JPWO2019069960A1 - Methods for producing compounds, latent UV absorbers, compositions, cured products and cured products - Google Patents

Abstract

A compound represented by the following general formula (I-1). (In the formula, A represents an atomic group having an ultraviolet absorbing ability, B represents a photoleaving group, and k represents an integer of 1 to 10.) With a compound represented by the following general formula (I-2). , A composition comprising a leaving product derived from a photoleaving group. (In the formula, A represents an atomic group capable of absorbing ultraviolet rays, and k represents an integer of 1 to 10.)

Description

The present invention relates to a compound that has little curing inhibition and can easily impart ultraviolet absorbing ability or the like to a cured product.

In order to improve the ultraviolet absorbing ability and heat resistance of the curable composition, a method of adding an ultraviolet absorber or an antioxidant to the curable composition to stabilize it is known (Patent Documents 1 to 3). ..

Japanese Unexamined Patent Publication No. 2011-048382 US20160116919A1 Japanese Unexamined Patent Publication No. 2015-108649

However, the ultraviolet absorbers described in Patent Documents 1 to 3 have a problem that they may inhibit the curing of the curable composition.
In response to such problems, the present inventors have an effect that the ultraviolet absorber has an action of absorbing the light irradiated to cure the curable composition, and because it has such an action, It has been found that the addition of an ultraviolet absorber into a polymerization system may cause curing inhibition.

As a means for solving the above problems, there is known a latent additive in which the above-mentioned light-absorbing action is inactivated in the polymerization system and can be activated after curing.
However, in some cases, heating or the like is required for activation of the latent additive that can be activated after curing, and in some cases, easier activation is required.

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

As a result of diligent studies to solve the above problems, the present inventors have used a photoleaving group as a protecting group and protected the phenolic hydroxyl group contained in the ultraviolet absorber with the photoleaving group. , It has been found that the timing of developing the ultraviolet absorbing ability can be easily adjusted and the above-mentioned problems can be solved, and the present invention has been completed.

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

(In the formula, A represents an atomic group capable of absorbing ultraviolet rays, B represents a photoleaving 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 a composition containing the compound represented by the above general formula (I-1) and a polymerizable compound.

Further, the present invention comprises a step of curing a composition containing the compound represented by the general formula (I-1) and a polymerizable compound to form a cured product, and irradiating the cured product with light. The present invention provides a method for producing a cured product, which comprises a step of removing a photoleaving group contained in the compound represented by the general formula (I-1).

Further, in the present invention, a compound represented by the following general formula (I-2) (hereinafter, may be referred to as “Compound I-2”) and a desorbed product derived from a photoleaving group (hereinafter, “Compound”). A composition containing (may be referred to as "B'") (hereinafter, may be referred to as "second composition") is provided.

(In the formula, A is an atomic group having an ultraviolet absorbing ability, and k represents an integer of 1 to 10.)

The present invention relates to a compound, an ultraviolet absorber using the compound, a composition, a cured product thereof, a method for producing the cured product, and a second composition. These will be described in detail below.

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

(In the formula, A is an atomic group capable of absorbing ultraviolet rays, B is a photoleaving group, and k represents an integer of 1 to 10.)

In the compound I-1 of the present invention, the atomic group A has an ultraviolet absorbing ability. The compound I-1 of the present invention has a low ultraviolet absorbing ability before the desorption of the photoleaving group B, but exhibits an excellent ultraviolet absorbing ability based on the atomic group A after the desorption of the photoleaving group B.
Therefore, when the compound I-1 before the photoleaving group B is eliminated is added into the polymerization system, for example, the compound I-1 has a low ability to absorb ultraviolet rays, so that the light absorbed for the polymerization is absorbed. The ability is low and it is difficult to inhibit the curing of the polymerization system.
On the other hand, the compound I-1 of the present invention is exposed to light to release photoleaving groups and exhibits excellent ultraviolet absorbing ability. Therefore, by irradiating the cured product containing the compound I-1 with light, the cured product can be easily imparted with an ultraviolet absorbing ability. Since compound I-1 does not need to be heat-treated in order to exhibit its ultraviolet absorbing ability, it has an advantage that it is difficult to damage the cured product and its peripheral members such as a base material by heating.
For the above reasons, the compound I-1 has little curing inhibition, for example, and can easily impart ultraviolet absorbing ability or the like to the cured product.

Further, the compound I-1 of the present invention has a low ability to absorb light irradiated for photosensitivity before desorption of the photoleaving group B. Therefore, when compound I-1 is added to a photosensitive composition whose solubility in an alkaline developer changes by light irradiation, the photosensitivity can be stably exhibited. Further, the compound I-1 can be easily imparted with an ultraviolet absorbing ability or the like by irradiating the photosensitive composition with light capable of desorbing a photoleaving group.
As described above, the compound I-1 has less inhibition of the expression of photosensitive with respect to the photosensitive composition, and can easily impart ultraviolet absorbing ability and the like to the photosensitive composition.

Further, the compound I-1 of the present invention can easily adjust the dispersion or dissolution stability in the composition, for example, by having the photoleaving group B.
Compound I-1 can be imparted with excellent dispersibility in the composition by selecting the photoleaving group B so as to improve the affinity with other components contained in the composition.
Therefore, the compound I-1 can impart 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. 1. Photoleaving group B
Compound I-1 of the present invention has a photoleaving group B.
The photoleaving group in the present invention can be a group that can be desorbed from compound I-1 by being irradiated with light of a specific wavelength. When compound I-1 is irradiated with light of a specific wavelength, the photoleaving group B is desorbed from compound I-1, and an atomic group having a hydroxyl group and an ultraviolet absorbing ability represented by the following general formula (I-2) A compound having A is produced.

(In the formula, A represents an atomic group capable of absorbing ultraviolet rays, and k represents an integer of 1 to 10.)

The wavelength of light that the photoleaving group B desorbs from compound I-1 is, for example, the wavelength range of ultraviolet rays or visible light. Specifically, it can contain a wavelength of 365 nm, more specifically, it can contain light having a wavelength of 250 nm or more and 450 nm or less, and preferably it contains light having a wavelength of 280 nm or more and 380 nm or less. Can be done.
Integrated light quantity of the light irradiated to detach the light leaving group B from above Compound I-1, for example, it is a 1000 mJ / cm ² or more 10000 mJ / cm ² or less, 1000 mJ / cm ² or more 5000mJ It is preferably ² / cm or less, and more preferably 2000 mJ / cm ² or more and 4000 mJ / cm ² or less. The integrated amount of light irradiated for curing the composition containing the polymerizable compound and the like is usually less than 1000 mJ / cm ² . Therefore, when the integrated light amount is in the above range, it can be easily applied to, for example, a photocurable composition.
The photoleaving group B is desorbed as long as it can impart a desired ultraviolet absorbing ability. For example, the desorption rate of the photoleaving group can be 50% or more. Above all, it is preferably 80% or more. This is because it can be easily applied to a photocurable composition.
On the other hand, the integrated light amount for which photodesorption is suppressed may be less than 1000 mJ / cm ^{2 as} long as the desired effect of suppressing hardening inhibition can be obtained. This is because it can be easily applied to a photocurable composition.
Further, the fact that photoresorption is suppressed means that a desired effect of suppressing hardening inhibition can be obtained, and for example, the desorption rate of the photoleaving group B can be less than 50%. Above all, it is preferably 20% or less. This is because it can be easily applied to a photocurable composition.
The integrated light amount can be measured by preparing a 0.01 mass% acetonitrile solution of compound I-1 and using the same method as the method for measuring the desorption rate described in Examples.

Specific examples of the photoleaving group B satisfying the above requirements include the following general formulas (B-1), (B-2), (B-3), (B-4), and (B-5). , (B-6), (B-7) and (B-8). Among them, the following general formulas (B-1-a), (B-2-a), (B-3-a), (B-4), (B-5), (B-6), (B) It is preferably a group represented by -7-a), (B-7-b) and (B-8-a), and is a group represented by the following general formula (B-1-a). Is preferable. This is because by adopting these photoleaving groups, the compound I-1 can be easily desorbed and the cured product can be easily imparted with an ultraviolet absorbing ability or the like. Further, as the photoleaving group B satisfying the above-mentioned requirements, specifically, groups represented by the following general formulas (B-9) and (B-10) can be mentioned.

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

(In the formula, R ³¹ and R ⁴⁰ are independently halogen atom, cyano group, hydroxyl group, nitro group, carboxyl group, alkyl group having 1 to 40 carbon atoms, aryl group having 6 to 20 carbon atoms, and carbon. Represents an arylalkyl group having 7 to 20 atoms or a heterocyclic group having 2 to 20 carbon atoms.
R ³² , R ³³ , R ⁴¹ , R ⁴² , R ⁴³ , and R ⁴⁴ are independently hydrogen atoms, halogen atoms, cyano groups, hydroxyl groups, nitro groups, carboxyl groups, and alkyl groups having 1 to 40 carbon atoms. Represents an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, or a heterocycle-containing group having 2 to 20 carbon atoms.
The methylene groups in the alkyl and arylalkyl groups represented by R ³¹ , R ³² , R ³³ , R ⁴⁰ , R ⁴¹ , R ⁴² , R ⁴³ and R ⁴⁴ are carbon-carbon double bonds, -O-, -S-, -CO-, -O-CO-, -CO-O-, -O-CO-O-, -O-CO-O-, -S-CO-, -CO-S-, -S -CO-O-, -O-CO-S-, -CO-NH-, -NH-CO-, -NH-CO-O-, -NR'-,> P = O, -S-S-, It may be replaced by -SO _2- or a combination of these.
The alkyl group, aryl group, arylalkyl group and heterocyclic group may have a substituent and may have a substituent.
c1 represents an integer from 0 to 5,
c2 represents an integer from 0 to 4 and represents
** represents the bonding position with the AO−. )

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

Examples of the aryl group having 6 to 20 carbon atoms represented by R ¹¹ or the like, for example, a phenyl group, a naphthyl group and anthracenyl group.

Examples of the arylalkyl group having 7 to 20 carbon atoms represented by R ¹¹ or the like, for example, a benzyl group, a fluorenyl group, an indenyl group and 9-fluorenylmethyl group.

Examples of the heterocyclic ring-containing group having 2 to 20 carbon atoms represented by R ¹¹ or the like, for example, a pyridyl group, pyrimidyl group, pyridazyl group, piperidyl group, pyranyl group, a pyrazolyl group, a triazyl group, a pyrrolyl group, a quinolyl group , Isoquinolyl group, imidazolyl group, benzoimidazolyl group, triazolyl group, furyl group, furanyl group, benzofuranyl group, thienyl group, thiophenyl group, benzothiophenyl group, thiadiazolyl group, thiazolyl group, benzothiazolyl group, oxazolyl group, benzoxazolyl group. , Isothiazolyl group, isooxazolyl group, indolyl group, 2-pyrrolidinone-1-yl group, 2-piperidone-1-yl group, 2,4-dioxyimidazolidine-3-yl group and 2,4-dioxyoxazolidine- 3-Il group and the like can be mentioned.

As the alkyl group having 1 to 8 carbon atoms represented by R', among those exemplified as the alkyl group represented by R ¹¹ or the like, those having 1 to 8 carbon atoms can be mentioned.

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

Examples of the substituent that may substitute a hydrogen atom such as an alkyl group, an aryl group, an arylalkyl group and a heterocyclic group include an ethylenically unsaturated group such as a vinyl group, an allyl group, an acrylic group and a methacryl group; Halogen atoms such as fluorine, chlorine, bromine and iodine; acetyl group, 2-chloroacetyl group, propionyl group, octanoyl group, acryloyl group, methacryloyl group, phenylcarbonyl (benzoyl) group, phthaloyl group, 4-trifluoromethylbenzoyl group. , Pivaloyl group, salicyloyl group, oxaloyl group, stearoyl group, methoxycarbonyl group, ethoxycarbonyl group, t-butoxycarbonyl group, n-octadecyloxycarbonyl group, carbamoyl group and other acyl groups; acetyloxy group and benzoyloxy group and the like. Acyloxy group; amino group, ethylamino group, dimethylamino group, diethylamino group, butylamino group, cyclopentylamino group, 2-ethylhexylamino group, dodecylamino group, anirino group, chlorophenylamino group, toluidino group, anisidino group, N- Methyl-anilino group, diphenylamino group, naphthylamino group, 2-pyridylamino group, methoxycarbonylamino group, phenoxycarbonylamino group, acetylamino group, benzoylamino group, formylamino group, pivaloylamino group, lauroylamino group, carbamoylamino group , N, N-dimethylaminocarbonylamino group, N, N-diethylaminocarbonylamino group, morpholinocarbonylamino group, methoxycarbonylamino group, ethoxycarbonylamino group, t-butoxycarbonylamino group, n-octadecyloxycarbonylamino group, Substituent amino groups such as N-methyl-methoxycarbonylamino group, phenoxycarbonylamino group, sulfamoylamino group, N, N-dimethylaminosulfonylamino group, methylsulfonylamino group, butylsulfonylamino group and phenylsulfonylamino group; Sulfonamide group, sulfonyl group, carboxyl group, cyano group, sulfo group, hydroxyl group, nitro group, mercapto group, imide group, carbamoyl group, sulfonamide group, phosphonic acid group, phosphoric acid group or carboxyl group, sulfo group, phosphonic acid Examples include salts of groups and phosphate groups.

In the present invention, the number of carbon atoms of a group defines the number of carbon atoms of the group after the hydrogen atom in the group is substituted with a substituent. For example, when the hydrogen atom of the alkyl group having 1 to 40 carbon atoms is substituted, the carbon atom number 1 to 40 refers to the number of carbon atoms after the hydrogen atom is substituted, and the hydrogen atom is substituted. It does not refer to the number of carbon atoms before.

In the present invention, the number of carbon atoms of a group defines the number of carbon atoms of the group after the methylene group in the group is replaced by the above divalent group. For example, in the present specification, when the methylene group in the alkyl group having 1 to 40 carbon atoms is replaced by the divalent group, the “1 to 40 carbon atoms” means after the methylene group is replaced. It refers to the number of carbon atoms in the above, not the number of carbon atoms before the replacement of the methylene group. Therefore, "-OC ₄₀ H ₈₁ " corresponds to "an alkyl group having 40 carbon atoms (= an alkoxy group having 40 carbon atoms) in which the methylene group at the terminal is replaced with -O-". Is. Similarly, "-CO-O-C _{39H 79} " corresponds to "an alkyl group having 40 carbon atoms in which the terminal methylene group is replaced with -CO-O-".

Methylene group of the alkyl group and in the arylalkyl group used in R ¹¹ or the like, a carbon - carbon double bond, -O -, - S -, - CO -, - O-CO -, - CO-O -, - O-CO-O-, -O-CO-O-, -S-CO-, -CO-S-, -S-CO-O-, -O-CO-S-, -CO-NH-,- It may be replaced by NH-CO-, -NH-CO-O-, -NR'-,> P = O, -SS-, -SO _2- or a combination thereof.
The combination for substituting the methylene group can be a combination under the condition that the oxygen atoms are not adjacent to each other.

In the alkyl group having 1 to 40 carbon atoms represented by R ¹¹ or the like, the methylene group at the terminal end side may be replaced with —O— to form an alkoxy group. Examples of such an alkoxy group include an alkoxy group having 1 to 10 carbon atoms. Specifically, methyloxy group, ethyloxy group, iso-propyloxy group, butyloxy group, sec-butyloxy group, tert-butyloxy group, iso-butyloxy group, amyloxy group, iso-amyloxy group, tert-amyloxy group, hexyl. Oxy group, 2-hexyloxy group, 3-hexyloxy group, cyclohexyloxy group, 4-methylcyclohexyloxy group, heptyloxy group, 2-heptyloxy group, 3-heptyloxy group, iso-heptyloxy group, tert- Examples thereof include a heptyloxy group, a 1-octyloxy group, an iso-octyloxy group and a tert-octyloxy group.

The R ¹¹ , R ¹³ , R ¹⁶ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²³ , R ²⁶ and R ²⁸ are preferably groups other than hydroxyl groups, and are preferably halogen atoms, cyano groups, nitro groups and carboxyl groups. , An alkyl group having 1 to 40 carbon atoms, an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, or a heterocyclic group containing 2 to 20 carbon atoms is preferable. This is because by using a group other than the hydroxyl group, the photoleaving group B is easily eliminated from the compound I-1, and the synthesis of the compound I-1 is facilitated.
It is particularly preferable that R ¹¹ and R ²³ are an alkoxy group having 1 to 10 carbon atoms such as a nitro group and a methoxy group, an alkyl group having 1 to 40 carbon atoms such as a methyl group, and a halogen atom. This is because the photoleaving group B is easily desorbed from compound I-1 and the synthesis of compound I-1 is facilitated.
The R ¹¹ is preferably an alkoxy group having 1 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms, or a halogen atom, and has an alkoxy group having 1 to 5 carbon atoms and 1 to 5 carbon atoms. It is more preferably an alkyl group or a halogen atom, further preferably an alkoxy group or a halogen atom having 1 to 5 carbon atoms, and further preferably an alkoxy group having 1 to 3 carbon atoms, a chlorine atom or a bromine atom. Especially preferable. This is because the photoleaving group B is easily desorbed from compound I-1 and the synthesis of compound I-1 is facilitated.
The R ¹³ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²⁶ and R ²⁸ are preferably alkyl groups having 1 to 40 carbon atoms. This is because the photoleaving group B is easily desorbed from compound I-1 and the synthesis of compound I-1 is facilitated.
The R ¹⁶ is preferably by bonding two R ¹⁶ adjacent to each other to form a benzene ring. This is because the photoleaving group B is easily desorbed from compound I-1 and the synthesis of compound I-1 is facilitated.
The R ³¹ and R ⁴⁰ are preferably groups other than a hydroxyl group, and are 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, and a carbon atom number. It is preferably an arylalkyl group having 7 to 20 or a heterocyclic group having 2 to 20 carbon atoms. This is because by using a group other than the hydroxyl group, the photoleaving group B is easily eliminated from the compound I-1, and the synthesis of the compound I-1 is facilitated.
The R ³¹ is preferably an alkyl group having 1 to 40 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, and further preferably an alkyl group having 1 to 5 carbon atoms. It is preferably an alkyl group having 1 to 3 carbon atoms, and particularly preferably.

When the methylene group in the alkyl group represented by R ¹⁸ and R ¹⁹ and the aryl alkyl group is replaced with -O-, the -O- replacing the methylene group interrupts the alkyl group and the aryl alkyl group, respectively. In other words, it may be replaced with a methylene group other than the ends of the alkyl group and the arylalkyl group.

The R ¹² is preferably a hydrogen atom, a carboxyl group, or an alkyl group having 1 to 5 carbon atoms, and particularly preferably a hydrogen atom or a methyl group. This is because the photoleaving group B is easily desorbed from compound I-1 and the synthesis of compound I-1 is facilitated.
The above R ¹⁴ , R ¹⁷ , R ²¹ , R ²⁴ , R ²⁵ , R ²⁷ , R ²⁹ and R ³⁰ are preferably hydrogen atoms and alkyl groups having 1 to 40 carbon atoms, and are preferably hydrogen atoms. It is particularly preferable to have. This is because the photoleaving group B is easily desorbed from compound I-1 and the synthesis of compound I-1 is facilitated.
The R ¹⁵ and R ²² are preferably alkyl groups having 1 to 5 carbon atoms, and particularly preferably methyl groups. This is because it is possible to provide a compound that has less curing inhibition and can easily impart ultraviolet absorption ability or the like to the cured product.
The R ³² and R ³³ are each independently 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 are hydrogen atoms. Is particularly preferable. This is because it is possible to provide a compound that has less curing inhibition and can easily impart ultraviolet absorption ability or the like to the cured product.
Each of the above R ^{41 to} R ⁴⁴ 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 is a hydrogen atom. Is particularly preferable. This is because it is possible to provide a compound that has less curing inhibition and can easily impart ultraviolet absorption ability or the like to the cured product.

The above b1, b2, b3, b6, b7, b8 and b9 can each be independently an integer of 0 to 4, but from the viewpoint of ease of synthesis, it is preferably an integer of 0 to 3. It is more preferably an integer of 0 to 2, further preferably 0 to 1, and particularly preferably 0. This is because it is possible to provide a compound that has less curing inhibition and can easily impart ultraviolet absorption ability or the like to the cured product.
The above b4 and b5 can be independently set to an integer of 0 to 5, but from the viewpoint of ease of synthesis, it is preferably an integer of 0 to 3, and more preferably an integer of 0 to 2. It is preferably 0 to 1, more preferably 0, and particularly preferably 0. This is because it is possible to provide a compound that has less curing inhibition and can easily impart ultraviolet absorption ability or the like to the cured product.
The above c1 can 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, and 0 to 1. It is more preferably an integer of 1, and particularly preferably 1. This is because it is possible to provide a compound that has less curing inhibition and can easily impart ultraviolet absorption ability or the like to the cured product.
The above c2 can be an integer of 0 to 4, 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, and 0 to 1. It is more preferably an integer of, and particularly preferably 0. This is because it is possible to provide a compound that has less curing inhibition and can easily impart ultraviolet absorption ability or the like to the cured product.

The type of photoleaving group B contained in the compound I-1 of the present invention may be one type per compound I-1 when k is 2 or more, and may be two or more types. From the viewpoint of less inhibition of curing, easy imparting ultraviolet absorbing ability to the cured product, and facilitating the synthesis of compound I-1, one type is preferable.

The content k of the photoleaving group is an integer of 1 to 10, but from the viewpoint of less curing inhibition, easy imparting ultraviolet absorbing ability to the cured product, and easiness of synthesis. It is preferably an integer of 1 to 5, more preferably an integer of 1 to 4, and particularly preferably an integer of 1 to 3.

2. 2. Atomic group A capable of absorbing ultraviolet rays
Atomic group A is an atomic group having an ultraviolet absorbing ability.
When the compound I-1 of the present invention is irradiated with light having a specific wavelength, the photoleaving group B is eliminated to produce the compound I-2 having a hydroxyl group. Then, since the atomic group A has an ultraviolet absorbing ability, the compound I-2 exerts an ultraviolet absorbing ability.

“Having an ultraviolet absorbing ability” means that, for example, a compound having an ultraviolet absorbing ability, specifically, compound I-1 after desorption of a photoleaving group B, that is, compound I-2 has a wavelength of 250 nm or more. It can absorb light in the range of 450 nm or less. In the present invention, the atomic group having an ultraviolet absorbing ability can be an aggregate of atoms having at least one group having an ultraviolet absorbing ability or a group having an ultraviolet absorbing ability.
More specifically, the compound I-1 after desorption of the photoremoving group B, that is, the compound I-2 has a maximum absorption wavelength in the wavelength range of 250 nm or more and 600 nm or less. It is preferable to be able to absorb light having a maximum absorption wavelength of 250 nm or more and 400 nm or less, preferably to absorb light having a maximum absorption wavelength of 260 nm or more and 390 nm or less, and particularly preferably to absorb light having a maximum absorption wavelength of 280 nm or more and 380 nm or less. .. This is because it is possible to provide a compound that has less curing inhibition and can easily impart ultraviolet absorption ability or the like to the cured product.
The maximum absorption wavelength of compound I-1, that is, compound I-2 after elimination of the photoleaving group B can be measured by, for example, the following measuring method.
As an evaluation sample, for example, compound I-1 after elimination of the photoleaving group B, that is, compound I-2 dissolved in a solvent (acetonitrile) at a concentration of 0.01% by mass was used. Use. Then, the evaluation sample is filled in a quartz cell (optical path length 10 mm, thickness 1.25 mm), and the absorbance is measured using an absorptiometer (for example, U-3900 (manufactured by Hitachi High-Tech Science Corporation)). Can be done.

Further, the compound I-1 of the present invention contains the maximum absorption wavelength of the compound I-1 before the desorption of the photoremoval group B and the compound I-1 (compound I-2) after the desorption of the photoremoval group B. In the range of 250 nm or more and 600 nm or less, the maximum absorption wavelength of compound I-1 before the desorption of the photoremoving group B is shorter than the maximum absorption wavelength of compound I-2. Is preferable. This is because it can be easily applied to a photocurable composition.
The difference in the maximum absorption wavelength of the compound I-1 from that of the compound I-2 after desorption of the photoleaving group B is preferably 1 nm or more, more preferably 1 nm or more and 100 nm or less. It is particularly preferably 1 nm or more and 50 nm or less. This is because it can be easily applied to a photocurable composition.

Such an atomic group A can be the same as the atomic group generally used for an ultraviolet absorber having a phenolic hydroxyl group. That is, the compound I-2 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, triaryltriazines and the like described in JP-A-2017-008221 are used. , Benzotriazole-based ultraviolet absorbers and benzophenone-based ultraviolet absorbers described in JP-A-2002-97224 can be used.

Examples of the atomic group A include a phenol structure in which a phenolic hydroxyl group is protected by a photoleaving group B, that is, a substance containing a benzene ring to which the BO— is directly bonded. Specifically, an atomic group containing a benzene ring and a benzotriazole ring to which BO- is directly bonded; an atomic group containing a benzophenone ring to which BO- is directly bonded; and benzene to which BO- is directly bonded. Atomic groups including rings and triazine rings can be mentioned. It is preferable that at least one group of the benzotriazole group, the benzophenone group and the triazine group contains a structure directly bonded to the benzene ring contained in the phenol structure, and among them, the benzotriazole group, the benzophenone group and the triazine group. It is preferable that the bond position of at least one group to the benzene ring is the ortho position with respect to the bond position of BO-. This is because it is easy to prepare a compound that has little curing inhibition and can easily impart ultraviolet absorbing ability or the like to the cured product.

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

(In the formula, R ¹ and R ² are independently hydrogen atom, halogen atom, cyano group, hydroxyl group, nitro group, carboxyl group, alkyl group having 1 to 40 carbon atoms, and aryl having 6 to 20 carbon atoms, respectively. Represents a group, an arylalkyl group having 7 to 20 carbon atoms, a heterocycle-containing group having 2 to 20 carbon atoms, or the above-OB.
At least one of R ¹ and R ² is the above-OB.
R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ independently have a halogen atom, a cyano group, a hydroxyl group, a nitro group, a carboxyl group, an alkyl group having 1 to 40 carbon atoms, and a carbon atom number. Represents an aryl group of 6 to 20, an arylalkyl group having 7 to 20 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms.
The methylene group in the alkyl group or arylalkyl group represented by R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ is a carbon-carbon double bond, -O-, -S-, -CO-, -O-CO-, -CO-O-, -O-CO-O-, -O-CO-O-, -S-CO-, -CO-S-, -S -CO-O-, -O-CO-S-, -CO-NH-, -NH-CO-, -NH-CO-O-, -NR'-,> P = O, -S-S-, It may be replaced by -SO _2- or a combination of these.
R'represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.
A plurality of R ³ to each other, a plurality of R ⁴ with each other, a plurality of R ⁵ to each other, a plurality of R ⁶ to each other and a plurality of R ⁷ each other, might be combined with each other to form a benzene ring or a naphthalene ring,
Multiple R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ may be the same or different, respectively.
m1 and m2 each independently represent an integer of 1 to 10.
n represents an integer from 1 to 3 and represents
a1 represents an integer from 0 to 4 and represents
a2 represents an integer from 0 to 2 and represents
a3 represents an integer from 0 to 4 and represents
a4 represents an integer from 0 to 3 and represents
a5 represents an integer from 0 to 3 and represents
a6 represents an integer of 0 to 3-n and represents
X ¹ and X ² represent m1-valent and m-valent binding groups, respectively. )

Alkyl groups having 1 to 40 carbon atoms, aryl groups having 6 to 20 carbon atoms, and carbon atoms represented by R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ^{8 above.} Examples of the arylalkyl group having the number 7 to 20, the heterocycle-containing group having 2 to 20 carbon atoms, and the alkyl group having the carbon number 1 to 8 represented by R'are the above-mentioned "1. Photoremoving group B". It may be mentioned those exemplified as R ¹¹ or the like and R 'according to the section.

At least one of R ¹ and R ² is −OB.
From the viewpoint of ease of synthesis, it is preferable that ^one of R ¹ and R ² is −OB.
It said R ¹ and R ^2, from the viewpoint of the larger the change in ultraviolet absorbing ability, it is preferable both R ¹ and R ² are the -O-B.
When only ^one of R ¹ and R ² is −OB, the other is a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 40 carbon atoms, an aryl group having 6 to 20 carbon atoms, and a carbon atom. It is preferably an arylalkyl group having a number of 7 to 20 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 other of R ¹ and R ² is the functional group, so that the compound I-1 has a large change in the ultraviolet absorbing ability. Further, the compound I-1 has less inhibition of curing.
Further, as the above-mentioned alkyl group, arylalkyl group and the like, for example, one in which the methylene group is interrupted by -O-, -CO- or the like can be preferably used.

The R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are preferably cyano groups, hydroxyl groups, alkyl groups having 1 to 40 carbon atoms, and aryl alkyl groups having 7 to 20 carbon atoms. , Cyano group, hydroxyl group, alkyl group having 1 to 20 carbon atoms, arylalkyl group having 7 to 10 carbon atoms, and more preferably an alkyl group having 3 to 20 carbon atoms. It is preferably an alkyl group having 3 to 10 carbon atoms, more preferably. This is because the compound I-1 of the present invention can be easily synthesized, and the compound I-1 exhibits an excellent ultraviolet absorbing ability after elimination of the photoleaving group B.

Further, the light from the viewpoint of enabling excellent ultraviolet absorptivity after elimination of the leaving group B, R ⁴ is preferably an alkyl group having a branched structure having a carbon number of 3 to 15, carbon atoms It is more preferably an alkyl group having a branched structure of several 5 to 12, further preferably an alkyl group having a branched structure having 6 to 11 carbon atoms, and an alkyl having a branched structure having 7 to 10 carbon atoms. It is particularly preferable that it is a group.
The bond site of R ^{4 in} the benzene ring may be any position at which it can be bonded, but it is preferably in the para position with respect to the bond site of −OB. This is because compound I-1 exhibits an excellent ultraviolet absorbing ability after elimination of the photoleaving group B.

From the viewpoint of enabling excellent ultraviolet absorptivity after elimination of the light leaving group B, R ⁵ and R ⁶ carbon atoms 1 methylene group on the benzene ring side ends are replaced by -O- It is preferably an alkyl group of 20, that is, an alkoxy group having 1 to 20 carbon atoms, and more preferably an alkoxy group having 3 to 15 carbon atoms, and an alkoxy group having 5 to 12 carbon atoms. It is particularly preferable to have.
The bonding site of R ⁵ and R ^{6 in} the benzene ring may be any position that can be bonded, but it is preferably in the meta position with respect to the bonding site of −OB. .. This is because compound I-1 exhibits an excellent ultraviolet absorbing ability after elimination of the photoleaving group B.

From the viewpoint of enabling excellent ultraviolet absorption ability after desorption of the photoleaving group B, R ⁷ is an alkyl having 1 to 20 carbon atoms in which the methylene group at the terminal on the benzene ring side is replaced with −O−. It is preferably a group, that is, an alkoxy group having 1 to 20 carbon atoms, and among them, a methylene chain other than the terminal on the benzene ring side is replaced with -O- or -O-CO- and has 3 to 3 carbon atoms. It is preferably an alkoxy group of 20, and particularly preferably an alkoxy group having 3 to 15 carbon atoms in which the methylene chain other than the terminal on the benzene ring side is replaced with -O- or -O-CO-. , The methylene chain other than the benzene ring side terminal is preferably an alkoxy group having 6 to 15 carbon atoms in which -O- and -O-CO- are replaced, and in particular, the methylene chain other than the benzene ring side end. Is preferably an alkoxy group having 8 to 13 carbon atoms substituted with −O− or −O—CO−.
The bond site of R ^{7 in} the benzene ring may be any position where it can be bonded, but it is preferably in the meta position with respect to the bond site of −OB. This is because compound I-1 exhibits an excellent ultraviolet absorbing ability after elimination of the photoleaving group B.
From the viewpoint of enabling excellent ultraviolet absorption ability after desorption of the photo-eliminating group B, R8 is preferably an aryl group having 6 to 20 carbon atoms, and among them, 6 to 12 carbon atoms. It is preferably an aryl group of, and particularly preferably a phenyl group which may have a substituent.

Further, as the alkyl group and the arylalkyl group, those in which the methylene group is not interrupted and those in which the methylene group is interrupted by -O-, -CO- or the like can be preferably used.

The above m1 and m2 represent integers of 1 to 10. From the viewpoint of ease of synthesis, m1 and m2 are preferably integers of 1 to 6, more preferably integers of 1 to 4, and preferably integers of 1 to 3, respectively. It is particularly preferable, and in particular, it is preferably an integer of 1 to 2. This is because the synthesis of the compound I-1 becomes easy, and the compound I-1 exhibits an excellent ultraviolet absorbing ability after the elimination of the photoleaving group B.
Further, from the viewpoint that compound I-1 exhibits an excellent ultraviolet absorbing ability after elimination of the photoleaving group B, m2 is preferably an integer of 1.

The above n represents an integer of 1 to 3. From the viewpoint that the change in the ultraviolet absorbing ability of the compound I-1 is large, the above n is preferably an integer of 2 to 3, and particularly preferably 3. From the viewpoint that compound I-1 exhibits an excellent ultraviolet absorbing ability after desorption of the photoleaving group B, the above n is preferably an integer of 1 to 2, and particularly preferably 1.

The above a1 and a3 independently represent an integer of 0 to 4. From the viewpoint of ease of synthesis, the above a1 and a3 are each independently preferably an integer of 0 to 3, more preferably an integer of 0 to 2, and preferably an integer of 0 to 1. Especially preferable. This is because compound I-1 can be a compound that exhibits excellent ultraviolet absorbing ability after elimination of the photoleaving group B.
The above a2 represents an integer of 0 to 2. From the viewpoint of solubility, the above a2 is preferably an integer of 1 to 2. Further, from the viewpoint that compound I-1 exhibits excellent ultraviolet absorbing ability after desorption of photoleaving group B, the above a2 is preferably 1.
The above a4 and a5 each independently represent an integer of 0 to 3. From the viewpoint of ease of synthesis, the above a4 and a5 are preferably an integer of 0 to 2, particularly preferably an integer of 1 to 2, and particularly preferably 1. This is because compound I-1 can be a compound that exhibits excellent ultraviolet absorbing ability after elimination of the photoleaving group B.
The above a6 represents an integer of 0 to 3-n. The a6 is preferably an integer of 0 to 1 from the viewpoint of the compound I-1 exhibiting an excellent ultraviolet absorbing ability after elimination of the photoleaving group B and the ease of synthesis, and is 0. Is preferable.

The compound I-1 represented by the general formulas (A-1) and (A-2) has an m1 valence or an m2 valence (hereinafter, may be referred to as X) represented by X ¹ and X ² (hereinafter, may be referred to as X). It has a structure in which m1 or m2 (hereinafter, may be referred to as m) specific groups are bonded to a specific atom or group of m-valence (hereinafter, may be referred to as m-valent). The m specific groups may be the same or different from each other.

The X represents an m-valent binding group.
Specific examples of the bonding group X include a direct bond, a hydrogen atom, a nitrogen atom, an oxygen atom, a sulfur atom, a phosphorus atom, a group represented by the following (II-a) or (II-b),> C. = O,> NR ⁵³ , -OR ⁵³ , -SR ⁵³ , -NR ⁵³ R ⁵⁴ or m, an aliphatic hydrocarbon group having 1 to 120 carbon atoms and an aromatic group having 6 to 35 carbon atoms. It represents a ring-containing hydrocarbon group or a heterocyclic group having 2 to 35 carbon atoms, and R ⁵³ and R ⁵⁴ are independently a hydrogen atom, an aliphatic hydrocarbon group having 1 to 35 carbon atoms, and a carbon atom number. The aromatic ring-containing hydrocarbon group of 6 to 35 or the heterocyclic ring-containing group having 2 to 35 carbon atoms is represented, and the aliphatic hydrocarbon group, the aromatic ring-containing hydrocarbon group and the heterocyclic ring-containing group are −O−, −. S-, -CO-, -O-CO-, -CO-O-, -O-CO-O-, -O-CO-O-, -S-CO-, -CO-S-, -S- CO-O -, - O- CO-S -, - CO-NH -, - NH-CO -, - NH-CO-O -, - NH-CO-O -, - NR '-, - S-S It may be interrupted by −, −SO ₂₋ , a nitrogen atom or a combination thereof, and the aromatic ring or heterocycle may be fused with another ring.
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, X is an oxygen atom or a sulfur atom,> C = O, If -NH-CO-, -CO-NH- or> NR ⁵³ , m is 2, and if X is -OR ⁵³ , -SR ⁵³ or -NR ⁵³ R ⁵⁴ , m is 1 and X is. In some cases, the ring is formed together with the benzene ring.

(* Means that it binds to an adjacent group at the * part.)

The aliphatic hydrocarbon group having the same number of valences as m and having 1 to 120 carbon atoms represented by the binding group X has, for example, a methyl group, an ethyl group, and a propyl group as those having a monovalent m. , Isopropyl group, cyclopropyl group, butyl group, secondary butyl group, tertiary butyl group, isobutyl group, amyl group, isoamyl group, tertiary amyl group, cyclopentyl group, hexyl group, 2-hexyl group, 3-hexyl group. , Cyclohexyl group, bicyclohexyl group, 1-methylcyclohexyl group, heptyl group, 2-heptyl group, 3-heptyl group, isoheptyl group, tertiary heptyl group, n-octyl group, isooctyl group, tertiary octyl group, 2- Alkyl groups such as ethylhexyl group, nonyl group, isononyl group and decyl group; methyloxy group, ethyloxy group, propyloxy group, isopropyloxy group, butyloxy group, secondary butyloxy group, tertiary butyloxy group, isobutyloxy group, amyloxy group , Isoamyloxy group, tertiary amyloxy group, hexyloxy group, cyclohexyloxy group, heptyloxy group, isoheptyloxy group, tertiary heptyloxy group, n-octyloxy group, isooctyloxy group, tertiary octyloxy group, Alkoxy groups such as 2-ethylhexyloxy group, nonyloxy group and decyloxy group; methylthio group, ethylthio group, propylthio group, isopropylthio group, butylthio group, second butylthio group, tertiary butylthio group, isobutylthio group, amylthio group, isoamyl. Alkylthio groups such as thio group, tertiary amylthio group, hexylthio group, cyclohexylthio group, heptylthio group, isoheptylthio group, tertiary heptylthio group, n-octylthio group, isooctylthio group, tertiary octylthio group and 2-ethylhexylthio group. Vinyl group, 1-methylethenyl group, 2-methylethenyl group, 2-propenyl group, 1-methyl-3-propenyl group, 3-butenyl group, 1-methyl-3-butenyl group, isobutenyl group, 3-pentenyl group, Alkenyl groups such as 4-hexenyl group, cyclohexenyl group, bicyclohexenyl group, heptenyl group, octenyl group, decenyl group, pentadecenyl group, eicosenyl group and tricosenyl group; and groups in which these groups are substituted with substituents described later. And so on.

The aliphatic hydrocarbon group having the same number of valences as m and having 1 to 120 carbon atoms represented by the bonding group X has a methylene group, an ethylene group, a propylene group and a butylene as having a divalent m. An alkylene group such as a group and a butyldiyl group; the methylene chain of the alkylene group is replaced with -O-, -S-, -CO-O-, -O-CO-; ethanediol, propanediol, butanediol, Residues of diol groups such as pentandiol and hexanediol; residues of dithiol groups such as ethanedithiol, propanedithiol, butanedithiol, pentandithiol and hexanedithiol and groups in which these groups are substituted with substituents described later are included. Can be mentioned.

The aliphatic hydrocarbon group having the same number of valences as m and having 1 to 120 carbon atoms represented by the above-mentioned bonding group X has, for example, a propyridine group and 1,1, as those having a trivalent m. Examples thereof include an alkylidine group such as a 3-butylidine propyridine group; and a group in which these groups are substituted 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, which is represented by the above-mentioned bonding group X, has a benzyl group, a phenethyl group or a diphenylmethyl as a monovalent m. Arylalkyl groups such as groups, triphenylmethyl groups, styryl groups and cinnamyl groups; aryl groups such as phenyl groups and naphthyl groups; aryloxy groups such as phenoxy groups and naphthyloxy groups; arylthio groups such as phenylthio groups and naphthylthio groups: In addition, a group in which these groups are substituted with a substituent described later can be mentioned.

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

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

The heterocyclic group having the same number of valences as m and having 2 to 35 carbon atoms represented by the above-mentioned bonding group X has a pyridyl group, a pyrimidyl group, a pyridadyl group, and a piperidyl group as those having a monovalent m. , Pyranyl group, pyrazolyl group, triazil group, pyrrolyl group, quinolyl group, isoquinolyl group, imidazolyl group, benzoimidazolyl group, triazolyl group, frill group, furanyl group, benzofuranyl group, thienyl group, thiophenyl group, benzothiophenyl group, thiadiazolyl group , Thiazolyl group, benzothiazolyl group, oxazolyl group, benzoxazolyl group, isothiazolyl group, isooxazolyl group, indolyl group, 2-pyrrolidinone-1-yl group, 2-piperidone-1-yl group, 2,4-dioxyimidazole Examples thereof include a lysine-3-yl group, a 2,4-dioxyoxazolidine-3-yl group, a benzotriazoyl group and the like, and a group in which these groups are substituted with a substituent described later.

The heterocyclic group having the same number of valences as m and having 2 to 35 carbon atoms represented by the above-mentioned bonding group X has a pyridine ring, a pyrimidine ring, a piperidine ring, and a piperazin ring as those having a divalent m. , A divalent group having a triazine ring, a furan ring, a thiophene ring, an indole ring and the like, and a group in which these groups are substituted with a substituent described later.

The heterocyclic group having the same number of valences as m and having 2 to 35 carbon atoms represented by the bonding group X is a triazine ring having an isocyanul ring as a trivalent group having m. Examples thereof include a trivalent group having the above and a group in which these groups are substituted with a substituent described later.

As the aliphatic hydrocarbon group having 1 to 35 carbon atoms represented by R ⁵³ and R ⁵⁴ , the aliphatic hydrocarbon group represented by X or the aliphatic hydrocarbon group is substituted with a substituent described later. Among the groups, those having 1 to 35 carbon atoms can be mentioned.
The aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms or the heterocyclic group having 2 to 35 carbon atoms represented by R ⁵³ and R ⁵⁴ has a carbon atom number of 6 to 35 represented by X. Examples thereof include an aromatic ring-containing hydrocarbon group, a heterocyclic ring-containing group having 2 to 35 carbon atoms, or a group in which these groups are substituted with a substituent described later.

Each functional group such as the aliphatic hydrocarbon group, the aromatic ring-containing hydrocarbon group and the heterocyclic ring-containing group may have a substituent. Unless otherwise specified, the compound I-1 of the present invention includes those having no substituent and those having a substituent.
Such aliphatic hydrocarbon group, the substituent group such as an aromatic ring-containing hydrocarbon group and heterocyclic ring-containing group, for example, the same as the substituents replacing a hydrogen atom and alkyl groups used for R ¹¹ or the like Can be mentioned.

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

(In the general formula (1), ^{Y 1} represents a single ^{bond, -CR 55 R 56 -, -} NR 57 -, a divalent aliphatic hydrocarbon group having a carbon number of 1 to 35, divalent carbon atoms Represents an aromatic ring-containing hydrocarbon group of 6 to 35, a heterocyclic ring-containing group having a divalent carbon atom number of 2 to 35, or any of the groups represented by (1-1) to (1-3) below. , The aliphatic hydrocarbon group, the aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms, and the heterocyclic ring-containing group having 2 to 35 carbon atoms are: -O-, -S-, -CO-, -COO-. , -OCO- or -NH- or a combination thereof may be interrupted.
R ⁵⁵ and R ⁵⁶ independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aryl alkyl group having 7 to 20 carbon atoms.
Z ¹ and Z ² are independently bonded directly, -O-, -S-,> CO, -CO-O-, -O-CO-, -SO _2- , -SS-, -SO-, respectively. Represents> NR ⁵⁷ or> PR ⁵⁸
R ⁵⁷ and R ⁵⁸ represent 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 ring-containing group having 2 to 35 carbon atoms. ,
* Means that the * portion is attached to an adjacent group. )

(In the above formula, R ⁵⁹ represents 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.
R ⁶⁰ represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms or a halogen atom, and the alkyl group, the alkoxy group and the alkenyl group are substituents. May have
c1 represents an integer from 0 to 5,
* Means that the * portion is attached to an adjacent group. )

(* Means that it is bonded to an adjacent group at the * part.)

(In the above formula, R ⁶¹ and R ⁶² are independently 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, and an aryl group having 6 to 20 carbon atoms, respectively. Represents an arylthio group of 6 to 20, an arylalkenyl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, a heterocycle-containing group having 2 to 20 carbon atoms or a halogen atom, and the alkyl group and The methylene group in the arylalkyl group may be replaced by an unsaturated bond, -O- or -S-.
R ⁶¹ may form a ring between adjacent R ^61s .
c2 represents a number from 0 to 4,
c3 represents a number from 0 to 8
c4 represents a number from 0 to 4,
c5 represents a number from 0 to 4,
The total number of c4 and c5 is 2-4,
* Means that the * portion is attached to an adjacent group. )

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

(In the above general formula (3), Y ¹² is a carbon atom, an aliphatic hydrocarbon group having 1 to 35 tetravalent carbon atoms, an aromatic ring-containing hydrocarbon group having 6 to 35 tetravalent carbon atoms, or A tetravalent heterocyclic group having 2 to 35 carbon atoms is represented, and the aliphatic hydrocarbon group, an aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms, or a heterocyclic ring-containing group having 2 to 35 carbon atoms is used. , -COO-, -O-, -OCO-, -NHCO-, -NH- or -CONH- may be interrupted, and Z ^{1 to} Z ⁴ are independently represented by the above general formula (2). Represents a group in the same range as the group represented by Z ^{1 to} Z ³ in.)

(In the above general formula (4), Y ¹³ is an aliphatic hydrocarbon group having a pentavalent carbon atom number of 2 to 35, an aromatic ring-containing hydrocarbon group having a pentavalent carbon atom number of 6 to 30, or a pentavalent carbon. The aliphatic hydrocarbon group having 2 to 30 atoms, the aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms, or the heterocyclic ring-containing group having 2 to 35 carbon atoms is −COO−. , -O-, -OCO-, -NHCO-, -NH- or -CONH- may be interrupted, and Z ^{1 to} Z ⁵ are independently Z ¹ to Z ¹ to the above general formula (2). Represents the same group as the group represented by Z ^3. )

(In the above general formula (5), Y ¹⁴ is a single bond, an aliphatic hydrocarbon group having hexavalent carbon atoms of 2 to 35, an aromatic ring-containing hydrocarbon group having hexavalent carbon atoms of 6 to 35, or six. The aliphatic hydrocarbon group, the aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms, or the heterocyclic ring-containing group having 2 to 35 carbon atoms represents a heterocyclic group having a valence of 2 to 35 carbon atoms. -COO -, - O -, - OCO -, - NHCO -, - may NH- or -CONH- is interrupted ^by, Z 1 to Z ⁶ are each independently, in the general formula (7) Represents the same group as the group represented by Z ^{1 to} Z ^3. )

Examples of the divalent aliphatic hydrocarbon group represented by Y1 in the group represented by the general formula (1) having ¹ to 35 carbon atoms include methane, ethane, propane, iso-propane, butane, and sec-. Butane, tert-butane, iso-butane, hexane, 2-methylhexane, 3-methylhexane, heptane, 2-methylheptane, 3-methylheptan, iso-heptane, tert-heptane, 1-methyloctane, iso-octane , Tart-octane, cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, 2,4-dimethylcyclobutane, 4-methylcyclohexane and the like, and divalent groups in which Z ¹ and Z ² are substituted. These groups may be interrupted by -O-, -S-, -CO-, -COO-, -OCO-, -NH- or a combination of these.

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

The divalent heterocyclic ring-containing group having a carbon number of 2 to 35 represented by Y ¹ in the group represented by the general formula (1), pyridine, pyrazine, piperidine, piperazine, pyrimidine, pyridazine, triazine, hexa hexahydrotriazine, furan, tetrahydrofuran, chroman, xanthene, thiophene, thiolane, etc. may be mentioned divalent groups substituted with Z ¹ and Z ^2.

Aliphatic hydrocarbon group represented by Y ¹ in the group represented by the general formula (1), aromatic ring-containing hydrocarbon group and heterocyclic ring-containing group, a halogen atom, a cyano group, a nitro group or a C 1 -C It may be substituted with ~ 8 alkoxy groups.
Each functional group such as the aliphatic hydrocarbon group, the aromatic ring-containing hydrocarbon group and the heterocyclic ring-containing group may have a substituent, and unless otherwise specified, each functional group has a substituent. It is not substituted or has a substituent.
Such aliphatic hydrocarbon group, the substituent group such as an aromatic ring-containing hydrocarbon group and heterocyclic ring-containing group include the same as the substituents replacing a hydrogen atom and alkyl groups used for R ¹¹ or the like ..

Examples of the alkyl group having 1 to 8 carbon atoms represented by ^{R 55} and ^{R 56} in the group represented by the general formula (1), a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, s- Butyl group, t-butyl group, isobutyl group, amyl group, isoamyl group, t-amyl group, hexyl group, 2-hexyl group, 3-hexyl group, cyclohexyl group, 4-methylcyclohexyl group, heptyl group, 2-heptyl group. Examples include a group, a 3-heptyl group, an isoheptyl group, a t-heptyl group, a 1-octyl group, an isooctyl group and a t-octyl group.

Examples of the aryl group having 6 to 20 carbon atoms represented by ^{R 55} and ^{R 56} in the group represented by the general formula (1), a phenyl group, a naphthyl group, 2-methylphenyl group, 3-methylphenyl group , 4-Methylphenyl group, 4-Vinylphenyl group, 3-iso-propylphenyl group, 4-iso-propylphenyl group, 4-butylphenyl group, 4-iso-butylphenyl group, 4-tert-butylphenyl group , 4-hexylphenyl group, 4-cyclohexylphenyl group, 4-octylphenyl group, 4- (2-ethylhexyl) phenyl group, 2,3-dimethylphenyl group, 2,4-dimethylphenyl group, 2,5-dimethyl Phenyl group, 2,6-dimethylphenyl group, 3,4-dimethylphenyl group, 3,5-dimethylphenyl group, 2,4-di-tert-butylphenyl group, 2,5-di-tert-butylphenyl group , 2,6-di-tert-butylphenyl group, 2,4-di-tert-pentylphenyl group, 2,5-di-tert-amylphenyl group, 2,4,5-trimethylphenyl group and the like. ..
The aryl alkyl group having 7 to 20 carbon atoms represented by ^{R 55} and ^{R 56} in the group represented by the general formula (1), benzyl group, phenethyl group, 2-phenyl-2-yl group, Examples thereof include a diphenylmethyl group, a triphenylmethyl group, styryl, and cinnamyl.

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

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

In the group represented by the general formula (1-1), the alkyl group having 1 to 10 carbon atoms represented by R ⁶⁰ is represented by R ¹¹ or the like in the above section “1. Photoleaving group B”. Among those exemplified as the represented alkyl groups, those having 1 to 10 carbon atoms can be mentioned.
In the group represented by the general formula ^(1-1), the alkoxy group having 1 to 10 carbon atoms represented by ^{R 60,} in the section of "1. light leaving group B" in ^{R 11} or the like Among those exemplified as the represented alkoxy groups, those having 1 to 10 carbon atoms can be mentioned.
In the group represented by the general formula ^(1-1), as the alkenyl group having 2 to 10 carbon atoms represented by ^{R 60,} a vinyl group, an allyl group, a 1-propenyl group, isopropenyl group, 2- Butenyl group, 1,3-butadienyl group, 2-pentenyl group, 2-octenyl and the like can be mentioned.
The alkyl group represented by R ^60, alkoxy and alkenyl groups may have been substituted with a halogen atom, the substituted position is not limited.

Among the groups represented by the above general formula (1-3), an alkyl group having 1 to 10 carbon atoms represented by R ⁶¹ and R ⁶² , an aryl group having 6 to 20 carbon cord atoms, and 7 to 7 carbon atoms. the arylalkyl group 20, in the section of "1. light leaving group B" among those exemplified as R ¹¹ or the like, include those satisfying a predetermined number of carbon atoms.

Among the groups represented by the above general formula (1-3), the aryloxy groups having 6 to 20 carbon atoms represented by R ⁶¹ and R ⁶² include phenyloxy group, naphthyloxy group and 2-methylphenyloxy. Group, 3-methylphenyloxy group, 4-methylphenyloxy group, 4-vinylphenyldioxy group, 3-iso-propylphenyloxy group, 4-iso-propylphenyloxy group, 4-butylphenyloxy group, 4 -Tert-Butylphenyloxy group, 4-hexylphenyloxy group, 4-cyclohexylphenyloxy group, 4-octylphenyloxy group, 4- (2-ethylhexyl) phenyloxy group, 2,3-dimethylphenyloxy group, 2,4-Dimethylphenyloxy group, 2,5-dimethylphenyloxy group, 2,6-dimethylphenyloxy group, 3,4-dimethylphenyloxy group, 3,5-dimethylphenyloxy group, 2,4-G tert-butylphenyloxy group, 2,5-di tert-butylphenyloxy group, 2,6-di tert-butylphenyloxy group, 2,4-di tert-pentylphenyloxy group, 2,5-tert-amyl Examples thereof include a phenyloxy group, a 4-cyclohexylphenyloxy group, a 2,4,5-trimethylphenyloxy group and a ferrosenyloxy group, and a group in which these groups are substituted with halogen atoms.

In the group represented by the general formula (1-3), the arylthio group having 6 to 20 carbon atoms represented by R ⁶¹ and R ⁶² may be substituted with the halogen atom. Examples thereof include those in which the oxygen atom of 6 to 20 aryloxy groups is replaced with a sulfur atom.

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

Examples of the heterocyclic group having 2 to 20 carbon atoms represented by R ⁶¹ and R ⁶² in the group represented by the general formula (1-3) include a pyridine group, a pyrazine group, a piperidine group and a piperazine group. Examples thereof include a pyrimidine group, a pyridazine group, a triazine group, a hexahydrotriazine group, a furan group, a tetrahydrofuran group, a chromane group, a xanthene group, a thiophene group and a thiofuran group, and a group in which these groups are substituted with halogen atoms.

In the group represented by the above general formula (1-3), each functional group such as the aryloxy group represented by R ⁶¹ and R ⁶² , the arylthio group, the arylalkenyl group, and the heterocycle-containing group has a substituent. Unless otherwise specified, it is an unsubstituted product having no substituent or a product having a substituent.
Aryloxy group, arylthio group, arylalkenyl group, the substituents replacing a hydrogen atom, such as heterocyclic ring-containing group, is similar to those in the substituents replacing a hydrogen atom and alkyl groups used for R ¹¹ or the like be able to.

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

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

The heterocyclic group having a trivalent carbon atom number of 2 to 35 represented by Y ¹¹ in the group represented by the general formula (2) is the heterocycle exemplified in the explanation of X in the general formula (1). Examples thereof include trivalent groups in which the contained group is substituted with Z ¹ , Z ² and Z ³ .

The group represented by the general formula (2) contains Z ¹ , Z ² and Z ³ and an aliphatic hydrocarbon group having 1 to 35 carbon atoms represented by R ⁶² and an aromatic ring having 6 to 35 carbon atoms. Examples of the hydrocarbon group or the heterocyclic group having 2 to 35 carbon atoms include the same groups as those exemplified as R ⁵³ and R ⁵⁴ described above.

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

The aromatic ring-containing hydrocarbon group having a tetravalent carbon atom number of 6 to 35 represented by Y ¹² in the group represented by the general formula (3) is exemplified in the description of X in the general formula (1). Examples thereof include tetravalent groups in which the aromatic ring-containing hydrocarbon group is substituted with Z ¹ , Z ² , Z ³ and Z ⁴ .

As the heterocyclic group having a tetravalent carbon atom number of 2 to 35 represented by Y ¹² in the group represented by the general formula (3), the heterocycle exemplified in the explanation of X in the general formula (1) is used. Examples thereof include tetravalent groups in which the contained group is substituted with Z ¹ , Z ² , Z ³ and Z ⁴ .

The pentavalent aliphatic hydrocarbon group having a carbon number of 2 to 35 represented by Y ¹³ in the group represented by the general formula (4), exemplified in the description of X in the general formula (1) Fat Examples include pentavalent groups in which the group hydrocarbon groups are substituted with Z ¹ , Z ² , Z ³ , Z ⁴ and Z ⁵ , and include -O-, -S-, -CO-, -CO-O-,. It may be replaced by -O-CO-, -SO _2- , -NH- or a combination of these groups.

The pentavalent aromatic ring-containing hydrocarbon group having a carbon number of 6 to 35 represented by Y ¹³ in the group represented by the general formula (4), exemplified in the description of X in the general formula (1) Examples thereof include pentavalent groups in which aromatic ring-containing hydrocarbon groups are substituted with Z ¹ , Z ² , Z ³ , Z ⁴ and Z ⁵ .

The pentavalent heterocyclic containing group having a carbon number of 2 to 35 represented by Y ¹³ in the group represented by the general formula (4), a heterocyclic ring exemplified in the description of X in the general formula (1) Examples thereof include pentavalent groups in which the contained groups are substituted with Z ¹ , Z ² , Z ³ , Z ⁴ and Z ⁵ .

As the aliphatic hydrocarbon group having hexavalent carbon atoms of 2 to 35 represented by Y ¹⁴ in the general formula (5), the aliphatic hydrocarbon group exemplified in the explanation of X in the general formula (1) is used. , Z ¹ , Z ² , Z ³ , Z ⁴ , Z ⁵ and Z ⁶ substituted hexavalent groups, the groups being -O-, -S-, -CO-, -COO-,-. It may be interrupted by OCO-, -SO _2- , -NH- or a combination of these.

As the aromatic ring-containing hydrocarbon group having a hexavalent carbon atom number of 6 to 35 represented by Y ¹⁴ in the general formula (5), the aromatic ring-containing hydrocarbon exemplified in the explanation of X in the general formula (1). Examples include hexavalent groups in which the groups are substituted with Z ¹ , Z ² , Z ³ , Z ⁴ , Z ⁵ and Z ⁶ .

As the heterocyclic group having hexavalent carbon atoms of 2 to 35 represented by Y ¹⁴ in the general formula (5), the heterocycle-containing group exemplified in the explanation of X in the general formula (1) is Z. Hexavalent groups substituted with ¹ , Z ² , Z ³ , Z ⁴ , Z ⁵ and Z ⁶ can be mentioned.

When m is 2, the bonding group X is preferably an aliphatic hydrocarbon group having 1 to 120 carbon atoms, more preferably a residue of an alkylene group or a diol, and has 1 to 1 carbon atoms. It is preferably an alkylene group of 10 or a diol residue having 1 to 10 carbon atoms, and more preferably an alkylene group having 1 to 5 carbon atoms or a diol residue having 1 to 5 carbon atoms. In particular, it is preferably an alkylene group having 1 to 3 carbon atoms. This is because it is possible to obtain a compound that has less curing inhibition and can easily impart ultraviolet absorbing ability or the like to the cured product, and further, it is easy to produce compound I-1.

The bonding position of the bonding group X with the benzene ring may be any position in the benzene ring that can be bonded, but for example, it is preferably the ortho position or the meta position with respect to R ² . This is because it is possible to obtain a compound that has less curing inhibition and can easily impart ultraviolet absorption ability or the like to the cured product.

When m = 1, the X is preferably a hydrogen atom or a group similar to R2.

The atomic group A may contain a phenolic hydroxyl group, that is, a compound I-1 may contain a phenolic hydroxyl group not protected by a photoleaving group B, but the number of phenolic hydroxyl groups is 2. The number is preferably less than, and more preferably 0. This is because the compound I-1 has less inhibition of curing.

3. 3. Compound The compound of the present invention may be represented by the above general formula (I-1), but is represented by the above general formula (A-1), (A-2) or (A-3). It is a compound, and it is preferable that the photoleaving group B contains a compound represented by the above general formula (B-1-a). This is because it is easy to synthesize and further, it is easy to photodesorb. Further, it is possible to easily impart an ultraviolet absorbing ability or the like 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), the light in the ultraviolet region is emitted by the elimination of the photoleaving group B. This is because it is possible to produce a compound that absorbs stably.

Specific examples of the above-mentioned compound I-1 include compounds represented by the following.

The molecular weight of the compound I-1 can be set according to the use of the compound I-1 and the like. The molecular weight of the compound I-1 is, for example, preferably 250 or more and 5000 or less, more preferably 300 or more and 2500 or less, and particularly preferably 350 or more and 1500 or less. This is because it is possible to obtain a compound that has less curing inhibition and can easily impart ultraviolet absorption ability or the like to the cured product.
When the compound I-1 is a polymer having a repeating structure as its structure, the molecular weight of the compound I-1 is expressed by the weight average molecular weight (Mw). The weight average molecular weight (Mw) can be determined as a standard polystyrene equivalent value by gel permeation chromatography (GPC).

For the weight average molecular weight Mw, for example, HLC-8120GPC manufactured by Tosoh Corporation was used, the elution solvent was N-methylpyrrolidone added with 0.01 mol / liter lithium bromide, and the polystyrene standard for the calibration curve was Mw377400. , 210500, 96000, 50400, 20650, 10850, 5460, 2930, 1300, 580 (above, Easi PS-2 series manufactured by Polymer Laboratories) and Mw1090000 (manufactured by Tosoh Corporation), and the measurement column was TSK-GEL ALPHA- It can be obtained by measuring as M × 2 (manufactured by Tosoh Corporation). The measurement temperature can be 40 ° C. and the flow velocity can be 1.0 mL / min.

The method for producing the compound I-1 is not particularly limited as long as it can obtain a desired structure, and for example, JP-A-57-11135, JP-A-3-173843, JP-A-6- Obtained by reacting an alkyl halide compound with a phenolic compound produced by the method described in JP-A-128195, JP-A-7-206771, JP-A-7-252191 or JP-A-2004-501128. Can be done.

The compound I-1 is inactive before light irradiation, and the photoleaving group is eliminated by light irradiation to produce compound I-2 having a phenolic hydroxyl group.
Further, the compound I-2 exhibits an ultraviolet absorbing ability.
The application of such compound I-1 is preferably an application that is required to exhibit an ultraviolet absorbing ability by light irradiation, and examples thereof include an ultraviolet absorber used in addition to a composition. Can be done.

B. Latent UV absorber Next, the latent UV absorber of the present invention will be described.
The latent UV absorber of the present invention comprises the compound I-1 of the present invention.

By containing the compound I-1 of the present invention, the latent ultraviolet absorber of the present invention, for example, has less curing inhibition and can easily impart ultraviolet absorbing ability or the like to the cured product.

The content of compound I-1 in the latent ultraviolet absorber of the present invention is not particularly limited and can be appropriately set according to the use of the latent ultraviolet absorber and the like.
The latent ultraviolet absorber of the present invention contains 100 parts by mass of compound I-1 in 100 parts by mass of the latent ultraviolet absorber, that is, the latent ultraviolet absorber is composed of only the compound I-1. Can be.
Further, the latent ultraviolet absorber of the present invention may contain other components in addition to compound I-1. When the latent ultraviolet absorber of the present invention contains other components, the content of the compound I-1 may be, for example, more than 20 parts by mass and 99 parts by mass or less in 100 parts by mass of the latent ultraviolet absorber. It is possible, 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. This is because the latent ultraviolet absorber has less inhibition of curing and can effectively exert the effect of easily imparting an ultraviolet absorbing ability or the like to the cured product.

The type of the compound I-1 contained in the latent ultraviolet absorber may be only one type, or may be two or more types. When the latent ultraviolet absorber contains several kinds of compounds I-1, the number of kinds can be, for example, two or more and five or less.

Since the above-mentioned compound I-1 can be the same as the content described in the section of "A. compound", the description thereof is omitted here.

As the other components contained in the latent ultraviolet absorber, for example, the same components as those described in the section "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 compound I-1 can be stably retained.

The shape of the latent UV absorber may be powdery or pelletized.
In the case of pellets, as a method for producing the latent ultraviolet absorber, for example, a method of mixing the compound I-1 and the resin component using an extruder or the like and then molding into pellets can be used. it can.

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

According to the composition of the present invention, for example, it is possible to provide a composition capable of obtaining an excellent ultraviolet absorbing ability cured product with less curing inhibition. Hereinafter, each component of the above composition will be described.

1. 1. Compound The content of 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 can be, for example, 0.001 part by mass or more and 20 parts by mass or less, and 0.005 parts by mass or more and 10 parts by mass, based on 100% by mass of the solid content of the composition. It is preferably less than a part. This is because it is easy to prepare a composition that does not hinder curing and can easily impart ultraviolet absorbing ability or the like to the cured product.
The solid content includes all components other than the solvent.
Unless otherwise specified in the present specification, the content is based on mass.
The content of the compound I-1 varies depending on the content of the solvent and the like, and can be, for example, 0.001 part by mass or more and 20 parts by mass or less in 100 parts by mass of the composition. , 0.005 part by mass or more and preferably 10 parts by mass or less. This is because it is easy to prepare a composition that does not hinder curing and can easily impart ultraviolet absorbing ability or the like to the cured product.

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

Since the above-mentioned compound I-1 can be the same as the content described in the section of "A. compound", the description thereof is omitted here.

2. 2. Other Ingredients The composition may contain other ingredients other than the above-mentioned compound I-1 depending on its use and the like.
Examples of the other components include a resin component. This is because the composition of the present invention contains, for example, curability and the like can be easily imparted to the composition by containing a resin component in addition to the compound I-1.
In addition, the composition of the present invention preferably contains a polymerization initiator together with the above resin component as another 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 Examples of the resin component include those capable of retaining the compound I-1, which are appropriately set according to the use of the composition and the like. For example, the resin component has a polymerizable group and is polymerizable. Examples thereof include compounds and polymers having no polymerizable group.
By containing a polymerizable compound as the resin component, the composition can be used, for example, as 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 radical polymerizable compounds, cationically polymerizable compounds, and anionic polymerizable compounds. it can.
The above-mentioned polymerizable compound preferably contains a radically polymerizable compound from the viewpoint of effectively exerting the effect of reducing curing inhibition.

(I) Radical Polymerizable Compound The radically polymerizable compound may have one or more radically polymerizable groups and may contain two or more.
The radically polymerizable compound is usually used together with a radical polymerization initiator.
Examples of the radically polymerizable polymerizable group include an ethylenically unsaturated double bond group such as a (meth) acrylic group and a vinyl group.
In addition, (meth) acrylic is used in the meaning including acrylic and methacrylic. Further, (meth) acrylate is used in the sense of including acrylate and methacrylate.

Further, the radically 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 and the like.
Since the composition contains a compound having an acid value as a radically polymerizable compound, the solubility of the light-irradiated portion in an alkaline developer is lowered. Therefore, the above composition can be used, for example, as a photosensitive composition whose solubility in a solvent such as an alkaline developer changes before and after light irradiation. More specifically, the above composition can be used as a negative type composition by containing a compound having an acid value.
As the alkaline developer, a tetramethylammonium hydroxide (TMAH) aqueous solution, a potassium hydroxide aqueous solution, or the like which is generally used as an alkaline developer can be used.

The radically polymerizable compound has, for example, an ethylenically unsaturated double bond group, and examples of the compound having an acid value include (meth) acrylic acid, α-chloroacrylic acid, itaconic acid, maleic acid, and citraconic acid. Fumaric acid, epoxy acid, crotonic acid, isocrotonic acid, vinyl acetic acid, allyl acetic acid, cinnamic acid, sorbic acid, mesaconic acid, monosuccinate [2- (meth) acryloyloxyethyl], mono phthalate [2- (meth) ) Acryloyloxyethyl] and ω-carboxypolycaprolactone mono (meth) acrylate, a polymer mono (meth) acrylate having a carboxy group and a hydroxyl group at both ends; hydroxyethyl (meth) acrylate malate, hydroxypropyl (meth) ) Unsaturated monobasic acids such as acrylate malate, dicyclopentadiene malate or polyfunctional (meth) acrylate with one carboxyl group and two or more (meth) acryloyl groups; phenol and / or cresol novolac epoxy. Novolac epoxy resin having resin, biphenyl skeleton, naphthalene skeleton, novolak type epoxy compound such as bisphenol A novolak type epoxy compound, dicyclopentadiene novolac type epoxy compound, polyphenylmethane type epoxy resin having polyfunctional epoxy group, the following general formula An unsaturated monobasic acid is allowed to act on the epoxy group of an epoxy resin such as an epoxy compound represented by (III), and the epoxy group of an epoxy resin such as an epoxy compound represented by the following general formula (III) is unsaturated. A resin obtained by allowing a monobasic acid to act and then a polybasic acid anhydride to act, a hydroxyl group-containing polyfunctional acrylate such as pentaerythritol triacrylate and dipentaerythritol pentaacrylate, and succinic anhydride, phthalic anhydride, and tetrahydroan anhydride. Examples thereof include a polyfunctional acrylate having an acid value, which is a reaction product of a dibasic acid anhydride such as phthalic acid.

(In the formula, X ⁴¹ is a direct bond, an alkylidene group having 1 to 4 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, -O-, -S-, -SO _2- , -SS-. , -SO-, -CO-, -OCO- or the substituents represented by the above (1-1) to (1-3).
R ⁴¹ , R ⁴² , R ⁴⁴ and R ⁴⁴ are independently hydrogen atoms, alkyl groups having 1 to 5 carbon atoms, alkoxy groups having 1 to 8 carbon atoms, alkenyl groups having 2 to 5 carbon atoms or Represents a halogen atom
d is an integer from 0 to 10. )

Examples of the alkyl group having 1 to 5 carbon atoms, the alkoxy group having 1 to 8 carbon atoms and the alkenyl group having 2 to 5 carbon atoms represented by R ⁴¹ , R ⁴² , R ⁴⁴ and R ⁴⁴ include the above-mentioned "A". . of the term compound "those exemplified as R ¹¹ or the like, can include those satisfying a predetermined number of carbon atoms.
Examples of the alkylidene group having 1 to 4 carbon atoms represented by X ⁴¹ include a methylidene group, an ethylidene group, a propylidene group and a butylidene group.
Examples of the alicyclic hydrocarbon group having 3 to 20 carbon atoms represented by X ⁴¹ include a cyclopropylene group, a cyclopentylene group, a cyclohexylene group and a cycloheptylene group.
The alkyl group, alkoxy group, alkenyl group, alkylidene group and alicyclic hydrocarbon group may have a substituent, and unless otherwise specified, the above-mentioned alkyl group, alkoxy group, alkenyl group, and alicyclic hydrocarbon group do not have a substituent and are not substituted. Or has a substituent. The alkyl group, alkoxy group, alkenyl group, examples of the substituent group for substituting a hydrogen atom of the alkylidene group and alicyclic hydrocarbon group, similar to the substituents replacing a hydrogen atom and alkyl groups used for R ¹¹ or the like Can be content.

The radically polymerizable compound has, for example, an ethylenically unsaturated double bond group, and examples of the compound having no acid value include -2-hydroxyethyl (meth) acrylate and -2-hydroxy (meth) acrylate. Propyl, glycidyl (meth) acrylate, the following compound No. A1 to No. A4, methyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, -t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, n-octyl (meth) acrylate, ( Isooctyl acrylate, isononyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, methoxyethyl (meth) acrylate, dimethylaminomethyl (meth) acrylate, dimethyl (meth) acrylate Aminoethyl, Aminopropyl (Meta) Acrylate, Dimethylaminopropyl (Meta) Acrylate, ethoxyethyl (Meta) Acrylate, Poly (ethoxy) Ethyl (Meta) Acrylate, Butoxyethoxyethyl (Meta) Acrylate, (Meta) ) Ethylhexyl acrylate, phenoxyethyl (meth) acrylate, tetrahydrofuryl (meth) acrylate, vinyl (meth) vinyl acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, ethylene glycol di (meth) acrylate, Diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol Di (meth) acrylate, trimethylol ethanetri (meth) acrylate, trimethylol propanthry (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, pentaerythritol tetra (meth) acrylate, Unsaturated monobasic acids such as pentaerythritol tri (meth) acrylate, tricyclodecanedimethylol di (meth) acrylate, tri [(meth) acryloyl ethyl] isocyanurate, polyester (meth) acrylate oligomer, and polyhydric alcohols or polyvalents. Esters of phenols; metal salts of unsaturated polybasic acids such as zinc (meth) acrylate, magnesium (meth) acrylate; maleic acid anhydride, itaconic acid anhydride, citraconic acid anhydride, methyltetrahydrophthalic anhydride, tetrahydro Acrylate, TrialkyltetrahydroAcrylate, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride, trialkyltetrahydrophthaliclate-anhydrous Acid anhydrides of unsaturated polybasic acids such as laine acid adduct, dodecenyl anhydride succinic acid, methylhymic anhydride; (meth) acrylamide, methylenebis- (meth) acrylamide, diethylenetriaminetris (meth) acrylamide, xylylenebis (meth) Amidos of unsaturated monobasic acids and polyvalent amines such as acrylamide, α-chloroacrylamide, N-2-hydroxyethyl (meth) acrylamide; unsaturated aldehydes such as achlorine; (meth) acrylonitrile, α-chloroacrylonitrile, cyanide Unsaturated nitriles such as vinylidene and allyl cyanide; styrene, 4-methylstyrene, 4-ethylstyrene, 4-methoxystyrene, 4-hydroxystyrene, 4-chlorostyrene, divinylbenzene, vinyltoluene, vinyl benzoic acid, vinylphenol , Vinyl sulfonic acid, 4-vinylbenzene sulfonic acid, vinylbenzyl methyl ether, vinylbenzyl glycidyl ether and other unsaturated aromatic compounds; unsaturated ketones such as methylvinyl ketone; vinylamine, allylamine, N-vinylpyrrolidone, vinylpiperidin and the like. Unsaturated amine compounds; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, n-butyl vinyl ether, isobutyl vinyl ether, allylglycidyl ether; unsaturated imides such as maleimide, N-phenylmaleimide, N-cyclohexylmaleimide; inden, 1 -Indens such as methyl inden; aliphatic conjugated dienes such as 1,3-butadiene, isoprene, chloroprene; polymer molecules such as polystyrene, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate, polysiloxane Macromonomers having a mono (meth) acryloyl group at the end of the chain; other vinyl compounds such as (meth) acrylonitrile, ethylene, propylene, butylene, vinyl chloride, vinyl acetate, polymethylmethacrylate macromonomer, polystyrene macromonomer, etc. Macromonomers, monomethacrylates of tricyclodecane skeleton, N-phenylmaleimide, methacryloyloxymethyl-3-ethyloxetane, etc., copolymers of (meth) acrylic acid, and Karenz manufactured by Showa Denko Co., Ltd. Copolymers of (meth) acrylic acid reacted with unsaturated bonds such as MOI and AOI, vinyl chloride, vinylidene chloride, divinyl succinate, Dialyl phthalate, triallyl phosphate, triallyl isocyanurate, vinyl thioether, vinyl imidazole, vinyl oxazoline, vinyl carbazole, vinyl pyrrolidone, vinyl pyridine, hydroxyl group-containing vinyl monomer and polyisocyanate compound vinyl urethane compound, hydroxyl group-containing vinyl monomer Examples thereof include vinyl epoxy compounds of polyepoxy compounds, hydroxyl group-containing polyfunctional acrylates such as pentaerythritol triacrylate and dipentaerythritol pentaacrylate, and polyfunctional isocyanates such as tolylene diisocyanate and hexamethylene diisocyanate.

The radically polymerizable compound may be used alone or in combination of two or more. Further, the radically polymerizable compound shall be used in combination with a compound having an ethylenically unsaturated double bond group and having an acid value and a compound having an ethylenically unsaturated double bond group and having no acid value. Can be done.
When two or more kinds of radically polymerizable compounds are mixed and used, they may be copolymerized in advance and used as a copolymer.
The content of the radically polymerizable compound can be appropriately set according to the intended use of the composition, and can be, for example, 1 part by mass or more and 99 parts by mass or less in 100 parts by mass of the composition, and 10 parts by mass. The amount is preferably 40 parts by mass or more and 90 parts by mass or less, and more preferably 40 parts by mass or more and 80 parts by mass or less. This is because, for example, the above composition can be used as a negative type composition having excellent sensitivity when the above content is in the above range. Further, it is possible to provide a composition which has less curing inhibition and can easily impart an ultraviolet absorbing ability or the like to a cured product.
The content of the polymerizable compound may be such that the composition can be used as a curable composition, but is 1 part by mass or more and 99 parts by mass in a total of 100 parts by mass of the compound I-1 and the polymerizable compound. It can be 5 parts by mass or less, preferably 50 parts by mass or more and 99 parts by mass or less, and more preferably 80 parts by mass or more and 99 parts by mass or less, and 90 parts by mass or more and 98 parts by mass or less. Is preferable. This is because when the content is in the above range, the composition can provide a composition which has less curing inhibition and can easily impart ultraviolet absorbing ability or the like to the cured product.
The contents of the compound I-1 and the radically polymerizable compound can be appropriately set according to the intended use of the composition, and for example, 1 part by mass or more and 99 parts by mass or less in 100 parts by mass of the composition. It is preferably 10 parts by mass or more and 90 parts by mass or less, and more preferably 40 parts by mass or more and 80 parts by mass or less. This is because, for example, the above composition can be used as a negative type composition having excellent sensitivity when the above content is in the above range. Further, it is possible to provide a composition which has less curing inhibition and can easily impart an ultraviolet absorbing ability or the like to a cured product.

(Ii) Cationicly polymerizable compound and anionically polymerizable compound The above-mentioned cationically polymerizable compound may have one or more cationically polymerizable polymerizable groups.
The cationically polymerizable compound is usually used together with a cationic polymerization initiator.
Examples of the cationically polymerizable polymerizable group include a cyclic ether group such as an epoxy group and an oxetane group, a vinyl ether group, and the like.
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 ether, phenyl-2-methyl glycidyl ether, cetyl glycidyl ether, stearyl glycidyl ether, and the like. 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 Glysidyl ether, 4-phenylphenol glycidyl ether, cresyl glycidyl ether, dibromocresyl glycidyl ether, decyl glycidyl ether, methoxypolyethylene glycol monoglycidyl ether, ethoxypolyethylene glycol monoglycidyl ether, butoxypolyethylene glycol monoglycidyl ether, phenoxypolyethylene glycol mono Glycidyl ether, dibromophenyl glycidyl ether, 1,4-butanediol diglycidyl ether, 1,5-pentanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,1,2 Glycidyl ethers such as 2-tetrakis (glycidyloxyphenyl) ethane and pentaerythritol tetraglycidyl ether; glycidyl esters such as glycidyl acetate and glycidyl stearate; 2- (3,4-epoxycyclohexyl-5,5-spiro-) 3,4-Epoxy) cyclohexane-metadioxane, methylenebis (3,4-epoxycyclohexane), propane-2,2-diyl-bis (3,4-epoxycyclohexane), 2,2-bis (3,4-epoxy) Cyclohexyl) propane, ethylene bis (3,4-epoxycyclohexanecarboxylate), bis (3,4-epoxycyclohexylmethyl) adipate, 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate, 3,4-epoxy -1-Methylcyclohexyl 3,4-epoxy-1-methylhexanecarboxylate, 6-methyl-3,4-epoxycyclohexyl Methyl 6-methyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-3-methylcyclohexanemethyl 3,4-epoxy-3-methylcyclohexanecarboxylate, 3,4-epoxy-5-methylcyclohexanemethyl 3 , 4-epoxy-5-methylcyclohexanecarboxylate, 1-epoxyethyl-3,4-epoxycyclohexane, 1,2-epoxy-2-epoxyethylcyclohexane, dicyclopentadienediepoxiside, 3,4-epoxy-6- Examples thereof include epoxycycloalkyl-type compounds such as methylcyclohexylcarboxylate, α-pineneoxide, styrene oxide, cyclohexene oxide and cyclopentene oxide, and N-glycidylphthalimide and the like.

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

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

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

Examples of the other monomers include unsaturated aliphatic hydrocarbons such as vinyl chloride, vinylidene chloride, vinylidene fluoride and tetrafluoroethylene; (meth) acrylic acid, α-chloroacrylic acid, itaconic acid, maleic acid, citraconic acid, etc. Fumaric acid, hymic acid, crotonic acid, isocrotonic acid, vinyl acetic acid, allyl acetic acid, cinnamic acid, sorbic acid, mesaconic acid, succinic acid mono [2- (meth) acrylicyloxyethyl], phthalic acid mono [2- (meth) ) Acryloyloxyethyl], ω-carboxypolycaprolactone Mono (meth) acrylate, etc. Polymer mono (meth) acrylate having carboxy groups and hydroxyl groups at both ends, hydroxyethyl (meth) acrylate malate, hydroxypropyl (meth) ) Unsaturated polybasic acids such as acrylate malate, dicyclopentadiene malate and polyfunctional (meth) acrylate having one carboxyl group and two or more (meth) acryloyl groups; (meth) acrylic acid-2 -Hydroxyethyl, -2-hydroxypropyl (meth) acrylate, methyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, -t-butyl (meth) acrylate, (meth) acrylic Cyclohexyl acid, n-octyl (meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, methoxyethyl (meth) acrylate, (meth) ) Dimethylaminomethyl acrylate, dimethylaminoethyl (meth) acrylate, aminopropyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, ethoxyethyl (meth) acrylate, poly (ethoxy) poly (ethoxy) acrylate Ethyl, butoxyethoxyethyl (meth) acrylate, ethylhexyl (meth) acrylate, phenoxyethyl (meth) acrylate, tetrahydrofuryl (meth) acrylate, vinyl (meth) acrylate, allyl (meth) acrylate, (meth) ) Acrylic acid benzyl, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,4-butane Didiole (meth) acrylate, 1,6-hexanedioldi (meth) acrylate, trimeticro Ruetantri (meth) acrylate, trimethylolpropantri (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, tri Cyclodecanedimethylol di (meth) acrylate, tri [(meth) acryloylethyl] isocyanurate and unsaturated monobasic acids such as polyester (meth) acrylate oligomers and esters of polyhydric alcohols or polyhydric phenols; (meth) acrylic acid. Metal salts of unsaturated polybasic acids such as zinc and magnesium (meth) acrylate; maleic acid anhydride, itaconic acid anhydride, citraconic acid anhydride, methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, trialkyltetrahydrophthalic anhydride Acids, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride, trialkyltetrahydrophthalic anhydride-maleic anhydride adduct, dodecenyl anhydride succinic acid and Acid anhydrides of unsaturated polybasic acids such as methylhymic anhydride; (meth) acrylamide, methylenebis- (meth) acrylamide, diethylenetriaminetris (meth) acrylamide, xylylenebis (meth) acrylamide, α-chloroacrylamide, N-2 -Amid of unsaturated monobasic acids such as hydroxyethyl (meth) acrylamide and polyvalent amines; unsaturated aldehydes such as achlorein; unsaturated nitriles such as (meth) acrylonitrile, α-chloroacrylamide, vinylidene cyanide, allyl cyanide, etc. Styrene, 4-methylstyrene, 4-ethylstyrene, 4-methoxystyrene, 4-hydroxystyrene, 4-chlorostyrene, divinylbenzene, vinyltoluene, vinyl benzoic acid, vinylphenol, vinylsulfonic acid, 4-vinylbenzenesulfone Unsaturated aromatic compounds such as acids, vinylbenzylmethyl ethers and vinylnaphthalene; unsaturated ketones such as methylvinylketones; unsaturated amine compounds such as vinylamine, allylamine, N-vinylpyrrolidone and vinylpiperidin; allylalcohol and crotylalcohol Vinyl alcohols such as vinyl methyl ethers, vinyl ethyl ethers, n-butyl vinyl ethers and vinyl ethers such as isobutyl vinyl ethers; Unsaturated imides such as nylmaleimide and N-cyclohexylmaleimide; indens such as inden and 1-methylinden; polymer molecules such as polystyrene, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate and polysiloxane Macromonomonics having a mono (meth) acryloyl group at the end of the chain; vinyl chloride, vinylidene chloride, divinyl succinate, diallyl phthalate, triallyl phosphate, triallyl isocyanurate, vinyl thioether, vinyl imidazole, vinyl oxazoline , Vinylcarbazole, vinylpyrrolidone, vinylpyridine, hydroxyl group-containing vinyl monomer and polyisocyanate compound vinyl urethane compound, hydroxyl group-containing vinyl monomer and polyepoxy compound vinyl epoxy compound, pentaerythritol triacrylate and dipentaerythritol pentaacrylate and other hydroxyl groups Polyfunctional acrylate; Reaction product of polyfunctional isocyanate such as tolylene diisocyanate and hexamethylene diisocyanate; hydroxyl group-containing polyfunctional acrylate such as pentaerythritol triacrylate and dipentaerythritol pentaacrylate and succinic anhydride, phthalic anhydride and tetrahydrophthalic anhydride Examples thereof include polyfunctional acrylates having an acid value which is a reaction product of a dibasic acid anhydride such as.

Commercially available products can also be used as the epoxidized polyolefin, for example, Epolide PB3600, Epolide PB4700 (manufactured by Daicel); BF-1000, FC-3000 (manufactured by ADEKA); Bond First 2C, Bond First E, Bond. First CG5001, Bond First CG5004, Bond First 2B, Bond First 7B, Bond First 7L, Bond First 7M, Bond First VC40 (manufactured by Sumitomo Chemical Co., Ltd.); JP-100, JP-200 (manufactured by Nippon Soda); Poly bd R -45HT, Poly bd R-15HT (manufactured by Idemitsu Kosan Co., Ltd.), Ricon 657 (manufactured by Arkema Corporation) and the like can be mentioned.

Since the heat resistance is good, it is more preferable to use a compound having a cardo skeleton represented by the general formula (II) as the epoxy compound.

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

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, and 2-. Examples thereof include hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, 1,6-cyclohexanedimethanol monovinyl ether, ethylene glycol divinyl ether, 1,4-butanediol divinyl ether and 1,6-cyclohexanedimethanol divinyl ether.

The anionic polymerizable compound may be any compound having one or more anionic polymerizable groups.
The anionic polymerizable compound is usually used together with an anionic polymerization initiator.
Examples of the anionic polymerizable polymerizable group include an epoxy group, a lactone group, and a (meth) acrylic group.
That is, examples of the anionic polymerizable compound include epoxy compounds, lactone compounds, and compounds having a (meth) acrylic group.
Examples of the lactone compound include β-propiolactone and ε-caprolactone.
As the epoxy compound, the epoxy compound exemplified as the above-mentioned cationically polymerizable compound can be used. Further, as the compound having a (meth) acrylic group, those exemplified as the above-mentioned radically polymerizable compound can be used.

The above-mentioned cationically polymerizable compound and anionically polymerizable compound can be used alone or in combination of two or more.

(B) Polymer having no polymerizable group As the resin that can be used in the composition of the present invention, a polymer having no polymerizable group can be used as described above.
The weight average molecular weight (Mw) of the polymer having no polymerizable group is appropriately set according to the use of the composition and the like, but can be, for example, 1500 or more, and 1500 or more and 300,000 or less. can do.
Examples of such a polymer may be any polymer containing a repeating structure, and examples thereof include a photosensitive resin having photosensitivity and a non-photosensitive resin having no photosensitivity.
The composition of the present invention can be used as a photosensitive composition, for example, by containing a photosensitive resin as a resin component.

(I) Photosensitive resin The above photosensitive resin has photosensitivity, and is used together with an acid generator, for example, and is dissolved in a developing solution by the action of an acid to break a chemical bond such as an ester group or an acetal group. A positive resin that changes in the direction of increasing properties can be mentioned.
By containing a positive resin as a resin component in the above composition, the solubility of the light-irradiated portion in the alkaline developer is increased.
Therefore, the composition can be used, for example, as a photosensitive composition in which the solubility in a solvent such as an alkaline developer changes before and after light irradiation, and more specifically, as a positive composition.

As the positive resin, a polymer polymer partially replaced with an acid unstable group having an alkali dissolution control ability can be used.
The polymer polymer includes two or more selected from polyhydroxystyrene and its derivatives; polyacrylic acid and its derivatives; polymethacrylic acid and its derivatives; hydroxystyrene, acrylic acid, methacrylic acid and their derivatives. Copolymers; 2 or more copolymers selected from hydroxystyrene, styrene and their derivatives; cycloolefins and their derivatives, maleic anhydride, and 3 or more copolymers selected from acrylic acid and its derivatives Combined; 3 or more copolymers selected from cycloolefin and its derivatives, maleimide, and acrylic acid and its derivatives; polynorbornene; one or more polymer polymers selected from the group consisting of metathesis ring-opening polymers. And so on.
Examples of the acid unstable group introduced into the above polymer polymer include heterolipid ring groups such as tertiary alkyl group, trialkylsilyl group, oxoalkyl group, aryl group substituted alkyl group and tetrahydropyran-2-yl group. Examples thereof include a tertiary alkylcarbonyl group, a tertiary alkylcarbonylalkyl group and an alkyloxycarbonyl group.

A detailed specific example of the positive resin shall be the same as that described in, for example, Japanese Patent Application Laid-Open No. 2003-192665, Claim 3 of Japanese Patent Application Laid-Open No. 2004-323704, and Japanese Patent Application Laid-Open No. 10-10733. Can be done.

As the acid generator used together with the positive resin, a known acid generator can be used. Specific examples of the acid generator include a photocationic polymerization initiator and a thermal cationic polymerization initiator described later.

(Ii) Non-photosensitive resin The non-photosensitive resin may be any non-photosensitive resin, for example, polystyrene, polymethylmethacrylate, methylmethacrylate-ethylacrylate copolymer, poly (meth) acrylic acid, and styrene. -(Meta) acrylic acid copolymer, (meth) acrylic acid-methyl methacrylate copolymer, ethylene-vinyl chloride copolymer, ethylene-vinyl copolymer, polyvinyl chloride resin, ABS resin, nylon 6, nylon 66 , Nylon 12, urethane resin, polycarbonate polyvinyl butyral, cellulose ester, polyacrylamide, saturated polyester, phenol resin, phenoxy resin, polyamideimide resin, polyamic acid resin, epoxy resin and the like.
As the non-photosensitive resin, for example, a polymer of the above-mentioned polymerizable compound can also be used.

(C) Resin component The content of the resin component in the composition of the present invention can be appropriately determined depending on the use of the composition and the like. For example, 1 part by mass in 100 parts by mass of the solid content of the composition. It is preferably 99 parts by mass or more, 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. This is because, when the content is in the above range, the composition can stably retain, for example, the compound I-1.
The content of the resin component can be appropriately set according to the intended use of the composition, and can be, for example, 1 part by mass or more and 99 parts by mass or less in 100 parts by mass of the composition, and 10 parts by mass or more. It is preferably 90 parts by mass or less, and more preferably 40 parts by mass or more and 80 parts by mass or less. This is because, for example, the above composition can be used as a negative type composition having excellent sensitivity when the above content is in the above range. Further, it is possible to provide a composition which has less curing inhibition and can easily impart an ultraviolet absorbing ability or the like to a cured product.
The content of the resin component varies depending on the use of the composition and the like, but can be 1 part by mass or more and 99 parts by mass or less in the total of 100 parts by mass of the compound I-1 and the resin component. , 50 parts by mass or more and 99 parts by mass or less, and more preferably 80 parts by mass or more and 99 parts by mass or less, and 90 parts by mass or more and 98 parts by mass or less. This is because when the content is in the above range, the composition can easily provide a composition capable of easily imparting an ultraviolet absorbing ability or the like to the cured product.
The content of the compound I-1 and the resin component can be appropriately set according to the intended use of the composition, and is, for example, 1 part by mass or more and 99 parts by mass or less in 100 parts by mass of the composition. It is preferably 10 parts by mass or more and 90 parts by mass or less, and more preferably 40 parts by mass or more and 80 parts by mass or less. This is because, for example, the above composition can be used as a negative type composition having excellent sensitivity when the above content is in the above range. Further, it is possible to provide a composition which has less curing inhibition and can easily impart an ultraviolet absorbing ability or the like to a cured product.

The type of the resin component contained in the composition of the present invention may be only one type or a combination of two or more types.
The resin component may contain, for example, only one of a polymerizable compound and a polymer, or may contain both.
When the resin component contains both a polymerizable compound and a polymer having no polymerizable group, the content of the polymerizable compound can be appropriately set depending on the use of the composition and the like. It can be 1 part by mass or more and 99 parts by mass or less in 100 parts by mass of the polymerizable compound and the polymer.

(2) Polymerization Initiator The above-mentioned polymerization initiator is contained as a curable component and is usually used together with a polymerizable compound or the like.
The polymerization initiator may be any one that can polymerize the polymerizable compound. For example, a photopolymerization initiator that can polymerize the polymerizable compound by being irradiated with light, and a polymerizable compound that can be polymerized by heating. Thermal polymerization initiators and the like can be mentioned.
The polymerization initiator is preferably a photopolymerization initiator from the viewpoint of effectively exerting the effect that the compound I-1 functions as an ultraviolet absorber.

(A) Photopolymerization Initiator The photopolymerization initiator may be any as long as it can polymerize a polymerizable compound by being irradiated with light. For example, a photoradical polymerization initiator, a photocationic polymerization initiator, and a photoanion. Examples thereof include a polymerization initiator.

The photoradical polymerization initiator is not particularly limited as long as it generates radicals by light irradiation, and conventionally known compounds can be used.
As the photoradical polymerization initiator, for example, acetophenone-based compounds, benzyl-based compounds, benzophenone-based compounds, thioxanthone-based compounds, oxime ester-based compounds and the like can be exemplified as preferable ones.

Examples of the acetophenone compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 4'-isopropyl-2-hydroxy-2-methylpropiophenone, and 2-hydroxymethyl-. 2-Methylpropiophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one, p-dimethylaminoacetophenone, p-tershalibutyldichloroacetophenone, p-tershaributyltrichloroacetophenone, p-azidoben Zaracetophenone, 1-hydroxycyclohexylphenylketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) ) -Butanone-1, 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-propane-1-one and the like can be mentioned.

Examples of the benzyl compound include benzyl and the like.

Examples of the benzophenone compound include benzophenone, methyl o-benzoyl benzoate, Michler ketone, 4,4'-bisdiethylaminobenzophenone, 4,4'-dichlorobenzophenone, 4-benzoyl-4'-methyldiphenylsulfide and the like. Be done.

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

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

(In the formula, R ⁷¹ and R ⁷² are independently hydrogen atom, cyano group, alkyl group having 1 to 20 carbon atoms, aryl group having 6 to 30 carbon atoms, and aryl alkyl having 7 to 30 carbon atoms, respectively. Represents a group or a heterocycle-containing group having 2 to 20 carbon atoms.
R ⁷³ and R ⁷⁴ are independently halogen atoms, nitro groups, cyano groups, hydroxyl groups, carboxyl groups, R ⁷⁵ , OR ⁷⁶ , SR ⁷⁷ , NR ⁷⁸ R ⁷⁹ , COR ⁸⁰ , SOR ⁸¹ , SO ₂ R ⁸² or Representing CONR ⁸³ R ⁸⁴ , R ⁷³ and R ⁷⁴ may combine with each other to form a ring.
R ⁷⁵ , R ⁷⁶ , R ⁷⁷ , R ⁷⁸ , R ⁷⁹ , R ⁸⁰ , R ⁸¹ , R ⁸² , R ⁸³ and R ⁸⁴ are each independently an alkyl group having 1 to 20 carbon atoms and 6 to 20 carbon atoms. Represents an aryl group of 30, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms.
X ³ represents an oxygen atom, a sulfur atom, a selenium atom, CR ⁸⁵ R ⁸⁶ , CO, NR ⁸⁷ or PR ⁸⁸ .
X ⁴ represents a single bond or CO
R ⁸⁵ , R ⁸⁶ , R ⁸⁷ and R ⁸⁸ are independently hydrogen atoms, alkyl groups having 1 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, or aryl alkyl groups having 7 to 20 carbon atoms. The methylene group in the alkyl group or arylalkyl group may be substituted with a halogen atom, a nitro group, a cyano group, a hydroxyl group, a carboxyl group or a heterocycle-containing group, and is replaced with −O−. In some cases,
R ⁷³ and R ⁷⁴ may independently form a ring together with either adjacent benzene ring.
e1 represents an integer from 0 to 4 and represents
e2 represents an integer from 0 to 5. )

The number of carbon atoms used in R ⁷¹ , R ⁷² , R ⁷⁵ , R ⁷⁶ , R ⁷⁷ , R ⁷⁸ , R ⁷⁹ , R ⁸⁰ , R ⁸⁵ , R ⁸⁶ , R ⁸⁷ and R ⁸⁸ in the above general formula (IV) is 1. Examples of the above-mentioned "1. Alkyl group of ~ 20, aryl group of 6 to 30 carbon atoms, arylalkyl group of 7 to 30 carbon atoms or heterocycle-containing group of 2 to 20 carbon atoms, and substituents thereof. among the terms of the light leaving group B 'of the content exemplified as R ¹¹ or the like, include those satisfying a predetermined number of carbon atoms.

Examples of the oxime compound include etanone-1- [9-ethyl-6- (2-methylbenzoyl-9H-carbazole-3-yl] -1- (O-acetyloxime), 1- [9-ethyl). -6-benzoyl-9H-carbazole-3-yl-octane-1-one oxime-O-acetate, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl] -ethane- 1-onexime-O-benzoate, 1- [9-n-butyl-6- (2-ethylbenzoyl) -9H-carbazole-3-yl] -ethane-1-oneoxime-O-benzoate, etanone-1- [ 9-Ethyl-6- (2-Methyl-4-tetrahydrofuranylbenzoyl) -9H-Carbazole-3-yl] -1- (O-acetyloxime), Etanone-1- [9-Ethyl-6- (2-) Methyl-4-tetrahydropyranylbenzoyl) -9H-carbazole-3-yl] -1- (O-acetyloxime), Etanone-1- [9-ethyl-6- (2-methyl-5-tetrahydrofuranylbenzoyl)) -9H-carbazole-3-yl] -1- (O-acetyloxime), etanone-1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3-dioxolanyl)) Methoxybenzoyl} -9H-carbazole-3-yl] -1- (O-acetyloxime), etanone-1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxybenzoyl) -9H-carbazole- Examples thereof include a carbazole-based oxime ester compound having a carbazole structure such as 3-yl] -1- (O-acetyloxime).

As the oxime compound, for example, an indole-based oxime ester compound having an indole structure can also be used.
Examples of the indole-based oxime ester compound include an oxime ester compound represented by the following general formula (V) described in International Publication No. 2017/051680.

(In the formula, R ²⁰¹ and R ²⁰² independently represent R ²¹¹ , OR ²¹¹ , COR ²¹¹ , SR ²¹¹ , CONR ²¹² R ²¹³ or CN, respectively.
R ²¹¹ , R ²¹² and R ²¹³ independently have a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms or a carbon atom. Represents a heterocyclic group of the number 2 to 20
The hydrogen atoms of the groups represented by R ²¹¹ , R ²¹² and R ²¹³ are further R ²²¹ and OR ²²¹ and COR ²²¹ and SR ²²¹ and NR ²²² R ²²³ , CONR ²²² R ²²³ , NR ²²² OR ²²³ and NCOR ²²² OCOR ^223. , NR ²²² COR ²²¹ ， OCOR ²²¹ ， COOR ²²¹ ， SCOR ²²¹ ， OCSR ²²¹ ， COSR ²²¹ ， CSO R ²²¹ may be substituted with hydroxyl group, nitro group, CN, halogen atom or COOR ²²¹ .
R ^{221, R 222} and ^{R 223} are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, aryl group having 6 to 30 carbon atoms, an arylalkyl group or a carbon atom having 7 to 30 carbon atoms Represents a heterocyclic group of the number 2 to 20
The hydrogen atom of the group represented by R ²²¹ and R ²²² and R ²²³ may be further substituted with a hydroxyl group, a nitro group, a CN, a halogen atom, a hydroxyl group or a carboxyl group.
The methylene group of the alkylene moiety of the group represented by R ²¹¹ , R ²¹² , R ²¹³ , R ²²¹ and R ²²² and R ²²³ is -O-, -S-, -COO-, -OCO-, -OCOO-, ^{-CONR 224 -, - NR 224 -} , - NR 224 CO -, - NR 224 COO -, - OCONR 224 -, - SCO -, - COS -, - OCS- or -SCOO- by sometimes replaced ,
^R224 contains a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocycle-containing group having 2 to 20 carbon atoms. Represent,
The alkyl moieties of the groups represented by R ²¹¹ , R ²¹² , R ²¹³ , R ²²¹ and R ²²² , R ²²³ and R ²²⁴ may have branched side chains or may be cyclic alkyls.
R ²⁰³ contains a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocycle-containing group having 2 to 20 carbon atoms. Represented, the alkyl moiety of the group represented by R ²⁰³ may have a branched side chain or a cyclic alkyl, and R ²⁰³ and R ²⁰⁷ and R ²⁰³ and R ²⁰⁸ may be together, respectively. It may form a ring,
The hydrogen atoms of the group represented by R ²⁰³ are further R ²²¹ and OR ²²¹ and COR ²²¹ and SR ²²¹ and NR ²²² R ²²³ , CONR ²²² R ²²³ , NR ²²² OR ²²³ , NCOR ²²² OCOR ²²³ and NR ²²² COR ²²¹ and It may be substituted with OCOR ²²¹ or COOR ²²¹ or SCOR ²²¹ or OCSR ²²¹ or COSR ²²¹ or CSO R ^{221 as} a hydroxyl group, nitro group, CN, halogen atom or COOR ²²¹ .
R ²⁰⁴ , R ²⁰⁵ , R ²⁰⁶ and R ²⁰⁷ are independently R ²¹¹ , OR ²¹¹ , SR ²¹¹ , COR ²¹⁴ , CONR ²¹⁵ R ²¹⁶ , NR ²¹² COR ²¹¹ , OCOR ²¹¹ , COOR ²¹⁴ , SCOR ²¹¹ , OCSR ²¹¹ , respectively. , COSR ²¹⁴ , CSOR ²¹¹ , hydroxyl group, CN or halogen atom, R ²⁰⁴ and R ²⁰⁵ , R ²⁰⁵ and R ²⁰⁶ and R ²⁰⁶ and R ²⁰⁷ may be combined to form a ring, respectively.
The hydrogen atoms of the groups represented by R ²⁰⁴ , R ²⁰⁵ , R ²⁰⁶ and R ²⁰⁷ are further R ²²¹ and OR ²²¹ and COR ²²¹ and SR ²²¹ and NR ²²² R ²²³ , CONR ²²² R ²²³ , NR ²²² OR ²²³ and NCOR. It may be replaced with ²²² OCOR ²²³ , NR ²²² COR ²²¹ , OCOR ²²¹ , COOR ²²¹ , SCOR ²²¹ or OCSR ²²¹ or COSR ²²¹ or CSO R ²²¹ or hydroxyl group, nitro group, CN, halogen atom or COOR ²²¹ .
R ²¹⁴ , R ²¹⁵ and R ²¹⁶ represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.
The alkyl moieties of the groups represented by R ²¹⁴ , R ²¹⁵ and R ²¹⁶ may have branched side chains or may be cyclic alkyls.
R ²⁰⁸ is R ²¹¹ , OR ²¹¹ , SR ²¹¹ , COR ²¹¹ , CONR ²¹² R ²¹³ , NR ²¹² COR ²¹¹ , OCOR ²¹¹ , COOR ²¹¹ , SCOR ²¹¹ , OCSR ²¹¹ , COSR ²¹¹ , CSOR ²¹¹ , hydroxyl group, CN or halogen atom. Represents
n1 represents 0 or 1. )

The number of carbon atoms 1 to 20 used in R ²⁰³ , R ²¹¹ , R ²¹² , R ²¹³ , R ²¹⁴ , R ²¹⁵ , R ²¹⁶ , R ²²¹ and R ²²² , R ²²³ and R ²²⁴ in the above general formula (V). Examples of the alkyl group, the aryl group having 6 to 30 carbon atoms, the arylalkyl group having 7 to 30 carbon atoms, or the heterocycle-containing group having 2 to 20 carbon atoms are described in the above section "1. Photoremoving group B". while the contents exemplified as R ¹¹ or the like, include those satisfying a predetermined number of carbon atoms.

Other radical polymerization initiators include phosphine oxide compounds such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis (cyclopentadienyl) -bis [2,6-difluoro-3- (pill-1). -Il)] Titanosen-based compounds such as titanium can be mentioned.

Commercially available radical polymerization initiators include ADEKA PUTMER N-1414, N-1717, N-1919, ADEKA ARCULS NCI-831, NCI-930 (manufactured by ADEKA), IRGACURE184, IRGACURE369, IRGACURE651, IRGACURE907, IRGACURE ORE. 01, IRGACURE OXE 02, OXE 03, OXE 04, IRGACURE784 (manufactured by BASF), TR-PBG-304, TR-PBG-305, TR-PBG-309 and TR-PBG-314 (manufactured by Trolly), etc. Be done.

One or more of these photoradical polymerization initiators can be blended and used according to desired performance.
The content of the photoradical polymerization initiator may be any as long as it can impart desired curability and photosensitivity. For example, 0.001 part by mass or more and 20 parts by mass with respect to 100 parts by mass of the polymerizable compound. It can be as follows, preferably 0.1 parts by mass or more and 30 parts by mass or less, and preferably 0.5 parts by mass or more and 10 parts by mass or less. This is because the composition has excellent curability and the like, and also has excellent dispersibility and the like because of the above content.

The photocationic polymerization initiator is not particularly limited as long as it is a compound capable of releasing a substance that initiates cationic polymerization by light irradiation, and an existing compound can be used, preferably an energy ray. It is a double salt, which is an onium salt that releases Lewis acid upon irradiation, or a derivative thereof. Typical examples of such compounds include the following general formulas.
[A1] ^{r +} [B1] ^r-
Examples of salts of cations and anions represented by.

The cation [A1] ^{r +} is preferably onium, and its structure can be represented by, for example, the following general formula.
[(R ¹⁰¹ ) _f1 Q] ^{r +}

Further, here, R ¹⁰¹ is an organic group having 1 to 60 carbon atoms and may contain a number of atoms other than carbon atoms. f1 is any integer from 1 to 5. The e R ^58s are independent and may be the same or different. Further, at least one of R ¹⁰¹ is preferably an organic group as described above having an aromatic ring. For example, it may be substituted with an alkyl group, an alkoxy group, a hydroxy group, a hydroxyalkoxy group, a halogen atom, a benzyl group, a thiophenoxy group, a 4-benzoylphenyl thio group, a 2-chloro-4-benzoyl phenyl thio group, or the like. There is a phenyl group. Q is an atom or atomic group selected from the group consisting of S, N, Se, Te, P, As, Sb, Bi, O, I, Br, Cl, F, N = N. Further, when the valence of Q in the cation [A1] ^{r +} is q, it is necessary that the relationship r = f1-q holds (however, N = N is treated as 0 valence).

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

Further, here, L is a metal or metalloid that is the 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 _f2 is a halogen atom, or a phenyl group that may be substituted with a halogen atom, an alkoxy group, or the like. f2 is an integer of 3 to 7.
Further, when the valence of L in the anion [B1] ^r- is p, it is necessary that the relationship r = f2-p is established.

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

The anion [B1] ^r- is a general formula below.
[LX _f2-1 (OH)] ^r-
The structure represented by is also preferably used. L, X, f2 are the same as above. Other anions that can be used include perchlorate ion (ClO ₄ ) ⁻ , trifluoromethyl sulfite ion (CF ₃ SO ₃ ) ⁻ , fluorosulfonic acid ion (FSO ₃ ) ⁻ , and toluene sulfonic acid anion. , Trinitrobenzene sulfonic acid anion, camphor sulfonate, nonafluorobutane sulfonate, hexadecafluorooctane sulfonate, tetraarylborate, tetrakis (pentafluorophenyl) borate and the like.

In the present invention, among such onium salts, it is particularly effective and preferable to use the following aromatic onium salts (e) to (g). From these, one of them can be used alone, or two or more of them can be mixed and used.

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

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

(G) A sulfonium salt such as a sulfonium cation represented by the following group I or group II, a hexafluoroantimony ion, and a tetrakis (pentafluorophenyl) borate ion.

Other preferred ones are (η5-2,4-cyclopentadiene-1-yl) [(1,2,3,4,5,6-η)-(1-methylethyl) benzene] -iron-. Iron-arene complex such as hexafluorophosphate; aluminum complex such as tris (acetylacetonato) aluminum, tris (ethylacetonatoacetato) aluminum, tris (salityl aldehyde) aluminum; mixture with silanols such as triphenylsilanol : Etc. can also be mentioned.

As the photocationic polymerization initiator, a commercially available product can also be used. For example, IRUGACURE261 (manufactured by BASF), ADEKA PUTMER SP-150, SP-151, SP-152, SP-170, SP-171, SP. -172 (manufactured by ADEKA), UVE-1014 (manufactured by General Electronics), CD-1012 (manufactured by Sartmer), CI-2064, CI-2481 (manufactured by Nippon Soda), Uvacure 1590, 1591 (Dycel UCB), CYRACURE UVI-6990 (manufactured by Union Carbide), BBI-103, MPI-103, TPS-103, MDS-103, DTS-103, NAT-103, NDS-103 (manufactured by Midori Chemical Co., Ltd.) and the like can be mentioned.

Among these, it is preferable to use an aromatic iodonium salt, an aromatic sulfonium salt, or an iron-arene complex from the viewpoint of practical use and photosensitivity.

As the photoanionic polymerization initiator, one that generates a base by light can be used, and a known photoanionic polymerization initiator can be used.
Examples of the photoanionic polymerization initiator include acetophenone O-aroyloxime and nifedipine.

(B) Thermal Polymerization Initiator The thermal polymerization initiator may be any one capable of polymerizing a polymerizable compound by heating, and examples thereof include a radical polymerization initiator, a cationic polymerization initiator, and an anionic polymerization initiator. Can be done.

As the thermal radical polymerization initiator, one that generates radicals by heating can be used, and a known thermal radical polymerization initiator can be used.
As the thermal radical polymerization initiator, for example, azo compounds, peroxides, persulfates and the like can be exemplified as preferable ones.

Examples of the azo compound include 2,2'-azobisisobutyronitrile, 2,2'-azobis (methylisobutyrate), 2,2'-azobis-2,4-dimethylvaleronitrile, and 1,1'. -Azobis (1-acetoxy-1-phenylethane) and the like can be mentioned.

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

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

As the thermal cationic polymerization initiator, one that generates a cationic species or Lewis acid by heating can be used, and a known thermal cationic polymerization initiator can be used.
Specific examples of the thermal cationic polymerization initiator include salts such as sulfonium salt, thiophenium salt, thiolanium salt, benzylammonium, pyridinium salt and hydrazinium salt; and polyalkylpolyamine such as diethylenetriamine, triethylenetriamine and tetraethylenepentamine. Classes; alicyclic polyamines such as 1,2-diaminocyclohexane, 1,4-diamino-3,6-diethylcyclohexane and isophoronediamine; aromatic polyamines such as m-xylylene diamine, diaminodiphenylmethane and diaminodiphenylsulfone. The above polyamines are reacted with various epoxy resins such as glycidyl ethers such as phenylglycidyl ether, butyl glycidyl ether, bisphenol A-diglycidyl ether and bisphenol F-diglycidyl ether, or glycidyl esters of carboxylic acid by a conventional method. Polyepoxy addition-modified product produced by reacting; an amidated modified product produced by reacting the above-mentioned organic polyamines with carboxylic acids such as phthalic acid, isophthalic acid and dimeric acid by a conventional method; the above-mentioned polyamines. Mannig modified product produced by reacting with aldehydes such as formaldehyde and phenols having at least one aldehyde reaction reaction site in the nucleus such as phenol, cresol, xylenol, tertiary butylphenol and resorcin by a conventional method. Polyvalent carboxylic acids (succinic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimeric acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, 2-methylsuccinic acid, 2-methyladipic acid, 3- Aliphatic dicarboxylic acids such as methyladipic acid, 3-methylpentanedioic acid, 2-methyloctanedioic 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 trimesters such as trimellitic acid, trimesic acid and castor oil fatty acid; Acid anhydrides of (tetracarboxylic acids such as merit acids); dicyandiamides, imidazoles, carboxylic acid esters, sulfonic acid esters, amineimides and the like can be mentioned.
Commercially available products can also be used as the thermal cationic polymerization initiator, for example, ADEKA OPTON CP-77, ADEKA OPTON CP-66 (manufactured by ADEKA), CI-2369, CI-2624 (manufactured by Nippon Soda), Sun Aid SI. -60L, Sun Aid SI-80L, Sun Aid SI-100L (manufactured by Sanshin Chemical Industry Co., Ltd.) and the like can be mentioned.

As the thermal anionic polymerization initiator, one that generates a base by heat can be used, and a known thermal anionic polymerization initiator can be used.
Specific examples of the anion polymerization initiator include an aliphatic amine compound, an aromatic amine compound, a secondary or tertiary amine compound, an imidazole compound, a polymercaptan compound, and a boron trifluoride-amine complex. , Diciandiamide, organic acid hydrazide and the like can be used.

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

(3) Others In addition to the resin component and the polymerization initiator, the other components include a colorant, a solvent, a chain transfer agent, a sensitizer, a surfactant, a silane coupling agent, a melamine compound and the like, if necessary. Can be included.
In addition to these, the other components may be heat polymerization inhibitors such as p-anisole, hydroquinone, pyrocatechol, t-butylcatechol, and phenothiazine; plasticizers; adhesion promoters; fillers; erasables, if necessary. Foaming agent; Leveling agent; Surface conditioner; Phenolic antioxidant, Phosphite antioxidant, Antioxidant such as thioether antioxidant; Ultraviolet absorber other than the compound represented by the above compound I-1; Additives such as dispersion aids; anti-aggregation agents; catalysts; effect promoters; cross-linking agents; thickeners can be included.

(A) Colorant As the colorant, for example, a dye or a pigment may be used as long as it can impart a desired color to the composition or a cured product thereof.
As the dye, a compound having an absorption at 380 to 1200 nm can be used, for example, an azo compound, an anthraquinone compound, an indigoid compound, a triarylmethane compound, a xanthene compound, an alizarin compound, an acridin compound, a stilben compound, a thiazole compound, and naphthol. Compounds, quinoline compounds, nitro compounds, indamine compounds, oxazine compounds, phthalocyanine compounds, cyanine compounds, diimmonium compounds, cyanoethenyl compounds, dicyanostyrene compounds, rhodamine compounds, perylene compounds, polyennaphtholactum compounds, coumarin compounds, squarylium compounds, croconium compounds, Spiropyran compound, spiroxazine compound, merocyanine compound, oxonol compound, styryl compound, pyrylium compound, rodonine compound, oxazolone compound, phthalimide compound, cinnoline compound, naphthoquinone compound, azaanthraquinone compound, porphyrin compound, azaporphyrin compound, pyromethene compound, quinacridone compound , Diketopyrrolopyrrole compounds, indigo compounds, aclysine compounds, azine compounds, azomethine compounds, aniline compounds, quinacridone compounds, quinophthalone compounds, quinoneimine compounds, iridium complex compounds, europium complex compounds and other dyes. It may be mixed and used.

As the pigment, an inorganic pigment or an organic pigment can be used, for example, a nitroso compound, a nitro compound, an azo compound, a diazo compound, a xanthene compound, a quinoline compound, an anthraquinone compound, a coumarin compound, a phthalocyanine compound, an isoindolinone compound, and an iso. Indoline compounds, quinacridone compounds, antanthurone compounds, perinone compounds, perylene compounds, diketopyrrolopyrrole compounds, thioindigo compounds, dioxazine compounds, triphenylmethane compounds, quinophthalone compounds, naphthalenetetracarboxylic acids; metal complex compounds of azo dyes and cyanine dyes; Lake pigment; carbon black obtained by furnace method, channel method, thermal method, or carbon black such as acetylene black, ketjen black or lamp black; the above carbon black adjusted and coated with an epoxy resin, the above carbon black is prepared in advance. A compound that is dispersed with a resin in a solvent and adsorbs 20 to 200 mg / g of resin, an acidic or alkaline surface-treated carbon black, an average particle size of 8 nm or more and a DBP oil absorption of 90 ml / 100 g or less. The total amount of oxygen calculated from CO and CO ₂ in the volatile matter at 950 ° C is 9 mg or more per 100 m ^{2 of} carbon black surface; graphite, graphite carbon black, activated carbon, carbon fiber, carbon nanotube, carbon. Microcoil, carbon nanohorn, carbon aerogel, fullerene; aniline black, pigment black 7, titanium black; hydrophobic resin, chromium oxide green, milloli blue, cobalt green, cobalt blue, manganese, ferrocyanide, phosphate ultramarine blue, dark blue , Ultramarine, Cerulean Blue, Pyridian, Emerald Green, Lead Sulfate, Yellow Lead, Zinc Yellow, Bengara (Red Iron Oxide (III)), Cadmium Red, Synthetic Iron Black, Amber, etc. it can. These pigments can be used alone or in combination of two or more.

As the above-mentioned inorganic pigment or organic pigment, a commercially available pigment can also be used. 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 and the like.

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 can be 0.01 part by mass or more and 20 parts by mass or less in 100 parts by mass of the composition.

(B) Solvent The solvent may be any solvent that can dissolve or disperse each of the above components. For example, methyl ethyl ketone, methyl amyl ketone, diethyl ketone, acetone, methyl isopropyl ketone, methyl isobutyl ketone, cyclohexanone, 2- Ketones such as heptanone; ether solvents such as ethyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane, dipropylene glycol dimethyl ether; methyl acetate, ethyl acetate, -n-propyl acetate, Ester solvents such as isopropyl acetate, n-butyl acetate, cyclohexyl acetate, ethyl lactate, dimethyl succinate, texanol; cellosolve solvents such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; methanol, ethanol, iso- or n- Alcohol-based solvents such as propanol, iso- or n-butanol, amyl alcohol, diacetone alcohol; ethylene glycol monomethyl acetate, ethylene glycol monoethyl acetate, propylene glycol-1-monomethyl ether-2-acetate (PGMEA), dipropylene glycol Ether ester solvents such as monomethyl ether acetate, 3-methoxybutyl acetate, ethoxyethyl propionate, 1-t-butoxy-2-propanol, 3-methoxybutyl acetate, cyclohexanol acetate; BTX such as benzene, toluene, xylene Solvents; aliphatic hydrocarbon solvents such as hexane, heptane, octane, cyclohexane; terpene hydrocarbons such as terepine oil, D-lymonen, pinen; mineral spirit, swazole # 310 (Cosmo Matsuyama Oil Co., Ltd.), Paraffin-based solvent such as Solbesso # 100 (Exxon Chemical Co., Ltd.); Halogenated aliphatic hydrocarbon solvent such as carbon tetrachloride, chloroform, trichloroethylene, methylene chloride, 1,2-dichloroethane; Halogenized aromatic solvent such as chlorobenzene Carbitol-based solvent; carbitol-based solvent, aniline, triethylamine, pyridine, acetic acid, acetonitrile, carbon disulfide, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, water, etc. These solvents can be used as one kind or a mixed solvent of two or more kinds.
The content of the solvent varies depending on the use of the composition and the like, but can be 1 part by mass or more and 99 parts by mass or less in 100 parts by mass of the composition, and 10 parts by mass or more and 70 parts by mass. It is preferably less than a part. This is because it is easy to make it excellent in coatability and the like.

(C) Chain Transfer Agent and Sensitizer As the chain transfer agent and sensitizer, the sensitivity of the composition and the like can be adjusted, and a sulfur atom-containing compound is generally used. For example, thioglycolic acid, thioapple acid, thiosalicylic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, 3-mercaptobutyric acid, N- (2-mercaptopropionyl) glycine, 2-mercaptonicotinic acid, 3-[N-( 2-Mercaptoethyl) carbamoyl] propionic acid, 3- [N- (2-mercaptoethyl) amino] propionic acid, N- (3-mercaptopropionyl) alanine, 2-mercaptoethanesulfonic acid, 3-mercaptopropanesulfonic acid, 4-mercaptobutansulfonic acid, dodecyl (4-methylthio) phenyl ether, 2-mercaptoethanol, 3-mercapto-1,2-propanediol, 1-mercapto-2-propanol, 3-mercapto-2-butanol, mercaptophenol , 2-Mercaptoethylamine, 2-Mercaptoimidazole, 2-Mercaptobenzoimidazole, 2-Mercapto-3-pyridinol, 2-Mercaptobenzothiazole, Mercaptoacetic acid, Trimethylolpropanthris (3-mercaptopropionate), Pentaerythritoltetrakis A mercapto compound such as (3-mercaptopropionate), a disulfide compound obtained by oxidizing the mercapto compound, iodoacetic acid, iodopropionic acid, 2-iodoethanol, 2-iodoethanesulfonic acid, 3-iodopropanesulfonic acid. Alkyliodated compounds such as, trimethylolpropanetris (3-mercaptoisobutyrate), butanediol bis (3-mercaptoisobutyrate), hexanedithiol, decandithiol, 1,4-dimethylmercaptobenzene, butanediol bisthio. Propionate, Butanediol Bisthioglycolate, Ethethylene Glycol Bisthioglycolate, Trimethylol Propanetristhioglycolate, Butanediol Bisthiopropionate, Trimethylol Propanetristhiopropionate, Trimethylol Propanetristhioglycolate , Pentaerythritol tetrakisthiopropionate, pentaerythritol tetraxthioglycolate, trishydroxyethyl tristhiopropionate, the following compound No. Examples thereof include aliphatic polyfunctional thiol compounds such as C1, tris (2-hydroxyethyl) trimercaptopropionate, isocyanurate, and Karenz MT BD1, PE1, NR ¹ manufactured by Showa Denko KK.

(D) Surfactant As the surfactant, one that can improve the dispersion stability, coatability, etc. of the composition can be used, and fluorine such as perfluoroalkyl phosphate and perfluoroalkyl carboxylate can be used. Surfactants, higher fatty acid alkali salts, alkyl sulfonates, anionic surfactants such as alkyl sulfates, higher amine halides, cationic surfactants such as quaternary ammonium salts, polyethylene glycol alkyl ethers, polyethylene Nonionic surfactants such as glycol fatty acid ester, sorbitan fatty acid ester, and fatty acid monoglyceride, and surfactants such as amphoteric surfactant and silicone-based surfactant can be used, and these may be used in combination.

(E) Silane Coupling Agent The silane coupling agent is a silane compound having a reactive group that chemically bonds with an inorganic material such as glass and a reactive group that chemically bonds with an organic material such as a synthetic resin, and has a composition. A substance or a cured product thereof that can improve the adhesion and the like can be used. As the silane coupling agent, for example, a silane coupling agent manufactured by Shin-Etsu Chemical Co., Ltd. can be used, among which silane couplings having an isocyanate group, a methacryloyl group, an epoxy group, etc. such as KBE-9007, KBM-502, and KBE-403 can be used. The agent is preferably used.

(F) Melamine compound As the melamine compound, a compound capable of improving curability can be used, for example, (poly) methylol melamine, (poly) methylol glycol uryl, (poly) methylol benzoguanamine, (poly) methylol urea and the like. Examples thereof include compounds in which all or part (at least two) of active methylol groups (CH ₂ OH groups) in the nitrogen compound of the above are alkyl etherified. Here, examples of the alkyl group constituting the alkyl ether include a methyl group, an ethyl group and a butyl group, which may be the same or different from each other. Further, the methylol group which has not been alkyl etherized may be self-condensed within one molecule, or may be condensed between two molecules to form an oligomer component as a result. Specifically, hexamethoxymethylmelamine, hexabutoxymethylmelamine, tetramethoxymethylglycol uryl, tetrabutoxymethyl glycol uryl and the like can be used. Among these, alkyl etherified melamines such as hexamethoxymethylmelamine and hexabutoxymethylmelamine are preferable.

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

The method for producing the above composition may be any method as long as the above-mentioned components can be blended in a desired content, or a method in which the above-mentioned components are simultaneously added and mixed, while each component is sequentially added. It may be a mixing method.

The above compositions are used for heat-curable paints, photo-curable paints or varnishes, heat-curable adhesives, photo-curable adhesives, printed substrates, or colors for color televisions, PC monitors, mobile information terminals, digital cameras, etc. Color filter for display liquid crystal display panel, color filter for CCD image sensor, photo spacer, black column spacer, electrode material for plasma display panel, touch panel, touch sensor, powder coating, printing ink, printing plate, adhesive, dental Compositions, photoforming resins, gel coats, electronic engineering photo resists, electroplating resists, etching resists, both liquid and dry films, solder resists, for manufacturing color filters for various display applications or for plasma display. Resists for forming structures in the manufacturing process of panels, electroluminescent indicators, and LCDs, compositions for encapsulating electrical and electronic components, solder resists, magnetic recording materials, micromechanical components, waveguides, optical switches, Plating mask, etching mask, color test system, glass fiber cable coating, screen printing stencil, material for manufacturing three-dimensional objects by stereolithography, holography recording material, image recording material, microelectronic circuit, decolorizing material , Decolorizing material for image recording material, Decolorizing material for image recording material using microcapsules, Photo resist material for printed wiring board, Photo resist material for UV and visible laser direct imaging system, Sequential stacking of printed circuit boards It can be used for various purposes such as a photoresist material used for forming a dielectric layer in the above, a photoresist material for 3D mounting, a protective film, and the like, and the use is not particularly limited.
Further, the above-mentioned applications are not limited to applications that require durability against ultraviolet rays when used as a product, and can be suitably used, for example, for members that receive ultraviolet irradiation or the like in the manufacturing process.
Examples of the member to be irradiated with ultraviolet rays in the manufacturing process include a member to be irradiated with ultraviolet rays in order to improve the wettability and adhesion of the surface.
Examples of the members required to improve wettability and adhesion as described above include members laminated with other members, for example, various types such as a plasma display panel, an organic electroluminescence display device, and a liquid crystal display device. Color filters, photo spacers, brightness improving plates, light guide plates, TFT substrates, alignment films, liquid crystal layers, insulating films, acoustic elements such as speakers, for imaging as members that make up various sensors such as image displays and touch panels, circuit boards, etc. Examples of members such as lenses, key pads, and magnetic heads for HDDs are required to be surface-modified and to prevent deterioration of the members in the manufacturing process.
Examples of the members required to modify the surface and prevent deterioration of the members in the above-mentioned manufacturing process include members that are laminated with other members via an adhesive and members that are covered with other members by paint or the like. For example, transportation equipment such as interior / exterior members of automobiles and aircraft, home appliances such as refrigerators and washing machines, and constituent members for various purposes such as housing building materials can also be mentioned.
In addition, after forming a patterned member on the base material, the above member may be irradiated with ultraviolet rays together with the base material in order to modify the surface of the exposed base material. As the above application, it can also be preferably used for a member used together with a member that requires surface modification or the like in such a manufacturing process. The above applications include, for example, members used together with members such as plastic films, glass, silicon wafers, various engineering plastics, optical lenses, metal surfaces, plating, ceramics, and molds that require surface cleaning and surface modification. Can be mentioned.

D. Hardened 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.

Since the composition of the present invention uses the above-mentioned composition, it has a good ultraviolet absorbing ability and the like.

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

The composition contains the compound I-1 and a polymerizable compound. Further, the composition may contain components other than the compound I-1 and the polymerizable compound.
The content of each component of such a composition can be the same as the content described in the section "2. Other components" of the above "C. composition".

The compound I-1 contained in the composition may be in the cured product before or after the desorption of the photoleaving group B, but it is preferably after the desorption. .. This is because the cured product has an excellent ultraviolet absorbing 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 intended use of the cured product, and is, for example, 10 parts by mass or less in 100 parts by mass of the cured product, and 1 mass by mass. It is preferably less than a part.

The cured product may be substantially free of solvents.
The content of the solvent contained in the cured product can be, for example, 1 part by mass or less, or 0.5 parts by mass or less, based on 100 parts by mass of the cured product.

The elastic modulus of the cured product is usually higher than that of the composition, and can be, for example, ^10-3 M or more, and 10 MPa or more. This is because the cured product can stably retain the compound I-1 and the like because of the elastic modulus.
The upper limit of the elastic modulus, can be appropriately set depending on the application of the cured product, for example, be a 10 ⁶ MPa or less.
Hereinafter, the elastic modulus refers to the compressive elastic modulus, and can be measured at 23 ° C. in accordance with JIS K7181.
As for the measurement sample, for example, a cubic test piece having a side length of 6 mm can be prepared or cut out, and the measurement can be performed under the condition of a test speed of 1 ± 0.2 mm / min according to JIS K7181.

The method for producing the cured product may be any method that can cure the composition described above, and may be the same as the method described in the section "F. Method for producing a cured product" described later. it can.

The uses of the cured product and the like can be the same as those described in the section of "C. Composition".

E. Composition Next, the second composition of the present invention will be described.
The second composition of the present invention comprises a compound represented by the following general formula (I-2) (hereinafter, may be referred to as "Compound I-2") and a desorbed product derived from a photoleaving group (hereinafter, referred to as "Compound I-2"). , "Sometimes referred to as" Compound B'"), and.

(In the formula, A is an atomic group having an ultraviolet absorbing ability, and k represents an integer of 1 to 10.)

According to the present invention, the second composition can be easily formed by using, for example, the above composition. In addition, the second composition can easily impart ultraviolet absorbing ability and the like.

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

1. 1. Compound I-2
The compound I-2 exhibits an ultraviolet absorbing ability.
The compound I-2 is obtained by substituting the B—O— in the compound I-1 with an −OH group.
Since the content of such compound I-1 can be the same as the content described in the above-mentioned "A. compound" section, the description thereof is omitted here.

The content of the compound I-2 in the composition may be any as long as it can impart a desired ultraviolet absorbing ability or the like. For example, the total of the compound I-2 and the compound B'is the above-mentioned "C. composition. It can be the same as the content of the above-mentioned compound I-1 in the solid content described in the section "Product".

2. 2. Compound B'
The compound B'is a leaving product derived from a photoleaving group.
Further, the photoleaving group may be a group that can be bonded to a phenolic hydroxyl group as a protecting group, and is the same as the content described in "1. Photoleaving group B" of the above "A. compound". be able to.
Such compound B'may be any compound that can be obtained after the photoleaving group is eliminated from the phenolic hydroxyl group.
The photoleaving group B after desorption from the phenolic hydroxyl group is usually highly reactive and can have various structures.
As the compound B', the photoleaving group B is the general formula (B-1-a), (B-2), (B-3), (B-4), (B-5), (B-5), ( When it is represented by B-6), (B-7), etc., for example, the following general formulas (B-111-a), (B-112), (B-113), (B), respectively. -114), (B-115), (B-116), (B-117) and the like can be included.

R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² , R ²³ , R ²⁴ , R contained in the above compound B'. ²⁵ , R ²⁶ and R ²⁷ and b1, b2, b3, b4, b5, b6, b7 and b8 are the same as those described in the above section "A. Compound", and the description thereof is described here. Omit.

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

3. 3. Others The above-mentioned second composition has compound I-2 and compound B', but usually contains other components.
Examples of such other components include the contents described in the section “2. Other components” of the above “C. composition”.
The other components preferably contain a resin component, and particularly preferably contain a polymer having no polymerizable group, such as a polymer of a polymerizable compound. This is because the second composition can effectively exert the effect of easily imparting an ultraviolet absorbing ability or the like to a cured product or the like, for example.
The type of resin component may be only one type, or two or more types may be used in combination.

The second composition may contain a solvent, a polymerizable compound, and the like and may have coatability, and the viscosity in that case is the same as that described in the above section "C. Composition". Can be.
When the second composition is a cured product containing a polymer of a polymerizable compound, the elastic modulus of the second composition is the same as that described in the section "D. Cured product". can do.

The uses of the second composition and the like can be the same as those described in the section of "D. Hardened product".

F. Method for producing cured product Next, the method for producing the 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 above-mentioned compound I-1 and a polymerizable compound to form a cured product, and a step of irradiating the cured product with light to obtain the above-mentioned cured product. It has a step of removing the photoleaving group B contained in the compound.

According to the present invention, in the above-mentioned production method, by using the above-mentioned composition and having the above-mentioned steps, curing is easy, and ultraviolet absorbing ability and the like can be easily imparted.

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

1. 1. Step of Forming a Hardened Product The step of forming the cured product is a step of forming a cured product of the above-mentioned composition.

The method for forming the cured product of the composition in this step may be any method capable of forming a cured product having a desired hardness, and is different depending on the components contained in the composition.
As the curing method, for example, when the composition contains a photopolymerization initiator as a polymerization initiator together with the polymerizable compound, the composition is irradiated with light to polymerize the polymerizable compounds. Can be done.
The light irradiated to the composition may include light having a wavelength of 300 nm to 450 nm.
Examples of the light source for light irradiation include ultra-high pressure mercury, mercury vapor arc, carbon arc, xenon arc and the like.
Laser light may be used as the light to be irradiated. As the laser light, one containing light having a wavelength of 340 to 430 nm can be used.
As the light source of the laser light, an argon ion laser, a helium neon laser, a YAG laser, a semiconductor laser, or the like that emits light in the visible to infrared region can also be used.
When these lasers are used, the composition may contain a sensitizing dye that absorbs the visible to infrared region.

The total amount of the emitted light is preferably one that can suppress the desorption of the photoleaving group B, for example, it can be less than 1000 mJ / cm ² and 800 mJ / cm ² or less. It can be 500 mJ / cm ² or less.

As the above-mentioned curing method, for example, when the composition contains a thermal polymerization initiator as a polymerization initiator together with the polymerizable compound, the composition is heat-treated and the polymerizable compounds are polymerized with each other. Can be done.
The heating temperature may be 60 ° C. or higher, preferably 100 ° C. or higher and 300 ° C. or lower, as long as the composition can be stably cured.
The heating temperature can be the temperature of the coating film surface of the composition.
The heating time can be about 10 seconds to 3 hours.

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

The composition used in this step contains the above-mentioned compound I-1 and a polymerizable compound.
In addition, the composition may contain other components other than the compound I-1 and the polymerizable compound.
Since the content of each component of such a composition can be the same as the content described in the section "2. Other components" of the above "C. composition", the description thereof is omitted here. ..

2. 2. Desorption Step The desorption step is a step of desorbing the photoleaving group B contained in the compound I-1.
The method for removing the photoleaving group B contained in the compound I-1 may be a method of irradiating the cured product with light.
The light irradiated to the cured product and the total amount of light thereof are not particularly limited as long as they can desorb the photoleaving group B, but are not particularly limited as long as they can desorb the photoleaving group B. The contents can be the same as those described in the section of "Leaving group B".
The light source for light irradiation is appropriately selected according to the wavelength of the irradiated light, and is the same as the content described in the above section "1. Step of forming a cured product". be able to.

The temperature of the cured product in this step can be appropriately set according to the heat resistance of the cured product and the base material supporting the cured product, and can be, for example, 200 ° C or lower, and 0 ° C or higher. The temperature is preferably 150 ° C. or lower, and more preferably 0 ° C. or higher and 100 ° C. or lower. This is because when the temperature is in the above range, the photoleaving group B can be easily desorbed. Further, as a result, for example, it is possible to reduce the damage caused by heating to the peripheral members such as the cured product and the base material.
The temperature of the cured product is the temperature of the surface of the cured product.

3. 3. Other Steps The above-mentioned production method includes a step of forming a cured product and a step of desorbing the cured product, but may include other steps as necessary.
Examples of the other steps include a step of applying the composition onto a substrate.
As a method for applying the composition, known methods such as a spin coater, a roll coater, a bar coater, a die coater, a curtain coater, various types of printing, and immersion can be used.
The base material can be appropriately set according to the intended use of the cured product, and examples thereof include soda glass, quartz glass, semiconductor substrates, metals, paper, plastics, and the like.
Further, the cured product may be formed on a substrate and then peeled off from the substrate, or transferred from the substrate to another adherend and used.

4. Others, the cured product produced by the above-mentioned production method, the intended use, and the like can be the same as those described in the above-mentioned "D. Cured product" section.

The present invention is not limited to the above embodiment. The above embodiment is an example, and any one having substantially the same configuration as the technical idea described in the present invention and exhibiting the same action and effect is the technical scope of the present invention. Included in.

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

[Example 1]
0.005 mol of the phenol compound (Compound I-2), 0.005 mol of potassium carbonate and 12 g of DMF in the following scheme 1 were mixed, 0.0075 mol of o-nitrobenzyl chloride was added dropwise at room temperature under a nitrogen atmosphere, and the mixture was added dropwise at 80 ° C. After stirring for 2 hours, compound I-1-2 corresponding to compound I-1 was obtained by the following reaction. 50 g of ethyl acetate and 50 g of ion-exchanged water were added to the reaction solution to perform oil-water separation. 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 ° C. for 2 hours to obtain the desired product (Compound I-1-2). It was confirmed by 1 H-NMR and IR that the obtained white solid was the target product.

[Examples 2 to 7]
The following compounds I-1-3, I-1-40, I-1-32, I-1-35, I-1-28, in the same manner as in Example 1 except that the o-nitrobenzyl chloride was changed. I-1-34 was obtained. Specifically, the compounds I-1-3, I-1-40, I-1-32, I-1-35, I-1-28 and 1-34 of Examples 2 to 7 are prepared by the following methods. Manufactured.
Further, it was confirmed by 1 H-NMR that the white solid obtained in Examples 2 to 7 was the target product.
[Example 2]
To 2-ethylnitrobenzene, 1.1 equivalents of N-bromosuccinimide and 0.01 equivalents of AIBN were used and heated and stirred at 90 ° C. for 4 hours in a chlorobenzene solvent. The mixture was separated into oil and water with ethyl acetate, washed with water, and purified on a silica column to obtain a 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 in place of o-nitrobenzyl chloride. It was confirmed by 1 H-NMR that the obtained white solid was the target product.
[Example 3]
Compound I-1-40 was obtained in the same manner as in Example 2 except that 4-chloro-2-nitrotoluene was used instead of 2-ethylnitrobenzene. It was confirmed by 1 H-NMR that the obtained white solid was the target product.
[Example 4]
Compound I-1-32 was obtained in the same manner as in Example 1 except that 4'-methoxyphenacil bromide was used instead of o-nitrobenzyl chloride. It was confirmed by 1 H-NMR that the obtained white solid was the target product.
[Example 5]
Compound I-1-35 was obtained in the same manner as in Example 1 except that 2-bromo-2-phenylacetophenone was used instead of o-nitrobenzyl chloride. It was confirmed by 1 H-NMR that the obtained white solid was the target product.
[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. It was confirmed by 1 H-NMR that the obtained white solid was the target product.
[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. It was confirmed by 1 H-NMR that the obtained white solid was the target product.

[Example 8]
1.1 equivalents of N-bromosuccinimide and 0.01 equivalents of AIBN were used with respect to 4-methoxy-2-nitrotoluene, and the mixture was heated and stirred at 90 ° C. for 4 hours in a chlorobenzene solvent. The mixture was separated into oil and water with ethyl acetate, washed with water, and purified on 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 in place of o-nitrobenzyl chloride. It was confirmed by 1 H-NMR that the obtained white solid was the target product.
[Example 9]
Compound I-1-4-1 was obtained in the same manner as in Example 8 except that 3-chloro-2-nitrotoluene was used instead of 4-methoxy-2-nitrotoluene. It was confirmed by 1 H-NMR that the obtained white solid was the target product.
[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. It was confirmed by 1 H-NMR that the obtained white solid was the target product.
[Example 11]
Compound I-1-43 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. It was confirmed by 1 H-NMR that the obtained white solid was the target product.
[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. It was confirmed by 1 H-NMR that the obtained white solid was the target product.

[Example 13]
An intermediate compound was obtained in the same manner as in Example 1 except that 4- (2-bromoacetyl) phenyl t-butyl carbonate was used instead of o-nitrobenzyl chloride. The intermediate compound 0.0035 mol was dissolved in 5 ml of ethyl acetate, 5 mL of a 4M HCl ethyl acetate solution was added, and the mixture was heated and stirred at 50 ° C. for 10 hours. The solvent of the reaction solution was distilled off, and the mixture was isolated on a silica column (ethyl acetate: hexane = 1: 2) to obtain the desired product (Compound I-1-45). It was confirmed by 1 H-NMR that the obtained white solid was the target product.
[Example 14]
0.004 mol of the phenol compound (phenolic compound in Scheme 1) was dissolved in 40 mL of pyridine, 0.006 mol of NPPOC-Cl (2- (2-nitrophenyl) propylchloroformate) was added dropwise, and the mixture was added dropwise at room temperature for 6 hours. Stirred. 200 g of ethyl acetate and 50 g of ion-exchanged water were added to the reaction solution for oil-water separation. The organic layer was washed twice with dilute hydrochloric acid and three times with ion-exchanged water, the solvent was distilled off, and the mixture was isolated on a silica column (ethyl acetate: hexane = 1: 4). The obtained white solid was dispersed with hexane and then dried under reduced pressure at 45 ° C. for 2 hours to obtain the desired product (Compound I-1-46). It was confirmed by 1 H-NMR that the obtained white solid was the target product.
[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 of the following formulas (1) to (3) were used as the phenol compound.

[Evaluation]
Examples 1, 2, 5-9, 12-14 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) prepared 0.01 mass% acetonitrile solution and put into a 1 cm square quartz cell. I put it in. Ultra-high pressure mercury lamp UL750 (manufactured by HOYA) was adjusted to 20 mW / cm ^2, in a quartz cell filled with the solution was irradiated with light quantity of ^{100mJ / cm 2, 3000mJ / cm} 2, 10000mJ / cm 2.
The liquid after irradiation was analyzed by high performance liquid chromatography (HPLC), and the desorption rate was calculated from the following formula. The results are shown in Table 3 below.
In the analysis by HPLC, it was calculated on the assumption that 100% elimination was performed when all the peaks at 230 nm derived from compound I-1 disappeared.
Elimination rate (%) = phenol compound (Compound I-2) / phenol compound (Compound I-2) + Compound I-1) × 100

Further, with respect to Examples 1, 2 and 7 (Compounds I-1-2, I-1-3 and I-1-34), before light irradiation (0 mJ / cm ² ) and after light irradiation (10000 mJ / cm). ^{In 2} ), the absorption spectrum of light in the wavelength range of 250 nm or more and 450 nm or less was confirmed. As a result, it was confirmed that after the light irradiation, the light on the long wavelength side can be widely absorbed in the wavelength range of 250 nm or more and 450 nm or less as compared with the case before the light irradiation. The measurement results of the maximum absorption wavelength (nm) are shown in Tables 3 and 4 below.

From Tables 3 and 4, it was confirmed that the photoleaving group B was eliminated from the compound I-1 by light irradiation.
Further, from Table 3, it was confirmed that the compound I-1 can efficiently absorb ultraviolet rays having a wide wavelength range of 250 nm or more and 450 nm or less by light irradiation. Along with this, a shift of the maximum absorption wavelength to the longer wavelength side was confirmed.
From the above, in compound I-1, the phenolic hydroxyl group is protected by the photoleaving group B before light irradiation, and the ultraviolet absorbing ability is suppressed, so that curing inhibition can be suppressed, and the ultraviolet absorbing ability can be easily obtained by light irradiation. It was confirmed that it could be granted.

The components shown in Table 5 below were mixed at the ratios shown in Table 5 to obtain the compositions of Examples 18 to 20 and Comparative Examples 1 and 2. The reference numerals in Table 5 indicate the following compounds. The numerical values in the table represent parts by mass.

A-1: Polymerizable compound (NK oligo EA-1020 manufactured by Shin-Nakamura Chemical Industry Co., Ltd. (bisphenol A type epoxy acrylate))
A-2: Radical polymerizable compound (Kayarad DPHA (mixture of dipentaerythritol penta and hexaacrylate) manufactured by Nippon Kayaku Co., Ltd.)
B-1: BASF's Irgacure 907 (radical polymerization initiator)
C-1: Silane coupling agent KBE-403 manufactured by Shin-Etsu Chemical Co., Ltd.
D-1: 2-butanone E-1: Compound represented by the following formula (1) (ultraviolet absorber)
F-1: Compound I-1-3
F-2: Compound I-1-35
F-3: Compound 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.

[Curable]
The compositions of Examples 18 to 20 and Comparative Examples 1 and 2 were respectively applied to a PET film with a bar coater to a thickness of about 3 μm. Then, after prebaking at 80 ° C. for 3 minutes, exposure was performed using an ultra-high pressure mercury lamp (UL750) as a light source (20 mW / cm ² ). The exposure was performed so that the amount of exposure light was 500 mJ / cm ² . At this time, a negative film made so that the light transmittance is gradually reduced so that the light sensitivity can be measured (optical density 0.05 is set as the first stage, and the optical density is 0.15 for each stage. An increasing step tablet) was used. Then, using isopropanol (IPA), the mixture was washed over 10 seconds in an environment of 25 ° C. for development, and then dried at 80 ° C. for 30 minutes. Then, the light sensitivity was evaluated by measuring the number of stages of the cured product step tablet formed on the PET film. The higher the number of steps of the step tablet, the higher the light sensitivity 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 each applied to a glass substrate with a spin coater, prebaked at 80 ° C. for 3 minutes, and then exposed using an ultrahigh pressure mercury lamp (UL750) as a light source. (20 mW / cm ² ). The exposure was performed so that the amount of exposure light was 100 mJ / cm ² . Then, it was further irradiated with 3000 mJ / cm ² to prepare a sample for light resistance evaluation. A 24-hour light resistance test was carried out on the evaluation sample using a xenon light resistance tester Table Sun XT-1500L manufactured by Suga Test Instruments Co., Ltd. The difference in transmittance (%) at a wavelength of 470 nm before and after the light resistance test of the evaluation sample ((transmission (%) before the light resistance test-transmittance (%) after the light resistance test)) was measured and described as follows. Light resistance was evaluated based on the standard.

〇: The transmittance difference (%) is less than 5% with respect to the transmittance before the light resistance test.
X: The transmittance difference (%) is 5% or more with respect to the transmittance before the light resistance test.

When the light resistance evaluation is "◯", it indicates that the cured product has excellent light resistance. The results are shown in Table 5 below.

From Table 5, the compositions of Examples 18 to 20 containing Compound I-1 have better light resistance than the compositions of Comparative Example 1 containing no ultraviolet absorber. Further, the compositions of Examples 18 to 20 have better curability than the composition of Comparative Example 2 containing a known ultraviolet absorber. From this, it can be seen that according to the present invention, a composition having less hardening inhibition and excellent light resistance can be obtained.

According to the compound of the present invention, it is possible to provide a compound which has less curing inhibition and can easily impart ultraviolet absorbing 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 or the like to the cured product.
According to the composition of the present invention, it is possible to provide a composition capable of obtaining a cured product having less curing inhibition and excellent ultraviolet absorption ability.
According to the cured product of the present invention, it is possible to provide a cured product having an excellent ultraviolet absorbing ability.
According to the method for producing a cured product of the present invention, a cured product having excellent ultraviolet absorbing ability and the like can be produced without causing curing inhibition.
According to the second composition of the present invention, it is possible to provide a composition capable of obtaining a cured product having an excellent ultraviolet absorbing ability without causing curing inhibition.

Claims (9)

A compound represented by the following general formula (I-1).
(In the formula, A represents an atomic group capable of absorbing ultraviolet rays, B represents a photoleaving group, and k represents an integer of 1 to 10.) B in the general formula (I-1) is the following general formula (B-1), (B-2), (B-3), (B-4), (B-5), (B-6). , (B-7), (B-8), (B-9) and (B-10). The compound according to claim 1, which comprises at least one of the groups represented by.
(In the formula, R ¹¹ , R ¹³ , R ¹⁶ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²³ , R ²⁶ and R ²⁸ are independently halogen atoms, cyano groups, hydroxyl groups, nitro groups, carboxyl groups, respectively. Represents an alkyl group having 1 to 40 carbon atoms, an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, or a heterocycle-containing group having 2 to 20 carbon atoms.
R ¹² , R ¹⁴ , R ¹⁷ , R ²¹ , R ²² , R ²⁴ , R ²⁵ , R ²⁷ , R ²⁹ and R ³⁰ are independently hydrogen atom, halogen atom, cyano group, hydroxyl group, nitro group, carboxyl. Represents a group, an alkyl group having 1 to 40 carbon atoms, an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, or a heterocycle-containing group having 2 to 20 carbon atoms.
R ¹⁵ represents an alkyl group having 1 to 40 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryl alkyl group having 7 to 20 carbon atoms, or a heterocycle-containing group having 2 to 20 carbon atoms.
R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ , R ²⁹ and R ³⁰ are represented by alkyl groups and arylalkyl groups in which the methylene group is a carbon-carbon double bond, −O−, −S−, −CO−, −O—CO−,. -CO-O-, -O-CO-O-, -O-CO-O-, -S-CO-, -CO-S-, -S-CO-O-, -O-CO-S-, -CO-NH-, -NH-CO-, -NH-CO-O-, -NR'-,> P = O, -SS-, -SO ₂ -or a combination thereof may be replaced. Yes,
The alkyl group, aryl group, arylalkyl group and heterocyclic group may have a substituent and may have a substituent.
R'represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.
A plurality of ^{R 11} to each other, a plurality of ^{R 13} to each other, between a plurality of ^{R 16,} together a plurality of ^{R 18,} together a plurality of ^{R 19,} a plurality of ^{R 20} to each other, between a plurality of ^{R 23,} a plurality of ^{R 26} to each other and a plurality of each other R ²⁸ is may each combine together to form a benzene ring or a naphthalene ring,
A plurality of ^{R 11, R 12, R 13} , R 14, R 16, R 17, R 18, R 19, R 20, R 23, R 25, R 26, R 27, R 28, R 29 and ^{R 30} , Each may be the same, may be different,
b1, b2, b3, b6, b7, b8 and b9 each independently represent an integer of 0 to 4.
b4 and b5 each independently represent an integer of 0 to 5, respectively.
** represents the bonding position with the AO−. )
(In the formula, R ³¹ and R ⁴⁰ are independently halogen atom, cyano group, hydroxyl group, nitro group, carboxyl group, alkyl group having 1 to 40 carbon atoms, aryl group having 6 to 20 carbon atoms, and carbon. Represents an arylalkyl group having 7 to 20 atoms or a heterocyclic group having 2 to 20 carbon atoms.
R ³² , R ³³ , R ⁴¹ , R ⁴² , R ⁴³ and R ⁴⁴ are independently hydrogen atom, halogen atom, cyano group, hydroxyl group, nitro group, carboxyl group and alkyl group having 1 to 40 carbon atoms. Represents an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, or a heterocycle-containing group having 2 to 20 carbon atoms.
The methylene groups in the alkyl and arylalkyl groups represented by R ³¹ , R ³² , R ³³ , R ⁴⁰ , R ⁴¹ , R ⁴² , R ⁴³ and R ⁴⁴ are carbon-carbon double bonds, -O-, -S-, -CO-, -O-CO-, -CO-O-, -O-CO-O-, -O-CO-O-, -S-CO-, -CO-S-, -S -CO-O-, -O-CO-S-, -CO-NH-, -NH-CO-, -NH-CO-O-, -NR'-,> P = O, -S-S-, It may be replaced by -SO _2- or a combination of these.
The alkyl group, aryl group, arylalkyl group and heterocyclic group may have a substituent and may have a substituent.
c1 represents an integer from 0 to 5 and represents
c2 represents an integer from 0 to 4 and represents
** represents the bonding position with the AO−. ) The compound represented by the general formula (I-1) is a compound represented by the following general formulas (A-1), (A-2) or (A-3).
The compound according to claim 2, wherein the photoleaving group B includes the following general formula (B-1-a).
(In the formula, R ¹ and R ² are independently hydrogen atom, halogen atom, cyano group, hydroxyl group, nitro group, carboxyl group, alkyl group having 1 to 40 carbon atoms, and aryl having 6 to 20 carbon atoms, respectively. Represents a group, an arylalkyl group having 7 to 20 carbon atoms, a heterocycle-containing group having 2 to 20 carbon atoms, or the above-OB.
At least one of R ¹ and R ² is the above-OB.
R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ independently have a halogen atom, a cyano group, a hydroxyl group, a nitro group, a carboxyl group, an alkyl group having 1 to 40 carbon atoms, and a carbon atom number. Represents an aryl group of 6 to 20, an arylalkyl group having 7 to 20 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms.
The methylene group in the alkyl group or arylalkyl group represented by R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ is a carbon-carbon double bond, -O-, -S-, -CO-, -O-CO-, -CO-O-, -O-CO-O-, -O-CO-O-, -S-CO-, -CO-S-, -S -CO-O-, -O-CO-S-, -CO-NH-, -NH-CO-, -NH-CO-O-, -NR'-,> P = O, -S-S-, It may be replaced by -SO _2- or a combination of these.
The alkyl group, aryl group, arylalkyl group and heterocyclic group may have a substituent and may have a substituent.
R'represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.
A plurality of R ³ to each other, a plurality of R ⁴ with each other, a plurality of R ⁵ to each other, a plurality of R ⁶ to each other and a plurality of R ⁷ each other, might be combined with each other to form a benzene ring or a naphthalene ring,
Multiple R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ may be the same or different, respectively.
m1 and m2 each independently represent an integer of 1 to 10.
n represents an integer from 1 to 3 and represents
a1 represents an integer from 0 to 4 and represents
a2 represents an integer from 0 to 2 and represents
a3 represents an integer from 0 to 4 and represents
a4 represents an integer from 0 to 3 and represents
a5 represents an integer from 0 to 3 and represents
a6 represents an integer of 0 to 3-n and represents
X ¹ and X ² represent m1-valent and m-valent binding groups, respectively. )
(In the formula, R ¹² is independently a hydrogen atom, a halogen atom, a cyano group, a hydroxyl group, a nitro group, a carboxyl group, an alkyl group having 1 to 40 carbon atoms, an aryl group having 6 to 20 carbon atoms, and carbon. Arylalkyl groups with 7 to 20 atoms or heterocyclic groups with 2 to 20 carbon atoms,
R ¹¹ is a halogen atom, a cyano group, a hydroxyl group, a nitro group, a carboxyl group, an alkyl group having 1 to 40 carbon atoms, an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, or carbon. Represents a heterocyclic group with 2 to 20 atoms
The methylene group in the alkyl group or arylalkyl group represented by R ¹¹ and R ¹² is a carbon-carbon double bond, -O-, -S-, -CO-, -O-CO-, -CO-O. -, -O-CO-O-, -O-CO-O-, -S-CO-, -CO-S-, -S-CO-O-, -O-CO-S-, -CO-NH -, -NH-CO-, -NH-CO-O-, -NR'-,> P = O, -S-S-, -SO ₂ -or or a combination thereof may be replaced.
The alkyl group, aryl group, arylalkyl group and heterocyclic group may have a substituent and may have a substituent.
R'represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.
The plurality of R ¹¹ together may form a benzene or naphthalene ring,
R ¹¹ and R ¹² may be the same or different, respectively.
b1 represents an integer from 0 to 4 and represents
** represents the bonding position with the AO−. ) A latent ultraviolet absorber containing the compound according to any one of claims 1 to 3. A composition containing the compound according to any one of claims 1 to 3. The composition according to claim 5, further comprising a resin component. A cured product of a composition containing the compound according to any one of claims 1 to 3 and a polymerizable compound. 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.
A step of irradiating the cured product with light to remove photoleaving groups contained in the compound, and
A method for producing a cured product having. A composition containing a compound represented by the following general formula (I-2) and a desorbed product derived from a photoleaving group.
(In the formula, A represents an atomic group capable of absorbing ultraviolet rays, and k represents an integer of 1 to 10.)