WO2017051680A1 - Oxime ester compound and polymerization initiator containing said compound - Google Patents

Abstract

An oxime ester compound represented by general formula (I) wherein at least one of Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７、Ｒ^８、Ｒ^９, and Ｒ^１０ is a group represented by general formula (II) in the oxime ester compound. At least one of Ｒ^２、Ｒ^３、Ｒ^４, and Ｒ^５ in general formula (I) is preferably a group represented by general formula (II) in the oxime ester compound. In addition, at least one of Ｒ^６、Ｒ^７、Ｒ^８、Ｒ^９, and Ｒ^１０ in general formula (I) is preferably an electron-withdrawing group.

Description

Oxime ester compound and polymerization initiator containing the compound

The present invention relates to a novel oxime ester compound useful as a polymerization initiator used in a polymerizable composition, a polymerization initiator containing the oxime ester compound, a polymerization composition containing the polymerization initiator and an ethylenically unsaturated compound. Product, a colored polymerizable resin composition obtained by further adding a coloring material to the polymerizable composition, and a cured product obtained from the polymerizable composition or the colored polymerizable resin composition.

The polymerizable composition is obtained by adding a polymerization initiator to an ethylenically unsaturated compound and can be polymerized and cured by irradiating energy rays (light). Therefore, a photocurable ink, a photosensitive printing plate, Used in various photoresists.

Patent Documents 1 to 3 propose using an oxime ester compound as a polymerization initiator used in the polymerizable composition.
On the other hand, in recent years, a highly transparent cured product obtained from a polymerizable composition has been demanded in the market. However, there is a problem that there is no polymerization initiator that is highly soluble in a solvent and is a highly sensitive polymerization initiator, and can obtain a cured product with high transparency.

US6596445 (B1) WO2013008652 pamphlet US2006 / 241259 A1

The problem to be solved by the present invention is that there has never been a polymerization initiator that has a high solubility in a solvent and is a highly sensitive polymerization initiator and can obtain a cured product with high transparency. It is.

Therefore, an object of the present invention is to provide a novel compound that is highly soluble in a solvent and useful as a highly sensitive polymerization initiator, a polymerization initiator using the compound, a polymerizable composition containing the polymerization initiator, And it is providing the hardened | cured material which is excellent in transparency.

The present invention achieves the above object by providing a novel oxime ester compound represented by the following general formula (I) and a polymerization initiator containing the oxime ester compound.

（式中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７、Ｒ^８、Ｒ^９及びＲ^１０（以下、Ｒ^１～Ｒ^１０とも記載）は、それぞれ独立に、下記一般式（ＩＩ）で表される基、水素原子、ハロゲン原子、ニトロ基、ニトリル基、シアノ基、水酸基、カルボキシル基、ホルミル基、スルホ基、Ｒ^１３、ＯＲ^１３、ＳＲ^１３、ＮＲ^１４Ｒ^１５、ＣＯＲ^１３、ＳＯＲ^１３、ＳＯ_２Ｒ^１３又はＣＯＮＲ^１４Ｒ^１５を表し、
　Ｒ^１３、Ｒ^１４及びＲ^１５は、それぞれ独立に、炭素原子数１～２０の炭化水素基又は炭素原子数２～２０の複素環含有基を表し、
　Ｒ^１３、Ｒ^１４及びＲ^１５で表される炭素原子数１～２０の炭化水素基又は炭素原子数２～２０の複素環含有基の水素原子は、下記一般式（ＩＩ）で表される基、ニトリル基、ハロゲン原子、ニトロ基、シアノ基、水酸基、アミノ基、カルボキシル基、メタクリロイル基、アクリロイル基、エポキシ基、ビニル基、ビニルエーテル基、メルカプト基、イソシアネート基又は複素環含有基で置換される場合があり、Ｒ^１３、Ｒ^１４及びＲ^１５で表される炭素原子数２～２０の炭化水素基又は炭素原子数２～２０の複素環含有基中のメチレン基は－Ｏ－、－ＣＯ－、－ＣＯＯ－、－ＯＣＯ－、－ＮＲ^１６－、－ＮＲ^１６ＣＯ－、－Ｓ－、－ＳＯ_２－、－ＳＣＯ－又は－ＣＯＳ－で置換される場合もあり、
　Ｒ^１６は、水素原子、炭素原子数１～２０の炭化水素基を表し、
　Ｒ^１１及びＲ^１２は、それぞれ独立に水素原子、ハロゲン原子、ニトロ基、シアノ基、炭素原子数１～２０の炭化水素基又は炭素原子数２～２０の複素環含有基を表し、
　Ｒ^１１及びＲ^１２で表される炭素原子数１～２０の炭化水素基又は炭素原子数２～２０の複素環含有基の水素原子はハロゲン原子、ニトロ基、シアノ基、水酸基、アミノ基、カルボキシル基、メタクリロイル基、アクリロイル基、エポキシ基、ビニル基、ビニルエーテル基、メルカプト基、イソシアネート基又は複素環含有基で置換される場合があり、Ｒ^１１及びＲ^１２で表される炭素原子数１～２０の炭化水素基又は炭素原子数２～２０の複素環含有基中のメチレン基は－Ｏ－、－ＣＯ－、－ＣＯＯ－、－ＯＣＯ－、－ＮＲ^１７－、－ＮＲ^１７ＣＯ－、－Ｓ－、－ＳＯ_２－、－ＳＣＯ－又は－ＣＯＳ－で置換される場合もあり、
　Ｒ^１７は、水素原子、炭素原子数１～２０の炭化水素基を表し、
　Ｒ^１～Ｒ^１０のうち少なくとも一つが、下記一般式（ＩＩ）で表される基であり、
　Ｒ^２とＲ^３、Ｒ^３とＲ^４、Ｒ^４とＲ^５、Ｒ^６とＲ^７、Ｒ^７とＲ^８、Ｒ^８とＲ^９及びＲ^９とＲ^１０が結合して環を形成する場合もあり、
　ｍは０又は１を表す。）

（式中、Ｒ^２１及びＲ^２２は、それぞれ独立に水素原子、ハロゲン原子、ニトロ基、シアノ基、炭素原子数１～２０の炭化水素基又は炭素原子数２～２０の複素環含有基を表し、
　Ｒ^２１及びＲ^２２で表される炭素原子数１～２０の炭化水素基又は炭素原子数２～２０の複素環含有基の水素原子はハロゲン原子、ニトロ基、シアノ基、水酸基、アミノ基、カルボキシル基、メタクリロイル基、アクリロイル基、エポキシ基、ビニル基、ビニルエーテル基、メルカプト基、イソシアネート基又は複素環含有基で置換される場合があり、Ｒ^２１及びＲ^２２で表される炭素原子数１～２０の炭化水素基又は炭素原子数２～２０の複素環含有基中のメチレン基は－Ｏ－、－ＣＯ－、－ＣＯＯ－、－ＯＣＯ－、－ＮＲ^２３－、－ＮＲ^２３ＣＯ－、－Ｓ－、－ＳＯ_２－、－ＳＣＯ－又は－ＣＯＳ－で置換される場合もあり、
　Ｒ^２３は、水素原子、炭素原子数１～２０の炭化水素基を表し、
　ｎは０又は１を表す。）

(Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ (hereinafter also referred to as R ¹ to R ¹⁰ ) are each independently Groups represented by the following general formula (II), hydrogen atom, halogen atom, nitro group, nitrile group, cyano group, hydroxyl group, carboxyl group, formyl group, sulfo group, R ¹³ , OR ¹³ , SR ¹³ , NR ¹⁴ R ¹⁵ , COR ¹³ , SOR ¹³ , SO ₂ R ¹³ or CONR ¹⁴ R ¹⁵ ,
R ¹³ , R ¹⁴ and R ¹⁵ each independently represents a hydrocarbon group having 1 to 20 carbon atoms or a heterocyclic group having 2 to 20 carbon atoms,
The hydrogen atom of the hydrocarbon group having 1 to 20 carbon atoms or the heterocyclic group having 2 to 20 carbon atoms represented by R ¹³ , R ¹⁴ and R ¹⁵ is a group represented by the following general formula (II) Substituted with nitrile group, halogen atom, nitro group, cyano group, hydroxyl group, amino group, carboxyl group, methacryloyl group, acryloyl group, epoxy group, vinyl group, vinyl ether group, mercapto group, isocyanate group or heterocyclic group-containing group In some cases, the methylene group in the hydrocarbon group having 2 to 20 carbon atoms or the heterocyclic group having 2 to 20 carbon atoms represented by R ¹³ , R ¹⁴ and R ¹⁵ is —O—, —CO—. , —COO—, —OCO—, —NR ¹⁶ —, —NR ¹⁶ CO—, —S—, —SO ₂ —, —SCO— or —COS— may be substituted,
R ¹⁶ represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms,
R ¹¹ and R ¹² each independently represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydrocarbon group having 1 to 20 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms,
The hydrogen atom of the hydrocarbon group having 1 to 20 carbon atoms or the heterocyclic group having 2 to 20 carbon atoms represented by R ¹¹ and R ¹² is a halogen atom, nitro group, cyano group, hydroxyl group, amino group, carboxyl Group, methacryloyl group, acryloyl group, epoxy group, vinyl group, vinyl ether group, mercapto group, isocyanate group or heterocyclic group-containing group, and may have 1 to 20 carbon atoms represented by R ¹¹ and R ¹² The methylene group in the hydrocarbon group or the heterocyclic group having 2 to 20 carbon atoms is —O—, —CO—, —COO—, —OCO—, —NR ¹⁷ —, —NR ¹⁷ CO—, —S _{-, - SO 2 -, -} SCO- or -COS- in some cases be substituted,
R ¹⁷ represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms,
At least one of R ¹ to R ¹⁰ is a group represented by the following general formula (II):
When R ² and R ³ , R ³ and R ⁴ , R ⁴ and R ⁵ , R ⁶ and R ⁷ , R ⁷ and R ⁸ , R ⁸ and R ⁹ and R ⁹ and R ¹⁰ combine to form a ring There is also
m represents 0 or 1; )

(Wherein R ²¹ and R ²² each independently represent a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydrocarbon group having 1 to 20 carbon atoms, or a heterocyclic-containing group having 2 to 20 carbon atoms) ,
The hydrogen atom of the hydrocarbon group having 1 to 20 carbon atoms or the heterocyclic group having 2 to 20 carbon atoms represented by R ²¹ and R ²² is a halogen atom, nitro group, cyano group, hydroxyl group, amino group, carboxyl May be substituted with a group, a methacryloyl group, an acryloyl group, an epoxy group, a vinyl group, a vinyl ether group, a mercapto group, an isocyanate group or a heterocyclic group, and the number of carbon atoms represented by R ²¹ and R ²² is 1 to 20 The methylene group in the hydrocarbon group or the heterocyclic group having 2 to 20 carbon atoms is —O—, —CO—, —COO—, —OCO—, —NR ²³ —, —NR ²³ CO—, —S _{-, - SO 2 -, -} SCO- or -COS- in some cases be substituted,
R ²³ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms,
n represents 0 or 1. )

Moreover, this invention provides the polymeric composition containing the said polymerization initiator and an ethylenically unsaturated compound.
Moreover, this invention provides the colored polymeric composition containing the said polymeric composition and a coloring material.

Further, the present invention provides a cured product obtained from the polymerizable composition or the colored polymerizable composition.

The present invention also provides a color filter having the cured product.

Hereinafter, the oxime ester compound of the present invention and the polymerization initiator containing the compound will be described in detail based on preferred embodiments.

The oxime ester compound of the present invention is a novel compound represented by the above general formula (I). The oxime ester compound has geometric isomers due to oxime double bonds, but these are not distinguished.
That is, in the present specification, the compound represented by the above general formula (I) and the exemplified compound thereof represent a mixture of both or one of them, and are not limited to structures showing isomers.

The hydrocarbon group having 1 to 20 carbon atoms represented by R ¹¹ to R ¹⁷ and R ²¹ to R ²³ in the general formulas (I) and (II) is not particularly limited, An alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, a cycloalkylalkyl group having 4 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and 7 to 20 carbon atoms. Represents an arylalkyl group or the like;

Examples of the alkyl group having 1 to 20 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, amyl, isoamyl, t-amyl, hexyl, heptyl, octyl, isooctyl. 2-ethylhexyl, t-octyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, tetradecyl, hexadecyl, octadecyl, icosyl and the like.

The above cycloalkyl group having 3 to 20 carbon atoms means a saturated monocyclic or saturated polycyclic alkyl group having 3 to 20 carbon atoms. Examples include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, adamantyl, decahydronaphthyl, octahydropentalene and bicyclo [1.1.1] pentanyl.

The cycloalkylalkyl group having 4 to 20 carbon atoms means a group having 4 to 20 carbon atoms in which at least one hydrogen atom of the alkyl group is substituted with a cycloalkyl group. Examples include cyclopropylmethyl, cyclobutylethyl, cyclopentylpropyl, cyclohexylbutyl, cycloheptylmethyl, cyclooctylmethyl, cyclononylethyl, cyclodecylethyl, adamantylpropyl and decahydronaphthylpropyl.

Examples of the aryl group having 6 to 20 carbon atoms include phenyl, tolyl, xylyl, ethylphenyl, naphthyl, anthryl, phenanthrenyl, phenyl, biphenylyl, naphthyl, anthryl substituted with one or more of the above alkyl groups. It is done.

The arylalkyl group having 7 to 20 carbon atoms means a group having 7 to 20 carbon atoms in which a hydrogen atom of the alkyl group is substituted with an aryl group. Examples include benzyl, α-methylbenzyl, α, α-dimethylbenzyl, phenylethyl and naphthylpropyl.

Examples of the heterocyclic group containing 2 to 20 carbon atoms represented by R ¹¹ to R ¹⁵ , R ²¹ and R ²² in the general formulas (I) and (II) include, for example, pyrrolyl, pyridyl, pyridylethyl. , Pyrimidyl, pyridazyl, piperazyl, piperidyl, pyranyl, pyranylethyl, pyrazolyl, triazyl, triazylmethyl, pyrrolidyl, quinolyl, isoquinolyl, imidazolyl, benzimidazolyl, triazolyl, furyl, furanyl, benzofuranyl, thienyl, thiophenyl, benzothiophenyl, thiadiazolyl, thiazolyl , Benzothiazolyl, oxazolyl, benzoxazolyl, isothiazolyl, isoxazolyl, indolyl, urolidyl, morpholinyl, thiomorpholinyl, 2-pyrrolidinon-1-yl, 2-piperidone-1- Le, 2,4-oxy-imidazolidin-3-yl and 2,4-dioxy-oxazolidinedione-3-yl, and the like.

As the halogen atom in the general formulas (I) and (II), fluorine, chlorine, bromine and iodine can be mentioned.

Rings formed by combining R ² and R ³ , R ³ and R ⁴ , R ⁴ and R ⁵ , R ⁶ and R ⁷ , R ⁷ and R ⁸ , R ⁸ and R ⁹ and R ⁹ and R ¹⁰ For example, 5 to 7 members such as cyclopentane ring, cyclohexane ring, cyclopentene ring, benzene ring, pyrrolidine ring, pyrrole ring, piperazine ring, piperidine ring, morpholine ring, thiomorpholine ring, tetrahydropyridine ring, lactone ring, lactam ring, etc. Examples thereof include condensed rings such as a ring, a naphthalene ring and an anthracene ring.

The oxime ester compound in which at least one of R ² to R ^{5 in} the general formula (I) is a group represented by the general formula (II) has a good absorption wavelength and high sensitivity when used as a polymerization initiator. This is preferable. Furthermore, it is more preferable that at least one of R ³ and R ⁸ is a group represented by the general formula (II) because synthesis is easy and the stability of the oxime ester compound is good. Further, when R ⁸ is a group represented by the general formula (II), when used as a polymerization initiator of the polymerizable composition, the cured product obtained from the polymerized composition has high transparency and coloring. Most preferable because it is less.

The oxime ester compound in which at least one of R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ^{10 in} the general formula (I) is an electron-withdrawing group has high sensitivity when used as a polymerization initiator. This is preferable.

Examples of the electron withdrawing group include a halogen atom, a cyano group, a nitro group, a benzoyl group, a carboxyl group, a trifluoromethyl group, a formyl group, and a sulfo group. Among these, the case of at least one selected from the group consisting of a halogen atom, a cyano group, a nitro group, a benzoyl group, a carboxyl group, and a trifluoromethyl group is preferable because of higher sensitivity.

When an oxime ester compound in which m = 1 in the general formula (I) is used as a polymerization initiator of the polymerization composition, the obtained cured product is preferable because of excellent transparency.

An oxime ester compound in which R ¹¹ in the general formula (I) is an alkyl group having 4 to 20 carbon atoms is converted into an ether ester solvent represented by PGMEA (propylene glycol-1-monomethyl ether-2-acetate). It is preferable because of its high solubility. The hydrogen atom of the alkyl group having 4 to 20 carbon atoms may be substituted with an aryl group. Examples of the alkyl group having 4 to 20 carbon atoms include those having 4 to 20 carbon atoms in the alkyl group exemplified as the aforementioned hydrocarbon group having 1 to 20 carbon atoms.

The oxime ester compound in which R ¹² in the general formula (I) is a methyl group is preferable because it has high sensitivity when used as a polymerization initiator.

Preferred examples of the oxime ester compound of the present invention represented by the above general formula (I) include the following compound No. 1-No. 128. However, the present invention is not limited by the following compounds.

Among the oxime ester compounds, R ³ or R ⁸ in the general formula (I) is a group represented by the general formula (II), R ¹² is a methyl group, and R ¹¹ has 4 to 20 carbon atoms. The oxime ester compound, which is an alkyl group, is easy to synthesize, is stable, has high solubility in various solvents, and has a good absorption wavelength when used as a polymerization initiator. It is more preferable because of high sensitivity and transparency of the cured product and less coloring.
Specifically, as the oxime ester compound of the present invention, the above compound No. 1 is used. 1-No. 90 etc. are preferable.

The oxime ester compound of the present invention represented by the general formula (I) is not particularly limited, but when m = 0, for example, it can be produced by the following method according to the following reaction formula [Chemical Formula 17]. .
That is, a known and commercially available indole compound 1 is reacted with an aryl halide to obtain indole compound 2, and indole compound 2 is reacted with acid chloride to obtain ketone compound 1, and ketone compound 1 and hydrochloric acid are obtained. Oxime compound 1 is obtained by reacting hydroxylamine. Subsequently, the oxime compound 1 of the present invention represented by the above general formula (I) is obtained by reacting the oxime compound 1 with an acid anhydride or acid chloride.
The oxime compound and the oxime ester compound can also be produced by the method described in Japanese Patent No. 4223071.

When m = 1, the oxime ester compound of the present invention represented by the above general formula (I) can be produced by the following method according to the following reaction formula [Chemical Formula 18].
That is, a known and commercially available indole compound 1 and an aryl halide are reacted to obtain indole compound 2, and indole compound 2 and acid chloride are reacted to obtain ketone compound 2, and By reacting isobutyl nitrate, oxime compound 2 is obtained. Subsequently, by reacting the oxime compound 2 with an acid anhydride or acid chloride, the oxime ester compound 2 of the present invention represented by the above general formula (I) is obtained.

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

The polymerization initiator of the present invention contains the oxime ester compound of the present invention represented by the general formula (I) as an essential component. Moreover, the polymerization initiator of this invention can use another polymerization initiator together with the oxime ester compound of this invention. As other polymerization initiators that can be used in combination, conventionally known compounds can be used. For example, benzophenone, phenylbiphenyl ketone, 1-hydroxy-1-benzoylcyclohexane, benzoin, benzyldimethyl ketal, 1-benzyl-1 -Dimethylamino-1- (4'-morpholinobenzoyl) propane, 2-morpholy-2- (4'-methylmercapto) benzoylpropane, thioxanthone, 1-chloro-4-propoxythioxanthone, isopropylthioxanthone, diethylthioxanthone, ethylanthraquinone 4-benzoyl-4′-methyldiphenyl sulfide, benzoin butyl ether, 2-hydroxy-2-benzoylpropane, 2-hydroxy-2- (4′-isopropyl) benzoylpropane, 4-buty Rubenzoyltrichloromethane, 4-phenoxybenzoyldichloromethane, methyl benzoylformate, 1,7-bis (9′-acridinyl) heptane, 9-n-butyl-3,6-bis (2′-morpholinoisobutyroyl) carbazole, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2-naphthyl-4,6-bis (trichloromethyl)- s-triazine, 2,2-bis (2-chlorophenyl) -4,5,4 ', 5'-tetraphenyl-1-2'-biimidazole, 4,4-azobisisobutyronitrile, triphenylphosphine , Camphorquinone, N-1414, N-1717, N-1919, NCI-831, NCI-930 (made by ADEKA), RGACURE369, IRGACURE907, IRGACURE OXE 01, IRGACURE OXE 02 (manufactured by BASF) and benzoyl peroxide and the like, these other polymerization initiators may be used singly or in combination of two or more kinds.

The content of the oxime ester compound of the present invention in the polymerization initiator of the present invention is preferably 30 to 100% by mass, more preferably 50 to 100% by mass.

The polymerizable composition of the present invention contains the polymerization initiator and an ethylenically unsaturated compound as essential components.

The ethylenically unsaturated compound is not particularly limited, and those conventionally used in polymerizable compositions can be used. Examples thereof include ethylene, propylene, butylene, isobutylene, vinyl chloride, vinylidene chloride, and fluorine. Unsaturated aliphatic hydrocarbons such as vinylidene fluoride and tetrafluoroethylene; (meth) acrylic acid, α-chloroacrylic acid, itaconic acid, maleic acid, citraconic acid, fumaric acid, hymic acid, crotonic acid, isocrotonic acid, vinylacetic acid Allylic acetic acid, cinnamic acid, sorbic acid, mesaconic acid, succinic acid mono [2- (meth) acryloyloxyethyl], phthalic acid mono [2- (meth) acryloyloxyethyl], ω-carboxypolycaprolactone mono ( Mono (meth) of a polymer having a carboxy group and a hydroxyl group at both ends, such as (meth) acrylate ) Acrylate; hydroxyethyl (meth) acrylate malate, hydroxypropyl (meth) acrylate malate, dicyclopentadiene malate or polyfunctional (meth) having one carboxyl group and two or more (meth) acryloyl groups Unsaturated polybasic acids such as acrylate; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, glycidyl (meth) acrylate, the following compound No. A1-No. A4, methyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, cyclohexyl (meth) acrylate, n-octyl (meth) acrylate, ( Isooctyl (meth) acrylate, isononyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, methoxyethyl (meth) acrylate, dimethylaminomethyl (meth) acrylate, dimethyl (meth) acrylate Aminoethyl, aminopropyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, ethoxyethyl (meth) acrylate, poly (ethoxy) ethyl (meth) acrylate, butoxyethoxyethyl (meth) acrylate, (meta ) Ethylhexyl acrylate, (meth) acrylic acid Phenoxyethyl, tetrahydrofuryl (meth) acrylate, vinyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol Di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, trimethylolethanetri (Meth) acrylate, trimethylolpropane tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, pentaerythritol Unsaturated monobasic acids such as tra (meth) acrylate, pentaerythritol tri (meth) acrylate, tricyclodecane dimethylol di (meth) acrylate, tri [(meth) acryloylethyl] isocyanurate, polyester (meth) acrylate oligomers and the like Esters of polyhydric alcohols or polyphenols; metal salts of unsaturated polybasic acids such as zinc (meth) acrylate and magnesium (meth) acrylate; maleic anhydride, itaconic anhydride, citraconic anhydride, methyl Tetrahydrophthalic anhydride, tetrahydrophthalic anhydride, trialkyltetrahydrophthalic anhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trialkyltetrahydro Phthalic anhydride-anhydrous Acid anhydrides of unsaturated polybasic acids such as rain acid adducts, dodecenyl succinic anhydride, methyl hymic anhydride; (meth) acrylamide, methylene bis- (meth) acrylamide, diethylenetriamine tris (meth) acrylamide, xylylene bis (meth) Unsaturated monobasic acids such as acrylamide, α-chloroacrylamide, N-2-hydroxyethyl (meth) acrylamide and amides of polyvalent amines; unsaturated aldehydes such as acrolein; (meth) acrylonitrile, α-chloroacrylonitrile, cyanide Unsaturated nitriles such as vinylidene and allyl cyanide; styrene, 4-methylstyrene, 4-ethylstyrene, 4-methoxystyrene, 4-hydroxystyrene, 4-chlorostyrene, divinylbenzene, vinyltoluene, vinylbenzoic acid, vinyl Unsaturated aromatic compounds such as ruphenol, vinyl sulfonic acid, 4-vinyl benzene sulfonic acid, vinyl benzyl methyl ether, vinyl benzyl glycidyl ether; unsaturated ketones such as methyl vinyl ketone; vinyl amine, allyl amine, N-vinyl pyrrolidone, vinyl Unsaturated amine compounds such as piperidine; vinyl alcohols such as allyl alcohol and crotyl alcohol; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, n-butyl vinyl ether, isobutyl vinyl ether, allyl glycidyl ether; maleimide, N-phenylmaleimide, N -Unsaturated imides such as cyclohexylmaleimide; Indenes such as indene and 1-methylindene; Aliphatic conjugated dienes such as 1,3-butadiene, isoprene and chloroprene Macromolecules having a mono (meth) acryloyl group at the end of the polymer molecular chain such as polystyrene, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate, polysiloxane, etc .; vinyl chloride, vinylidene chloride, divinyls Cuccinate, diallyl phthalate, triallyl phosphate, triallyl isocyanurate, vinyl thioether, vinyl imidazole, vinyl oxazoline, vinyl carbazole, vinyl pyrrolidone, vinyl pyridine, hydroxyl group-containing vinyl monomers and vinyl isocyanate compounds of polyisocyanate compounds, hydroxyl groups Examples thereof include vinyl monomers containing vinyl monomers and polyepoxy compounds.
Among these, a mono (meth) acrylate of a polymer having a carboxy group and a hydroxyl group at both ends, a polyfunctional (meth) acrylate having one carboxy group and two or more (meth) acryloyl groups, an unsaturated one A polymerization initiator containing the oxime ester compound of the present invention in an ester of a basic acid and a polyhydric alcohol or polyhydric phenol is suitable.
These ethylenically unsaturated compounds can be used alone or in admixture of two or more, and when used in admixture of two or more, they are copolymerized in advance as a copolymer. May be used.

In addition, an ethylenically unsaturated compound having an acid group such as a carboxyl group (hereinafter also referred to as a compound having alkali developability) can be used for the purpose of imparting alkali developability to the polymerizable composition of the present invention. The compound having alkali developability is not particularly limited as long as it is soluble in an aqueous alkali solution. For example, resins described in JP-A No. 2004-264414, copolymers of acrylic acid esters, phenols, cresol novolac epoxy resins Examples thereof include resins obtained by further allowing polybasic acid anhydrides to act on polyphenylmethane type epoxy resins having polyfunctional epoxy groups, epoxy acrylate resins and epoxy acrylate resins.

Commercially available products can be used as the ethylenically unsaturated compound, such as Kayrad DPHA, DPEA-12, PEG400DA, THE-330, RP-1040, NPGDA, PET30 (manufactured by Nippon Kayaku), SPC-1000, SPC. -3000 (manufactured by Showa Denko), Aronix M-140, M-215, M-350, M-450 (manufactured by Toagosei), NK ester A-DPHA-TMPT, A-DCP, A-HD-N, A- 9300, TMPT, DCP, NPG and HD-N (manufactured by Shin-Nakamura Chemical Co., Ltd.).

The content of the polymerization initiator used in the polymerizable composition of the present invention is not particularly limited, but is preferably 0.5 to 70 parts by mass with respect to 100 parts by mass of the ethylenically unsaturated compound. More preferably, it is 0.5 to 50 parts by mass, and most preferably 0.5 to 30 parts by mass.

The colored polymerizable composition of the present invention contains the polymerizable composition and a coloring material.

Examples of the coloring material include pigments, dyes, and natural pigments. These color materials can be used alone or in admixture of two or more.

Examples of the pigment include a nitroso compound; a nitro compound; an azo compound; a diazo compound; a xanthene compound; a quinoline compound; an anthraquinone compound; a coumarin compound; a phthalocyanine compound; an isoindolinone compound; an isoindolinone compound; Compound; perylene compound; diketopyrrolopyrrole compound; thioindigo compound; dioxazine compound; triphenylmethane compound; quinophthalone compound; naphthalene tetracarboxylic acid; azo dye, metal complex compound of cyanine dye; lake pigment; furnace method, channel method or thermal Carbon black obtained by the method, or carbon black such as acetylene black, ketjen black or lamp black; Prepared by coating or coating with epoxy resin, carbon black previously dispersed in a resin in a solvent and adsorbed with 20 to 200 mg / g of resin, carbon black treated with an acidic or alkaline surface, average Graphite having a particle size 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 a volatile content at 950 ° C. of 9 mg or more per 100 m ² of the surface area of carbon black; Graphite , Graphitized carbon black, activated carbon, carbon fiber, carbon nanotube, carbon microcoil, carbon nanohorn, carbon aerogel, fullerene; aniline black, pigment black 7, titanium black; chromium oxide green, miloli blue, cobalt green, cobalt blue, manganese series , Ferrocyanide Organic or inorganic such as phosphate ultramarine, bitumen, ultramarine, cerulean blue, pyridian, emerald green, lead sulfate, yellow lead, zinc yellow, red bean (red iron (III) oxide), cadmium red, synthetic iron black, amber Pigments can be used. These pigments can be used alone or in combination.

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, 220, 223, 224, 226, 227, 228, 240, 254; Pigment Orange 13, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 65, 71; Pigment Yellow 1, 3, 12, 13, 14, 16, 17, 20, 24, 55, 60, 73, 81, 83, 86, 93, 95, 9 98, 100, 109, 110, 113, 114, 117, 120, 125, 126, 127, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 166, 168, 175 , 180, 185; Pigment Green 7, 10, 36; Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 5, 15: 6, 22, 24, 56, 60 61, 62, 64; Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 50, and the like.

As the above dyes, 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, oxazine dyes, phthalocyanine dyes And dyes such as cyanine dyes, and a plurality of these may be used in combination.

In the colored polymerizable composition of the present invention, the content of the coloring material is preferably 50 to 350 parts by mass, more preferably 100 to 250 parts by mass with respect to 100 parts by mass of the ethylenically unsaturated compound.

If necessary, a solvent capable of dissolving or dispersing the polymerization initiator, the ethylenically unsaturated compound, and the coloring material can be added to the polymerizable composition and the colored polymerizable composition. For example, ketones such as methyl ethyl ketone, methyl amyl ketone, diethyl ketone, acetone, methyl isopropyl ketone, methyl isobutyl ketone, cyclohexanone, 2-heptanone; ethyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-di Ether solvents such as ethoxyethane, dipropylene glycol dimethyl ether and propylene glycol monomethyl ether (PGM); methyl acetate, ethyl acetate, acetic acid-n-propyl, isopropyl acetate, n-butyl acetate, cyclohexyl acetate, ethyl lactate, dimethyl succinate Ester solvents such as texanol; cellosolve solvents such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; methanol, ethanol, iso- Is an alcohol solvent such as n-propanol, iso- or n-butanol, amyl alcohol; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol-1-monomethyl ether-2-acetate, dipropylene glycol monomethyl ether Ether ester solvents such as acetate, 3-methoxybutyl ether acetate and ethoxyethyl ether propionate; BTX solvents such as benzene, toluene and xylene; Aliphatic hydrocarbon solvents such as hexane, heptane, octane and cyclohexane; Terpene hydrocarbon oils such as D-limonene and pinene; mineral spirits, Swazol # 310 (Cosmo Matsuyama Oil), Solvesso # 100 (Exxon Chemical) Paraffinic solvents such as carbon tetrachloride, chloroform, trichloroethylene, methylene chloride, 1,2-dichloroethane and other halogenated aliphatic hydrocarbon solvents; chlorobenzene and other halogenated aromatic hydrocarbon solvents; carbitol solvents; Aniline, triethylamine, pyridine, acetic acid, acetonitrile, carbon disulfide, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, water, and the like. It can be used as a mixed solvent of seeds or more.
Among these, ketones and ether ester solvents, etc., particularly cyclohexanone and PGMEA are preferable in the polymerizable composition because the compatibility between the ethylenically unsaturated compound and the polymerization initiator is good.

As long as the effects of the present invention are not impaired, the polymerizable composition and the colored polymerizable composition of the present invention include, if necessary, a polymer excluding an ethylenically unsaturated compound (hereinafter also referred to as a polymer), an inorganic compound, and a dispersant. , Chain transfer agent, sensitizer excluding oxime ester compound of the present invention (hereinafter also referred to as sensitizer), surfactant, silane coupling agent, melamine, leveling agent, latent additive, ethylenically unsaturated compound Monomers to be removed, antifoaming agents, thickeners, thixotropic agents, flame retardants, plasticizers, stabilizers, polymerization inhibitors, UV absorbers, organic fillers, antioxidants, antistatic agents, flow regulators and adhesion promoters Various resin additives such as can be added.

The characteristics of the cured product can be improved by using the polymer together with the ethylenically unsaturated compound. Examples of the polymer include polystyrene, polymethyl methacrylate, methyl methacrylate-ethyl acrylate copolymer, poly (meth) acrylic acid, styrene- (meth) acrylic acid copolymer, (meth) acrylic acid-methyl methacrylate copolymer. Polymer, 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, Examples include phenol resin, phenoxy resin, polyamideimide resin, polyamic acid resin, and epoxy resin. Among these, polystyrene, (meth) acrylic acid-methyl methacrylate copolymer, and epoxy resin are preferred. There.

In the polymerizable composition and colored polymerizable composition of the present invention, the content of the polymer is preferably 0 to 500 parts by mass with respect to 100 parts by mass of the ethylenically unsaturated compound.

Examples of the inorganic compound include nickel oxide, iron oxide, iridium oxide, titanium oxide, zinc oxide, magnesium oxide, calcium oxide, potassium oxide, silica, alumina, and other metal oxides; layered clay mineral, miloli blue, calcium carbonate, Magnesium carbonate, cobalt, manganese, glass powder (especially glass frit), mica, talc, kaolin, ferrocyanide, various metal sulfates, sulfides, selenides, aluminum silicate, calcium silicate, aluminum hydroxide, platinum, Gold, silver, copper, etc. are mentioned.
Among these, glass frit, titanium oxide, silica, layered clay mineral, silver and the like are preferable.

These inorganic compounds are used, for example, as fillers, antireflection agents, conductive agents, stabilizers, flame retardants, mechanical strength improvers, special wavelength absorbers, ink repellents, and the like.

In the polymerizable composition and colored polymerizable composition of the present invention, the content of the inorganic compound is preferably 0 to 1000 parts by mass, more preferably 0 to 800 parts per 100 parts by mass of the ethylenically unsaturated compound. Part by mass. These inorganic compounds can be used alone or in combination of two or more.

The dispersing agent is not limited as long as it can disperse and stabilize a coloring material or an inorganic compound, and a commercially available dispersing agent, for example, BYK series manufactured by BYK Chemie can be used. In particular, a polymer dispersant comprising a polyester, polyether, or polyurethane having a basic functional group, a nitrogen atom as the basic functional group, and the functional group having a nitrogen atom is an amine and / or a quaternary salt thereof. And those having an amine value of 1 to 100 mgKOH / g are preferably used.

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-mercaptoethanesulfonic acid, 3-mercaptopropanesulfonic acid, 4-mercaptobutanesulfonic acid, dodecyl (4-methylthio) phenyl ether, 2-mercaptoethanol, 3-mercapto-1,2-propanediol, 1-mercapto-2-propanol, 3-mercapto-2-butanol, mercaptophenol , 2-me Captoethylamine, 2-mercaptoimidazole, 2-mercaptobenzimidazole, 2-mercapto-3-pyridinol, 2-mercaptobenzothiazole, mercaptoacetic acid, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3- Mercapto compounds such as mercaptopropionate), disulfide compounds obtained by oxidizing the mercapto compound, iodoacetates such as iodoacetic acid, iodopropionic acid, 2-iodoethanol, 2-iodoethanesulfonic acid, 3-iodopropanesulfonic acid, etc. Alkyl compounds, trimethylolpropane tris (3-mercaptoisobutyrate), butanediol bis (3-mercaptoisobutyrate), hexanedithiol, decanedithiol, 1,4- Methyl mercaptobenzene, butanediol bisthiopropionate, butanediol bisthioglycolate, ethylene glycol bisthioglycolate, trimethylolpropane tristhioglycolate, butanediol bisthiopropionate, trimethylolpropane tristhiopropionate , Trimethylolpropane tristhioglycolate, pentaerythritol tetrakisthiopropionate, pentaerythritol tetrakisthioglycolate, trishydroxyethyltristhiopropionate, diethylthioxanthone, diisopropylthioxanthone, the following compound No. C1, aliphatic polyfunctional thiol compounds such as trimercaptopropionic acid tris (2-hydroxyethyl) isocyanurate, Showa Denko Karenz MT BD1, PE1, NR1 and the like.

Examples of the surfactant include fluorine surfactants such as perfluoroalkyl phosphates and perfluoroalkyl carboxylates; anionic surfactants such as higher fatty acid alkali salts, alkyl sulfonates, and alkyl sulfates; higher amines Cationic surfactants such as halogenates 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; silicone surfactants Surfactants such as agents 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. Among them, silanes having an isocyanate group, a methacryloyl group, or an epoxy group, such as KBE-9007, KBM-502, and KBE-403. A coupling agent is preferably used.

Examples of the melamine compound include all or part of active methylol groups (CH ₂ OH groups) in nitrogen compounds such as (poly) methylol melamine, (poly) methylol glycoluril, (poly) methylol benzoguanamine, and (poly) methylol urea. Examples include compounds in which (at least two) are alkyl etherified.
Here, examples of the alkyl group constituting the alkyl ether include a methyl group, an ethyl group, and a butyl group, which may be the same as or different from each other, and are methylol groups that are not alkyl etherified. May be self-condensed within one molecule or may be condensed between two molecules, resulting in the formation of an oligomer component.
Specifically, hexamethoxymethyl melamine, hexabutoxymethyl melamine, tetramethoxymethyl glycoluril, tetrabutoxymethyl glycoluril and the like can be used.
Among these, alkyl etherified melamines such as hexamethoxymethyl melamine and hexabutoxymethyl melamine are preferable.

Commercially available products can be used as the leveling agent. Examples of commercially available leveling agents include BYK-300, BYK-301, BYK-302, BYK-306, BYK-307, BYK-310, BYK-313, BYK-315, BYK-320, BYK-322, BYK-323, BYK-325, BYK-330, BYK-331, BYK-333, BYK-337, BYK-341, BYK-344, BYK-345, BYK-346, BYK-347, BYK-348, BYK- 349, BYK-370, BYK-375, BYK-377, BYK-378, BYK-UV3500, BYK-UV3510, BYK-UV3570, BYK-340, BYK-3550, BYK-SILCLEAN3700, BYK-SILCLEAN3720, BYK-DYNET Tsu-made click Chemie Japan) Polyflow No. 3, Polyflow No. 50HF, Polyflow No. 54, Polyflow No. 64HF, Polyflow No. 75, Polyflow No. 77, Polyflow No. 85HF, Polyflow No. 90, polyflow no. 95, Polyflow No. ATF-2, Granol 100, Granol 115, Granol 400, Granol 410, Granol 420, Granol 440, Granol 450, Granol B-1484 (manufactured by Kyoeisha Chemical), L-7001, L-7002, L-7006, 56ADDITIVE, 57ADDITIVE 67ADDITIVE, 8032ADDITIVE, FZ-2105, FZ-2110, FZ-2122 and FZ-2123 (manufactured by Dow Corning Toray).

The latent additive is inactive at room temperature, in the light exposure step and in the pre-bake step, and is protected at 100 to 250 ° C. or heated at 80 to 200 ° C. in the presence of an acid / base catalyst. Is activated by desorption. Examples of the effects obtained by activation include oxidation prevention, ultraviolet absorption, antifouling property, recoatability and adhesion.
As the latent additive, those described in the pamphlet of WO2014 / 021023 can be preferably used.

As the latent additive, commercially available products can be used, and examples thereof include Adeka Arcles GPA-5001.

In the polymerizable composition and colored polymerizable composition of the present invention, optional components other than the ethylenically unsaturated compound, the oxime ester compound of the present invention and the color material (however, the polymer, inorganic compound, color material and solvent are The amount of (excluding) is appropriately selected according to the purpose of use 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.

The polymerizable composition and colored polymerizable composition of the present invention include a photocurable paint or varnish; a photocurable adhesive; a printing ink; a dental composition; an electronic photoresist; an electroplating resist; Solder resists; and resists for forming structures in LCD manufacturing processes; compositions for encapsulating electrical and electronic components; solder resists; magnetic recording materials; plating masks; etching masks; three-dimensional objects by stereolithography 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; Photoresist material used for dielectric layer formation in sequential lamination of printed circuit boards or Can be used in various applications such as Mamorumaku, there is no particular limitation on the application.

The polymerizable composition and the colored polymerizable composition of the present invention can also be used for the purpose of forming spacers for liquid crystal display panels and for forming protrusions for vertical alignment type liquid crystal display elements. In particular, it is useful as a polymerizable composition and a colored polymerizable composition for simultaneously forming protrusions and spacers for a vertical alignment type liquid crystal display element.

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

The polymerizable composition and colored polymerizable composition of the present invention to which an ink repellent agent is added are useful as a partition-forming resin composition for an ink jet system, and the composition is used for a color filter, and particularly has a profile angle of 50. It is preferably used for a partition for an ink jet type color filter having a temperature equal to or higher than °. As the ink repellent agent, a composition comprising a fluorosurfactant and a fluorosurfactant is preferably used.

The polymerizable composition and the colored polymerizable composition of the present invention can be used as a polymerizable paste composition by containing an inorganic material (inorganic compound). The polymerizable paste composition is used to form a fired product pattern such as a partition pattern, a dielectric pattern, an electrode pattern, and a black matrix pattern of a plasma display panel.

A method for producing a cured product obtained from the polymerizable composition or the colored polymerizable composition of the present invention is described below.

The polymerizable composition or colored polymerizable composition of the present invention is a known method such as spin coater, roll coater, bar coater, die coater, curtain coater, various printing, dipping, soda glass, quartz glass, and semiconductor substrate. It can be applied on a supporting substrate such as metal, paper, and plastic. Moreover, after once applying on support bases, such as a film, it can also transfer on another support base | substrate, There is no restriction | limiting in the application method.

As a light source for energy rays used for curing the polymerizable composition or colored polymerizable composition of the present invention, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a medium pressure mercury lamp, a low pressure mercury lamp, a mercury vapor arc lamp, Xenon arc lamps, carbon arc lamps, metal halide lamps, fluorescent lamps, tungsten lamps, excimer lamps, germicidal lamps, light-emitting diodes, CRT light sources, etc. Although high energy rays such as radiation can be used, preferably, an ultra-high pressure mercury lamp, a mercury vapor arc lamp, a carbon arc lamp, a xenon arc lamp and the like that emit light having a wavelength of 300 to 450 nm are exemplified.

Furthermore, by using laser light as an exposure light source, a laser direct drawing method that directly forms an image from digital information such as a computer without using a mask can be applied. Use of the laser direct drawing method is useful because not only productivity but also resolution and position accuracy can be improved. Laser light with a wavelength of 340 to 430 nm is suitably used as the laser direct drawing method, but excimer laser, nitrogen laser, argon ion laser, helium cadmium laser, helium neon laser, krypton ion laser, various semiconductors Lasers and YAG lasers that emit light in the visible to infrared region are also used. When these lasers are used, a sensitizing dye that absorbs the visible to infrared region is added to the polymerizable composition and the colored polymerizable composition of the present invention.

The cured product obtained from the polymerizable composition or colored polymerizable composition of the present invention is a printed circuit board; a color filter in a color display liquid crystal display element such as a color television, a PC monitor, a portable information terminal, a digital camera; a CCD image sensor Color filter; electrode material for plasma display panel; powder coating; printing plate; magnetic recording material; micromechanical component; waveguide; optical switch; color test system; glass fiber cable coating; It can be used for various applications such as materials, protective films, insulating films, optical elements, etc. There are no particular restrictions on the applications.

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

Compound No. shown in [Chemical Formula 3] The production of 1 and its intermediate is shown below.

<Step 1; Production of Intermediate 1A>
Under a nitrogen atmosphere, 18.1 g (743 mmol) of magnesium, 22222.1 g of THF, and 1 piece of I ₂ were charged. Next, 111.1 g (681 mmol) of 2-bromothiophene was added dropwise at 20 ° C. or lower. After completion of the dropwise addition, the mixture was reacted at 17 ° C. for 1 hour. After completion of the reaction, 75.0 g (619 mmol) of 4-fluorobenzonitrile was dissolved in 120.4 g of THF, and the solution was added dropwise. After completion of the dropwise addition, the temperature was raised to 60 ° C. and reacted for 22 hours.
After completion of the reaction, the mixture was cooled to 30 ° C., 10% hydrochloric acid was added dropwise, and the mixture was stirred until the remaining magnesium was dissolved. After completion of the stirring, ethyl acetate was added to carry out oil / water separation. After oil-water separation, washing with water was carried out four times to remove the solvent, and the following intermediate 1A was obtained in a yield of 124.1 g and a yield of 97.1%.

<Step 2: Production of intermediate 1B>
Under a nitrogen atmosphere, 36.3 g (176 mmol) of Intermediate 1A, 120.1 g of DMSO, 17.2 g of indole, and 60.0 g of potassium carbonate were mixed and reacted at an oil bath temperature of 150 ° C. for 8.5 hours.
After completion of the reaction, 120.1 g of water was added dropwise at 85 ° C., and 120.4 g of toluene was added and separated. After washing 3 times with hydrochloric acid and water, the mixture was concentrated to obtain a crude product with 54.8 g. Thereafter, 167.1 g of toluene was added, heated and dissolved at 50 ° C., 104.8 g of ethanol and 51.4 g of hexane were further added, and the mixture was cooled to 5 ° C. and stirred for 1 hour, followed by filtration. .6 g, yield 71.4%.

<Step 3; Production of Intermediate 1C>
Under a nitrogen atmosphere, 27.4 g (90 mmol) of the intermediate 1B synthesized above was added to 194.0 g of EDC, dissolved at room temperature, and then cooled by adding zinc chloride. Next, 22.0 g (135 mmol) of octanoyl chloride was added dropwise at 5 ° C. over 20 minutes, and the reaction was performed at room temperature for 25 hours.
After completion of the reaction, ethyl acetate / water was added, and after separation of oil and water, treatment was carried out in the order of hydrochloric acid, aqueous sodium hydrogen carbonate solution and saturated brine three times to remove the solvent. 46.1 g of the crude product was subjected to column chromatography to obtain 21.8 g of the following intermediate 1C in a yield of 56.2%.

<Step 4; Production of Intermediate 1D>
7.5 g (17 mmol) of Intermediate 1C was added to 24.0 g of pyridine, and after stirring and dissolving, 2.4 g (34 mmol) of hydroxylamine hydrochloride was added, heated to 60 ° C., and reacted for 2 hours. After completion of the reaction, washing with water was performed 3 times to remove the solvent. 9.7 g of the crude product was subjected to column chromatography on silica gel 40 times to obtain 3.3 g of the following intermediate 1D in a yield of 42.3%.

<Step 4; Compound No. Production of 1>
Intermediate 1D 0.7 g (2 mmol) was added to 4.1 g of DMF, and dissolved by stirring. Then, 0.5 g (4.7 mmol) of acetic anhydride and 1 piece of sodium acetate were added and reacted at 40 ° C. for 4 hours. After completion of the reaction, washing with water was performed 3 times to remove the solvent. 0.7 g of the crude product was column chromatographed with silica gel 40 times, and the compound no. 1 was obtained in a yield of 0.4 g and a yield of 50.6%.

Compound No. shown in [Chemical Formula 3] The production of 2 and its intermediate is shown below.

<Step 1; Production of Intermediate 2A>
After adding 80.0 g (1200 mmol) of aluminum chloride to 365.0 g of EDC at 0 ° C., 97.6 g (1200 mmol) of n-octanoyl chloride was added dropwise at 2 ° C. or lower to make it uniform. An EDC solution in which 58.6 g of indole was dissolved in 292.9 g of EDC was added dropwise at 2 ° C. or lower, and then reacted at 20-23 ° C. for 4.5 hours. After completion of the reaction, the mixture was poured into ice water to precipitate a Wax-like solid. Methanol was added to the precipitated wax-like solid, heated and dissolved, then water was added dropwise, and the precipitate was filtered and dried. 116.5 g of the crude product was column chromatographed with 60 times silica gel to obtain 31.0 g, and then crystallized with 60 times methanol to obtain 12.6 g of the following intermediate 2A.

<Step 2: Production of intermediate 2B>
A solution of 10.0 g (27 mmol) of Intermediate 2A, 5.5 g (28 mmol) of 4-fluorobenzophenone, 11.2 g (81 mmol) of potassium carbonate, and 44.6 g of DMSO was stirred at 130 ° C. for 3 hours to be reacted. The reaction solution was allowed to cool to 45 ° C., and ion-exchanged water and hydrochloric acid were added and filtered. The residue was dissolved in ethyl acetate, washed with ion-exchanged water, and then desolvated. The solvent removal crude was crystallized with a mixed solvent of ethyl acetate, isopropyl alcohol and hexane, filtered and dried to obtain 12.5 g of the following intermediate 2B.

＜ステップ３；化合物Ｎｏ．２の製造＞
　中間体２Ｂ１１．０ｇ(２０ｍｍｏｌ)にＤＭＦ５４．７ｇを加え、氷冷し、３５％塩酸２．１ｇ(２０ｍｍｏｌ)を滴下後、亜硝酸イソブチル８．３ｇ(８０ｍｍｏｌ)を加え室温で２４時間攪拌した。再度氷冷し、イオン交換水と酢酸エチルを加え油水分離した。有機層をイオン交換水で洗浄し、脱溶媒を行い、化合物Ｎｏ．２を１３．１ｇ得た。

<Step 3; Compound No. Production of 2>
To 11.0 g (20 mmol) of Intermediate 2B was added 54.7 g of DMF, ice-cooled, 2.1 g (20 mmol) of 35% hydrochloric acid was added dropwise, 8.3 g (80 mmol) of isobutyl nitrite was added, and the mixture was stirred at room temperature for 24 hours. The mixture was ice-cooled again, and ion-exchanged water and ethyl acetate were added to separate the oil and water. The organic layer was washed with ion-exchanged water, desolvated, and Compound No. 13.1 g of 2 was obtained.

Comparative compound No. The production of 1 and its intermediate is shown below.

<Step 1; Production of Intermediate 1a>
6.4 g of 3-acetylindole, 0.8 g (4 mmol) of copper (I) iodide, 0.9 g (8 mmol) of cyclohexanediamine (cis-trans mixture), 8.5 g (40 mmol) of tripotassium phosphate, And 18.8 g of toluene were mixed and stirred at room temperature. 8.2 g (40 mmol) of iodobenzene was added dropwise thereto. After completion of the dropping, the reaction was carried out by heating and stirring at an oil bath temperature of 135 ° C. for 18 hours. After completion of the reaction, it was cooled to room temperature. The reaction solution was poured into 150 g of ion-exchanged water, 200 g of toluene was added, and oil-water separation was performed with a separatory funnel. After washing the organic layer 3 times with water, white insoluble matter was observed, and it was filtered with a Kiriyama funnel. The filtrate was dried over anhydrous sodium sulfate, and then the solvent was removed to obtain 6.3 g of the following intermediate 1a in a yield of 67%.

<Step 2: Production of intermediate 1b>
Intermediate 1a 4.7 g (20 mmol), hydroxylamine hydrochloride 1.7 g (24 mmol), DMF 25.0 g and pyridine 1.9 g (24 mmol) were mixed and reacted at an oil bath temperature of 80 ° C. for 6 hours. After completion of the reaction, the reaction solution was cooled to room temperature, poured into 150 g of ion-exchanged water, 200 g of ethyl acetate was added, and oil-water separation was performed with a separatory funnel. The organic layer was washed with water three times, dried over anhydrous sodium sulfate, and then the solvent was removed. The crude product was dispersed and washed with 150 g of hexane and dried to obtain 4.0 g of the following intermediate 1b with a yield of 81%.

<Step 3; Production of 1>
2.8 g (10 mmol) of the intermediate 1b, 0.1 g (1 mmol) of sodium acetate and 9.6 g of DMF were mixed, and 1.1 g (11 mmol) of acetic anhydride was added dropwise at 5 ° C. on an ice bath. After raising the temperature to room temperature, the reaction was carried out by stirring for 8 hours. The reaction solution was poured into 100 g of ion-exchanged water, 150 g of ethyl acetate was added, and oil-water separation was performed with a separatory funnel. The organic layer was washed with water three times, dried over anhydrous sodium sulfate, and then the solvent was removed. Hexane is added to the obtained crude product for crystallization, and the crystals are collected by filtration and dried. 1 was obtained as light yellow crystals in 2.6 g in a yield of 82%.

Comparative compound No. The production of 2 and its intermediate is shown below.

<Step 1; Production of Intermediate 2a>
7.1 g of 5-cyanoindole and 10.4 g (75 mmol) of potassium carbonate were added to 23.4 g of DMF, and the mixture was stirred at 5 ° C. on an ice bath. Thereto, 7.8 g (55 mmol) of methyl iodide was added dropwise. After completion of the dropping, the reaction was carried out by stirring for 8 hours at room temperature. After completion of the reaction, the reaction solution was cooled to room temperature, the reaction solution was poured into 150 g of ion-exchanged water, 200 g of ethyl acetate was added, and oil-water separation was performed with a separatory funnel. The organic layer was washed with water three times, dried over anhydrous sodium sulfate, and then the solvent was removed. The crude product was subjected to column chromatography to obtain 4.0 g of the following intermediate 2a in a yield of 51%.

＜ステップ２；中間体２ｂの製造＞
　中間体２ａ３．１ｇ(２０ｍｍｏｌ)と１，２－ジクロロエタン３９．６ｇとを混合し、氷浴上３℃で撹拌を行った。そこに塩化亜鉛３．３ｇ(２４ｍｍｏｌ)を添加した。その後、１０℃以下でアセチルクロライドを１．９ｇ(２４ｍｍｏｌ)、滴下した。滴下終了後、室温まで昇温し９時間撹拌し、反応を行った。反応終了後、イオン交換水１５０ｇにあけた。これにクロロホルム１００ｇを加えた後、分液ロートに移し油水分離を行った。有機層を３回水洗し、無水硫酸ナトリウムで乾燥後、脱溶媒した。粗生成物をカラムクロマトし、下記の中間体２ｂを２．５ｇ、収率６８％で得た。

<Step 2: Production of intermediate 2b>
Intermediate 2a 3.1 g (20 mmol) and 1,2-dichloroethane 39.6 g were mixed and stirred at 3 ° C. on an ice bath. Thereto was added 3.3 g (24 mmol) of zinc chloride. Thereafter, 1.9 g (24 mmol) of acetyl chloride was added dropwise at 10 ° C. or lower. After completion of the dropwise addition, the mixture was warmed to room temperature and stirred for 9 hours to carry out the reaction. After completion of the reaction, it was poured into 150 g of ion exchange water. After adding chloroform 100g to this, it moved to the separating funnel and performed oil-water separation. The organic layer was washed with water three times, dried over anhydrous sodium sulfate, and then the solvent was removed. The crude product was subjected to column chromatography to obtain 2.5 g of the following intermediate 2b in a yield of 68%.

＜ステップ３；中間体２ｃの製造＞
　中間体２ｂ２．０ｇ(１０ｍｍｏｌ)と塩酸ヒドロキシルアミン０．８ｇ(１２ｍｍｏｌ)とをＤＭＦ１０．７gに加え、オイルバス温度８０℃で５時間加熱撹拌し、反応を行った。反応終了後、室温まで冷却した。反応液をイオン交換水１００ｇにあけ、酢酸エチル１５０ｇを加え分液ロートで油水分離を行った。有機層を３回水洗し、無水硫酸ナトリウムで乾燥後、脱溶媒した。粗生成物にヘキサン１５０ｇを入れ分散洗浄し、乾燥し、下記の中間体２ｃを２．０ｇ、収率９４％で得た。

<Step 3; Production of Intermediate 2c>
Intermediate 2b (2.0 g, 10 mmol) and hydroxylamine hydrochloride (0.8 g, 12 mmol) were added to 10.7 g of DMF, and the mixture was heated and stirred at an oil bath temperature of 80 ° C. for 5 hours to carry out the reaction. After completion of the reaction, it was cooled to room temperature. The reaction solution was poured into 100 g of ion-exchanged water, 150 g of ethyl acetate was added, and oil-water separation was performed with a separatory funnel. The organic layer was washed with water three times, dried over anhydrous sodium sulfate, and then the solvent was removed. The crude product was dispersed and washed with 150 g of hexane, and dried to obtain 2.0 g of the following intermediate 2c in a yield of 94%.

＜ステップ４；比較化合物Ｎｏ．２の製造＞
　中間体２ｃ１．７ｇ(８ｍｍｏｌ)と酢酸ナトリウム０．１ｇ(１ｍｏｌ)とをＤＭＦ５．６ｇに加え、氷浴上５℃で無水酢酸１．２g(１２ ｍｍｏｌ)を滴下して加えた。室温まで昇温後、６時間撹拌を行った。析出した白色の結晶をろ取した。得られた結晶をイオン交換水、メタノールで分散洗浄し、乾燥させ、下記の比較化合物Ｎｏ．２を白色結晶として０．８g、収率４３％で得た。

<Step 4: Comparative compound No. Production of 2>
1.7 g (8 mmol) of the intermediate 2c and 0.1 g (1 mol) of sodium acetate were added to 5.6 g of DMF, and 1.2 g (12 mmol) of acetic anhydride was added dropwise at 5 ° C. on an ice bath. After raising the temperature to room temperature, stirring was performed for 6 hours. The precipitated white crystals were collected by filtration. The obtained crystals were dispersed and washed with ion-exchanged water and methanol, dried, and the following comparative compound No. 2 was obtained as white crystals in 0.8 g in a yield of 43%.

The analysis results of the above oxime ester compounds are shown in [Table 1] to [Table 3].

[Evaluation Examples 1 and 2 and Comparative Evaluation Examples 1 to 3]
The solvent solubility of the oxime ester compound was evaluated by the following method. The results are shown in [Table 4].

(Solubility)
Compound No. 1, compound no. 2, Comparative Compound No. 1, Comparative Compound No. 2 and the following comparative compound No. 3 was evaluated for solubility in PGMEA, PGM, and cyclohexanone (CHN) at room temperature. What melt | dissolved 10 wt% or more was set to (circle), what melted | dissolved 3 wt% or more and less than 10 wt% was set to (triangle | delta), and what melt | dissolved only less than 3 wt% was set as x.

[Table 4] shows that the oxime ester compound of the present invention has high solubility in a solvent. In particular, it is clear that the solubility in ether ester solvents represented by PGMEA is high.

Therefore, when the oxime ester compound of the present invention is used as a polymerization initiator of the polymerizable composition, a wide range of solvents, raw materials, and the like can be selected, so that the degree of freedom of blending is high, and precipitation of the oxime ester compound is difficult to occur during storage. The polymerizable composition has excellent storage stability and is useful.

[Examples 3 and 4 and Comparative Examples 4 to 6] Preparation of Polymerizable Composition The following components were prepared according to the formulation of [Table 5], and polymerizable compositions (Examples 3 and 4 and Comparative Examples 4 to 6). ) In addition, the number in a table | surface represents a mass part. As a polymerization initiator, Compound No. 1, compound no. 2, Comparative Compound No. 1, Comparative Compound No. 2 and comparative compound no. 3 was used alone.
Moreover, the code | symbol of each component in a table | surface represents the following component.
A-1 Compound No. 1 (Oxime ester compound of the present invention)
A-2 Compound No. 2 (Oxime ester compound of the present invention)
A′-3 Comparative compound No. 1 (Oxime ester compound not belonging to the present invention)
A′-4 Comparative compound No. 2 (Oxime ester compound not belonging to the present invention)
A′-5 Comparative compound No. 3 (Oxime ester compound not belonging to the present invention)
B-1 SPC-1000
(Ethylenically unsaturated compound having an acid group; Showa Denko)
B-2 Aronix M-450 (ethylenically unsaturated compound; manufactured by Toagosei)
C-1 PGMEA (solvent)
D-1 KBE-403 (Silane coupling agent; manufactured by Shin-Etsu Chemical)
D-2 FZ-2122 (Leveling agent; manufactured by Toray Dow Corning)
D-3 Adeka Arcles GPA-5001 (latent additive; manufactured by ADEKA)

[Evaluation Examples 3 and 4 and Comparative Evaluation Examples 4 to 6]
The sensitivity and transparency of the polymerizable composition were evaluated by the following methods. The results are shown in [Table 6].

(transparency)
The polymerizable composition was spin-coated on a glass substrate (500 rpm, 2 seconds, 900 rpm, 5 seconds), and prebaked at 90 ° C. for 90 seconds using a hot plate. 100 mJ / cm ² exposure was performed using a high-pressure mercury lamp as a light source, and post-baking was performed at 230 ° C. for 30 minutes using an oven. The transmittance at 380 nm and 400 nm was measured using an absorptiometer. The case where the transmittance at 400 nm was 95% or more and the transmittance at 380 nm was 92% or more was evaluated as ◯, the case satisfying only one of them as Δ, and the case satisfying neither one as X.

(sensitivity)
The polymerizable composition was spin-coated on a glass substrate (500 rpm, 2 seconds, 900 rpm, 5 seconds), prebaked at 90 ° C. for 90 seconds using a hot plate, and then 10 mJ / second using a high-pressure mercury lamp. The exposure was performed at 20 mJ / cm ² intervals from cm ² to 1000 mJ / cm ² . Thereafter, development was performed for 27 to 28 seconds using a basic developer.
When the exposure is less than 100 mJ / cm ² , the cured film remains on the glass substrate after development, and ◎ indicates that the cured film remains on the glass substrate at 100 mJ / cm ² or more and less than 1000 mJ / cm ² , and 1000 mJ / cm ^{The case} where the cured film did not remain on the glass substrate even when the number was ² or more was evaluated as x.

From [Table 5], [Table 6] and [Table 7], it is clear that when the oxime ester compound of the present invention is used as a polymerization initiator, a highly sensitive polymerization composition and a highly transparent cured product can be obtained. is there. Among the oxime ester compounds of the present invention, a compound having a structure represented by Compound No. 2 is particularly preferred because of its higher sensitivity.

Therefore, when the oxime ester compound of the present invention is used as a polymerization initiator of a polymerizable composition, a highly sensitive polymerizable composition and a highly transparent cured product are obtained, which is useful. It is particularly useful as a polymerization initiator for optical applications.

The oxime ester compound of the present invention is useful as a highly sensitive polymerization initiator used in the polymerizable composition.

Claims (8)

The oxime ester compound represented by the following general formula (I).

(Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ (hereinafter also referred to as R ¹ to R ¹⁰ ) are each independently Groups represented by the following general formula (II), hydrogen atom, halogen atom, nitro group, nitrile group, cyano group, hydroxyl group, carboxyl group, formyl group, sulfo group, R ¹³ , OR ¹³ , SR ¹³ , NR ¹⁴ R ¹⁵ , COR ¹³ , SOR ¹³ , SO ₂ R ¹³ or CONR ¹⁴ R ¹⁵ ,
R ¹³ , R ¹⁴ and R ¹⁵ each independently represents a hydrocarbon group having 1 to 20 carbon atoms or a heterocyclic group having 2 to 20 carbon atoms,
The hydrogen atom of the hydrocarbon group having 1 to 20 carbon atoms or the heterocyclic group having 2 to 20 carbon atoms represented by R ¹³ , R ¹⁴ and R ¹⁵ is a group represented by the following general formula (II) Substituted with nitrile group, halogen atom, nitro group, cyano group, hydroxyl group, amino group, carboxyl group, methacryloyl group, acryloyl group, epoxy group, vinyl group, vinyl ether group, mercapto group, isocyanate group or heterocyclic group-containing group In some cases, the methylene group in the hydrocarbon group having 2 to 20 carbon atoms or the heterocyclic group having 2 to 20 carbon atoms represented by R ¹³ , R ¹⁴ and R ¹⁵ is —O—, —CO—. , —COO—, —OCO—, —NR ¹⁶ —, —NR ¹⁶ CO—, —S—, —SO ₂ —, —SCO— or —COS— may be substituted,
R ¹⁶ represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms,
R ¹¹ and R ¹² each independently represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydrocarbon group having 1 to 20 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms,
The hydrogen atom of the hydrocarbon group having 1 to 20 carbon atoms or the heterocyclic group having 2 to 20 carbon atoms represented by R ¹¹ and R ¹² is a halogen atom, nitro group, cyano group, hydroxyl group, amino group, carboxyl Group, methacryloyl group, acryloyl group, epoxy group, vinyl group, vinyl ether group, mercapto group, isocyanate group or heterocyclic group-containing group, and may have 1 to 20 carbon atoms represented by R ¹¹ and R ¹² The methylene group in the hydrocarbon group or the heterocyclic group having 2 to 20 carbon atoms is —O—, —CO—, —COO—, —OCO—, —NR ¹⁷ —, —NR ¹⁷ CO—, —S _{-, - SO 2 -, -} SCO- or -COS- in some cases be substituted,
R ¹⁷ represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms,
At least one of R ¹ to R ¹⁰ is a group represented by the following general formula (II):
R ² and R ³ , R ³ and R ⁴ , R ⁴ and R ⁵ , R ⁶ and R ⁷ , R ⁷ and R ⁸ , R ⁸ and R ⁹ and R ⁹
And R ¹⁰ may combine to form a ring,
m represents 0 or 1; )

(Wherein R ²¹ and R ²² each independently represent a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydrocarbon group having 1 to 20 carbon atoms, or a heterocyclic-containing group having 2 to 20 carbon atoms) ,
The hydrogen atom of the hydrocarbon group having 1 to 20 carbon atoms or the heterocyclic group having 2 to 20 carbon atoms represented by R ²¹ and R ²² is a halogen atom, nitro group, cyano group, hydroxyl group, amino group, carboxyl May be substituted with a group, a methacryloyl group, an acryloyl group, an epoxy group, a vinyl group, a vinyl ether group, a mercapto group, an isocyanate group or a heterocyclic group, and the number of carbon atoms represented by R ²¹ and R ²² is 1 to 20 The methylene group in the hydrocarbon group or the heterocyclic group having 2 to 20 carbon atoms is —O—, —CO—, —COO—, —OCO—, —NR ²³ —, —NR ²³ CO—, —S _{-, - SO 2 -, -} SCO- or -COS- in some cases be substituted,
R ²³ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms,
n represents 0 or 1. ) ^2. The oxime ester compound according to claim 1, wherein at least one of R ² , R ³ , R ⁴ and R ^{5 in} the general formula (I) is a group represented by the general formula (II). The oxime ester compound according to claim 1 or 2, wherein at least one of R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ^{10 in} the general formula (I) is an electron-withdrawing group. A polymerization initiator containing the oxime ester compound according to any one of claims 1 to 3. A polymerizable composition comprising the polymerization initiator according to claim 4 and an ethylenically unsaturated compound. A colored polymerizable composition comprising the polymerizable composition according to claim 5 and a coloring material. A cured product obtained from the polymerizable composition according to claim 5 or the colored polymerizable composition according to claim 6. A color filter having the cured product according to claim 7.