 parts by mass or less, 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 ultraviolet absorption ability to a cured product can be easily formed.

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

In the present specification, 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 ultraviolet absorption ability to a cured product can be easily formed.

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 the composition of the present invention can easily impart curability or the like to the composition by containing a resin component in addition to the compound I-1.

The composition of the present invention preferably contains a polymerization initiator as another component together with the resin component. This is because the composition of the present invention can easily impart curability and the like to the composition by containing the resin component and the polymerization initiator as other components.

(1) Resin component

The resin component includes a component capable of holding the compound I-1, and is suitably set according to the use of the composition, and examples thereof include a polymerizable compound having a polymerizable group, a polymer 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 or a thermosetting composition.

(a) Polymerizable compound

The polymerizable compound differs depending on the type of polymerizable group, that is, the type of polymerization reaction, and examples thereof include a radical polymerizable compound, a cation polymerizable compound, and an anion polymerizable compound.

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.

Among the radical polymerizable compounds, examples of the compound having an ethylenically unsaturated double bond group and an acid value include a compound obtained by reacting a mono-or poly-unsaturated epoxy resin having a hydroxyl group, such as a mono-or poly-epoxy acrylate having a hydroxyl group, a pentaerythritol-or poly-epoxy anhydride, with a polyhydric epoxy resin having a hydroxyl group, such as a pentaerythritol-containing epoxy anhydride, a pentaerythritol-or poly-epoxy anhydride-containing epoxy resin, and a pentaerythritol-containing epoxy resin, wherein the polyhydric epoxy anhydride is reacted with a polyhydric epoxy group-containing epoxy resin such as a polyhydric epoxy anhydride-containing epoxy resin having a hydroxyl group, such as a (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 ] phthalate, omega-carboxy-polycaprolactone mono- (meth) acrylate, and poly (meth) acrylate having a carboxyl group at both ends, a hydroxyl group, and a polyhydric epoxy group.

(in the formula, X⁴¹Is 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. )

As R⁴¹、R⁴²、R⁴³And R⁴⁴The 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, which are represented by the above-mentioned formula, include those mentioned as R in the above item "A. Compound¹¹And the like, which satisfy a predetermined number of carbon atoms.

As X⁴¹Examples of the alkylidene group having 1 to 4 carbon atoms include methylidene, ethylidene, propylidene and butylidene groups.

As X⁴¹Examples of the alicyclic hydrocarbon group having 3 to 20 carbon atoms include cyclopropylene, cyclopentylene, cyclohexylene, cycloheptylene and the like.

The alkyl group, alkoxy group, alkenyl group, alkylidene group, and alicyclic hydrocarbon group may have a substituent, and unless otherwise specified, the alkyl group, alkoxy group, alkenyl group, alkylidene group, and alicyclic hydrocarbon group may be unsubstituted or substituted. The substituent for substituting the hydrogen atom of the alkyl group, alkoxy group, alkenyl group, alkylidene group and alicyclic hydrocarbon group may be R¹¹The same applies to the substituent substituted with a hydrogen atom such as an alkyl group.

Examples of the radical polymerizable compound include unsaturated vinyl methacrylate, etc. such as well as maleic anhydride, maleic anhydride.

Compound No. A1

Compound No. A2

Compound No. A3

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 ultraviolet absorption 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 parts by mass or less, particularly preferably 80 parts by mass or more and 99 parts by mass or less, and more preferably 90 parts by mass or more and 98 parts by mass or less, in 100 parts by mass of the total 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 ultraviolet absorption ability or 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 ultraviolet absorption 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 represented by the above general formula (II) 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 having no polymerizable group

As the resin that can be used in the composition of the present invention, as described above, a polymer having no polymerizable group can be used.

The weight average molecular weight (Mw) of the polymer having no polymerizable group 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.

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 of the present invention 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 in which chemical bonds such as ester groups and acetal groups are broken by 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.

(c) Resin component

The content of the resin component in the composition of the present invention may be appropriately set according to the use of the composition, and for example, is preferably 1 part by mass or more and 99 parts by mass or less, more preferably 20 parts by mass or more and 95 parts by mass or less, and particularly preferably 30 parts by mass or more and 90 parts by mass or less, in 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 ultraviolet absorption 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 may be 1 part by mass or more and 99 parts by mass or less, preferably 50 parts by mass or more and 99 parts by mass or less, particularly preferably 80 parts by mass or more and 99 parts by mass or less, and more preferably 90 parts by mass or more and 98 parts by mass or less, in 100 parts by mass of the total 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 capable of easily imparting ultraviolet absorbing ability 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 ultraviolet absorption ability to a cured product can be provided.

The kind of the resin component contained in the composition of the present invention 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 having no polymerizable group, 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 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.

The polymerization initiator is preferably a photopolymerization initiator from the viewpoint that the compound I-1 effectively exerts an effect of functioning as an ultraviolet absorber.

(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 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).

(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 aralkyl 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, or 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 an alkyl group having 1 to 20 carbon atoms,An aryl group having 6 to 30 carbon atoms, an aralkyl 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 aralkyl group having 7 to 20 carbon atoms, and a methylene group in the alkyl group or the aralkyl group may be substituted with a halogen atom, a nitro group, a cyano group, a hydroxyl group, a carboxyl group or a heterocyclic group-containing group, or may be substituted with-O-,

R⁷³and R⁷⁴Sometimes 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, the aryl group having 6 to 30 carbon atoms, the aralkyl group having 7 to 30 carbon atoms or the heterocyclic group having 2 to 20 carbon atoms and the substituent thereof used in the above-mentioned step (1) may be mentioned as R in the above-mentioned "1. light leaving 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.

(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 aralkyl group having 7 to 30 carbon atoms or a heterocyclic group having 2 to 20 carbon atoms,

R²¹¹、R²¹²and R²¹³The hydrogen atom of the group shown is 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,

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 aralkyl 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 aralkyl 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 sometimes have branched side chains, sometimes cyclic alkyl groups,

R²⁰³represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl 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, and may be a cyclic alkyl group, and R²⁰³And R²⁰⁷And R²⁰³And R²⁰⁸And sometimes together form a ring,

R²⁰³the hydrogen atom of the group shown is 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,

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 atom of the group shown is 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 sometimes have branched side chains, sometimes cyclic alkyl groups,

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 the above-mentioned channelR in the 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 aralkyl group having 7 to 30 carbon atoms or the heterocyclic group having 2 to 20 carbon atoms used in the above-mentioned step may be, for example, R in the above-mentioned "1. light leaving group B" as R¹¹And 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, and TR-PBG-314 (manufactured by onTrly 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-Specific examples of the (B) include tetrakis (pentafluorophenyl) borate, tetrakis (3, 5-difluoro-4-methoxyphenyl) borate, and tetrafluoroborate (B)F₄)^-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.

< group I >

< 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-aroyloxime (acetophenone O-aroyloxime), nifedipine (nifedipine), and the like.

(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 radical polymerization initiator, a cationic polymerization initiator, and an anionic polymerization initiator.

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 can be provided. 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, the other components may contain, if necessary, 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; ultraviolet absorbers such as phenol-based ultraviolet absorbers, phosphite-based ultraviolet absorbers, and thioether-based ultraviolet absorbers; an ultraviolet absorber other than the compound represented by the above-mentioned compound I-1; 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, and a coating containing CO, CO and a volatile component at 950 ℃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; hydrophobic resin, chromium oxide green, Melolol blue, cobalt green, cobalt blue, manganese series, ferrocyanide, and ultramarine phosphateInorganic pigments or organic pigments such as prussian blue, ultramarine blue, azure blue, chrome 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 these solvents can be used as a mixed solvent of 1 or 2 or more kinds.

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 a compound containing a sulfur atom is generally used. 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 acidAcids, 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, iodoacetic acid, iodopropionic acid, 2-iodoethanol, 2-iodoethanesulfonic acid, and 3-iodopropanesulfonic acid and other iodinated alkyl compounds, trimethylolpropane tris (3-mercaptoisobutyrate), Aliphatic polyfunctional thiol compounds such as butanediol di (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 Karenz MT 1, PE1, NR produced by Showa Denko K.K., and K.K., a product of Tokarenz MT 1, a product of Towa Denko K, and K.K., a product of Mo.K. K¹And the like.

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, a compound capable of improving curability can be used, and examples thereof include compounds in which all or a part (at least 2) of the active methylol groups (CH2OH groups) in the nitrogen compound such as (poly) methylolmelamine, (poly) methylolglycoluril, (poly) methylolbenzoguanamine, and (poly) methylolurea are etherified with an alkyl group. 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 or different. The methylol group not etherified with an alkyl group may be self-condensed in one molecule or condensed between two molecules, and as a result, an oligomer component is formed. 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 addition, in the present specification, nothing specifically statedThe treatment and measurement at the respective predetermined temperatures 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.

The above-mentioned applications are not limited to applications requiring durability against ultraviolet rays, such as when used as products, and can be suitably used for members that are subjected to ultraviolet irradiation or the like in a production process, for example.

Examples of the member to be irradiated with ultraviolet rays during the production process include a member to be irradiated with ultraviolet rays for the purpose of surface modification such as improvement of wettability and adhesion of the surface.

Examples of the member required to improve wettability and improve adhesion include members laminated with other members, for example, various image displays such as a plasma display panel, an organic electroluminescence display device, and a liquid crystal display device, various sensors such as a touch panel, color filters, optical spacers, luminance improving plates, light guide plates, TFT substrates, alignment films, liquid crystal layers, insulating films, acoustic elements such as speakers, imaging lenses, keyboards, magnetic heads for HDDs, and the like, which are members constituting a circuit board and the like, and which require surface modification and prevention of deterioration of the members during the manufacturing process.

The member required to be surface-modified and prevented from deterioration in the above-described production process includes a member laminated with another member by an adhesive, a member covered with another member by a paint or the like, and components for various applications such as transportation equipment such as interior and exterior parts of automobiles and airplanes, home electric appliances such as refrigerators and washing machines, and building materials for houses.

After forming a patterned member on a base material, the member may be subjected to ultraviolet irradiation or the like together with the base material in order to modify the surface of the exposed base material. The above-described application can be preferably applied to a member used together with a member which requires surface modification or the like in such a production process. Examples of the above-mentioned applications include those used together with members requiring surface cleaning, surface modification, and the like of plastic films, glass, silicon wafers, various engineering plastics, optical lenses, metal surfaces, plating, ceramics, molds, and the like.

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 containing the compound I-1 of the present invention and a polymerizable compound.

The composition of the present invention has good ultraviolet absorption ability and the like because the composition is used.

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 leaving the photo-leaving group B in the cured product, but is preferably after leaving. This is because the cured product has excellent ultraviolet absorption ability.

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, per 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, 10⁶MPaThe following.

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) (hereinafter, sometimes referred to as "compound I-2") and a leaving compound derived from a photoleaving group (hereinafter, sometimes referred to as "compound B'").

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 ultraviolet absorption 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 above-mentioned compound I-2 exerts ultraviolet-absorbing 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 any content as long as it can impart a desired ultraviolet absorbing ability, but for example, the total of the compound I-2 and the compound B' may be the same as the content of the compound I-1 in the solid content described in the section "C.

2. Compound B'

The above compound B' is a leaving species from a photo-leaving group.

The photo-leaving group may be the same as that described in "1. photo-leaving group B" of the above "a. compound", as long as it is a group capable of bonding to a phenolic hydroxyl group as a protecting group.

The compound B' may be any compound that can be obtained after the above-mentioned photoleaving group is removed from the phenolic hydroxyl group.

The photo-leaving group B after leaving from the phenolic hydroxyl group is generally highly reactive and can have various structures.

When the light leaving 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.

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 hereAnd (5) clearing.

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

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, for example, easily imparting ultraviolet absorbing ability to a cured product.

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".

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 and a polymerizable compound to form a cured product, and a step of irradiating the cured product with light to remove a photo-leaving group B contained in the compound.

According to the present invention, the above-mentioned production method can easily provide excellent ultraviolet absorption ability and the like by using the above-mentioned composition and having the above-mentioned steps, and curing is easy.

The production method of the present invention includes a step of forming a cured product and a step of removing the cured product.

Hereinafter, each step of the production method of the present invention 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 light irradiated is preferably an amount of light capable of suppressing the leaving of the photoleaving 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. Leaving procedure

The leaving step is a step of leaving the photo-leaving group B contained in the compound I-1.

The method for removing the photo-leaving 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 leaving the photo-leaving group B, and may be the same as those described in the section "1. photo-leaving group B" of the above-mentioned "a. compound".

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 leaving of the photo-leaving group B becomes easy by setting the temperature to the above range. 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 is 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 removing 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 embodiments are illustrative, and any embodiments having substantially the same configuration as the technical idea described in 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.

[ example 1]

0.005mol of phenol compound (compound I-2) in the following scheme 1, 0.005mol of potassium carbonate and DMF12g were mixed, 0.0075mol of o-nitrobenzyl chloride was added dropwise at room temperature under a nitrogen atmosphere, and stirred at 80 ℃ for 2 hours to obtain compound I-1-2 corresponding to 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 crystallization was performed with methanol. The obtained white solid was dried under reduced pressure at 45 ℃ for 2 hours to obtain the objective compound (Compound I-1-2). The obtained white solid was confirmed by H-NMR and IR as the objective substance.

[ examples 2 to 7]

The following compounds I-1-3, I-1-40, I-1-32, I-1-35, I-1-28 and I-1-34 were obtained in the same manner as in example 1 except that o-nitrobenzyl chloride was changed. Specifically, the compounds I-1-3, I-1-40, I-1-32, I-1-35, I-1-28 and I-1-34 of examples 2 to 7 were produced by the following methods.

Further, it was confirmed by H-NMR that the white solids obtained in examples 2 to 7 were the target compounds.

[ example 2]

1.1 equivalents of N-bromosuccinimide and 0.01 equivalent of AIBN relative to 2-ethylnitrobenzene were used and heated and stirred in chlorobenzene solvent at 90 ℃ for 4 hours. And performing oil-water separation by ethyl acetate, washing with water, and refining by a silica column to obtain the benzyl bromide compound. Compound I-1-3 was obtained in the same manner as in example 1, except that this benzyl bromide compound was used instead of o-nitrobenzyl chloride. The obtained white solid was confirmed by H-NMR to be the objective substance.

[ example 3]

Compounds I-1 to 40 were obtained in the same manner as in example 2, except that 4-chloro-2-nitrotoluene was used in place of 2-ethylnitrobenzene. The obtained white solid was confirmed by H-NMR to be the objective substance.

[ example 4]

Compounds I-1 to 32 were obtained in the same manner as in example 1 except that 4' -methoxybenzoylmethyl bromide was used instead of o-nitrobenzyl chloride. The obtained white solid was confirmed by H-NMR to be the objective substance.

[ example 5]

Compounds I-1 to 35 were obtained in the same manner as in example 1, except that 2-bromo-2-phenylacetophenone was used instead of the o-nitrobenzyl chloride. The obtained white solid was confirmed by H-NMR to be the objective substance.

[ example 6]

Compound I-1-28 was obtained in the same manner as in example 1, except that 2-bromo-2' -nitroacetophenone was used instead of o-nitrobenzyl chloride. The obtained white solid was confirmed by H-NMR to be the objective substance.

[ example 7]

Compound I-1-34 was obtained in the same manner as in example 1, except that 4-bromomethyl-7-methoxycoumarin was used instead of o-nitrobenzyl chloride. The obtained white solid was confirmed by H-NMR to be the objective substance.

[ example 8]

1.1 equivalents of N-bromosuccinimide and 0.01 equivalent of AIBN relative to 4-methoxy-2-nitrotoluene were used, and the mixture was heated and stirred in a chlorobenzene solvent at 90 ℃ for 4 hours. And (3) performing oil-water separation by ethyl acetate, washing with water, and refining by a silica column to obtain the corresponding benzyl bromide compound. Compound I-1-4 was obtained in the same manner as in example 1, except that this benzyl bromide compound was used instead of o-nitrobenzyl chloride. The obtained white solid was confirmed by H-NMR to be the objective substance.

[ example 9]

Compound I-1-41 was obtained in the same manner as in example 8, except that 3-chloro-2-nitrotoluene was used instead of 4-methoxy-2-nitrotoluene. The obtained white solid was confirmed by H-NMR to be the objective substance.

[ example 10]

Compound I-1-42 was obtained in the same manner as in example 8, except that 3-methoxy-2-nitrotoluene was used instead of 4-methoxy-2-nitrotoluene. The obtained white solid was confirmed by H-NMR to be the objective substance.

[ example 11]

Compound I-1 to 43 was obtained in the same manner as in example 8, except that 3-methoxy-2-nitro-6-bromotoluene was used instead of 4-methoxy-2-nitrotoluene. The obtained white solid was confirmed by H-NMR to be the objective substance.

[ example 12]

Compound I-1-44 was obtained in the same manner as in example 1, except that 2-bromo-2' -methylacetophenone was used instead of o-nitrobenzyl chloride. The obtained white solid was confirmed by H-NMR to be the objective substance.

[ example 13]

An intermediate compound was obtained in the same manner as in example 1, except that 4- (2-bromoacetyl) phenyl tert-butyl carbonate was used instead of o-nitrobenzyl chloride. 0.0035mol of this intermediate compound was dissolved in 5mL of ethyl acetate, and 5mL of 4M HCl ethyl acetate solution was added thereto, followed by heating and stirring at 50 ℃ for 10 hours. The solvent of the reaction solution was distilled off, and the reaction solution was isolated by a silica column (ethyl acetate: hexane ═ 1: 2) to obtain the target compound (compound I-1 to 45). The obtained white solid was confirmed by H-NMR to be the objective substance.

[ example 14]

0.004mol of a phenol compound (phenol compound in scheme 1) was dissolved in 40mL of pyridine, and 0.006mol of NPPOC-Cl (2-nitrophenyl) propyl chloroformate) was added dropwise thereto, followed by stirring at room temperature for 6 hours. To the reaction mixture were added 200g of ethyl acetate and 50g of ion-exchanged water, followed by oil-water separation. The organic layer was washed 2 times with dilute hydrochloric acid, 3 times with ion-exchanged water, the solvent was distilled off, and the product was isolated by passing through a silica column (ethyl acetate: hexane ═ 1: 4). The obtained white solid was dispersed in hexane and then dried under reduced pressure at 45 ℃ for 2 hours to obtain the objective compound (compound I-1-46). The obtained white solid was confirmed by H-NMR to be the objective substance.

[ examples 15 to 17]

The following compounds I-1-8, I-1-47 and I-1-48 were obtained in the same manner as in example 1 except that the compounds represented by the following formulae (1) to (3) were used as the phenol compounds.

TABLE 1

TABLE 2

[ evaluation ]

A0.01 mass% acetonitrile solution of the compounds of examples 1,2, 5 to 9, 12 to 14 and 16 (compounds I-1-2, I-1-3, I-1-35, I-1-28, I-1-34, I-1-4, I-1-41, I-1-44, I-1-45, I-1-46 and I-1-47) 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 leaving rate was calculated from the following formula. The results are shown in table 3 below.

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

Leaving ratio (%) ═ phenol compound (compound I-2)/phenol compound (compound I-2) + compound I-1) × 100

In addition, in examples 1,2 and 7 (Compounds I-1-2, I-1-3 and I-1-34), before light irradiation (0 mJ/cm)²) And (10000 mJ/cm) after light irradiation²) The absorption spectrum of light having a wavelength of 250nm to 450nm was confirmed. It is composed ofAs a result, it was confirmed that light on the long wavelength side was absorbed more widely in the range of the wavelength of 250nm or more and 450nm or less after the light irradiation than before the light irradiation. The measurement results of the maximum absorption wavelength (nm) are shown in tables 3 and 4 below.

TABLE 3

TABLE 4

As is clear from tables 3 and 4, it was confirmed that Compound I-1 was irradiated with light to remove the photo-leaving group B.

Further, as is clear from Table 3, it was confirmed that the compound I-1 can efficiently absorb ultraviolet rays having a wide wavelength ranging from 250nm to 450nm by light irradiation. In addition, along with this, a shift of the maximum absorption wavelength to the longer wavelength side was observed.

From the above, it was confirmed that compound I-1 had a phenolic hydroxyl group protected by a photo-leaving group B before light irradiation to inhibit ultraviolet absorbability, and thus inhibited curing inhibition, and that ultraviolet absorbability could be easily imparted by light irradiation.

The components shown in the following table 5 were mixed in the proportions shown in table 5 to obtain compositions of examples 18 to 20 and comparative examples 1 and 2. The symbols in table 5 represent the following compounds. The numerical values in the table represent parts by mass.

A-1: 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

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

F-1: compound I-1-3

F-2: compounds I-1-35

F-3: compounds I-1-47

The curability and light resistance of the obtained compositions of examples 18 to 20 and comparative examples 1 and 2 were evaluated by the following methods.

[ curability ]

The compositions of examples 18 to 20 and comparative examples 1 and 2 were coated on a PET film with a thickness of about 3 μm by a bar coater. 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 higher the number of stages in the stepwise exposure table, the higher the photosensitivity and the better the curability. The results are shown in table 5 below.

[ light resistance ]

The compositions of examples 18 to 20 and comparative examples 1 and 2 were applied to a glass substrate using a spin coater. 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). Exposure was carried out so that the exposure light amount became 100mJ/cm²Is carried out in the manner of (1). Then, the resultant was further irradiated with 3000mJ/cm²Samples for light resistance evaluation were prepared. Xenon light resistance tester using Suga test mechanismTable Sun XT-1500L, for the evaluation of samples for 24 hours light resistance test. The difference in transmittance (%) at a wavelength of 470nm before and after the light resistance test of the sample for evaluation (transmittance (%) before the light resistance test-transmittance (%) before the light resistance test) was measured, and the light resistance evaluation was performed according to the following criteria.

Good: the transmittance difference (%) was less than 5% with respect to the transmittance before the light resistance test.

X: the transmittance difference (%) was 5% or more with respect to the transmittance before the light resistance test.

The light resistance was evaluated as "○", which indicates that the cured product was excellent in light resistance, and the results are shown in Table 5 below.

TABLE 5

	Example 18	Example 19	Example 20	Comparative example 1	Comparative example 2
						A-1	50	50	50	50	50
A-2	50	50	50	50	50
						B-1	5	5	5	5	5
C-1	1	1	1	1	1
						D-1	50	50	50	50	50
E-1					5
						F-1	5
F-2		5
						F-3			5
Curing Properties	16	17	16	17	12
						Light resistance	○	○	○	×	○

As is clear from Table 5, the compositions of examples 18 to 20 containing the compound I-1 were superior in light resistance to the composition of comparative example 1 containing no ultraviolet absorber. The compositions of examples 18 to 20 were more excellent in curability than the composition of comparative example 2 containing a known ultraviolet absorber. From this, it is understood that the present invention can provide a composition having less curing inhibition and excellent light resistance.

Industrial applicability

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

The latent ultraviolet absorber of the present invention has less curing inhibition, and can easily impart ultraviolet absorbing ability to a cured product.

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

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

According to the method for producing a cured product of the present invention, a cured product having excellent ultraviolet absorption ability and the like 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 ultraviolet absorbability.

Claims

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

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

2. The compound according to claim 1, wherein B in the general formula (I-1) contains at least 1 of the groups represented by the following general formulae (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 aralkyl 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 group in the alkyl group and the aralkyl group may be substituted with 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-、-NH-CO-O-、-NR’-、>P＝O、-S-S-、-SO₂-or a combination thereof,

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

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

indicates a bonding position to said 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 aralkyl group having 7 to 20 carbon atoms or a heterocyclic group having 2 to 20 carbon atoms,

R³²、R³³、R⁴¹、R⁴²、R⁴³and R⁴⁴Independently represent 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, a C7 to E20 aralkyl group or heterocyclic group having 2 to 20 carbon atoms,

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 according to claim 2, wherein the compound represented by the general formula (I-1) is a compound represented by the following general formula (A-1), (A-2) or (A-3),

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

in the formula, R¹And R²Each 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 aralkyl group having 7 to 20 carbon atoms, a heterocyclic group having 2 to 20 carbon atoms or the group-O-B,

R¹and R²Is the-O-B group at least one of,

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

m1 and m2 each independently represent an integer of 1 to 10,

n represents an integer of 1 to 3,

a1 represents an integer of 0 to 4,

a2 represents an integer of 0 to 2,

a3 represents an integer of 0 to 4,

a4 represents an integer of 0 to 3,

a5 represents an integer of 0 to 3,

a6 represents an integer of 0 to 3-n,

X¹and X²A bonding group representing m1 valence and m2 valence respectively;

in the formula, 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 aralkyl group having 7 to 20 carbon atoms or a C2 to 20-containing groupA heterocyclic group,

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 aralkyl group having 7 to 20 carbon atoms or a heterocyclic group having 2 to 20 carbon atoms,

R¹¹and R¹²The methylene group in the alkyl or aralkyl group represented by the above-mentioned formula is sometimes replaced with 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-S-、-SO₂-or a combination thereof,

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

plural R¹¹Sometimes bonded to each other to form a benzene ring or a naphthalene ring,

R¹¹and R¹²Sometimes the same, sometimes different,

b1 represents an integer of 0 to 4,

indicates the bonding position to said a-O-.

4. A latent ultraviolet absorber comprising the compound according to any one of claims 1 to 3.

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

6. The composition of claim 5, further comprising a resin component.

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

8. 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 photo-leaving group contained in the compound.

9. A composition comprising a compound represented by the following general formula (I-2) and a leaving substance derived from a photo-leaving group,

wherein A represents an atomic group having ultraviolet absorptivity, and k represents an integer of 1 to 10.