KR20230084120A - Compound, polymerization initiator, polymerizable composition, cured product, color filter and method for producing cured product - Google Patents

Abstract

An object of the present invention is to provide a polymerization initiator having excellent sensitivity, good solubility in solvents, and high transmittance in the visible light region of a cured product obtained. The present invention is a compound having a group represented by the following general formula (I) and a group represented by the following general formula (II) in the same molecule. In the formula, R ¹ , R ² and R ⁴ are each independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydrocarbon having 1 to 20 carbon atoms, or one or more methylene groups in the above hydrocarbon group, such as -O- A group substituted with a divalent group, a heterocyclic group having 2 to 10 carbon atoms, a heterocyclic group having 3 to 20 carbon atoms, or one or more of the methylene groups in the heterocyclic containing group is -O-, etc. represents a group substituted by a divalent group, n represents 0 or 1, and * represents the number of bonds.

Description

Compound, polymerization initiator, polymerizable composition, cured product, color filter and method for producing cured product

The present invention relates to an oxime ester compound and a polymerization initiator containing the same.

The polymerizable composition is obtained by adding a polymerization initiator to an ethylenically unsaturated compound and can be polymerized and cured by irradiation with energy rays (light), and therefore is used for photocurable inks, photosensitive printing plates, various photoresists, and the like.

As a polymerization initiator used in these polymerizable compositions, Patent Document 1 proposes an oxime ester photopolymerization initiator having a carbazole skeleton, and Patent Document 2 proposes a polymerization initiator having an oxime ester compound having a triarylamine skeleton. In addition, a polymerizable composition containing a colorant such as a color filter is required to be highly sensitive, and the polymerization initiator in the resist needs to be at a high concentration.

International Publication WO2008/138732 International Publication WO2017/033880

However, in the oxime ester compounds proposed in Patent Documents 1 and 2, sensitivity, solubility in solvents, and transparency of the resulting cured product were not compatible at a satisfactory level.

Therefore, the subject to be solved by the present invention is to provide a polymerization initiator having excellent sensitivity, good solubility in solvents, and high transmittance in the visible light region of a cured product obtained. Specifically, it is to provide an oxime ester compound useful as a polymerization initiator used in a polymerizable composition and a polymerization initiator containing the same.

As a result of repeated earnest examinations in order to solve the above-mentioned problems, the present inventors have found that a compound having an oxime ester group and a diketonyl group can solve the above-mentioned problems, and have completed the present invention.

That is, the present invention is a compound having a group represented by the following general formula (I) and a group represented by the following general formula (II) in the same molecule.

In the formula, R ¹ and R ² are each independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydrocarbon group having 1 to 20 carbon atoms, or one or more methylene groups among the above hydrocarbon groups in <Group A> At least one of a group substituted with a selected divalent group, a heterocyclic group having 2 to 10 carbon atoms, a heterocyclic group having 3 to 20 carbon atoms, or a methylene group in the above heterocycle-containing group, <Group A Represents a group substituted with a divalent group selected from >,

n represents 0 or 1;

* indicates the number of bonds,

When there are a plurality of groups represented by the general formula (I) in the compound, the plurality of R ¹ , R ² and n may be the same or different.

<Group A>: -O-, -CO-, -COO-, -OCO-, -NR ³ -, -NR ³ CO-, -S-

R ³ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.

In the formula, R ⁴ is a hydrocarbon group having 1 to 20 carbon atoms, or a group in which one or more of the methylene groups in the above hydrocarbon group is substituted with a divalent group selected from <Group B> below, or a complex group having 2 to 10 carbon atoms. represents a group in which one or more of the heterocycle-containing groups of 3 to 20 carbon atoms or the methylene groups in the heterocycle-containing groups is substituted with a divalent group selected from the following <Group B>;

* indicates the number of bonds,

When there are a plurality of groups represented by the general formula (II) in the compound, the plurality of R ⁴ may be the same or different.

<Group B>: -O-, -CO-, -COO-, -OCO-, -NR ⁵ -, -NR ⁵ CO-, -S-

R ⁵ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.

Hereinafter, the compound of the present invention, a polymerization initiator containing the same, a polymerizable composition containing the polymerization initiator, a cured product thereof, a color filter, and a method for producing the cured product will be described in detail based on preferred embodiments.

The compound of the present invention is a compound having a group represented by the following general formula (I) and a group represented by the following general formula (II) in the same molecule.

In the formula, R ¹ and R ² are each independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydrocarbon group having 1 to 20 carbon atoms, or one or more methylene groups among the above hydrocarbon groups in <Group A> At least one of a group substituted with a selected divalent group, a heterocyclic group having 2 to 10 carbon atoms, a heterocyclic group having 3 to 20 carbon atoms, or a methylene group in the above heterocycle-containing group, <Group A Represents a group substituted with a divalent group selected from >,

n represents 0 or 1;

* represents the number of bonds,

When there are a plurality of groups represented by the general formula (I) in the compound, the plurality of R ¹ , R ² and n may be the same or different.

<Group A>: -O-, -CO-, -COO-, -OCO-, -NR ³ -, -NR ³ CO-, -S-

R ³ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.

In the formula, R ⁴ is a hydrocarbon group having 1 to 20 carbon atoms, or a group in which one or more of the methylene groups in the above hydrocarbon group is substituted with a divalent group selected from <Group B> below, or a complex group having 2 to 10 carbon atoms. represents a group in which one or more of the heterocycle-containing groups of 3 to 20 carbon atoms or the methylene groups in the heterocycle-containing groups is substituted with a divalent group selected from the following <Group B>;

* indicates the number of bonds,

When there are a plurality of groups represented by the general formula (II) in the compound, the plurality of R ⁴ may be the same or different.

<Group B>: -O-, -CO-, -COO-, -OCO-, -NR ⁵ -, -NR ⁵ CO-, -S-

R ⁵ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.

A fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. are mentioned as a halogen atom in the said general formula (I).

The hydrocarbon group having 1 to 20 carbon atoms in the general formula (I) and the general formula (II) may be a group having 1 to 20 carbon atoms composed of carbon atoms and hydrogen atoms, and is not particularly limited. and an aliphatic hydrocarbon group of 1 to 20 and an aromatic hydrocarbon ring-containing group of 6 to 20 carbon atoms.

The aliphatic hydrocarbon group of 1 to 20 carbon atoms is a hydrocarbon group that does not contain an aromatic hydrocarbon ring or a heterocyclic ring, and may have a substituent. The aliphatic hydrocarbon group having a substituent is a group having a structure in which at least one hydrogen atom in the aliphatic hydrocarbon group is substituted with a substituent.

Examples of the unsubstituted aliphatic hydrocarbon group include an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, and a cycloalkylalkyl group having 4 to 20 carbon atoms. there is. Further, examples of the aliphatic hydrocarbon group having a substituent include groups in which at least one hydrogen atom in the unsubstituted aliphatic hydrocarbon group is substituted with a substituent, and examples of the substituent include a halogen atom, a cyano group, a nitro group, and a hydroxyl group , an amino group, a carboxyl group, a methacryloyl group, an acryloyl group, an epoxy group, a vinyl group, a vinyl ether group, a mercapto group, and an isocyanate group.

The alkyl group having 1 to 20 carbon atoms may be linear or branched. Examples of straight-chain alkyl groups include methyl, ethyl, propyl, butyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl and octadecyl. Branched alkyl groups include iso-propyl, sec-butyl, tert-butyl, iso-butyl, iso-pentyl, tert-pentyl, 2-hexyl, 3-hexyl, 2-heptyl, 3-heptyl, iso-heptyl, tert -heptyl, iso-octyl, tert-octyl, 2-ethylhexyl and isononyl; and the like.

The alkenyl group having 2 to 20 carbon atoms may be linear or branched. Further, it may be a terminal alkenyl group having an unsaturated bond at the terminal, or an internal alkenyl group having an unsaturated bond inside. Terminal alkenyl groups include vinyl, allyl, 2-methyl-2-propenyl, 3-butenyl, 4-pentenyl and 5-hexenyl. Internal alkenyl groups include 2-butenyl, 3-pentenyl, 2-hexenyl, 3-hexenyl, 2-heptenyl, 3-heptenyl, 4-heptenyl, 3-octenyl, 3-nonenyl, 4-decenyl, 3-undecenyl, 4-dodecenyl, and 4,8,12-tetradecatrienyl allyl; and the like.

The cycloalkyl group having 3 to 20 carbon atoms includes a saturated monocyclic alkyl group having 3 to 20 carbon atoms, a saturated polycyclic alkyl group having 3 to 20 carbon atoms, and an alkyl group in which one or more of the hydrogen atoms in the rings of these groups are selected. and groups having 4 to 20 carbon atoms substituted with . Examples of the saturated monocyclic alkyl group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl and cyclodecyl. Examples of the saturated polycyclic alkyl group include adamantyl, decahydronaphthyl, octahydropentalene, and bicyclo[1.1.1]pentanyl. Examples of the alkyl group substituting the hydrogen atom in the ring of the saturated monocyclic or saturated polycyclic alkyl group include the groups exemplified as the alkyl group having 1 to 20 carbon atoms. Examples of groups in which one or more hydrogen atoms in the ring of the saturated polycyclic alkyl group are substituted with an alkyl group include bornyl.

The cycloalkylalkyl group having 4 to 20 carbon atoms means a group having 4 to 20 carbon atoms in which a hydrogen atom of an alkyl group is substituted with a cycloalkyl group. The cycloalkyl group in the cycloalkylalkyl group may be monocyclic or polycyclic. Cyclopropylmethyl, 2-cyclobutylethyl, 3-cyclopentylpropyl, 4-cyclohexylbutyl, cycloheptylmethyl, cyclooctylmethyl, 2-cycloalkylalkyl group having 4 to 20 carbon atoms in which the cycloalkyl group is monocyclic. nonylethyl and 2-cyclodecylethyl; and the like. Examples of the cycloalkylalkyl group having 4 to 20 carbon atoms in which the cycloalkyl group is polycyclic include 3-adamantylpropyl and 3-decahydronaphthylpropyl.

The aromatic hydrocarbon ring-containing group of 6 to 20 carbon atoms is a hydrocarbon group containing an aromatic hydrocarbon ring and not containing a heterocyclic ring, and may have an aliphatic hydrocarbon group or may have a substituent. The aromatic hydrocarbon ring-containing group having a substituent is a group having a structure in which one or more hydrogen atoms in the aromatic hydrocarbon ring-containing group are substituted with substituents.

Examples of the unsubstituted aromatic hydrocarbon ring-containing group include aryl groups of 6 to 20 carbon atoms and arylalkyl groups of 7 to 20 carbon atoms. Further, examples of the aromatic hydrocarbon ring-containing group having a substituent include a group in which one or more hydrogen atoms in the unsubstituted aromatic hydrocarbon ring-containing group are substituted with a substituent, and examples of the substituent include a halogen atom, a cyano group, and a nitro group, a hydroxyl group, an amino group, a carboxyl group, a methacryloyl group, an acryloyl group, an epoxy group, a vinyl group, a vinyl ether group, a mercapto group, or an isocyanate group.

The aryl group having 6 to 20 carbon atoms may have a monocyclic structure or a condensed ring structure, and may also have two aromatic hydrocarbon rings linked to each other.

Examples of the monocyclic aryl group include phenyl, tolyl, xylyl, ethylphenyl, and 2,4,6-trimethylphenyl. Examples of the aryl group having a condensed ring structure include naphthyl, anthracenyl, phenanthryl, and pyrenyl.

The aryl group in which two aromatic hydrocarbon rings are connected may be one in which two monocyclic aromatic hydrocarbon rings are connected, or may be one in which a monocyclic aromatic hydrocarbon ring and a condensed ring structure are connected, or a condensed ring structure of an aromatic hydrocarbon ring and a condensed ring structure. The aromatic hydrocarbon ring may be connected.

A linking group connecting two aromatic hydrocarbon rings includes a single bond, a sulfide group (-S-), and a carbonyl group.

Examples of the aryl group in which two monocyclic aromatic hydrocarbon rings are connected include biphenyl, diphenyl sulfide, and benzoylphenyl.

The arylalkyl group having 7 to 20 carbon atoms is a group in which at least one hydrogen atom in the alkyl group is substituted with an aryl group. Examples of the arylalkyl group having 7 to 20 carbon atoms include benzyl, fluorenyl, indenyl, 9-fluorenylmethyl, α-methylbenzyl, α,α-dimethylbenzyl, phenylethyl and naphthylpropyl groups. there is.

The heterocyclic group in the above general formula (I) and the above general formula (II) is a group obtained by removing one hydrogen atom from a heterocyclic compound.

Examples of the heterocyclic group having 2 to 10 carbon atoms include a pyridyl group, a quinolyl group, a thiazolyl group, a tetrahydrofuran group, a dioxolanyl group, a tetrahydropyranyl group, a morpholylfuran group, a methylthiophene group, and a hexylthiophene. group, benzothiophene group, pyrrole group, pyrrolidine group, imidazole group, imidazolidine group, imidazoline group, pyrazole group, pyrazolidine group, piperidine group, piperazine group, pyrimidyl group, furyl group, thienyl group, benzooxazol-2-yl group, thiazole group, isothiazole group, oxazole group, isoxazole group, morphonyl group, etc. are mentioned.

The heterocyclic group having 2 to 10 carbon atoms may have a substituent, and examples of the substituent include a halogen atom, a cyano group, a nitro group, a hydroxyl group, a thiol group, -COOH and -SO ₂ H.

The heterocycle-containing group in the above general formula (I) and the above general formula (II) is a group in which a hydrogen atom in a hydrocarbon group is substituted with a heterocyclic group.

Examples of the heterocyclic group having 3 to 20 carbon atoms include groups in which one or more hydrogen atoms of an alkyl group are substituted with a heterocyclic ring, and the heterocyclic group is exemplified as a heterocyclic group having 2 to 10 carbon atoms. one can lift.

The heterocycle-containing group having 3 to 20 carbon atoms may have an aromatic hydrocarbon ring-containing group, may have an aliphatic hydrocarbon group, or may have a substituent. Examples of the substituent include a halogen atom, a cyano group, a nitro group, a hydroxyl group, a thiol group, -COOH, and -SO ₂ H.

In addition, "3 to 20 carbon atoms" of a heterocycle-containing group having 3 to 20 carbon atoms is the number of carbon atoms of the entire heterocycle-containing group.

The heterocycle-containing group may be one in which a heterocyclic ring and an aromatic hydrocarbon ring of a monocyclic structure are connected, or one in which a heterocycle and an aromatic hydrocarbon ring of a condensed ring structure are connected. A single bond, a carbonyl group, etc. are mentioned as a linking group which connects two aromatic hydrocarbon rings. Benzothiophene etc. are mentioned as a heterocyclic containing group in which the heterocyclic ring and the aromatic hydrocarbon ring of monocyclic structure were connected.

A group in which two or more of the methylene groups in the hydrocarbon group and the heterocyclic group in the general formula (I) are substituted with divalent groups selected from <Group A> does not have a structure in which a plurality of divalent groups adjoin each other. A plurality of divalent groups may be the same or different. The same applies to groups in which two or more of the methylene groups in the hydrocarbon group and heterocycle-containing group in the general formula (II) are substituted with divalent groups selected from <Group B>.

In the present invention, the number of carbon atoms in a group defines the number of carbon atoms in a group after substitution when hydrogen atoms in the group are substituted with substituents. For example, when the hydrogen atoms of the alkyl group having 1 to 20 carbon atoms are substituted, the number of carbon atoms 1 to 20 refers to the number of carbon atoms after the hydrogen atoms are substituted, and refers to the number of carbon atoms before the hydrogen atoms are substituted. no.

In the present invention, the number of carbon atoms in a group in which a methylene group is substituted with a divalent group in a group having a predetermined number of carbon atoms defines the number of carbon atoms in the group before the substitution. For example, when the methylene group in an alkyl group having 1 to 20 carbon atoms is a group substituted with a divalent group, the number of carbon atoms in the alkyl group having 1 to 20 carbon atoms refers to the number of carbon atoms before the methylene group in the alkyl group is substituted with a divalent group, and the carbon after the substitution It does not refer to the number of atoms.

A compound in which n is 1 in the general formula (I) is preferable because it has high sensitivity, excellent solubility in solvents, and excellent transparency of the resulting cured product.

Compounds in which R ¹ in the general formula (I) is a cycloalkylalkyl group having 4 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms are highly sensitive, and are particularly preferred for cycloalkylalkyl groups having 4 to 10 carbon atoms. Or a compound which is a phenyl group is preferable.

Compounds in which R ² in the general formula (I) is an alkyl group of 1 to 10 carbon atoms are highly sensitive, and therefore, compounds having an alkyl group of 1 to 4 carbon atoms are more preferred, and compounds having a methyl group are particularly preferred. .

A compound in which R ² is a branched alkyl group in the general formula (I) is preferable because of its excellent solubility in solvents.

Compounds in which R ⁴ is an alkoxy group of 1 to 10 carbon atoms in the above general formula (II) are preferred because of their high sensitivity, compounds having an alkoxy group of 1 to 4 carbon atoms are more preferred, and compounds having a methoxy group are particularly preferred. do.

Since the compound of the present invention has high sensitivity and excellent solubility in solvents, it is preferable to have a structure represented by the following general formula (III).

In the formula, A ¹ represents an aromatic ring having 6 to 20 carbon atoms;

R ¹¹ represents a group represented by the general formula (I);

R ¹² is a group represented by the general formula (II), a hydrocarbon group having 1 to 20 carbon atoms substituted with a group represented by the general formula (II), or one or more of the methylene groups in the hydrocarbon group described below. A group substituted with a divalent group selected from C>, a heterocyclic group having 2 to 10 carbon atoms substituted with a group represented by the above general formula (II), or a carbon atom substituted with a group represented by the above general formula (II) Representing a heterocycle-containing group of 3 to 20, or a group in which one or more of the methylene groups in the heterocycle-containing group is substituted with a divalent group selected from the following <Group C>,

R ¹³ is each independently a halogen atom, a nitro group, a cyano group, a hydrocarbon group having 1 to 20 carbon atoms, or a methylene group in which one or more of the hydrocarbon groups is substituted with a divalent group selected from <Group C> below. group, a heterocyclic group of 2 to 10 carbon atoms, a heterocyclic group of 3 to 20 carbon atoms, or a divalent group in which at least one of the methylene groups in the heterocyclic group is selected from the following <Group C> represents a substituted group,

a represents an integer of 1 to 20, and when a is an integer of 2 or greater, a plurality of R ¹¹ may be the same or different;

b represents an integer of 1 to 20, and when b is an integer of 2 or greater, a plurality of R ¹² may be the same or different;

c represents an integer from 0 to 20, and when c is an integer of 2 or greater, a plurality of R ¹³ may be the same or different;

However, a+b+c is 20 or less.

<Group C>: -O-, -CO-, -COO-, -OCO-, -NR ¹⁴ -, -NR ¹⁴ CO-, -S-

R ¹⁴ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.

Examples of the aromatic ring having 6 to 20 carbon atoms in the general formula (III) include aromatic hydrocarbon rings and aromatic heterocycles, specifically indole, carbazole, diphenylsulfide, fluorene, and triarylamine. , coumarin, benzene, diphenyl, naphthalene and anthracene; and the like.

The hydrocarbon group having 1 to 20 carbon atoms, the heterocyclic group having 2 to 10 carbon atoms, and the heterocyclic group having 3 to 20 carbon atoms in the general formula (III) is a carbon atom in the general formula (I) It is the same as a hydrocarbon group of 1 to 20 atoms, a heterocyclic group of 2 to 10 carbon atoms, and a heterocyclic group of 3 to 20 carbon atoms.

Compounds in which c in Formula (III) is an integer of 1 to 20 are preferable, and compounds having a branched alkyl group or cycloalkyl group having 3 to 20 carbon atoms in the molecule are preferable because of their excellent solubility in solvents, and R ¹³ A compound in which at least one of is a branched alkyl group or cycloalkyl group of 3 to 20 carbon atoms is more preferable, and a compound which is a branched alkyl group of 3 to 20 carbon atoms is more preferable, especially a branched alkyl group of 3 to 10 carbon atoms Phosphorus compounds are preferred.

Compounds in which A ¹ in the general formula (III) has a structure represented by the following general formula (IVα) or the following general formula (IVβ) are preferred because of their high sensitivity, and particularly compounds having a structure represented by the following general formula (IVα) this is preferable

The general formula (IVα) shows the structure when the groups represented by R ¹¹ , R ¹² and R ¹³ in the general formula (III) are substituted with a hydrogen atom, wherein X ¹ is an oxygen atom, a sulfur atom, or a selenium atom. , CH ₂ , CO, NH or PH,

X ² represents a single bond, no bond, an oxygen atom, a sulfur atom, a selenium atom, CH ₂ , CO, NH or PH.

The general formula (IVβ) shows the structure when the groups represented by R ¹¹ , R ¹² and R ¹³ in the general formula (III) are substituted with hydrogen atoms.

A compound in which A ¹ is represented by the above general formula (IVα), X ¹ is NR ¹³ , and X ² is a single bond is particularly preferable because of its excellent sensitivity. Further, compounds in which R ¹³ is a branched alkyl group or cycloalkyl group of 3 to 20 carbon atoms are preferable because of their excellent solubility in solvents, and compounds which are branched alkyl groups of 3 to 20 carbon atoms are more preferable, particularly The compound which is a branched alkyl group of 3-10 is preferable.

Compounds in which a is an integer of 1 to 3 are preferable because they are excellent in solubility and sensitivity to solvents, and compounds in which a is 1 are particularly preferable.

Compounds in which b is an integer of 1 to 3 are preferable because they are excellent in solubility and sensitivity to solvents, and compounds in which b is 1 are particularly preferable.

Compounds in which c is an integer of 1 to 3 are preferable because they are excellent in solubility and sensitivity to solvents, and compounds in which c is 1 are particularly preferable.

A compound in which the substituent positions of R ¹¹ and R ¹² in Formula (IVα) are para to the binding site of X ¹ is preferable because it can be synthesized in high yield and has excellent storage stability.

Preferred specific examples of the compound of the present invention include the following compounds.

The compound of the present invention can be produced by a known method. For example, the compound represented by the general formula (III) can be produced by the method shown below.

When n in the general formula (I) is 0, ketone compound 1 is obtained by reacting a known aromatic ring-containing compound with an acid chloride, and ketone compound 1' is obtained by reacting ketone compound 1 with a chloride having a diketonyl group. Oxime compound 1 is obtained by reacting compound 1' with hydroxylamine hydrochloride. Then, the oxime compound 1 is reacted with an acid anhydride or an acid chloride in the presence of triethylamine (TEA) to prepare a compound having the group represented by formula (I) and the group represented by formula (II) in the same molecule can do. It can also be produced by the method described in Japanese Patent Publication No. 4223071.

When n in formula (I) is 1, ketone compound 2 is obtained by reacting a known aromatic ring-containing compound with an acid chloride, and ketone compound 2' is obtained by reacting ketone compound 2 with a chloride having a diketonyl group, Oxime compound 2 is obtained by reacting compound 2' with isobutyl nitrite. Then, by reacting the oxime compound 2 with an acid anhydride or an acid chloride in the presence of TEA, a compound having the group represented by formula (I) and the group represented by formula (II) in the same molecule can be produced.

The compound of the present invention described above is useful as a polymerization initiator, specifically a radical polymerization initiator, particularly a photopolymerization initiator or a thermal polymerization initiator. In addition, the compound of the present invention can be suitably used also as a base generator and a sensitizer.

The polymerization initiator of the present invention contains at least one compound having the group represented by the general formula (I) and the group represented by the general formula (II) in the same molecule.

The content of the compound in the polymerization initiator is preferably 1 to 100% by mass, and more preferably 50 to 100% by mass, since the sensitivity is high and the obtained cured product has excellent transparency.

The polymerizable composition of the present invention contains the polymerization initiator (A) of the present invention and an ethylenically unsaturated compound (B), and optionally components such as a colorant (C), an alkali developable compound (D), an inorganic compound, and a solvent. You may contain in combination.

The polymerization initiator (A) contains at least one compound having the group represented by the general formula (I) and the group represented by the general formula (II) in the same molecule, and the radical polymerization initiator of the ethylenically unsaturated compound (B) is useful as

The polymerization initiator (A) may use other polymerization initiators in combination. The other polymerization initiator is not particularly limited as long as it generates radicals by light irradiation or heating, and it is possible to use conventionally known compounds. For example, an oxime ester type compound, an acetophenone type compound, a benzyl type compound, a benzophenone type compound, and a thioxanthone type compound etc. are mentioned as a preferable thing.

Examples of the oxime ester compound include compounds having a group represented by the general formula (I), and can be suitably used for the polymerizable composition of the present invention because of their good sensitivity.

Acetophenone-based compounds include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 4'-isopropyl-2-hydroxy-2-methylpropiophenone, 2-hydroxy Roxymethyl-2-methylpropiophenone, 2,2-dimethoxy-1,2-diphenylethan-1-one, p-dimethylaminoacetophenone, p-tert-butyldichloroacetophenone, p-tert-butyl Trichloroacetophenone, p-azidbenzalacetophenone, 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, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, etc. are mentioned.

Benzyl etc. are mentioned as a benzyl type compound.

Benzophenone-based compounds include benzophenone, o-methylbenzoylbenzoate, Michler's ketone, 4,4'-bisdiethylaminobenzophenone, 4,4'-dichlorobenzophenone, and 4-benzoyl-4'-methyldiphenyl. Sulfide etc. are mentioned.

Thioxanthone-based compounds include thioxanthone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, 2,4-diethylthioxanthone, and the like. can be heard

Other polymerization initiators include phosphine oxide compounds such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis(cyclopentadienyl)-bis[2,6-difluoro-3-(phil- 1-yl)] titanocene-based compounds such as titanium; and the like.

Commercially available radical initiators include Adeka Optomer N-1414, N-1717, N-1919, Adeka Arcles NCI-831 and NCI-930 (above, manufactured by ADEKA); IRGACURE184, IRGACURE369, IRGACURE651, IRGACURE907, IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE784 (above BASF products); TR-PBG-304, TR-PBG-305, TR-PBG-309 and TR-PBG-314 (above, TRONLY products); etc. can be mentioned.

The content of the polymerization initiator (A) in the polymerizable composition is not particularly limited, but is preferably 0.1 to 70 parts by mass because the sensitivity of the polymerizable composition to 100 parts by mass of the radically polymerizable compound having an ethylenically unsaturated group is excellent. part, more preferably 0.5 to 10 parts by mass, most preferably 1 to 5 parts by mass.

The said ethylenically unsaturated compound (B) should just be a compound which has an ethylenically unsaturated bond and does not have an acidic group. The ethylenically unsaturated compound (B) is not particularly limited, and those conventionally used in polymerizable compositions can be used, for example, ethylene, propylene, butylene, isobutylene, vinyl chloride, vinylidene chloride, vinylidene fluoride , unsaturated aliphatic hydrocarbons such as tetrafluoroethylene; Hydroxyethyl (meth)acrylate maleate, hydroxypropyl (meth)acrylate maleate, dicyclopentadiene maleate, or polyfunctional having one carboxyl group and two or more (meth)acryloyl groups ( unsaturated polybasic acids such as meth)acrylate; (meth)acrylic acid-2-hydroxyethyl, (meth)acrylic acid-2-hydroxypropyl, (meth)acrylate glycidyl, the following compounds No.A1 to No.A4, (meth)acrylate methyl, (meth)acrylic acid Butyl, isobutyl (meth)acrylate, t-butyl (meth)acrylate, cyclohexyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, isononyl (meth)acrylate, (metha)acrylate ) Stearyl acrylate, lauryl (meth)acrylate, methoxyethyl (meth)acrylate, dimethylaminomethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, aminopropyl (meth)acrylate, dimethylaminopropyl (meth)acrylate , Ethoxyethyl (meth)acrylate, poly(ethoxy)ethyl (meth)acrylate, butoxyethoxyethyl (meth)acrylate, ethylhexyl (meth)acrylate, phenoxyethyl (meth)acrylate, tetra(meth)acrylate Hydrofuryl, vinyl (meth)acrylate, allyl (meth)acrylate, benzyl (meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, Polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, 1,4-butanedioldi(meth)acrylate, 1,6-hexanedioldi(meth)acrylate, trimethylolethane tri(meth) Acrylates, trimethylolpropane tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol tri( unsaturated monobasic acids such as meth)acrylate, tricyclodecanedimethylol di(meth)acrylate, tri[(meth)acryloylethyl]isocyanurate, and polyester (meth)acrylate oligomers and polyhydric alcohols or polyhydric acids esters of phenol; metal salts of unsaturated polybasic acids such as zinc (meth)acrylate and magnesium (meth)acrylate; Maleic Anhydride, Itaconic Anhydride, Citraconic Anhydride, Methyltetrahydrophthalic Anhydride, Tetrahydrophthalic Anhydride, Trialkyltetrahydrophthalic Anhydride, 5-(2,5-dioxotetrahydrofuryl)-3-methyl-3 - Acid anhydrides of unsaturated polybasic acids such as cyclohexene-1,2-dicarboxylic acid anhydride, trialkyltetrahydrophthalic anhydride-maleic anhydride adduct, dodecenylsuccinic anhydride and methylhymic acid anhydride; (meth)acrylamide, methylenebis-(meth)acrylamide, diethylenetriaminetris(meth)acrylamide, xylylenebis(meth)acrylamide, α-chloroacrylamide, N-2-hydroxyethyl ( amides of unsaturated monobasic acids and polyvalent amines such as meta)acrylamide; unsaturated aldehydes such as acrolein; unsaturated nitriles such as (meth)acrylonitrile, α-chloroacrylonitrile, vinylidene cyanide, and allyl cyanide; Unsaturated compounds such as styrene, 4-methylstyrene, 4-ethylstyrene, 4-methoxystyrene, 4-hydroxystyrene, 4-chlorostyrene, divinylbenzene, vinyltoluene, vinylbenzylmethyl ether, and vinylbenzylglycidyl ether aromatic compounds; unsaturated ketones such as methyl vinyl ketone; unsaturated amine compounds such as vinylamine, allylamine, N-vinylpyrrolidone, and vinylpiperidine; Vinyl alcohol, such as allyl alcohol and crotyl alcohol; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, n-butyl vinyl ether, isobutyl vinyl ether, and allyl glycidyl ether; unsaturated imides such as maleimide, N-phenylmaleimide, and N-cyclohexylmaleimide; indenes such as indene and 1-methylindene; aliphatic conjugated dienes such as 1,3-butadiene, isoprene, and chloroprene; macromonomers having mono(meth)acryloyl groups at terminals of polymer molecular chains, such as polystyrene, polymethyl(meth)acrylate, poly-n-butyl(meth)acrylate, and polysiloxane; Vinyl chloride, vinylidene chloride, divinyl succinate, diallyl phthalate, triallyl phosphate, triallyl isocyanurate, vinylthioether, vinylimidazole, vinyloxazoline, vinylcarbazole, vinylpyrrolidone, vinyl and vinyl urethane compounds of pyridine, hydroxyl group-containing vinyl monomers and polyisocyanate compounds, and vinylepoxy compounds of hydroxyl group-containing vinyl monomers and polyepoxy compounds.

A commercial item can also be used as an ethylenically unsaturated compound (B). For example, Kayarad DPHA, DPEA-12, PEG400DA, THE-330, RP-1040, NPGDA, PET30 (manufactured by Nippon Kayaku Co., Ltd.), Aronix M-140, M-215, M-350 (manufactured by Toagosei Co., Ltd.) ), NK esters A-DPHA-TMPT, A-DCP, A-HD-N, A-9300, TMPT, DCP, NPG, and HD-N (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.).

Ethylenically unsaturated compounds can be used individually or in mixture of 2 or more types, and when 2 or more types are used in mixture, they may be copolymerized beforehand and used as a copolymer.

The polymerizable composition of the present invention may further contain a colorant (C) to be a colored polymerizable composition. As the colorant (C), pigments, dyes, natural pigments, and the like are exemplified. These coloring agents (C) can be used individually or in mixture of 2 or more types.

As a pigment, it is a nitroso compound, for example; nitro compounds; azo compounds; diazo compounds; xanthene compounds; quinoline compounds; anthraquinone compounds; coumarin compounds; phthalocyanine compounds; isoindolinone compounds; isoindoline compounds; quinacridone compounds; antantrone compounds; perinone compounds; perylene compounds; diketopyrrolopyrrole compounds; thioindigo compounds; dioxazine compounds; triphenylmethane compounds; quinophthalone compounds; naphthalenetetracarboxylic acid; metal complex compounds of azo dyes and cyanine dyes; lake pigment; carbon black obtained by a furnace method, channel method or thermal method, or carbon black such as acetylene black, ketjen black or lamp black; The carbon black prepared or coated with an epoxy resin, the carbon black previously dispersed with a resin in a solvent and 20 to 200 mg/g of the resin adsorbed, the carbon black subjected to acidic or alkaline surface treatment , having an average particle diameter of 8 nm or more and a DBP oil absorption of 90 ml/100 g or less, and a total oxygen amount calculated from CO and CO ₂ in the volatile matter at 950 ° C. of 9 mg or more per 100 m 2 of carbon black surface area; graphite, graphitized carbon black, activated carbon, carbon fiber, carbon nanotube, carbon microcoil, carbon nanohorn, carbon airgel, fullerene; aniline black, pigment black 7, titanium black; Chromium Oxide Green, Milori Blue, Cobalt Green, Cobalt Blue, Manganese, Ferrocyanide, Phosphate Ultramarine, Prussian Blue, Ultramarine, Cerulean Blue, Pyridian, Emerald Green, Lead Sulfate, Lead Yellow, Zinc Sulfur, Bengala ( Organic or inorganic pigments such as red iron(III) oxide, cadmium red, synthetic iron black, and amber may be used. These pigments can be used individually or in mixture of a plurality.

Commercially available pigments can also be used as the pigment, for example, Pigment Red 1, 2, 3, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48, 49, 88, 90, 97,112,119,122,123,144,149,166,168,169,170,171,177,179,180,184,185,192,200,202,209,215,216,217,22 0, 223, 224, 226, 227, 228, 240, 254; Pigment Orange 13, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 65, 71; Pigment Yellow 1, 3, 12, 13, 14, 16, 17, 20, 24, 55, 60, 73, 81, 83, 86, 93, 95, 97, 98, 100, 109, 110, 113, 114 117, 120, 125, 126, 127, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 166, 168, 175, 180, 185; Pigment Green 7, 10, 36; Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:5, 15:6, 22, 24, 56, 60, 61, 62, 64; Pigment violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 50 etc. are mentioned.

Dyes include azo dyes, anthraquinone dyes, indigoid dyes, triarylmethane dyes, xanthene dyes, alizarin dyes, acridine dyes, stilbene dyes, thiazole dyes, naphthol dyes, quinoline dyes, nitro dyes, indamine Dyes, such as a dye, an oxazine dye, a phthalocyanine dye, and a cyanine dye, etc. are mentioned, These may mix and use plurality.

The content of the colorant (C) in the polymerizable composition is preferably 5 to 350 parts by mass, more preferably 10 parts by mass, because the balance of curability and colorability is good with respect to 100 parts by mass of the radically polymerizable compound having an ethylenically unsaturated group. ~ 50 parts by mass.

The polymerizable composition according to the present invention may further contain an alkali developable compound (D) to obtain an alkali developable photosensitive resin composition. The one containing the coloring agent (C) and the alkali developable compound (D) is also referred to as a colored alkali developable photosensitive resin composition.

Although it will not specifically limit as long as it is a compound which has an acidic group as an alkali developable compound (D), For example, resin of Unexamined-Japanese-Patent No. 2004-264414, etc. are mentioned. The alkali developable compound (D) may have an ethylenically unsaturated bond. As the alkali developable compound, a polymer having a carboxyl group is preferable because of excellent developability and compatibility with ethylenically unsaturated compounds and the like.

In addition, as the alkali developable compound (D), an epoxy group of an epoxy compound such as a copolymer of acrylic acid ester, a phenol and/or cresol novolak epoxy resin, a polyphenylmethane type epoxy resin having a polyfunctional epoxy group, and an epoxy acrylate resin A resin obtained by reacting with an unsaturated monobasic acid and further reacting with a polybasic acid anhydride can be used. The epoxy acrylate resin referred to herein is a product obtained by applying (meth)acrylic acid to an epoxy compound, and examples thereof include Ripoxy SPC-1000, SPC-2000, and SPC-3000 manufactured by Showa Denko, Dick Light UE-777 manufactured by DIC, and Nihon and Yupica 4015 manufactured by Yupica Corporation.

Moreover, since the compound which has alkali developability is excellent in the sensitivity of the polymeric composition obtained, the compound which has an ethylenically unsaturated bond is preferable.

For the same reason, among ethylenically unsaturated bonds, an acryl group and a methacryl group are preferable, and an acryl group is particularly preferable.

The polymer having a carboxyl group may have a structural unit having a carboxyl group (hereinafter referred to as "structural unit (U1)"), and is not particularly limited, but is not particularly limited, but is methacryloyl, acryloyl, epoxy, vinyl, or vinyl ether. , a structural unit having a crosslinkable group such as a mercapto group, an oxetanyl group or an isocyanate group (hereinafter referred to as “structural unit (U2)”), a structural unit having a silyl group (hereinafter referred to as “structural unit (U3)”). The polymer having a carboxyl group may have structural units (hereinafter referred to as "structural unit (U4)") other than the structural units (U1) to (U3).

The structural unit (U1) is preferably a structural unit derived from at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides (hereinafter referred to as "compound (u1)").

Examples of the compound (u1) include monocarboxylic acids, dicarboxylic acids, and anhydrides of dicarboxylic acids. Examples of monocarboxylic acids include acrylic acid, methacrylic acid, crotonic acid, 2-acryloyloxyethylsuccinic acid, 2-methacryloyloxyethylsuccinic acid, and 2-acryloyloxyethylhexahydrophthalic acid. , 2-methacryloyloxyethylhexahydrophthalic acid and the like; Examples of dicarboxylic acids include maleic acid, fumaric acid, and citraconic acid; Examples of dicarboxylic acid anhydrides include dicarboxylic acid anhydrides and the like.

Among these, acrylic acid, methacrylic acid, 2-acryloyloxyethylsuccinic acid, 2-methacryloyloxyethylsuccinic acid, or maleic anhydride is preferable from the viewpoint of copolymerization reactivity and the solubility of the resulting copolymer in a developing solution. And compound (u1) can be used individually or in mixture of 2 or more types.

The structural unit (U2) is preferably a structural unit derived from a polymerizable unsaturated compound having an epoxy group or an oxetanyl group (hereinafter referred to as “compound (u2)”).

The compound (u2) is preferably at least one selected from the group consisting of a polymerizable unsaturated compound having an epoxy group and a polymerizable unsaturated compound having an oxetanyl group.

Examples of the polymerizable unsaturated compound having an epoxy group include oxiranyl (meth)acrylate (cyclo)alkyl esters, oxiranyl (cyclo)alkyl esters of α-alkylacrylates, and glycidyl ether compounds having polymerizable unsaturated bonds; Examples of the polymerizable unsaturated compound having an oxetanyl group include (meth)acrylic acid esters each having an oxetanyl group.

Regarding compound (u2), specific examples thereof include oxiranyl (meth)acrylate (cyclo)alkyl esters, for example, glycidyl (meth)acrylate, 2-methylglycidyl (meth)acrylate, 4- Hydroxybutyl (meth)acrylate glycidyl ether, (meth)acrylate 3,4-epoxybutyl, (meth)acrylate 6,7-epoxyheptyl, (meth)acrylate 3,4-epoxycyclohexyl, (meth)acrylate 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxytricyclo[5.2.1.0 ^2.6 ]decyl (meth)acrylate, etc. are mentioned.

Examples of the α-alkyl acrylate oxiranyl (cyclo)alkyl ester include α-ethyl glycidyl acrylate, α-n-propyl glycidyl acrylate, α-n-butyl glycidyl acrylate, α-ethyl acrylate 6 , 7-epoxyheptyl, α-ethyl acrylate 3,4-epoxycyclohexyl, and the like.

As a glycidyl ether compound which has a polymerizable unsaturated bond, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether etc. are mentioned, for example.

As the (meth)acrylic acid ester having an oxetanyl group, for example, 3-((meth)acryloyloxymethyl)oxetane, 3-((meth)acryloyloxymethyl)-3-ethyloxetane, 3 -((meth)acryloyloxymethyl)-2-methyloxetane, 3-((meth)acryloyloxyethyl)-3-ethyloxetane, 2-ethyl-3-((meth)acryloyl Oxyethyl) oxetane, 3-methyl-3-(meth)acryloyloxymethyl oxetane, 3-ethyl-3-(meth)acryloyloxymethyl oxetane, etc. are mentioned.

Among these specific examples, in particular, glycidyl methacrylate, 2-methylglycidyl methacrylate, 3,4-epoxycyclohexyl methacrylate, 3,4-epoxycyclohexylmethyl methacrylate, 3,4- Epoxytricyclo[5.2.1.0 ^2.6 ]decylmethacrylate, 3,4-epoxytricyclo[5.2.1.0 ^2.6 ]decylacrylate, 3-methacryloyloxymethyl-3-ethyloxetane, 3-methyl- 3-methacryloyloxymethyl oxetane or 3-ethyl-3-methacryloyloxymethyl oxetane is preferable from a polymerizable point.

These compounds (u2) can be used individually or in mixture of 2 or more types.

As the crosslinkable group of the structural unit (U2), a structural unit having a (meth)acryloyloxy group can be preferably used as the structural unit having a methacryloyl group or an acryloyl group in terms of good sensitivity.

The structural unit having a (meth)acryloyloxy group is obtained by reacting a (meth)acrylic acid ester having an epoxy group with a carboxyl group in a polymer. It is preferable that the structural unit which has the (meth)acryloyloxy group after reaction is a structural unit represented by the following general formula (U).

In Formula (U), R ¹⁰⁰⁰ and R ¹⁰⁰¹ are each independently a hydrogen atom or a methyl group. u is an integer from 1 to 6; R ¹⁰⁰² is a divalent group represented by the following general formula (Uα) or the following general formula (Uβ), and * represents the number of bonds.

In formula (Uα), R ¹⁰⁰³ is a hydrogen atom or a methyl group. In formulas (Uα) and (Uβ), * represents the number of bonds.

Regarding the structural unit represented by the general formula (U), for example, when a copolymer having a carboxyl group is reacted with a compound such as glycidyl methacrylate or 2-methylglycidyl methacrylate, the general formula ( R ¹⁰⁰² in U) has the general formula (Uα). On the other hand, when a compound such as 3,4-epoxycyclohexylmethyl methacrylate is reacted with a copolymer having a carboxyl group, R ¹⁰⁰² in general formula (U) becomes general formula (Uβ).

In the reaction of the carboxyl group in the polymer described above with an unsaturated compound such as (meth)acrylic acid ester having an epoxy group, the unsaturated compound having an epoxy group is added to a polymer solution preferably containing a polymerization inhibitor in the presence of an appropriate catalyst as necessary. It throws in and stirs for a predetermined time under heating. As a catalyst, tetrabutylammonium bromide etc. are mentioned, for example. As a polymerization inhibitor, p-methoxyphenol etc. are mentioned, for example. As for reaction temperature, 70 degreeC - 100 degreeC are preferable. As for reaction time, 8 hours - 12 hours are preferable.

In the structural unit ratio of the polymer having a carboxyl group, the content ratio of the structural unit having a (meth)acryloyloxy group as a crosslinkable group is preferably 10 mol% to 70 mol% of the total structural units of the polymer having a carboxyl group, and 20 It is more preferable that it is mol% - 50 mol%.

When the ratio of the structural unit having a (meth)acryloyloxy group is within the above-mentioned range, heat resistance and development failure during development are reduced, and generation of development residue can be suppressed.

The structural unit (U3) is preferably a structural unit derived from a polymerizable unsaturated compound having a silyl group (hereinafter referred to as “compound (u3)”).

Examples of the compound (u3) include 3-(meth)acryloyloxypropylmethyldimethoxysilane, 3-(meth)acryloyloxypropylethyldimethoxysilane, and 3-(meth)acryloyloxypropyl. Trimethoxysilane, 3-(meth)acryloyloxypropyl triethoxysilane, etc. are mentioned.

The compound (u3) described above can be used alone or in combination of two or more.

Structural unit (U4) is a structural unit other than (U1) to (U3) above, and is a structure derived from a polymerizable unsaturated compound (hereinafter referred to as "compound (u4)") other than (u1) to (u3) above. Units are preferred. Examples of the compound (u4) include (meth)acrylic acid alkyl esters, (meth)acrylic acid cycloalkyl esters, (meth)acrylic acid aryl esters, (meth)acrylic acid aralkyl esters, unsaturated dicarboxylic acid dialkyl esters, and oxygen-containing complexes. (meth)acrylic acid esters having a 5-membered ring or an oxygen-containing hetero6-membered ring, vinyl aromatic compounds, conjugated diene compounds, and other polymerizable unsaturated compounds.

Examples of the (meth)acrylic acid alkyl ester include methyl acrylate, n-propyl (meth)acrylate, i-propyl (meth)acrylate, n-butyl (meth)acrylate, sec-butyl (meth)acrylate, and (meth)acrylic acid i-propyl. t-butyl acrylate etc. are mentioned.

Examples of the (meth)acrylic acid cycloalkyl ester include cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, tricyclo[5.2.1.0 ^2,6 ]decan-8-yl (meth)acrylate, (meth)acrylic acid 2-(tricyclo[5.2.1.0 ^2,6 ]decan-8-yloxy)ethyl, (meth)acrylic acid isobornyl, etc. are mentioned.

Examples of the aryl (meth)acrylate include phenyl acrylate and the like, and examples of the aralkyl (meth)acrylate ester include benzyl (meth)acrylate and the like.

As an unsaturated dicarboxylic acid dialkyl ester, diethyl maleate, diethyl fumarate, etc. are mentioned, for example.

As a (meth)acrylic acid ester having an oxygen-containing hetero 5-membered ring or an oxygen-containing hetero 6-membered ring, for example, (meth)acrylate tetrahydrofuran-2-yl, (meth)acrylate tetrahydropyran-2-yl, (meth)acrylate ) 2-methyltetrahydropyran-2-yl acrylic acid; etc. are mentioned.

As a vinyl aromatic compound, styrene, (alpha)-methylstyrene etc. are mentioned, for example.

Examples of the conjugated diene compound include 1,3-butadiene and isoprene.

Examples of other polymerizable unsaturated compounds include 2-hydroxyethyl (meth)acrylic acid, acrylonitrile, methacrylonitrile, acrylamide and methacrylamide.

Among the compounds (u4) mentioned above, n-butyl methacrylate, 2-methylglycidyl methacrylate, benzyl methacrylate, and tricyclo[5.2.1.02,6]decane-8 methacrylate in terms of copolymerization reactivity. -yl, styrene, p-methoxy styrene, tetrahydrofuran-2-yl methacrylate, 1,3-butadiene and the like are preferable.

Compound (u4) can be used alone or in combination of two or more.

A polymer having a preferred carboxyl group according to the present invention can be synthesized by copolymerizing a mixture of polymerizable unsaturated compounds each containing the above compounds (u1) to (u4) in the following proportions.

Further, a structural unit having a (meth)acryloyloxy group can be obtained by reacting a (meth)acrylic acid ester having an epoxy group with the carboxyl group in the structural unit derived from the compound (u1) in the obtained copolymer.

Compounds (u1) to (u4) are preferably used within the following ranges.

Compound (u1): preferably 0.1 mol% to 30 mol%, more preferably 1 mol% to 20 mol%, still more preferably 5 mol% to 15 mol%

Compound (u2): preferably 1 mol% to 95 mol%, more preferably 10 mol% to 60 mol%, still more preferably 20 mol% to 30 mol%

Compound (u3): preferably 50 mol% or less, more preferably 1 mol% to 40 mol%, still more preferably 10 mol% to 30 mol%

Compound (u4): preferably 80 mol% or less, more preferably 1 mol% to 60 mol%, still more preferably 25 mol% to 50 mol%

A polymerizable composition containing a polymer having a carboxyl group obtained by copolymerizing a mixture of polymerizable unsaturated compounds containing compounds (u1) to (u4) in the above ranges achieves high resolution without impairing good coatability. , Even if it is a high-definition pattern, it is preferable because a cured film with a highly adjusted balance of properties can be provided.

The weight average molecular weight (Mw) of the polymer having a carboxyl group is preferably 2000 to 100000, more preferably 5000 to 50000. By using a polymer having a carboxyl group having an Mw within this range, since high resolution is achieved without deteriorating good applicability, it is possible to provide a cured film with a highly adjusted balance of properties even in a high-definition pattern. Meanwhile, the method for measuring the weight average molecular weight here refers to the weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography (GPC).

A polymer having a carboxyl group can be produced by polymerizing a mixture of the above polymerizable unsaturated compounds, preferably in a suitable solvent, preferably in the presence of a radical polymerization initiator.

Examples of the solvent used for polymerization include diethylene glycol monoethyl ether acetate, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether, and ethylene glycol monobutyl ether. Acetate, propylene glycol monomethyl ether acetate (PGMEA), dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, cyclohexanol acetate, benzyl alcohol, 3-methoxybutanol, etc. are mentioned. These solvents can be used individually or in mixture of 2 or more types.

The radical polymerization initiator is not particularly limited, and examples thereof include 2,2'-azobisisobutyronitrile, 2,2'-azobis-(2,4-dimethylvaleronitrile), and 2,2' -Azobis-(4-methoxy-2,4-dimethylvaleronitrile), 4,4'-azobis(4-cyanobalic acid), dimethyl-2,2'-azobis(2-methylpropanol) cionate), and azo compounds such as 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile). These radical polymerization initiators can be used individually or in mixture of 2 or more types.

Among the polymers having a carboxyl group, preferred is a polymer described in Japanese Unexamined Patent Publication No. 2005-234362, obtained by reacting an unsaturated monobasic acid with an epoxy group of an epoxy compound represented by the following general formula (VI), and further reacting with a polybasic acid anhydride. Polymers are preferred.

In Formula (VI), X ²¹ is a direct bond, a methylene group, 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 a group represented by the following (VIα), (VIβ) or the following (VIγ), the alkylidene group may be substituted with a halogen atom, R ⁶¹ , and R ⁶² each independently represents an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or a halogen atom, and the alkyl group, the alkoxy group and the alkenyl group It may be substituted with a halogen atom, and when a plurality of R ⁶¹ and R ⁶² are present, they may be the same or different, f is an integer of 0 to 4, g is an integer of 0 to 4, and m is an integer of 0 to 10. , and the optical isomers present when m is not 0 may be any isomers.

In general formula (VIα), Z ¹ is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a phenyl group optionally substituted with an alkoxy group having 1 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms, or a carbon atom number. represents a cycloalkyl group having 3 to 10 carbon atoms which may be substituted with an alkoxy group having 1 to 10 carbon atoms, Y ¹ is an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a cycloalkyl group having 2 to 10 carbon atoms 10 represents an alkenyl group or a halogen atom, the alkyl group, alkoxy group and alkenyl group may be substituted with a halogen atom, j represents an integer of 0 to 5, and * represents the number of bonds.

In formula (VIβ), * represents the number of bonds.

In Formula (VIγ), Y ² and Z ² are each independently an alkyl group having 1 to 10 carbon atoms which may be substituted with a halogen atom, an aryl group having 6 to 20 carbon atoms which may be substituted with a halogen atom, or a halogen atom. An aryloxy group having 6 to 20 carbon atoms which may be present, an arylthio group having 6 to 20 carbon atoms which may be substituted with a halogen atom, an arylalkenyl group having 6 to 20 carbon atoms which may be substituted with a halogen atom, a halogen atom An arylalkyl group having 7 to 20 carbon atoms which may be substituted, a heterocyclic group having 2 to 20 carbon atoms which may be substituted with a halogen atom, or a methylene group in the group represented by Y ² that represents a halogen atom is an unsaturated bond, -O - or -S- may be substituted, Z ² adjacent Z ² may form a ring, k represents an integer of 0 to 4, r represents an integer of 0 to 8, s is 0 to Represents an integer of 4, t represents an integer of 0 to 4, the sum of the numbers of s and t is an integer of 2 to 4, and * represents the number of bonds.

Examples of the unsaturated monobasic acid acting on the epoxy compound include acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, sorbic acid, hydroxyethyl methacrylate maleate, hydroxyethyl acrylate maleate, and hydroxypropyl methacrylic acid. Rate maleate, hydroxypropyl acrylate maleate, dicyclopentadiene maleate, etc. are mentioned.

Examples of the polybasic acid anhydride to be acted upon after the action of an unsaturated monobasic acid include biphenyltetracarboxylic dianhydride, tetrahydrophthalic anhydride, succinic anhydride, nonphthalic anhydride, maleic anhydride, trimellitic anhydride, and pyromellitic anhydride. , 2,2'-3,3'-benzophenonetetracarboxylic acid anhydride, ethylene glycol bisanhydrotrimellitate, glycerol trisanhydrotrimellitate, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, nadic acid anhydride , methylnadic anhydride, trialkyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, 5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride , trialkyltetrahydrophthalic anhydride-maleic anhydride adduct, dodecenyl succinic anhydride, methylhymic acid anhydride, and the like.

The molar ratio of the reaction between the epoxy compound, the unsaturated monobasic acid and the polybasic acid anhydride is preferably as follows. That is, in an epoxy adduct having a structure in which 0.1 to 1.0 carboxyl groups of an unsaturated monobasic acid are added to one epoxy group of the epoxy compound, the acid anhydride structure of the polybasic acid anhydride is 0.1 to 1.0 to one hydroxyl group of the epoxy adduct. It is desirable that the ratio be The reaction of the epoxy compound, unsaturated monobasic acid and polybasic acid anhydride can be carried out according to a conventional method.

Preferable examples of the polymer having a carboxyl group include the following [Polymer U1] and [Polymer U2].

[Polymer U1] 4 parts by mass of 2,2'-azobisisobutyronitrile and 190 parts by mass of propylene glycol monomethyl ether acetate were put into a flask equipped with a cooling tube and a stirrer, followed by 55 parts by mass of methacrylic acid, meta 45 parts by mass of benzyl acrylate and 2 parts by mass of α-methylstyrene dimer as a molecular weight regulator were added, and the temperature of the solution was raised to 80° C. while gently stirring, and the temperature was maintained for 4 hours, then raised to 100° C., A solution containing a copolymer was obtained by maintaining this temperature for 1 hour and performing polymerization. Next, to the solution containing this copolymer, 1.1 parts by mass of tetrabutylammonium bromide and 0.05 part by mass of 4-methoxyphenol as a polymerization inhibitor were added, and after stirring in an air atmosphere at 90°C for 30 minutes, glycymethacrylate was added. Polymer U1 having a weight average molecular weight Mw of 9000 obtained by adding 74 parts by mass of dill and reacting at 90°C for 10 hours was obtained. Polymer U1 has a structural unit (U1), a structural unit (U2) and a structural unit (U4).

[Polymer U2] To a flask equipped with a cooling tube and a stirrer, 5 parts by mass of 2,2'-azobisisobutyronitrile and 250 parts by mass of 3-methoxybutyl acetate were charged, and further 18 parts by mass of methacrylic acid, meta 25 parts by mass of tricyclo[5.2.1.02.6]decan-8-yl acrylate, 5 parts of styrene, 20 parts by mass of 3-acryloxypropyltrimethoxysilane, and 32 parts by mass of glycidyl methacrylate were added to perform nitrogen substitution After that, the temperature of the solution was raised to 80 °C while gently stirring. Polymer U2 having a weight average molecular weight Mw of 12000 obtained by polymerization while maintaining this temperature for 5 hours was obtained. The polymer U2 has a structural unit (U1), a structural unit (U2), a structural unit (U3) and a structural unit (U4).

The alkali developable photosensitive resin composition of the present invention, which is one of the embodiments of the polymerizable composition according to the present invention, contains a polymerization initiator (A), an ethylenically unsaturated compound (B) and an alkali developable compound (D) as essential components, , Inorganic compounds and solvents as optional components are contained in combination. On the other hand, among the alkali developable photosensitive resin compositions according to the present invention, those containing the colorant (C) are also referred to as colored alkali developable photosensitive resin compositions according to the present invention. The ethylenically unsaturated compound (B) and the alkali developable compound (D) may be the same compound or different, and may be used alone or in combination of two or more.

In order to improve the developability of the (colored) alkali developable photosensitive resin composition according to the present invention by adjusting the acid value, together with the alkali developable compound which may have the above ethylenically unsaturated bond, further monofunctional or multifunctional epoxy compound can be used. The acid value of the solid content of the alkali developable compound that may have an ethylenically unsaturated bond is preferably in the range of 5 to 120 mgKOH / g, and the amount of monofunctional or polyfunctional epoxy compound is selected to satisfy the acid value it is desirable

Monofunctional epoxy compounds include glycidyl methacrylate, methyl glycidyl ether, ethyl glycidyl ether, propyl glycidyl ether, isopropyl glycidyl ether, butyl glycidyl ether, isobutyl glycidyl ether , t-butyl glycidyl ether, pentyl glycidyl ether, hexyl glycidyl ether, heptyl glycidyl ether, octyl glycidyl ether, nonyl glycidyl ether, decyl glycidyl ether, undecyl glycidyl Ether, dodecyl glycidyl ether, tridecyl glycidyl ether, tetradecyl glycidyl ether, pentadecyl glycidyl ether, hexadecyl glycidyl ether, 2-ethylhexyl glycidyl ether, allyl glycidyl Ether, propargyl glycidyl ether, p-methoxyethyl glycidyl ether, phenyl glycidyl ether, p-methoxy glycidyl ether, p-butylphenol glycidyl ether, cresyl glycidyl ether , 2-methyl cresyl glycidyl ether, 4-nonylphenyl glycidyl ether, benzyl glycidyl ether, p-cumylphenyl glycidyl ether, trityl glycidyl ether, 2,3-epoxypropyl methacryl Relate, epoxidized soybean oil, epoxidized linseed oil, glycidylbutyrate, vinylcyclohexane monooxide, 1,2-epoxy-4-vinylcyclohexane, styrene oxide, pinene oxide, methyl styrene oxide, cyclohexene oxide, propylene oxide , the above compounds No.A2, No.A3 and the like.

As the polyfunctional epoxy compound, it is preferable to use at least one compound selected from the group consisting of bisphenol-type epoxy compounds and glycidyl ethers because a (coloring) alkali developable photosensitive resin composition with even better properties can be obtained. . As the bisphenol-type epoxy compound, besides the epoxy compound represented by general formula (VI) can be used, for example, bisphenol-type epoxy compounds such as hydrogenated bisphenol-type epoxy compounds can also be used.

In addition, as glycidyl ethers, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, 1, 8-octanediol diglycidyl ether, 1,10-decanediol diglycidyl ether, 2,2-dimethyl-1,3-propanediol diglycidyl ether, diethylene glycol diglycidyl ether, tri Ethylene glycol diglycidyl ether, tetraethylene glycol diglycidyl ether, hexaethylene glycol diglycidyl ether, 1,4-cyclohexanedimethanol diglycidyl ether, 1,1,1-tri(glycidyl ether) Dyloxymethyl) propane, 1,1,1-tri (glycidyloxymethyl) ethane, 1,1,1-tri (glycidyloxymethyl) methane, 1,1,1,1-tetra (glycidyl Diloxymethyl)methane or the like can be used.

Other novolak-type epoxy compounds such as phenol novolak-type epoxy compounds, biphenyl novolac-type epoxy compounds, cresol novolak-type epoxy compounds, bisphenol A novolac-type epoxy compounds, and dicyclopentadiene novolac-type epoxy compounds; 3,4-epoxy-6-methylcyclohexylmethyl-3,4-epoxy-6-methylcyclohexanecarboxylate, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 1- alicyclic epoxy compounds such as epoxyethyl-3,4-epoxycyclohexane; glycidyl esters such as phthalic acid diglycidyl ester, tetrahydrophthalic acid diglycidyl ester, and dimer acid glycidyl ester; glycidylamines such as tetraglycidyldiaminodiphenylmethane, triglycidyl P-aminophenol, and N,N-diglycidylaniline; heterocyclic epoxy compounds such as 1,3-diglycidyl-5,5-dimethylhydantoin and triglycidyl isocyanurate; Dioxide compounds, such as dicyclopentadiene dioxide; naphthalene type epoxy compounds; triphenylmethane type epoxy compounds; A dicyclopentadiene type epoxy compound or the like can also be used.

In particular, when the polymerizable composition according to the present invention is an alkali developable photosensitive resin composition, the content of the alkali developable compound which may have an ethylenically unsaturated bond is 1 to 1 in the alkali developable photosensitive resin composition according to the present invention. 20% by mass, particularly preferably 3 to 12% by mass.

A solvent may be further added to the polymerizable composition according to the present invention. As the solvent, a solvent capable of dissolving or dispersing each of the above components (polymerization initiator (A) and ethylenically unsaturated compound (B), etc.) as needed usually, for example, methyl ethyl ketone, methyl amyl ketone, diethyl ketone, ketones such as acetone, methyl isopropyl ketone, methyl isobutyl ketone, cyclohexanone, and 2-heptanone; ether solvents such as ethyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane, and dipropylene glycol dimethyl ether; Ester solvents, such as methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, cyclohexyl acetate, ethyl lactate, dimethyl succinate, and texanol; cellosolve solvents such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; alcohol solvents such as methanol, ethanol, iso- or n-propanol, iso- or n-butanol, and amyl alcohol; Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol-1-monomethyl ether-2-acetate, dipropylene glycol monomethyl ether acetate, 3-methoxybutyl ether acetate, ethoxyethyl ether propionate ether ester solvents such as the like; BTX solvents such as benzene, toluene and xylene; aliphatic hydrocarbon-based solvents such as hexane, heptane, octane, and cyclohexane; terpene hydrocarbon oils such as turpentine oil, D-limonene, and pinene; paraffinic solvents such as mineral spirits, Swasol #310 (Cosmo Matsuyama Sekiyu Co., Ltd.), and Solvesso #100 (Exxon Chemical Co., Ltd.); halogenated aliphatic hydrocarbon-based solvents such as carbon tetrachloride, chloroform, trichloroethylene, methylene chloride, and 1,2-dichloroethane; halogenated aromatic hydrocarbon solvents such as chlorobenzene; carbitol-based solvents; aniline; triethylamine; pyridine; acetic acid; acetonitrile; carbon disulfide; N,N-dimethylformamide; N,N-dimethylacetamide (DMAc); N-methylpyrrolidone; dimethyl sulfoxide; Water etc. are mentioned, These solvents can be used as 1 type, or a mixed solvent of 2 or more types.

Among these, ketones, ether ester solvents, and the like, particularly propylene glycol-1-monomethyl ether-2-acetate, cyclohexanone, and the like are preferable because compatibility between the resist and the polymerization initiator (A) is good in the polymerizable composition.

In addition, p-anisole, hydroquinone, pyrocatechol, t-butylcatechol, inorganic compounds, latent additives, organic polymers, chain transfer agents, sensitizers, surfactants, Silane coupling agents, melamine compounds, thermal polymerization inhibitors; plasticizer; adhesion promoter; filler; antifoam; leveling agent; surface conditioner; antioxidants; UV absorbers; dispersing aid; anti-agglomeration agents; catalyst; effect enhancers; cross-linking agent; Customary additives such as thickeners may be added.

A dispersant for dispersing a colorant (C) and/or an inorganic compound may be added to the polymerizable composition according to the present invention. The dispersant is not limited as long as it can disperse and stabilize the colorant (C) or inorganic compound, and a commercially available dispersant such as the BYK series manufactured by Big Chemie can be used. In particular, a polymer dispersant made of polyester, polyether, or polyurethane having a basic functional group, having a nitrogen atom as a basic functional group, the functional group having a nitrogen atom is an amine, and / or a quaternary salt thereof, and an amine value of 1 to 100 One of mgKOH/g is suitably used.

Latent additives are represented by the following general formulas (A) to (C).

In formula (A), ring A ² is a 6-membered alicyclic, aromatic or heterocyclic ring, and R ⁸¹ , R ⁸² , R ⁸³ , R ⁸⁴ and R ⁸⁵ are hydrogen atoms, halogen atoms, cyano groups, hydroxyl groups, or nitro groups. , a carboxyl group, an alkyl group having 1 to 40 carbon atoms which may have a substituent, an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, a heterocyclic group containing 2 to 20 carbon atoms, or - represents OR ⁸⁶ ;

At least one of R ⁸¹ , R ⁸² , R ⁸³ , R ⁸⁴ and R ⁸⁵ is not a hydrogen atom;

R ⁸⁶ is an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, and a compound having 2 to 20 carbon atoms. represents a ring-containing group or a trialkylsilyl group.

Ring A ² and R ⁹¹ in Formula (B) are the same as R ⁸⁶ in Formula (A);

X ⁷ is a group represented by the following general formula (2);

R ⁹² , R ⁹³ , R ⁹⁴ and R ⁹⁵ are hydrogen atoms, halogen atoms, cyano groups, hydroxyl groups, nitro groups, carboxyl groups, optionally substituted alkyl groups of 1 to 40 carbon atoms, and aryl groups of 6 to 20 carbon atoms group, an arylalkyl group having 7 to 20 carbon atoms or a heterocyclic group containing 2 to 20 carbon atoms,

At least one of R ⁹² , R ⁹³ , R ⁹⁴ and R ⁹⁵ is not a hydrogen atom.

In Formula (2), X ⁸ is -CR ⁹⁷ R ⁹⁸ -, -NR ⁹⁹ -, a divalent aliphatic hydrocarbon group having 1 to 35 carbon atoms, an aromatic hydrocarbon group having 6 to 35 carbon atoms, or a divalent hydrocarbon group having 2 to 35 carbon atoms represents the same as the heterocyclic group of 35 or any substituent represented by (VIα), (VIβ) or (VIγ) above;

The methylene group in the aliphatic hydrocarbon group may be substituted with -O-, -S-, -CO-, -COO-, -OCO-, or -NH-, or a bonding group in which oxygen atoms do not adjoin each other and combine them,

R ⁹⁷ and R ⁹⁸ represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an arylalkyl group having 7 to 20 carbon atoms;

Z ⁵ and Z ⁶ are each independently a direct bond, -O-, -S-, >CO, -CO-O-, -O-CO-, -SO ₂ -, -SS-, -SO- or >NR represents ¹⁰⁰ ,

R ⁹⁹ and R ¹⁰⁰ are a hydrogen atom, an aliphatic hydrocarbon group which may have a substituent having 1 to 35 carbon atoms, an aromatic hydrocarbon group which may have a substituent having 6 to 35 carbon atoms, or a substituent which may have 2 carbon atoms represents a heterocyclic group of ˜35, and * represents the number of bonds.

In general formula (C), k = 2 to 6, X ⁹ is a group represented by the general formula (2) when k = 2, and a group represented by the following general formula (3) when k = 3, It is a group represented by the following general formula (4) when k = 4, the following general formula (5) when k = 5, and the following general formula (6) when k = 6, R ¹¹¹ , R ¹¹² , R ¹¹³ and R ¹¹⁴ are 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 which may have a substituent, an aryl group having 6 to 20 carbon atoms, and a carbon atom having 7 to 20 carbon atoms. represents an arylalkyl group of 20 or a heterocyclic group containing 2 to 20 carbon atoms, at least one of R ¹¹¹ , R ¹¹² , R ¹¹³ and R ¹¹⁴ is not a hydrogen atom, and rings A ¹ and R ⁸⁶ are represented by the general formula (A ) is the same as

In Formula (3), Y ¹¹ is a trivalent aliphatic hydrocarbon group having 3 to 35 carbon atoms, an alicyclic hydrocarbon group having 3 to 35 carbon atoms, an aromatic hydrocarbon group having 6 to 35 carbon atoms, or a hydrocarbon group having 2 to 35 carbon atoms. represents a heterocyclic group of 35, Z ¹¹ , Z ¹² and Z ¹³ are each independently a direct bond, -O-, -S-, >CO, -CO-O-, -O-CO-, -SO ₂ -, -SS-, -SO-, -NR ¹²¹ -, -PR ¹²¹ - or an aliphatic hydrocarbon group of 1 to 35 carbon atoms which may have a substituent, an aromatic hydrocarbon group of 6 to 35 carbon atoms which may have a substituent, or represents a heterocyclic group having 2 to 35 carbon atoms which may have a substituent, R ¹²¹ is a hydrogen atom, an aliphatic hydrocarbon group having 1 to 35 carbon atoms which may have a substituent, and an aliphatic hydrocarbon group having 6 to 35 carbon atoms which may have a substituent represents an aromatic hydrocarbon group or a heterocyclic group having 2 to 35 carbon atoms which may have a substituent, and the methylene group in the aliphatic hydrocarbon group is a carbon-carbon double bond, -O-, -CO-, -O-CO-, -CO -O- or -SO ₂ - may be substituted.

In Formula (4), Y ¹² represents a carbon atom, a tetravalent aliphatic hydrocarbon group having 1 to 35 carbon atoms, an aromatic hydrocarbon group having 6 to 35 carbon atoms, or a heterocyclic group having 2 to 35 carbon atoms, and an aliphatic The methylene group in the hydrocarbon group may be substituted with -COO-, -O-, -OCO-, -NHCO-, -NH- or -CONH-, and Z ¹¹ to Z ¹⁴ are each independently It is a group in the same range as the group represented by Z ¹¹ to Z ¹³ .

In Formula (5), Y ¹³ represents a pentavalent aliphatic hydrocarbon group having 2 to 35 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms, or a heterocyclic group having 2 to 30 carbon atoms, and methylene in the aliphatic hydrocarbon group The group may be substituted with -COO-, -O-, -OCO-, -NHCO-, -NH- or -CONH-, and Z ¹¹ to Z ¹⁵ are each independently Z ¹¹ to Z in the general formula (3) It is a group in the same range as the group represented by ¹³ .

In formula (6), Y ¹⁴ represents a hexavalent aliphatic hydrocarbon group having 2 to 35 carbon atoms, an aromatic hydrocarbon group having 6 to 35 carbon atoms, or a heterocyclic group having 2 to 35 carbon atoms, and methylene in the aliphatic hydrocarbon group The group may be substituted with -COO-, -O-, -OCO-, -NHCO-, -NH- or -CONH-, and Z ¹¹ to Z ¹⁶ are each independently Z ¹¹ to Z in the general formula (3) It is a group in the same range as the group represented by ¹³ .

In the polymerizable composition, organic polymers (excluding the ethylenically unsaturated compound (B)) may be used to improve the properties of the cured product, for example, polystyrene, polymethyl methacrylate, and methyl methacrylate. -Ethyl acrylate copolymer, poly(meth)acrylic acid, styrene-(meth)acrylic acid copolymer, (meth)acrylic acid-methyl methacrylate copolymer, ethylene-vinyl chloride copolymer, ethylene-vinyl copolymer, polyvinyl chloride Resin, ABS resin, nylon 6, nylon 66, nylon 12, urethane resin, polycarbonate polyvinyl butyral, cellulose ester, polyacrylamide, saturated polyester, phenolic resin, phenoxy resin, polyamideimide resin, polyamic acid resin and epoxy resins, among which polystyrene, (meth)acrylic acid-methyl methacrylate copolymers and epoxy resins are preferred. When using an organic polymer, the amount used is preferably 10 to 500 parts by mass based on 100 parts by mass of the polymerizable compound having an ethylenically unsaturated bond.

As the chain transfer agent or sensitizer, a sulfur atom-containing compound is generally used. For example, thioglycolic acid, thiomalic acid, thiosalicylic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, 3-mercaptobutyric acid, N-(2-mercaptopropionyl)glycine, 2-mercaptonicotinic acid, 3 -[N-(2-mercaptoethyl)carbamoyl]propionic acid, 3-[N-(2-mercaptoethyl)amino]propionic acid, N-(3-mercaptopropionyl)alanine, 2-mercaptoethane Sulfonic acid, 3-mercaptopropanesulfonic acid, 4-mercaptobutanesulfonic acid, dodecyl (4-methylthio) phenyl ether, 2-mercaptoethanol, 3-mercapto-1,2-propanediol, 1-mercapto- 2-propanol, 3-mercapto-2-butanol, mercaptophenol, 2-mercaptoethylamine, 2-mercaptoimidazole, 2-mercaptobenzoimidazole, 2-mercapto-3-pyridinol, Mercapto compounds and mercapto compounds such as 2-mercaptobenzothiazole, mercaptoacetic acid, trimethylolpropanetris (3-mercaptopropionate), and pentaerythritol tetrakis (3-mercaptopropionate) Disulfide compounds obtained by oxidation, iodinated alkyl compounds such as iodoacetic acid, iodopropionic acid, 2-iodoethanol, 2-iodoethanesulfonic acid and 3-iodopropanesulfonic acid, trimethylolpropanetris (3-mercaptoisobutyrate), butanediol Bis(3-mercaptoisobutyrate), hexanedithiol, decanedithiol, 1,4-dimethylmercaptobenzene, butanediolbisthiopropionate, butanediolbisthioglycolate, ethylene glycolbisthioglycolate, trimethylol Propane Trithioglycolate, Butanediol Bisthiopropionate, Trimethylolpropane Trithiopropionate, Trimethylolpropane Trithioglycolate, Pentaerythritol Tetrakithiopropionate, Pentaerythritol Tetrakithioglycolate, Tris Aliphatic polyfunctional thiols such as hydroxyethyltrithiopropionate, diethylthioxanthone, diisopropylthioxanthone, the following compound No.C1, and tris(2-hydroxyethyl)isocyanurate trimercaptopropionate Compounds such as Karenz MT BD1, PE1, and NR1 manufactured by Showa Denko Co., Ltd. are exemplified.

Examples of surfactants include fluorosurfactants such as perfluoroalkyl phosphate esters and perfluoroalkyl carboxylates; anionic surfactants such as alkali salts of higher fatty acids, alkyl sulfonates, and alkyl sulfates; cationic surfactants such as higher amine halide salts and quaternary ammonium salts; nonionic surfactants such as polyethylene glycol alkyl ethers, polyethylene glycol fatty acid esters, sorbitan fatty acid esters, and fatty acid monoglycerides; amphoteric surfactants; Surfactants such as silicone surfactants can be used, and these may be used in combination.

As the silane coupling agent, for example, a silane coupling agent manufactured by Shin-Etsu Chemical Co., Ltd. can be used, and among them, isocyanate group, acryloyl group, methacrylic A silane coupling agent having a loyl group or an epoxy group is suitably used.

Melamine compounds include all active methylol groups (CH ₂ OH groups) in nitrogen compounds such as (poly) methylolmelamine, (poly)methylolglycoluril, (poly)methylolbenzoguanamine, and (poly)methylolurea. or a compound in which some (at least two) have been alkyl-etherified.

Here, the alkyl group constituting the alkyl ether includes a methyl group, an ethyl group, or a butyl group, which may be the same or different. In addition, the methylol group that has not been alkyl-etherified may self-condense within one molecule or condense between two molecules, and as a result, an oligomer component may be formed.

Specifically, hexamethoxymethylmelamine, hexabutoxymethylmelamine, tetramethoxymethylglycoluril, tetrabutoxymethylglycoluril, etc. can be used. Among these, alkyl etherified melamine, such as hexamethoxymethyl melamine and hexabutoxymethyl melamine, is preferable.

As the leveling agent, conventional leveling agents may be used as long as they have a leveling effect, and among them, a silicon-based leveling agent and a fluorine-based leveling agent may be particularly preferably used.

As the silicone-based leveling agent, a commercially-available silicone-based leveling agent can be used, for example, BYK-300, BYK-306, BYK-307, BYK-310, BYK-315, BYK-313, BYK-320, BYK-322, BYK-323, BYK-325, BYK-330, BYK-331, BYK-333, BYK-337, BYK-341, BYK-344, BYK-347, BYK-348, BYK-349, BYK-370, BYK- 375, BYK-377, BYK-378, BYK-UV3500, BYK-UV3510, BYK-UV3570, BYK-3550, BYK-SILCLEAN 3700, BYK-SILCLEAN 3720 (above, manufactured by Big Chemie Japan); AC FS 180, AC FS 360, AC S 20 (and above, manufactured by Algin Chemie); Polyflow KL-400X, Polyflow KL-400HF, Polyflow KL-401, Polyflow KL-402, Polyflow KL-403, Polyflow KL-404 (above, manufactured by Kyoeisha Chemical); KP-323, KP-326, KP-341, KP-104, KP-110, KP-112 (above, manufactured by Shin-Etsu Chemical Industry Co., Ltd.); Commercial products such as LP-7001, LP-7002, 8032 ADDITIVE, 57 ADDITIVE, L-7604, FZ-2110, FZ-2105, 67 ADDITIVE, 8618 ADDITIVE, 3 ADDITIVE, 56 ADDITIVE (above, manufactured by Dow Corning and Torre) can be used

As the fluorine-based leveling agent, a commercially available fluorine-based leveling agent can be used, for example, Optool DSX, Optool DAC-HP (above, manufactured by Daikin Kogyo); Suplon S-242, Suplon S-243, Suplon S-420, Suplon S-611, Suplon S-651, Suplon S-386 (above, manufactured by AGC Semi Chemical); BYK-340 (product of Big Chemie Japan); AC 110a, AC 100a (above, Algin Chemie product); Mega Pack F-114, Mega Pack F-410, Mega Pack F-444, Mega Pack EXP TP-2066, Mega Pack F-430, Mega Pack F-472SF, Mega Pack F-477, Mega Pack F-552, Mega Megapack F-553, Megapack F-554, Megapack F-555, Megapack R-94, Megapack RS-72-K, Megapack RS-75, Megapack F-556, Megapack EXP TF-1367, Megapack EXP TF-1437, Megapack F-558, Megapack EXP TF-1537 (and above, DIC products); FC-4430, FC-4432 (above, manufactured by Sumitomo 3M); Fragent 100, Fragent 100C, Fragent 110, Fragent 150, Fragent 150CH, Fragent A-K, Fragent 501, Fragent 250, Fragent 251, Fragent 222F, Fragent 208G, Fragent 300, Fragent 310, Ptergent 400SW (above, Neos product); PF-136A, PF-156A, PF-151N, PF-636, PF-6320, PF-656, PF-6520", PF-651, PF-652, PF-3320 (above, made by Kitamura Kagaku Sangyo), etc. commercially available products can be used.

In the polymerizable composition, the amount of any component except for the polymerization initiator (A), the ethylenically unsaturated compound (B), the colorant (C), the alkali developable compound (D), the solvent, the inorganic compound, and the organic polymer is determined according to the purpose of use. It is appropriately selected according to the content and is not particularly limited, but is preferably 50 parts by mass or less in total with respect to 100 parts by mass of the ethylenically unsaturated compound (B).

The hardened|cured material of this invention is obtained by hardening the said polymeric composition or alkali-developable photosensitive resin composition.

The polymerizable composition, alkali developable photosensitive resin composition or cured product according to the present invention is a photocurable paint or varnish; photocurable adhesives; printed board; color filters in liquid crystal display elements for color display of display devices (color TVs, PC monitors, portable information terminals, digital cameras, etc.); color filters of CCD image sensors; electrode materials for plasma display panels; powder coating; printing ink; print edition; glue; dental compositions; gelcoat; photoresists for electronics; electroplating resist; etch resist; dry film; solder resist; resists for forming structures of various display devices; compositions for encapsulating electrical and electronic components; solder resist; magnetic recording materials; micro mechanical parts; waveguide; light switch; a mask for plating; etching mask; color test system; fiberglass cable coating; stencils for screen printing; materials for manufacturing three-dimensional objects by stereolithography; materials for holographic recording; image recording materials; microelectronic circuit; decolorizing materials; decolorizing materials for image recording materials; decolorizing materials for image recording materials using microcapsules; photoresist materials for printed wiring boards; photoresist materials for UV and visible laser direct imaging systems; It can be used for various applications, such as a photoresist material used for forming a dielectric layer in sequential lamination of a printed circuit board or a protective film, and the application is not particularly limited.

Since the polymerizable composition or alkali-developable photosensitive resin composition according to the present invention can form a cured product having high brightness, it is useful as a polymerizable composition for color filters.

The polymerizable composition or alkali-developable photosensitive resin composition according to the present invention may be used for the purpose of forming a spacer for a liquid crystal display panel and for forming projections for a vertical alignment type liquid crystal display element. In particular, it is useful as a polymerizable composition for simultaneously forming projections and spacers for a vertical alignment type liquid crystal display device.

Next, a method for producing a cured product of the polymerizable composition or alkali-developable photosensitive resin composition will be described in detail below.

The polymerizable composition or the alkali developable photosensitive resin composition may be prepared by a known method such as a spin coater, a roll coater, a bar coater, a die coater, a curtain coater, various types of printing, dipping, etc., for soda glass, quartz glass, semiconductor substrates, metal, It can be applied on a support substrate such as paper or plastic. Further, once applied on a support substrate such as a film, it may be transferred onto another support substrate, and there is no limitation on the application method.

The method for producing a cured product of the polymerizable composition includes a step of curing the polymerizable composition by light irradiation or a step of curing by heating.

Light sources used in the curing process by light irradiation include ultra-high pressure mercury lamps, high-pressure mercury lamps, medium-pressure mercury lamps, low-pressure mercury lamps, mercury vapor arc lamps, xenon arc lamps, carbon arc lamps, metal halide lamps, fluorescent lamps, and tungsten lamps. , Electromagnetic wave energy having a wavelength of 2000 angstroms to 7000 angstroms obtained from an excimer lamp, sterilization lamp, light emitting diode, CRT light source, etc., or high energy rays such as electron beams, X-rays, and radiation can be used, preferably with a wavelength of 300 to 450 An ultra-high pressure mercury lamp, a mercury vapor arc lamp, a carbon arc lamp, a xenon arc lamp, etc. which emit light of nm are mentioned.

In addition, by using laser light as an exposure light source, the laser direct writing method, which forms an image directly from digital information such as a computer without using a mask, is useful because it can improve not only productivity but also resolution and positional accuracy. , As the laser light, light with a wavelength of 340 to 430 nm is suitably used, and excimer lasers, nitrogen lasers, argon ion lasers, helium cadmium lasers, helium neon lasers, krypton ion lasers, various semiconductor lasers, and visible lasers such as YAG lasers are used. It is also used to emit light in the infrared region from. In the case of using these laser lights, a sensitizing dye that absorbs the corresponding region from visible to infrared is preferably added.

The process of hardening by heating is demonstrated. The heating temperature is appropriately set according to the thickness of the coating film or cured material of the composition to be treated, the polymerization initiation temperature of the thermal polymerization initiator, etc., and can be, for example, 50 ° C. or higher and 250 ° C. or lower, and among them, 100 ° C. or higher and 200 ° C. or higher. It is preferable that it is below degreeC, and it is especially preferable that it is 100 degreeC or more and 150 degreeC or less. On the other hand, in the method for producing a cured product of the present invention, the heating temperature indicates, for example, the surface temperature of the polymerizable composition or cured product. Moreover, heating time can be made into 10 minutes or more and 2 hours or less. On the other hand, the heating time indicates the time to maintain the temperature after the composition or cured product reaches a predetermined temperature.

The spacer for the liquid crystal display panel is (1) a step of forming a coating film of the polymerizable composition according to the present invention on a substrate, (2) a process of irradiating the coating film with radiation through a mask having a predetermined pattern shape, (3) ) It is preferably formed by a baking step after exposure, (4) a step of developing the film after exposure, and a step of heating the film after (5) development.

The polymerizable composition according to the present invention to which an ink repellant is added is useful as a resin composition for forming a barrier rib for an inkjet method, and the composition is used for a color filter, particularly preferably for a barrier rib for an inkjet method color filter having a profile angle of 50° or more. used As the ink repellent agent, a fluorine-based surfactant and a composition comprising a fluorine-based surfactant are preferably used.

An optical element is manufactured by a method in which a barrier rib formed of the polymerizable composition according to the present invention partitions an image to be transferred, and forms an image area by applying a droplet to a concave portion on the partitioned transfer object by an inkjet method. do. At this time, it is preferable that the liquid droplet contains a colorant and the image area is colored, and has at least a pixel group comprising a plurality of colored areas on a substrate and a barrier rib separating each colored area of the pixel group, and An optical element produced by a method for manufacturing an element is preferably used.

Example

Hereinafter, the present invention will be described in more detail by way of Examples and Comparative Examples, but the present invention is not limited to these Examples and the like.

<Example 1: Synthesis of Compound 1>

(Preparation of Intermediate 1-A)

Carbazole (10.7g, 63.7mmol), DMF (45.0g), bromocyclopentane (38.0g, 255mmol), and potassium hydroxide (14.3g, 255mmol) were added to the reaction vessel, followed by 6 hours at 50°C. reacted After the reaction, ion-exchanged water and ethyl acetate were added, and oil and water separation was performed. The organic layer was washed with water 3 times, and silica gel column purification was performed to obtain intermediate 1-A.

(Preparation of Intermediate 1-B)

Aluminum chloride (9.5g, 71.8mmol) and 100g of dichloroethane were added to the reaction vessel, and under ice-cooling, intermediate 1-A (15.4g, 62.3mmol), cyclohexylpropionyl chloride (12.5g, 71.8mmol) put in order. After reacting at room temperature for 1 hour, the reaction solution was poured into ice water. After oil-water separation, the organic layer was washed with water three times and purified by silica gel column to obtain Intermediate 1-B.

(Preparation of Intermediate 1-C)

Aluminum chloride (12.8 g, 95.7 mmol) and 100 g of dichloroethane were added to the reaction vessel, and under ice-cooling, intermediate 1-B (18.2 g, 43.5 mmol), methyl chloroglyoxylate (5.9 g, 47.9 mmol) put in order. After reacting at room temperature for 1 hour, the reaction solution was poured into ice water. After oil-water separation, the organic layer was washed with water three times and purified by silica gel column to obtain Intermediate 1-C.

(Preparation of Intermediate 1-D)

Intermediate 1-C (8.0 g, 17.4 mmol) and DMF (30.0 g) were added to the reaction vessel, followed by 1.8 g of 35% hydrochloric acid and isobutyl nitrite (3.6 g, 34.8 mmol) while stirring at 5 ° C. It threw in and was made to react at room temperature for 12 hours. Ethyl acetate was added, and after oil-water separation, the organic layer was washed with water three times, and purified by silica gel column to obtain intermediate 1-D.

(Preparation of Compound 1)

Intermediate 1-D (9.24g, 17.9mmol) and 30.0g of ethyl acetate were added to the reaction vessel, and under ice-cooling, acetyl chloride (1.54g, 19.7mmol) and triethylamine (1.99g, 19.7mmol) were added in this order. was loaded with After stirring at room temperature for 1 hour, ion-exchanged water was added and oil-water separation was performed. The organic layer was washed with water 3 times, and after solvent removal, silica gel column purification was performed (ethyl acetate/hexane = 3/10) to obtain compound 1 (2.1 g, yield 21%).

The obtained compound was dissolved in deuterated chloroform, and ¹ H-NMR measurement was performed. The results are shown in Table 1.

<Example 2: Synthesis of Compound 2>

Compound 2 was obtained in the same manner as in Example 1, except that bromocyclopentane used in the preparation of Intermediate 1-A was changed to 1-bromo-2-ethylhexane.

The obtained compound was dissolved in deuterated chloroform, and ¹ H-NMR measurement was performed. The results are shown in Table 1.

<Example 3: Synthesis of Compound 3>

Compound 3 was obtained in the same manner as in Example 1, except that bromocyclopentane used in the preparation of Intermediate 1-A was changed to 1-bromo-2-methylpropane.

The obtained compound was dissolved in deuterated chloroform, and ¹ H-NMR measurement was performed. The results are shown in Table 1.

<Example 4: Synthesis of Compound 4>

Examples except that bromocyclopentane used in the preparation of Intermediate 1-A was changed to 1-bromo-2-ethylhexane and cyclohexylpropionyl chloride used in the preparation of Compound 1-B was changed to phenylacetyl chloride. Compound 4 was obtained in the same manner as in 1.

The obtained compound was dissolved in deuterated chloroform, and ¹ H-NMR measurement was performed. The results are shown in Table 1.

<Preparation Example 1: Blue Pigment Dispersion No. 1>

Dispersing DISPERBYK-161 (12.5 parts by mass; manufactured by Big Chemie Japan) as a dispersant and Pigment Blue 15:6 (15 parts by mass) as a colorant in PGMEA (72.5 parts by mass) using a bead mill to prepare a blue pigment dispersion. did.

<Evaluation method: Solubility>

Compounds 1 to 4 prepared in Examples 1 to 4 and Comparative Compound A′-1 below were each dissolved in an organic solvent (propylene glycol monomethyl ether acetate (PGMEA)) at room temperature, and solubility was evaluated according to the following criteria. The results are shown in Table 2.

A: 2wt% or more

B: less than 2wt%

<Evaluation method: sensitivity>

The polymerizable composition was adjusted according to the formulation described in Table 3. The polymerizable composition was spin-coated on a glass substrate (so that chromaticity coordinates (x, y) = (0.135, 0.098) after post-baking), and pre-baking was performed at 90 ° C. for 120 seconds using a hot plate, followed by 23 ° C. cooled for 60 seconds. Thereafter, exposure was performed through a photomask (mask opening: 30 μm) using an ultra-high pressure mercury lamp (exposure gap: 100 μm, exposure amount: 40 mJ/cm 2 ). After developing using 0.04 mass % KOH aqueous solution as a developing solution, it rinsed well with water, post-baking was performed at 230 degreeC for 20 minutes using a clean oven, and the pattern was fixed. The obtained pattern was observed with an electron microscope, the line width of the portion corresponding to the mask opening was measured, and the sensitivity was evaluated according to the following criteria. The results are shown in Table 3. The larger the line width, the better the sensitivity.

A line width of 30㎛ or more

Line width less than 30㎛ B

<Evaluation method: luminance>

The polymerizable composition was spin-coated on a glass substrate (so that chromaticity coordinates (x, y) = (0.135, 0.098) after post-baking), and pre-baking was performed at 90 ° C. for 120 seconds using a hot plate, followed by 23 ° C. cooled for 60 seconds. Then, after exposure at 150 mJ/cm 2 using an ultra-high pressure mercury lamp, post-baking was performed at 230° C. for 20 minutes using a clean oven to prepare evaluation samples. Based on JIS Z8701, Y value was calculated|required from the transmittance|permeability at 380-780 nm of the obtained sample, and brightness was evaluated according to the following criteria. The results are shown in Table 3. The higher the Y value, the higher the luminance and high transmittance in the visible light region, which is useful.

Y value of 11.0 or higher A

Y value less than 11.0 B

Symbols in the table are as follows.

A-1: compound 1

A-2: compound 2

A-3: compound 3

A-4: compound 4

A'-1: Comparative compound A'-1

B-1: Kayarad DPHA (ethylenically unsaturated compound; manufactured by Nippon Kayaku Co., Ltd.)

C-1: Blue Pigment Dispersion No. 1

D-1: SPC-3000 (alkaline developable compound; polymer having an acrylic group and a carboxy group; Showa Denko Co., Ltd., solid content 42.7%, PGMEA solution)

E-1: KBE-403 (coupling agent, manufactured by Shin-Etsu Chemical Co., Ltd.)

F-1: PGMEA (solvent)

As shown in Table 2, the compounds of the present invention have excellent solubility in solvents. In addition, as shown in Table 3, it was confirmed that a cured product having excellent sensitivity, high luminance and high transmittance in the visible light region was obtained from the polymerizable composition using a polymerization initiator containing the compound of the present invention.

The compound of the present invention is useful as a polymerization initiator because of its high sensitivity and excellent solubility in solvents. Further, since a cured product having a high transmittance in the visible light region can be obtained, a polymerizable composition using a polymerization initiator containing the compound of the present invention is useful as a polymerizable composition for color filters in particular.

Claims (12)

A compound having a group represented by the following general formula (I) and a group represented by the following general formula (II) in the same molecule.

In the formula, R ¹ and R ² are each independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydrocarbon group having 1 to 20 carbon atoms, or one or more methylene groups among the above hydrocarbon groups in <Group A> At least one of a group substituted with a selected divalent group, a heterocyclic group having 2 to 10 carbon atoms, a heterocyclic group having 3 to 20 carbon atoms, or a methylene group in the above heterocycle-containing group, <Group A Represents a group substituted with a divalent group selected from >,
n represents 0 or 1;
* indicates the number of bonds,
When there are a plurality of groups represented by the general formula (I) in the compound, the plurality of R ¹ , R ² and n may be the same or different.
<Group A>: -O-, -CO-, -COO-, -OCO-, -NR ³ -, -NR ³ CO-, -S-
R ³ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.

In the formula, R ⁴ is a hydrocarbon group having 1 to 20 carbon atoms, or a group in which at least one methylene group in the above hydrocarbon group is substituted with a divalent group selected from <Group B> below, or a complex group having 2 to 10 carbon atoms. represents a group in which one or more of the heterocycle-containing groups of 3 to 20 carbon atoms or the methylene groups in the heterocycle-containing groups is substituted with a divalent group selected from the following <group B>;
* indicates the number of bonds,
In the case where a plurality of groups represented by the general formula (II) exist in the compound, the plurality of R ^{4 '} s may be the same or different.
<Group B>: -O-, -CO-, -COO-, -OCO-, -NR ⁵ -, -NR ⁵ CO-, -S-
R ⁵ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. According to claim 1,
A compound in which R ⁴ in formula (II) is an alkoxy group having 1 to 10 carbon atoms. According to claim 1 or 2,
A compound having a structure represented by the following general formula (III).

In the formula, A ¹ represents an aromatic ring having 6 to 20 carbon atoms;
R ¹¹ represents a group represented by the general formula (I);
R ¹² is a group represented by the general formula (II), a hydrocarbon group having 1 to 20 carbon atoms substituted with a group represented by the general formula (II), or one or more of the methylene groups in the hydrocarbon group described below. A group substituted with a divalent group selected from C>, a heterocyclic group having 2 to 10 carbon atoms substituted with a group represented by the above general formula (II), or a carbon atom substituted with a group represented by the above general formula (II) Representing a heterocycle-containing group of 3 to 20, or a group in which one or more of the methylene groups in the heterocycle-containing group is substituted with a divalent group selected from the following <Group C>,
R ¹³ is each independently a halogen atom, a nitro group, a cyano group, a hydrocarbon group having 1 to 20 carbon atoms, or a methylene group in which one or more of the hydrocarbon groups is substituted with a divalent group selected from <Group C> below. group, a heterocyclic group of 2 to 10 carbon atoms, a heterocyclic group of 3 to 20 carbon atoms, or a divalent group in which at least one of the methylene groups in the heterocyclic group is selected from the following <Group C> represents a substituted group,
a represents an integer of 1 to 20, and when a is an integer of 2 or greater, a plurality of R ¹¹ may be the same or different;
b represents an integer of 1 to 20, and when b is an integer of 2 or greater, a plurality of R ¹² may be the same or different;
c represents an integer from 0 to 20, and when c is an integer of 2 or greater, a plurality of R ¹³ may be the same or different;
However, a+b+c is 20 or less.
<Group C>: -O-, -CO-, -COO-, -OCO-, -NR ¹⁴ -, -NR ¹⁴ CO-, -S-
R ¹⁴ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. According to any one of claims 1 to 3,
A compound having at least one branched alkyl group or cycloalkyl group of 3 to 20 carbon atoms in its molecule. According to claim 3 or 4,
A compound wherein A ¹ is a structure represented by the following general formula (IVα) or (IVβ).

The general formula (IVα) shows the structure when the groups represented by R ¹¹ , R ¹² and R ¹³ in the general formula (III) are substituted with a hydrogen atom, wherein X ¹ is an oxygen atom, a sulfur atom, or a selenium atom. , CH ₂ , CO, NH or PH,
X ² represents a single bond, no bond, an oxygen atom, a sulfur atom, a selenium atom, CH ₂ , CO, NH or PH.

The general formula (IVβ) shows the structure when the groups represented by R ¹¹ , R ¹² and R ¹³ in the general formula (III) are substituted with hydrogen atoms. According to claim 5,
A compound in which A ¹ is a structure represented by Formula (IVα), X ¹ is NR ¹³ , and X ² is a single bond. A polymerization initiator containing the compound according to any one of claims 1 to 6. A polymerizable composition containing the polymerization initiator (A) according to claim 7 and an ethylenically unsaturated compound (B). According to claim 8,
A polymerizable composition further containing a colorant (C). A cured product of the polymerizable composition according to claim 8 or 9. A color filter containing the cured product according to claim 10. A method for producing a cured product comprising a step of curing the polymerizable composition according to claim 8 or 9 by light irradiation or a step of curing by heating.