JP6799540B2 - Oxime ester compound and polymerization initiator containing the compound - Google Patents

Description

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

The polymerizable composition is an ethylenically unsaturated compound to which a polymerization initiator is added, and can be polymerized and cured by irradiating with energy rays (light). Therefore, photocurable inks, photosensitive printing plates, etc. It is used in various photoresists and the like.

Patent Documents 1 to 3 propose to use an oxime ester compound as a polymerization initiator used in a 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 which is highly soluble in a solvent and has high sensitivity and can obtain a cured product having high transparency.

US6596445 (B1) WO201308652 Pamphlet US2006 / 241259 A1

The problem to be solved by the present invention is that there has never been a polymerization initiator that is highly soluble in a solvent and has high sensitivity and can obtain a cured product having high transparency. Is.

Therefore, an object of the present invention is a novel compound having high solubility in a solvent and useful as a highly sensitive polymerization initiator, a polymerization initiator using the compound, and a polymerizable composition containing the polymerization initiator. And to provide a cured product having excellent transparency.

The present invention has achieved 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。）

(In the formula, 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 independently described. Group 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 Represents ¹⁵ , COR ¹³ , SOR ¹³ , SO ₂ R ¹³ or CONR ¹⁴ R ¹⁵ .
R ¹³ , R ¹⁴ and R ¹⁵ each independently represent 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). , Nitrigen 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. 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- in some cases be substituted,
R ¹⁶ represents a hydrogen atom and a hydrocarbon group having 1 to 20 carbon atoms.
R ¹¹ and R ¹² 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 heterocycle-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 ¹¹ and R ¹² is a halogen atom, a nitro group, a cyano group, a hydroxyl group, an amino group, or a carboxyl group. It 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 heterocycle-containing group, and has 1 to 20 carbon atoms represented by R ¹¹ and R ^12. , - - -O methylene group in the heterocyclic ring-containing group of a hydrocarbon group or a C2-20's CO -, - COO -, - OCO -, - NR 17 -, - NR 17 CO -, - S It may be replaced by −, −SO ₂₋ , −SCO− or −COS−.
R ¹⁷ represents a hydrogen atom and 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, ^{if R 7} and ^R 8, ^{R 8} and ^{R 9} and ^{R 9} and ^{R 10} are combined to form a ring There is also
m represents 0 or 1. )

(In the formula, R ²¹ and R ²² 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 heterocycle-containing group having 2 to 20 carbon atoms, respectively. ,
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, a nitro group, a cyano group, a hydroxyl group, an amino group, or a carboxyl group. It 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 heterocycle-containing group, and has 1 to 20 carbon atoms represented by R ²¹ and R ^22. , - - -O methylene group in the heterocyclic ring-containing group of a hydrocarbon group or a C2-20's CO -, - COO -, - OCO -, - NR 23 -, - NR 23 CO -, - S It may be replaced by −, −SO ₂₋ , −SCO− or −COS−.
R ²³ represents a hydrogen atom and a hydrocarbon group having 1 to 20 carbon atoms.
n represents 0 or 1. )

The present invention also provides a polymerizable composition containing the above-mentioned polymerization initiator and ethylenically unsaturated compound.
The present invention also provides a colored polymerizable composition containing the above-mentioned polymerizable composition and coloring material.

The present invention also provides a cured product obtained from the above-mentioned polymerizable composition or the above-mentioned 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 double bonds of oxime, but these are not distinguished.
That is, in the present specification, the compound represented by the above general formula (I) and the exemplary compound thereof represent a mixture of both or one of them, and are not limited to the structure showing an isomer.

The hydrocarbon groups 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) are not particularly limited, but are preferable. Alkyl group with 1 to 20 carbon atoms, cycloalkyl group with 3 to 20 carbon atoms, cycloalkylalkyl group with 4 to 20 carbon atoms, aryl group with 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, and isooctyl. , 2-Ethylhexyl, t-octyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, tetradecyl, hexadecyl, octadecyl, icosyl and the like.

The cycloalkyl group having 3 to 20 carbon atoms means a saturated monocyclic or saturated polycyclic alkyl group having 3 to 20 carbon atoms. For example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, adamantyl, decahydronaphthyl, octahydropentalene, bicyclo [1.1.1] pentanyl and the like can be mentioned.

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

Examples of the aryl group having 6 to 20 carbon atoms include phenyl, trill, xsilyl, ethylphenyl, naphthyl, anthryl, phenanthrenyl, phenyl, biphenylyl, naphthyl, anthryl and the like substituted with one or more of the above alkyl groups. Be done.

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

Examples of the heterocyclic group having 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 pyrrolyl, pyridyl and pyridyl ethyl. , Pyrimidyl, Pyridadyl, Piperazil, Piperidil, Pyranyl, Pyranylethyl, Pyrazolyl, Triazyl, Triazylmethyl, Pyrrolidyl, Kinolyl, Isoquinolyl, Imidazolidine, Benomidazolidine, Triazolyl, Frill, Furanyl, Benzofuranyl, Thienyl, Thiophenyl, Benzothiophenyl, Thiasiazolyl , Benzothiazolyl, oxazolyl, benzoxazolidine, isothiazolyl, isooxazolidine, indolyl, urolysyl, morpholinyl, thiomorpholinyl, 2-pyrrolidinone-1-yl, 2-piperidone-1-yl, 2,4-dioxyimidazolidine- Examples thereof include 3-yl and 2,4-dioxyoxazolidine-3-yl.

Examples of the halogen atom in the general formulas (I) and (II) include fluorine, chlorine, bromine and iodine.

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 are combined to form a ring. , For example, 5 to 7 members of cyclopentane ring, cyclohexane ring, cyclopentene ring, benzene ring, pyrrolidine ring, pyrrol ring, piperazine ring, piperidine ring, morpholine ring, thiomorpholine ring, tetrahydropyridine ring, lactone ring, lactam ring and the like. Examples thereof include a ring and a fused ring such as a naphthalene ring and an anthracene ring.

At least one of R ² to R ⁵ in the general formula (I) is an oxime ester compound is a group represented by the general formula (II), good high sensitivity absorption wavelength when used as a polymerization initiator It is preferable because it becomes. Further, when at least one of R ³ and R ⁸ is a group represented by the general formula (II), it is more preferable because it is easy to synthesize and the stability of the oxime ester compound is good. Further, when R ⁸ is a group represented by the general formula (II), when it is used as a polymerization initiator of a polymerizable composition, the cured product obtained from the polymerization composition has high transparency and coloring. Most preferable because it is small.

An 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 becomes highly sensitive when used as a polymerization initiator. Therefore, it 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, 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 the sensitivity is higher.

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

The oxime ester compound in which R ¹¹ in the general formula (I) is an alkyl group having 4 to 20 carbon atoms is converted to an ether ester solvent typified 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 among the alkyl groups exemplified as the above-mentioned hydrocarbon groups 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.

As a preferable specific example of the oxime ester compound of the present invention represented by the above general formula (I), the following compound No. 1-No. 128 is mentioned. However, the present invention is not limited by the following compounds.

Among the above 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 the alkyl group of, is easy to synthesize, the oxime ester compound is stable, has high solubility in various solvents, and has a good absorption wavelength and high absorption when used as a polymerization initiator. It is more preferable because it has high sensitivity and transparency of the cured product and is less colored.
Specifically, the oxime ester compound of the present invention includes the above-mentioned compound No. 1-No. 90 and the like are preferable.

The oxime ester compound of the present invention represented by the general formula (I) is not particularly limited, but can be produced by the following method when m = 0, for example, according to the reaction formula of [Chemical Formula 17] below. ..
That is, an indole compound 2 is obtained by reacting a known and commercially available indole compound 1 with an aryl halide, a ketone compound 1 is obtained by reacting the indole compound 2 with an acid chloride, and the ketone compound 1 and hydrochloric acid are obtained. Oxym compound 1 is obtained by reacting with a hydroxylamine. Subsequently, the oxime compound 1 is reacted with an acid anhydride or an acid chloride to obtain the oxime ester compound 1 of the present invention represented by the above general formula (I).
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 general formula (I) can be produced by the following method according to the reaction formula of the following [Chemical formula 18].
That is, an indole compound 2 is obtained by reacting a known and commercially available indole compound 1 with an aryl halide, a ketone compound 2 is obtained by reacting the indole compound 2 with an acid chloride, and the ketone compound 2 and sub are obtained. Oxym compound 2 is obtained by reacting with isobutyl nitrate. Subsequently, the oxime compound 2 is reacted with an acid anhydride or an acid chloride to obtain the oxime ester compound 2 of the present invention represented by the above general formula (I).

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. In addition, the novel oxime ester compound of the present invention can 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. In addition, the polymerization initiator of the present invention can be used in combination with another polymerization initiator together with the oxime ester compound of the present invention. As other polymerization initiators that can be used in combination, conventionally known compounds can be used, for example, benzophenone, phenylbiphenylketone, 1-hydroxy-1-benzoylcyclohexane, benzoin, benzyldimethylketal, 1-benzyl-1. -Dimethylamino-1- (4'-morpholinobenzoyl) propane, 2-morpholyl-2- (4'-methylmercapto) benzoylpropane, thioxanthone, 1-chloro-4-propoxythioxanthone, isopropylthioxanthone, diethylthioxanthone, ethylanthraquinone , 4-benzoyl-4'-methyldiphenyl sulfide, benzoin butyl ether, 2-hydroxy-2-benzoyl propane, 2-hydroxy-2- (4'-isopropyl) benzoyl propane, 4-butyl benzoyl trichloromethane, 4-phenoxy benzoyl Dichloromethane, methyl benzoylate, 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 (manufactured by ADEKA), IRGACURE369, IRGACURE907, IRGACURE OXE 01, IRGACURE OXE 02 (manufactured by BASF), benzoyl peroxide and the like, and other polymerization initiators thereof. Can be used alone or in combination of two or more.

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 above-mentioned polymerization initiator and ethylenically unsaturated compound as essential components.

The ethylenically unsaturated compound is not particularly limited, and those conventionally used in a polymerizable composition can be used. For example, ethylene, propylene, butylene, isobutylene, vinyl chloride, vinylidene chloride, and foot. Unsaturated aliphatic hydrocarbons such as vinylidene chemistry and tetrafluoroethylene; (meth) acrylic acid, α-chloroacrylic acid, itaconic acid, maleic acid, citraconic acid, fumaric acid, hymic acid, crotonic acid, isocrotonic acid, vinyl acetate , Allylacetic acid, cinnamic acid, sorbic acid, mesaconic acid, monosuccinate [2- (meth) acrylicyloxyethyl], mono-phthalate [2- (meth) acrylicyloxyethyl], ω-carboxypolycaprolactone mono ( Mono (meth) acrylate of polymer having carboxy group and hydroxyl group at both ends such as meta) acrylate; hydroxyethyl (meth) acrylate malate, hydroxypropyl (meth) acrylate malate, dicyclopentadiene malate or one Unsaturated polybasic acids such as polyfunctional (meth) acrylates having a carboxyl group and two or more (meth) acryloyl groups; -2-hydroxyethyl (meth) acrylate, -2-hydroxypropyl (meth) acrylate , (Meta) glycidyl acrylate, the following compound No. A1 to No. A4, methyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, -t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, n-octyl (meth) acrylate, ( Isooctyl acrylate, isononyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, methoxyethyl (meth) acrylate, dimethylaminomethyl (meth) acrylate, dimethyl (meth) acrylate Aminoethyl, Aminopropyl (Meta) Acrylate, Dimethylaminopropyl (Meta) Acrylate, ethoxyethyl (Meta) Acrylate, Poly (ethoxy) Ethyl (Meta) Acrylate, Butoxyethoxyethyl (Meta) Acrylate, (Meta) ) Ethylhexyl acrylate, phenoxyethyl (meth) acrylate, tetrahydrofuryl (meth) acrylate, vinyl (meth) vinyl acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, ethylene glycol di (meth) acrylate, Diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol Di (meth) acrylate, trimethylol ethanetri (meth) acrylate, trimethylol propanthry (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, pentaerythritol tetra (meth) acrylate Unsaturated monobasic acids such as pentaerythritol tri (meth) acrylate, tricyclodecanedimethylol di (meth) acrylate, tri [(meth) acryloyl ethyl] isocyanurate, polyester (meth) acrylate oligomer, and polyhydric alcohols or polyvalents. Esters of phenols; metal salts of unsaturated polybasic acids such as zinc (meth) acrylate, magnesium (meth) acrylate; maleic acid anhydride, itaconic acid anhydride, citraconic acid anhydride, methyltetrahydrophthalic anhydride, tetrahydro Acrylate, TrialkyltetrahydroAcrylate, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride, trialkyltetrahydrophthaliclate-anhydrous Acid anhydrides of unsaturated polybasic acids such as maleic acid adduct, dodecenyl anhydride succinic acid, methylhymicic anhydride; (meth) acrylamide, methylenebis- (meth) acrylamide, diethylenetriaminetris (meth) acrylamide, xylylenebis (meth) Amid of unsaturated monobasic acids and polyvalent amines such as acrylamide, α-chloroacrylamide, N-2-hydroxyethyl (meth) acrylamide; unsaturated aldehydes such as achlorine; (meth) acrylonitrile, α-chloroacrylonitrile, cyanide Unsaturated nitriles such as vinylidene and allyl cyanide; styrene, 4-methylstyrene, 4-ethylstyrene, 4-methoxystyrene, 4-hydroxystyrene, 4-chlorostyrene, divinylbenzene, vinyltoluene, vinyl benzoic acid, vinylphenol , Vinyl sulfonic acid, 4-vinylbenzene sulfonic acid, vinylbenzyl methyl ether, vinylbenzyl glycidyl ether and other unsaturated aromatic compounds; unsaturated ketones such as methyl vinyl ketone; vinylamine, allylamine, N-vinylpyrrolidone, vinylpiperidin and the like. Unsaturated amine compounds; 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 and allyl glycidyl ether; maleimide, N-phenylmaleimide, N-cyclohexyl Unsaturated imides such as maleimide; indens such as inden and 1-methylinden; aliphatic conjugated dienes such as 1,3-butadiene, isoprene and chloroprene; polystyrene, polymethyl (meth) acrylate, poly-n-butyl ( Macromonomers having a mono (meth) acryloyl group at the end of polymer molecular chains such as meta) acrylates and polysiloxanes; vinyl chlorides, vinylidene chlorides, divinylsuccinates, diallylphthalates, triallyl phosphates, triallyl isothias Examples thereof include vinyl urethane compounds of nurate, vinyl thioether, vinyl imidazole, vinyl oxazoline, vinyl carbazole, vinyl pyrrolidone, vinyl pyridine, hydroxyl group-containing vinyl monomer and polyisocyanate compound, and vinyl epoxy compound of hydroxyl group-containing vinyl monomer and polyepoxy compound.
Among these, mono (meth) acrylates of polymers having carboxy groups and hydroxyl groups at both ends, polyfunctional (meth) acrylates having one carboxy group and two or more (meth) acryloyl groups, unsaturated ones. A polymerization initiator containing the oxime ester compound of the present invention in an ester of a basic acid and a polyhydric alcohol or a polyhydric phenol is suitable.
These ethylenically unsaturated compounds can be used alone or in admixture of two or more, and when two or more of them are mixed and used, they are copolymerized in advance to form a copolymer. You may use it.

Further, 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 alkaline aqueous solution. For example, the resin described in JP-A-2004-264414, a copolymer of an acrylic acid ester, phenol, and a cresol novolac epoxy resin. , Polyphenylmethane type epoxy resin having a polyfunctional epoxy group, epoxy acrylate resin, and a resin obtained by further reacting a polybasic acid anhydride with an epoxy acrylate resin and the like can be mentioned.

Commercially available products can be used as the ethylenically unsaturated compound, for example, Kayarad 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- Examples thereof include 9300, TMPT, DCP, NPG and HD-N (manufactured by Shin Nakamura Chemical Industry 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 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 above-mentioned polymerizable composition and coloring material.

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

Examples of the pigment include nitroso compounds; nitro compounds; azo compounds; diazo compounds; xanthene compounds; quinoline compounds; anthraquinone compounds; coumarin compounds; phthalocyanine compounds; isoindolinone compounds; isoindolin compounds; quinacridone compounds; antanthurone compounds; perinone. Compounds; perylene compounds; diketopyrrolopyrrole compounds; thioindigo compounds; dioxazine compounds; triphenylmethane compounds; quinophthalone compounds; naphthalenetetracarboxylic acids; azo dyes, cyanine dye metal complex compounds; lake pigments; furnace method, channel method or thermal Carbon black obtained by the method, or carbon black such as acetylene black, ketjen black, or lamp black; the above carbon black adjusted or coated with an epoxy resin, the above carbon black is previously dispersed in a resin in a solvent, and 20 A compound adsorbed with a resin of ~ 200 mg / g, an acidic or alkaline surface treatment of the above carbon black, a compound having an average particle size of 8 nm or more and a DBP oil absorption of 90 ml / 100 g or less, CO in a volatile matter at 950 ° C. And the total oxygen content calculated from CO ₂ is 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 aerogel, fullerene. Aniline Black, Pigment Black 7, Titanium Black; Chromium Oxide Green, Miloli Blue, Cobalt Green, Cobalt Blue, Manganese, Ferocyanide, Phosphate Ultramarine, Navy Blue, Ultramarine, Cerulean Blue, Pyridian, Emerald Green, Lead Sulfate , Yellow lead, zinc yellow, red iron oxide (III), cadmium red, synthetic iron black, amber and other organic or inorganic pigments can be used. These pigments can be used alone or in combination of two or more.

As the pigment, a commercially available pigment may be used, for example, Pigment Red 1, 2, 3, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48, 49, 88, 90, 97, 112, 119, 122, 123, 144, 149, 166, 168, 169, 170, 171, 177, 179, 180, 184, 185, 192, 200, 202, 209, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, 254; Pigment Orange 13, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 65, 71; Pigment Yellow 1, 3, 12, 13, 14, 16, 17, 20, 24, 55, 60, 73, 81, 83, 86, 93, 95, 97, 98, 100, 109, 110, 113, 114, 117, 120, 125, 126, 127, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 166, 168, 175, 180, 185; Pigment Green 7, 10, 36; Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 5, 15: 6, 22, 24, 56, 60, 61, 62, 64; Pigment Violet Examples thereof include 1, 19, 23, 27, 29, 30, 32, 37, 40 and 50.

Examples of the above dyes include azo dyes, anthraquinone dyes, indigoid dyes, triarylmethane dyes, xanthene dyes, alizarin dyes, acrydin dyes, stillben dyes, thiazole dyes, naphthol dyes, quinoline dyes, nitro dyes, indamine dyes, oxazine dyes, and phthalocyanine dyes. , Dyes such as cyanine dyes, and the like, and a plurality of these may be mixed and used.

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.

A polymerization initiator, an ethylenically unsaturated compound, and a solvent capable of dissolving or dispersing a coloring material can be added to the above-mentioned polymerizable composition and colored polymerizable composition, if necessary. 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. Ethereal solvents such as ethoxyethane, dipropylene glycol dimethyl ether and propylene glycol monomethyl ether (PGM); methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, cyclohexyl acetate, ethyl lactate, dimethyl succinate , Texanol and other ester solvents; 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, amyl alcohol; Ether ester solvents such as 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, and ethoxyethyl ether propionate. BTX solvents such as benzene, toluene and xylene; aliphatic hydrocarbon solvents such as hexane, heptane, octane and cyclohexane; terpene solvents such as terepine oil, D-lymonen and pinen; mineral spirit, swazole # 310 (Cosmo Matsuyama Petroleum Co., Ltd.), Solbesso # 100 (Exxon Chemical Co., Ltd.) and other paraffinic solvents; Carbon tetrachloride, chloroform, trichloroethylene, methylene chloride, 1,2-dichloroethane and other halogenated aliphatic hydrocarbon solvents; Chlorobenzene, etc. Halogenized aromatic hydrocarbon solvent; carbitol solvent; aniline; triethylamine; pyridine; acetic acid; acetonitrile; carbon disulfide; N, N-dimethylformamide; N, N-dimethylacetamide; N-methylpyrrolidone; dimethylsulfoxide Examples thereof include water, and these solvents can be used as one kind or a mixed solvent of two or more kinds.
Among these, ketones and ether ester solvents and the like, particularly cyclohexanone and PGMEA, are preferable because they have good compatibility between the ethylenically unsaturated compound and the polymerization initiator in the polymerizable composition.

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 polymers excluding ethylenically unsaturated compounds (hereinafter, also referred to as polymers), inorganic compounds, and dispersants, if necessary. , Chain transfer agent, sensitizer excluding the 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. Excluding monomers, defoaming agents, thickeners, thixants, flame retardants, plasticizers, stabilizers, polymerization inhibitors, UV absorbers, organic fillers, antioxidants, antioxidants, flow modifiers and adhesion promoters Various resin additives and the like can be added.

The properties of the cured product can also be improved by using the polymer together with the ethylenically unsaturated compound. Examples of the polymer include polystyrene, polymethylmethacrylate, methylmethacrylate-ethylacrylate copolymer, poly (meth) acrylic acid, styrene- (meth) acrylic acid copolymer, and (meth) acrylic acid-methylmethacrylate copolymer. Combined, 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 thereof 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 preferable.

In the polymerizable composition and the 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 metal oxides such as nickel oxide, iron oxide, iridium oxide, titanium oxide, zinc oxide, magnesium oxide, calcium oxide, potassium oxide, silica and alumina; layered clay minerals, miloli blue and calcium carbonate. Magnesium carbonate, cobalt-based, manganese-based, glass powder (especially glass frit), mica, talc, kaolin, ferrocyanide, various metal sulfates, sulfides, serenes, aluminum silicates, calcium silicates, aluminum hydroxide, platinum, Examples include gold, silver and copper.
Among these, glass frit, titanium oxide, silica, layered clay mineral, silver and the like are preferable.

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

In the polymerizable composition and the 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 by mass with respect to 100 parts by mass of the ethylenically unsaturated compound. It is a mass part. In addition, one kind or two or more kinds of these inorganic compounds can be used.

The dispersant is not limited as long as it can disperse and stabilize the coloring material or the inorganic compound, and a commercially available dispersant, for example, 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, an amine as a basic functional group and a functional group having a nitrogen atom, and / or a quaternary salt thereof. 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, thioapple acid, thiosalicylic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, 3-mercaptobutyric acid, N- (2-mercaptopropionyl) glycine, 2-mercaptonicotinic acid, 3-[N-( 2-Mercaptoethyl) carbamoyl] propionic acid, 3- [N- (2-mercaptoethyl) amino] propionic acid, N- (3-mercaptopropionyl) alanine, 2-mercaptoethanesulfonic acid, 3-mercaptopropanesulfonic acid, 4-mercaptobutansulfonic acid, dodecyl (4-methylthio) phenyl ether, 2-mercaptoethanol, 3-mercapto-1,2-propanediol, 1-mercapto-2-propanol, 3-mercapto-2-butanol, mercaptophenol , 2-Mercaptoethylamine, 2-Mercaptoimidazole, 2-Mercaptobenzoimidazole, 2-Mercapto-3-pyridinol, 2-Mercaptobenzothiazole, Mercaptoacetic acid, Trimethylolpropanthris (3-mercaptopropionate), Pentaerythritoltetrakis A mercapto compound such as (3-mercaptopropionate), a disulfide compound obtained by oxidizing the mercapto compound, iodoacetic acid, iodopropionic acid, 2-iodoethanol, 2-iodoethanesulfonic acid, 3-iodopropanesulfonic acid. Alkyliodated compounds such as, trimethylolpropanetris (3-mercaptoisobutyrate), butanediolbis (3-mercaptoisobutyrate), hexanedithiol, decandithiol, 1,4-dimethylmercaptobenzene, butanediolbisthio. Propionate, Butanediol Bisthioglycolate, Ethethylene Glycol Bisthioglycolate, Trimethylol Propanetristhioglycolate, Butanediol Bisthiopropionate, Trimethylol Propanetristhiopropionate, Trimethylol Propanetristhioglycolate , Pentaerythritol tetrakisthiopropionate, pentaerythritol tetrakisthioglycolate, trishydroxyethyl tristhiopropionate, diethylthioxanthone, diisopropylthioxanthone, the following compound No. Examples thereof include aliphatic polyfunctional thiol compounds such as C1, tris (2-hydroxyethyl) trimercaptopropionate, isocyanurate, and Karenz MT BD1, PE1, NR1 manufactured by Showa Denko.

Examples of the surfactant include fluorine surfactants such as perfluoroalkyl phosphate and perfluoroalkyl carboxylate; anionic surfactants such as higher fatty acid alkali salts, alkyl sulfonates and alkyl sulfates; higher amines. Cationic surfactants such as halides and quaternary ammonium salts; Nonionic surfactants such as polyethylene glycol alkyl ethers, polyethylene glycol fatty acid esters, sorbitan fatty acid esters, 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 which silanes having an isocyanate group, a methacryloyl group, or an epoxy group such as KBE-9007, KBM-502, and KBE-403 can be used. Coupling agents are preferably used.

Examples of the melamine compound include all or a part of active methylol groups (CH ₂ OH groups) in nitrogen compounds such as (poly) methylol melamine, (poly) methylol glycol uryl, (poly) methylolbenzoguanamine, and (poly) methylol urea. Examples thereof 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 or different from each other, or a methylol group which is not alkyl etherified. May be self-condensed within one molecule, or may be condensed between two molecules to form an oligomer component as a result.
Specifically, hexamethoxymethylmelamine, hexabutoxymethylmelamine, tetramethoxymethylglycol uryl, tetrabutoxymethyl glycol uryl and the like can be used.
Among these, alkyl etherified melamines such as hexamethoxymethylmelamine and hexabutoxymethylmelamine are preferable.

As the leveling agent, a commercially available product can be used. 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-DYN (Made by Big 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 Co., Ltd.), L-7001, L-7002, L-7006, 56ADDITIVE, 57ADDITIVE , 67ADDITIVE, 8032ADDITIVE, FZ-2105, FZ-2110, FZ-2122 and FZ-2123 (manufactured by Toray Dow Corning) and the like.

The latent additive is inactive at room temperature, in the light exposure step and in the prebaking step, and is a protecting group by heating at 100 to 250 ° C. or heating at 80 to 200 ° C. in the presence of an acid / base catalyst. Is desorbed and activated. Examples of the effect obtained by activation include antioxidant, ultraviolet absorption, antifouling property, recoating property and adhesion.
As the latent additive, those described in WO2014 / 021023 pamphlet can be preferably used.

As the latent additive, a commercially available product can be used, and examples thereof include ADEKA ARCLUS GPA-5001.

In the polymerizable composition and the colored polymerizable composition of the present invention, any component other than the ethylenically unsaturated compound, the oxime ester compound of the present invention and the coloring material (provided that the above polymer, the inorganic compound, the coloring material and the solvent are used. The amount of (excluding) to be used 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 the colored polymerizable composition of the present invention are a photocurable paint or varnish; a photocurable adhesive; a printing ink; a dental composition; a photoresist for electronic engineering; an electroplating resist; an etching resist; Solder resist; and resist for forming structures in the LCD manufacturing process; composition for encapsulating electrical and electronic components; solder resist; magnetic recording material; plating mask; etching mask; three-dimensional object by stereolithography Materials for manufacturing; 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 purposes such as a photoresist material or a protective film used for forming a dielectric layer in successive lamination of printed circuit boards, and the application is not particularly limited.

The polymerizable composition and the colored polymerizable composition of the present invention can also be used for the purpose of forming a spacer for a liquid crystal display panel and for forming a protrusion for a vertically oriented liquid crystal display element. In particular, it is useful as a polymerizable composition and a colored polymerizable composition for simultaneously forming protrusions and spacers for a vertically oriented liquid crystal display element.

The above 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) irradiating the coating film with radiation through a mask having a predetermined pattern shape. It is preferably formed by the steps of (3) baking after exposure, (4) developing the film after exposure, and (5) heating the film after development.

The polymerizable composition and the colored polymerizable composition of the present invention to which an ink repellent is added are useful as a partition forming resin composition for an inkjet method, and the composition is used for a color filter, particularly having a profile angle of 50. It is preferably used for partition walls for inkjet color filters with a temperature of ° or higher. As the ink repellent, a composition composed of a fluorine-based surfactant and a fluorine-based surfactant 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 wall pattern, a dielectric pattern, an electrode pattern and a black matrix pattern of a plasma display panel.

The 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 soda glass, quartz glass, semiconductor substrate by known means such as a spin coater, a roll coater, a bar coater, a die coater, a curtain coater, various types of printing, and immersion. , Metal, paper, plastic and the like. Further, once applied on a support substrate such as a film, it can be transferred onto another support substrate, and there is no limitation on the application method.

As the light source of the energy ray used for curing the polymerizable composition or the colored polymerizable composition of the present invention, an ultra-high pressure mercury lamp, a high pressure mercury lamp, a medium pressure mercury lamp, a low pressure mercury lamp, a mercury vapor arc lamp, etc. Electromagnetic energy, electron beam, X-ray, etc. with wavelengths of 2000 angstrom to 7000 angstrom obtained from xenon arc lamp, carbon arc lamp, metal halide lamp, fluorescent lamp, tungsten lamp, excimer lamp, sterilization lamp, light emitting diode, CRT light source, etc. High-energy rays such as radiation can be used, but preferred examples thereof include an ultra-high pressure mercury lamp, a mercury vapor arc lamp, a carbon arc lamp, and a xenon arc lamp that emit light having a wavelength of 300 to 450 nm.

Further, by using a laser beam as an exposure light source, a laser direct drawing method for directly forming an image from digital information of a computer or the like can be applied without using a mask. The direct laser drawing method is useful because it can improve not only productivity but also resolution and position accuracy. As the laser light used in the laser direct drawing method, light having a wavelength of 340 to 430 nm is preferably used, but an excimer laser, a nitrogen laser, an argon ion laser, a helium cadmium laser, a helium neon laser, a krypton ion laser, and various semiconductors. Lasers, YAG lasers, and other 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 polymerizable composition of the present invention or the cured product obtained from the colored polymerizable composition 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 mobile information terminal, or a digital camera; a CCD image sensor. Color filters; electrode materials for plasma display panels; powder coatings; printed plates; magnetic recording materials; micromechanical parts; waveguides; optical switches; color test systems; glass fiber cable coatings; image recording materials; microelectronic circuits; decolorization It can be used for various purposes such as a material; a protective film; an insulating film; an optical element, and the use is not particularly limited.

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. 2 shown in [Chemical Formula 3]. The production of 1 and its intermediates 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 one fragment 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 dropping, the reaction was carried out 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 dropping, the temperature was raised to 60 ° C. and the reaction was carried out 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 stirring, ethyl acetate was added and oil-water separation was performed. After the 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 for separation. After washing with hydrochloric acid and water three times, the mixture was concentrated to obtain a crude product at 54.8 g. Then, 167.1 g of toluene was added, and after heating and dissolving at 50 ° C., 104.8 g of ethanol and 51.4 g of hexane were further added, cooled to 5 ° C., stirred for 1 hour, and then filtered to yield 28 the following intermediate 1B. It was obtained in 0.6 g and a yield of 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 zinc chloride was added and cooled. Next, 22.0 g (135 mmol) of octanoyl chloride was added dropwise at 5 ° C. over 20 minutes, and the reaction was carried out at room temperature for 25 hours.
After completion of the reaction, ethyl acetate / water was added, and after oil-water separation, treatment was performed 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 column chromatographed to obtain 21.8 g of the following intermediate 1C in a yield of 56.2%.

<Step 4; Manufacturing 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, and the mixture was 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 column chromatographed with silica gel 40 times to obtain 3.3 g of the following intermediate 1D in a yield of 42.3%.

<Step 4; Compound No. Manufacture of 1>
0.7 g (2 mmol) of 1D of the intermediate was added to 4.1 g of DMF, and after stirring and dissolving, 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 compound No. 1 was obtained in a yield of 0.4 g and a yield of 50.6%.

Compound No. 2 shown in [Chemical Formula 3]. The production of 2 and its intermediates 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 prepared by dissolving 58.6 g of indole in 292.9 g of EDC was added dropwise at 2 ° C. or lower, and then reacted at 20 to 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, and after heating and dissolving, 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 and reacted. The reaction mixture was allowed to cool to 45 ° C., ion-exchanged water and hydrochloric acid were added, and the mixture was filtered. The filter was dissolved in ethyl acetate, washed with ion-exchanged water, and then desolvated. The desolvent crude was crystallized from 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. Manufacture of 2>
54.7 g of DMF was added to 11.0 g (20 mmol) of the intermediate 2B, 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. It was ice-cooled again, ion-exchanged water and ethyl acetate were added, and oil-water separation was performed. 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 intermediates 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), and 8.5 g (40 mmol) of tripotassium phosphate. , 18.8 g of toluene was 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, the mixture 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 separating funnel. After washing the organic layer with water three times, white insoluble matter was observed, so the organic layer was filtered through a Kiriyama funnel. The filtrate was dried over anhydrous sodium sulfate and then desolvated 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 mixture 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 separating funnel. The organic layer was washed with water three times, dried over anhydrous sodium sulfate, and then desolvated. 150 g of hexane was added to the crude product, dispersed and washed, and then dried to obtain 4.0 g of the following intermediate 1b in a yield of 81%.

<Step 3; Comparative Compound No. Manufacture of 1>
Intermediate 1b 2.8 g (10 mmol), sodium acetate 0.1 g (1 mmol) and DMF 9.6 g were mixed, and acetic anhydride 1.1 g (11 mmol) 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 separating funnel. The organic layer was washed with water three times, dried over anhydrous sodium sulfate, and then desolvated. Hexane was added to the obtained crude product for crystallization, and the crystals were collected by filtration and dried. 1 was obtained as pale yellow crystals in an amount of 2.6 g and a yield of 82%.

Comparative Compound No. The production of 2 and its intermediates 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 on an ice bath at 5 ° C. 7.8 g (55 mmol) of methyl iodide was added dropwise thereto. After completion of the dropping, the reaction was carried out by stirring at room temperature for 8 hours. After completion of the reaction, the mixture was cooled to room temperature, the 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 separating funnel. The organic layer was washed with water three times, dried over anhydrous sodium sulfate, and then desolvated. The crude product was column chromatographed 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>
3.1 g (20 mmol) of the intermediate 2a and 39.6 g of 1,2-dichloroethane were mixed and stirred on an ice bath at 3 ° C. 3.3 g (24 mmol) of zinc chloride was added thereto. Then, 1.9 g (24 mmol) of acetyl chloride was added dropwise at 10 ° C. or lower. After completion of the dropping, the temperature was raised to room temperature and the mixture was stirred for 9 hours to carry out the reaction. After completion of the reaction, the mixture was poured into 150 g of ion-exchanged water. After adding 100 g of chloroform to this, it was transferred to a separating funnel for oil-water separation. The organic layer was washed with water three times, dried over anhydrous sodium sulfate, and then desolvated. The crude product was column chromatographed 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>
2.0 g (10 mmol) of the intermediate 2b and 0.8 g (12 mmol) of hydroxylamine hydrochloride 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, the mixture 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 separating funnel. The organic layer was washed with water three times, dried over anhydrous sodium sulfate, and then desolvated. 150 g of hexane was added to the crude product, dispersed and washed, 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. Manufacture 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 and 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 above 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. The solubility of 3 in PGMEA, PGM and cyclohexanone (CHN) at room temperature was evaluated. Those in which 10 wt% or more were dissolved were marked with ◯, those in which 3 wt% or more and less than 10 wt% were dissolved were marked with Δ, and those in which less than 3 wt% were dissolved were marked with x.

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

Therefore, when the oxime ester compound of the present invention is used as a polymerization initiator for a polymerizable composition, a wide range of solvents, raw materials, etc. can be selected, so that the degree of freedom of compounding is high, and precipitation of the oxime ester compound is unlikely 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 shown in [Table 5] to obtain polymerizable compositions (Examples 3 and 4 and Comparative Examples 4 to 6). The numbers in the table represent parts by mass. Compound No. as a polymerization initiator. 1. Compound No. 2. Comparative compound No. 1. Comparative compound No. 2 and Comparative Compound No. 3 was used alone.
The reference numerals of the respective components in the table represent the following components.
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
(Ethylene unsaturated compound with acid group; manufactured by Showa Denko)
B-2 Aronix M-450 (Ethylene 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 Arklus 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 above polymerizable composition were evaluated by the following methods. The results are shown in [Table 6].

(transparency)
The above polymerizable composition was spin-coated (500 rpm, 2 seconds, 900 rpm, 5 seconds) on a glass substrate, and prebaked at 90 ° C. for 90 seconds using a hot plate. A high-pressure mercury lamp was used as a light source for 100 mJ / cm ² exposure, and an oven was used for post-baking at 230 ° C. for 30 minutes. The transmittance at 380 nm and 400 nm was measured using an absorptiometer. Those having a transmittance of 400 nm of 95% or more and a transmittance of 380 nm of 92% or more were evaluated as ◯, those satisfying only one of them were evaluated as Δ, and those not satisfying both were evaluated as x.

(sensitivity)
The above polymerizable composition was spin-coated (500 rpm, 2 seconds, 900 rpm, 5 seconds) on a glass substrate, prebaked at 90 ° C. for 90 seconds using a hot plate, and then 10 mJ / using a high-pressure mercury lamp. Exposure was performed at intervals of 20 mJ / cm ² from cm ^{2 to} 1000 mJ / cm ² . Then, it was developed with a basic developer for 27 to 28 seconds.
In 100 mJ / cm ² less than the exposure of those cured film after development remained on the glass substrate and ◎, those 100 mJ / cm ² or more 1000 mJ / cm ² less than the cured film remained on the glass substrate as ○, 1000 mJ / cm Those in which the cured film did not remain on the glass substrate even if it was ² or more were marked with 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 preferable because it has 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 can be 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 a polymerizable composition.

Claims (8)

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

(In the formula, 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 independently described. Group 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 Represents ¹⁵ , COR ¹³ , SOR ¹³ , SO ₂ R ¹³ or CONR ¹⁴ R ¹⁵ .
R ¹³ , R ¹⁴ and R ¹⁵ each independently represent 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). It may be substituted with a 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. Yes, 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- in some cases be substituted,
R ¹⁶ represents a hydrogen atom and a hydrocarbon group having 1 to 20 carbon atoms.
R ¹¹ and R ¹² 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 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, a nitro group, a cyano group, a hydroxyl group, an amino group or a carboxyl group. , Methacryloyl group, acryloyl group, epoxy group, vinyl group, vinyl ether group, mercapto group, isocyanate group or heterocyclic group, which may be substituted with carbon atoms of 1 to 20 carbon atoms represented by R ¹¹ and R ^12. methylene groups in the heterocyclic group hydrogen group or a C2-20 is -O -, - CO -, - COO -, - OCO -, - NR 17 -, - NR 17 CO -, - S -, - It may be replaced with SO _2- , -SCO- or -COS-
R ¹⁷ represents a hydrogen atom and 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. )

(In the formula, R ²¹ and R ²² 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 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, a nitro group, a cyano group, a hydroxyl group, an amino group or a carboxyl group. , Methacryloyl group, acryloyl group, epoxy group, vinyl group, vinyl ether group, mercapto group, isocyanate group or heterocyclic group, which may be substituted with carbon atoms of 1 to 20 carbon atoms represented by R ²¹ and R ^22. methylene groups in the heterocyclic group hydrogen group or a C2-20 is -O -, - CO -, - COO -, - OCO -, - NR 23 -, - NR 23 CO -, - S -, - It may be replaced with SO _2- , -SCO- or -COS-
R ²³ represents a hydrogen atom and a hydrocarbon group having 1 to 20 carbon atoms.
n represents 0 or 1. ) 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 containing the polymerization initiator and the ethylenically unsaturated compound according to claim 4. A colored polymerizable composition containing the polymerizable composition and coloring material according to claim 5. 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.