KR20180058657A - Oxime ester compound and polymerization initiator containing the compound - Google Patents

Abstract

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 an oxime ester compound represented by the following general formula (II). ≪ / RTI > The oxime ester compound is preferably 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). It is preferable that 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.

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 polymerizable composition containing the polymerization initiator and an ethylenically unsaturated compound, A colored polymeric resin composition comprising a colorant and a colorant, and a cured product obtained from the polymerizable composition or the colored polymeric resin composition.

The polymerizable composition, which is obtained by adding a polymerization initiator to an ethylenically unsaturated compound, can be polymerized and cured by irradiation with an energy ray (light), and is therefore used in a photo-curable ink, a photosensitive printing plate,

As the polymerization initiator used in the polymerizable composition, it has been proposed in the Patent Documents 1 to 3 to use an oxime ester compound.

On the other hand, a cured product having high transparency obtained from a polymerizable composition in recent years is required in the market. However, there is a problem that there is no polymerization initiator which can obtain a cured product having high transparency as a polymerization initiator having a high solubility in a solvent and a high sensitivity.

US6596445 (B1) WO2013008652 pamphlet US2006 / 241259 A1

A problem to be solved by the present invention is that there is no polymerization initiator capable of obtaining a cured product having high transparency as a polymerization initiator having a high solubility in a solvent and a high sensitivity.

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

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

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 ) A group represented by the following general formula (II), a hydrogen atom, a halogen atom, a nitro group, a nitrile group, a cyano group, a hydroxyl group, a carboxyl group, a formyl group, a 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 represent a hydrocarbon group having 1 to 20 carbon atoms or a heterocyclic ring-containing group having 2 to 20 carbon atoms,

The hydrogen atom of a hydrocarbon group having 1 to 20 carbon atoms or a heterocyclic ring-containing group having 2 to 20 carbon atoms represented by R ¹³ , R ¹⁴ and R ¹⁵ is a group represented by the following formula (II), a nitrile group, a halogen A hydroxyl group, an amino group, a carboxyl group, a methacryloyl group, an acryloyl group, an epoxy group, a vinyl group, a vinyl ether group, a mercapto group, an isocyanate group or a heterocyclic ring containing group, and R ^The methylene group in the hydrocarbon group of 2 to 20 carbon atoms or the heterocyclic ring-containing group of 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-,

R ¹⁶ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms,

R ¹¹ and R ¹² 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 ring-containing group having 2 to 20 carbon atoms,

The hydrogen atom of the hydrocarbon group having 1 to 20 carbon atoms or the heterocyclic ring-containing group having 2 to 20 carbon atoms represented by R ¹¹ and R ¹² is preferably a halogen atom, a nitro group, a cyano group, a hydroxyl group, an amino group, a carboxyl group, An acryloyl group, an epoxy group, a vinyl group, a vinyl ether group, a mercapto group, an isocyanate group, or a heterocyclic ring-containing group, a hydrocarbon group having 1 to 20 carbon atoms represented by R ¹¹ and R ¹² , in methylene group-containing heterocyclic atoms, 2 to 20 groups -O-, -CO-, -COO-, -OCO-, -NR 17 -, -NR 17 CO-, -S-, -SO 2 -, - SCO- or -COS-,

R ¹⁷ represents a hydrogen atom or 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 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 are combined to form a ring However,

and 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 ring-containing group having 2 to 20 carbon atoms,

The hydrogen atom of a hydrocarbon group having 1 to 20 carbon atoms or a heterocyclic ring-containing group having 2 to 20 carbon atoms represented by R ²¹ and R ²² is preferably a halogen atom, a nitro group, a cyano group, a hydroxyl group, an amino group, a carboxyl group, An alkoxy group, an acryloyl group, an epoxy group, a vinyl group, a vinyl ether group, a mercapto group, an isocyanate group or a heterocyclic ring-containing group, and a hydrocarbon group having 1 to 20 carbon atoms represented by R ²¹ and R ²² , The methylene group in the heterocyclic containing group having 2 to 20 atoms is preferably -O-, -CO-, -COO-, -OCO-, -NR ²³ -, -NR ²³ CO-, -S-, -SO ₂ -, - SCO- or -COS-,

R ²³ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms,

and n represents 0 or 1.)

The present invention also provides a polymerizable composition containing the polymerization initiator and the ethylenically unsaturated compound.

The present invention also provides a colored polymerizable composition containing the above polymerizable composition and a colorant.

The present invention also provides a cured product obtained from the polymerizable composition or the colored polymerizable composition.

Further, the present invention 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 includes a geometric isomer of a oxime double bond, but does not distinguish them.

That is, in the present specification, the compound represented by the general formula (I) and the exemplified compound thereof represent a mixture or both of them, and the present invention is not limited to the structure showing the isomer.

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, but is preferably 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 an arylalkyl group having 7 to 20 carbon atoms.

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, , Octyl, isooctyl, 2-ethylhexyl, t-octyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, tetradecyl, hexadecyl, octadecyl and icosyl.

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, octahydrophthalene and bicyclo [1.1.1] And the like.

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

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

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

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, pyridyl Wherein R is selected from the group consisting of methyl, ethyl, pyrimidyl, pyridazyl, piperazyl, piperidyl, pyranyl, pyranylethyl, pyrazolyl, triazyl, triazylmethyl, pyrrolidyl, quinolyl, isoquinolyl, Wherein the substituent is selected from the group consisting of hydrogen, alkyl, alkenyl, alkynyl, aryl, heteroaryl, heteroaryl, heteroaryl, heteroaryl, Indolyl, julolidyl, morpholinyl, thiomorpholinyl, 2-pyrrolidinone-1-yl, 2-piperidone-1-yl, 2,4-deoxyimidazolidin- Yl and 2,4-dioxoxazolidin-3-yl.

Examples of the halogen atom in the general formulas (I) and (II) include fluorine, chlorine, bromine and iodine. As the ring 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 , Examples of the cyclic ring include cyclopentane ring, cyclohexane ring, cyclopentene ring, benzene ring, pyrrolidine ring, pyrrole ring, piperazine ring, piperidine ring, morpholine ring, thiomorpholine ring, tetrahydropyridine ring, 5-to 7-membered rings such as a lactam ring, condensed rings such as naphthalene ring and anthracene ring, and the like.

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) is preferable because it has good absorption wavelength and high sensitivity when used as a polymerization initiator. When at least one of R ³ and R ⁸ is a group represented by the general formula (II), it is more preferable because the synthesis is easy and the stability of the oxime ester compound is good. The case where R < ⁸ > is a group represented by the general formula (II) is most preferable because the cured product obtained from the above polymerization composition when used as a polymerization initiator of the polymerizable composition has high transparency and little coloration.

At least one of R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ in the general formula (I) is preferably an electron-withdrawing group oxime ester compound because it becomes highly sensitive when used as a polymerization initiator.

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 them, at least one member 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 higher sensitivity is obtained.

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

The oxime ester compound wherein R ¹¹ in general formula (I) is an alkyl group having 4 to 20 carbon atoms has solubility in an ether ester solvent represented by PGMEA (propylene glycol-1-monomethyl ether-2-acetate) High. 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 above as the 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 is highly sensitive when it is used as a polymerization initiator.

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

Of the above oxime ester compounds, the oxime ester compound wherein 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 is an alkyl group having 4 to 20 carbon atoms It is more preferable that the oxime ester compound is easy to be synthesized, the oxime ester compound is stable, the solubility in various solvents is high, and it is used as a polymerization initiator since the absorption wavelength is good, high sensitivity, transparency of the cured product is high and coloration is small.

Specifically, as the oxime ester compound of the present invention, the above-mentioned compounds No. 1 to No. 90 are preferable.

The oxime ester compound of the present invention represented by the above general formula (I) is not particularly limited, but when m = 0, it can be prepared by the following method, for example, according to the reaction formula shown below.

The indole compound 2 is obtained by reacting a commercially available indole compound 1 with a halogenated aryl compound to obtain a ketone compound 1 by reacting the indole compound 2 with an acid chloride and reacting the ketone compound 1 with hydroxylamine hydrochloride, Oxime compound 1 is obtained.

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 compounds and oxime ester compounds can also be prepared by the method described in Japanese Patent No. 4223071.

In the case of 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 reaction formula shown below.

The indole compound 2 is obtained by reacting a commercially available indole compound 1 with a halogenated aryl compound to obtain a ketone compound 2 by reacting the indole compound 2 with an acid chloride and reacting the ketone compound 2 with isobutyl nitrite To obtain an oxime compound 2. 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. Further, the novel oxime ester compound of the present invention can be preferably used as a base generator and a sensitizer.

The polymerization initiator of the present invention contains, as an essential component, the oxime ester compound of the present invention represented by the above general formula (I). The polymerization initiator of the present invention may be used in combination with the oxime ester compound of the present invention together with other polymerization initiators. 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, benzyldimethylketal, (4'-methylmercapto) benzoyl propane, thioxanthone, 1-chloro-4-methoxybenzoyl chloride, Benzoyl-4'-methyldiphenylsulfide, benzoin butyl ether, 2-hydroxy-2-benzoylpropane, 2-hydroxy- , 2-hydroxy-2- (4'-isopropyl) benzoyl propane, 4-butylbenzoyl trichloromethane, 4-phenoxybenzoyl dichloromethane, methyl benzoate, 1,7- ) Heptane, 9-n-butyl-3,6-bis (2'-morpholinoisobutyloyl) carbazole, 2-methyl-4,6-bis (trichloromethyl) Phenyl-4,6-bis (trichloromethyl) -s- Bis (trichloromethyl) -s-triazine, 2,2-bis (2-chlorophenyl) -4,5,4 ', 5'-tetraphenyl- N-1419, NCI-831, NCI-930 (product of ADEKA), 4,4-azobisisobutyronitrile, triphenylphosphine, camphorquinone, N-1414, N-1717, , IRGACURE 369, IRGACURE 907, IRGACURE OXE 01, IRGACURE OXE 02 (product of BASF), and benzoyl peroxide. The other polymerization initiators may be used singly 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 mass%, more preferably 50 to 100 mass%.

The polymerizable composition of the present invention contains the polymerization initiator and the 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. Examples of the ethylenically unsaturated compound include ethylene, propylene, butylene, isobutylene, vinyl chloride, vinylidene chloride, vinyl fluoride Unsaturated aliphatic hydrocarbons such as diene, tetrafluoroethylene and the like; (Meth) acrylic acid,? -Chloroacrylic acid, itaconic acid, maleic acid, citraconic acid, fumaric acid, hymic acid, crotonic acid, isocrotonic acid, vinylacetic acid, allylacetic acid, cinnamic acid, sorbic acid, (Meth) acryloyloxyethyl] mono [2- (meth) acryloyloxyethyl] phthalate mono [2- (meth) acryloyloxyethyl], omega -carboxypolycaprolactone mono A mono (meth) acrylate of a polymer having a hydroxyl group; (Meth) acrylate maleate, hydroxypropyl (meth) acrylate maleate, dicyclopentadiene maleate or polyfunctional (meth) acrylate having one carboxyl group and two or more Unsaturated polybasic acids such as methacrylic acid and methacrylic acid; (Meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, glycidyl Butyl (meth) acrylate, isobutyl (meth) acrylate, cyclohexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, isononyl Stearyl acrylate, lauryl (meth) acrylate, methoxyethyl (meth) acrylate, dimethylaminomethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, aminopropyl (meth) acrylate, dimethylaminopropyl (Meth) acrylate, ethoxyethyl (meth) acrylate, poly (ethoxy) ethyl (meth) acrylate, butoxyethoxyethyl (meth) acrylate, ethylhexyl (Meth) acrylate, allyl (meth) acrylate, (Meth) acrylate, benzyl (meth) acrylate, ethyleneglycol di (meth) acrylate, diethyleneglycol di (meth) acrylate, triethyleneglycol di Acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6- Pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, tricyclodecane dimethylol (meth) acrylate, pentaerythritol hexa (meth) acrylate, dipentaerythritol penta Esters of unsaturated monobasic acids and polyhydric alcohols or polyhydric phenols such as tri [(meth) acryloylethyl] isocyanurate and polyester (meth) acrylate oligomer; Metal salts of unsaturated polybasic acids such as zinc (meth) acrylate and magnesium (meth) acrylate; Maleic anhydride, maleic anhydride, itaconic anhydride, citraconic anhydride, methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, trialkyltetrahydrophthalic anhydride, 5- (2,5-dioxotetrahydrofuryl) Acid anhydrides of unsaturated polybasic acids such as cyclohexene-1,2-dicarboxylic acid anhydride, trialkyltetrahydrophthalic anhydride-maleic anhydride adduct, dodecenyl ansuccinic acid, and anhydrous methyl hemiamic acid; (Meth) acrylamide, methylenebis- (meth) acrylamide, diethylenetriamintris (meth) acrylamide, xylylenebis (meth) acrylamide, alpha -chloroacrylamide, N-2-hydroxyethyl Amides of unsaturated monobasic acids and polyamines such as methacrylamide; Unsaturated aldehydes such as acrolein; Unsaturated nitriles such as (meth) acrylonitrile,? -Chloroacrylonitrile, vinylidene cyanide and allyl cyanide; unsaturated nitriles such as styrene, 4-methylstyrene, 4-ethylstyrene, 4-methoxystyrene, 4-hydroxystyrene, Unsaturated aromatic compounds such as chlorostyrene, divinylbenzene, vinyltoluene, vinylbenzoic acid, vinylphenol, vinylsulfonic acid, 4-vinylbenzenesulfonic acid, vinylbenzylmethylether and vinylbenzylglycidylether; Unsaturated ketones such as methyl vinyl ketone; Unsaturated amine compounds such as vinylamine, allylamine, N-vinylpyrrolidone and vinylpiperidine; 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; Unsaturated imides such as maleimide, N-phenylmaleimide and N-cyclohexylmaleimide; Indene such as indene and 1-methylindene; Aliphatic conjugated dienes such as 1,3-butadiene, isoprene and chloroprene; Macromonomers having a mono (meth) acryloyl group at the end of a polymer molecular chain such as polystyrene, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate and polysiloxane; Vinyl chloride, vinylidene chloride, divinyl succinate, diallyl phthalate, triallyl phosphate, triallyl isocyanurate, vinyl thioether, vinyl imidazole, vinyl oxazoline, vinyl carbazole, vinyl pyrrolidone, vinyl Pyridine, a vinyl urethane compound of a hydroxyl group-containing vinyl monomer and a polyisocyanate compound, a vinyl epoxy compound of a hydroxyl group-containing vinyl monomer and a polyepoxy compound.

Among them, mono (meth) acrylate of a polymer having a carboxyl group and a hydroxyl group at both terminals, polyfunctional (meth) acrylate having one carboxyl group and two or more (meth) acryloyl groups, unsaturated monobasic acid and polyhydric alcohol Or an ester of a polyhydric phenol, a polymerization initiator containing the oxime ester compound of the present invention is preferable.

These ethylenically unsaturated compounds may be used singly or as a mixture of two or more kinds. When two or more kinds of the ethylenically unsaturated compounds are mixed and used, they may be copolymerized in advance and used as a copolymer.

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) may be used for 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, a copolymer of a resin and an acrylate ester described in JP 2004-264414 A, a phenol, a cresol novolak Epoxy resins, polyphenylmethane type epoxy resins having polyfunctional epoxy groups, epoxyacrylate resins and resins obtained by further reacting an epoxy acrylate resin with a polybasic acid anhydride.

DPA-12, PEG400DA, THE-330, RP-1040, NPGDA, PET30 (manufactured by Nippon Kayaku), SPC- N-ester A-DPHA-TMPT, A-DCP, A-HD (manufactured by Nippon Kayaku Co., Ltd.), SPC-3000 (manufactured by Showa Denko K.K.), Aronix M-140, M-215, M- -N, A-9300, TMPT, DCP, NPG and HD-N (available from 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, more preferably 0.5 to 50 parts by mass, per 100 parts by mass of the ethylenically unsaturated compound , And most preferably 0.5 to 30 parts by mass.

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

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

As the pigment, for example, a nitroso compound; Nitro compounds; Azo compounds; Diazo compounds; Xanthene compounds; Quinoline compounds; Anthraquinone compounds; Coumarin compounds; Phthalocyanine compounds; Isoindolinone compounds; Isoindoline compounds; Quinacridone compounds; Anthanthrone compounds; Perinone compounds; Perylene compounds; Diketopyrrolopyrrole compounds; Thioindigo compounds; Dioxadine compounds; Triphenylmethane compounds; Quinophthalone compounds; Naphthalene tetracarboxylic acid; Azo dyes, metal complex compounds of cyanine dyes; Lake pigment; A carbon black obtained by a furnace method, a channel method or a thermal method, or carbon black such as acetylene black, Ketjen black or lamp black; The carbon black is adjusted or coated with an epoxy resin, the carbon black is dispersed in a resin in advance in a solvent to adsorb a resin of 20 to 200 mg / g, an acidic or alkaline surface-treated carbon black , An average particle diameter of 8 nm or more and a DBP oil absorption of 90 ml / 100 g or less, a total oxygen amount calculated from CO and CO ₂ in volatile matter 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 airgel, fullerene; Aniline black, pigment black 7, titanium black; Chromium oxide green, milori blue, cobalt green, cobalt blue, manganese, ferrocyanide, phosphate salt, ultramarine, cerulean blue, viridian, emerald green, lead sulfate, yellow Organic or inorganic pigments such as lead, zinc sulfur, red iron oxide (red iron oxide (III)), cadmium red, synthetic iron black and amber may be used. These pigments can be used singly or in combination of plural.

Examples of the pigment include commercially available pigments such as Pigment Red 1, 2, 3, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48, 49, 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, , 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.

Examples of the dye include azo dyes, anthraquinone dyes, indigoid dyes, triarylmethane dyes, xanthene dyes, alizarin dyes, acridine dye stilbene dyes, naphthol dyes, quinoline dyes, Dyes such as indanamine dyes, oxazine dyes, phthalocyanine dyes, 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, based on 100 parts by mass of the ethylenically unsaturated compound.

In the polymerizable composition and the colored polymerizable composition, a solvent capable of dissolving or dispersing a polymerization initiator, an ethylenically unsaturated compound and a coloring material may be added, if necessary. Examples thereof include ketones such as methyl ethyl ketone, methyl amyl ketone, diethyl ketone, acetone, methyl isopropyl ketone, methyl isobutyl ketone, cyclohexanone and 2-heptanone; Ether solvents such as ethyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane, dipropylene glycol dimethyl ether and propylene glycol monomethyl ether (PGM); Ester solvents such as methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, cyclohexyl acetate, ethyl lactate, dimethyl succinate, and texanol; Cellosolve solvents such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; Alcohol-based solvents such as methanol, ethanol, iso-or n-propanol, iso- or n-butanol, and amyl alcohol; Propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, 3-methoxybutyl ether acetate, ethoxyethyl ether propionate Ether-based solvents such as N-methylpyrrolidone; BTX type solvents such as benzene, toluene and xylene; Aliphatic hydrocarbon solvents such as hexane, heptane, octane and cyclohexane; Terpene-based hydrocarbon oils such as terphenyl oil, D-limonene, and pinene; Paraffin solvents such as Mineral Spirit, Swazol # 310 (Cosmo Matsuyama), Solvesso # 100 (Exxon Gakusa); Halogenated aliphatic hydrocarbon solvents such as carbon tetrachloride, chloroform, trichlorethylene, methylene chloride and 1,2-dichloroethane; halogenated aromatic hydrocarbon solvents such as chlorobenzene; Carbitol-based solvents; aniline; Triethylamine; Pyridine; Acetic acid; Acetonitrile; Carbon disulfide; N, N-dimethylformamide; N, N-dimethylacetamide; N-methylpyrrolidone; Dimethyl sulfoxide; Water, and the like. These solvents can be used singly or as a mixed solvent of two or more kinds.

Of these, ketones and ether ester-based solvents, such as cyclohexanone and PGMEA, are preferred because they have good compatibility between the ethylenically unsaturated compound and the polymerization initiator in the polymerizable composition.

(Hereinafter also referred to as a polymer) other than the ethylenically unsaturated compound, an inorganic compound, a dispersing agent, a chain transfer agent, a binder, and the like may be added to the polymerizable composition and the colored polymerizable composition of the present invention, A surfactant, a silane coupling agent, a melamine, a leveling agent, a latent additive, a monomer other than an ethylenically unsaturated compound, a defoaming agent, a thickener (thickening agent), and a thickener other than the oxime ester compound of the invention Various kinds of resin additives such as a plasticizer, a flame retardant, a plasticizer, a stabilizer, a polymerization inhibitor, an ultraviolet absorber, an organic filler, an antioxidant, an antistatic agent, a flow regulator and an adhesion promoter.

By using the polymer in combination with the ethylenically unsaturated compound, the properties of the cured product may be improved. 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- Polyvinyl chloride resin, ABS resin, nylon 6, nylon 66, nylon 12, urethane resin, polycarbonate polyvinyl butyral, cellulose ester, polyacrylamide , A saturated polyester, a phenol resin, a phenoxy resin, a polyamideimide resin, a polyamic acid resin, and an epoxy resin. Of these, polystyrene, a (meth) acrylic acid-methyl methacrylate copolymer and an epoxy resin are preferable Do.

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 based on 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; (In particular, glass frit), mica, talc, kaolin, ferrocyanide, various metal sulfates, sulfides, selenides (such as calcium carbonate, magnesium carbonate, cobalt, manganese, , Aluminum silicate, calcium silicate, aluminum hydroxide, platinum, 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, for example, as fillers, antireflective agents, conductive agents, stabilizers, flame retardants, mechanical strength improvers, special wavelength absorbents, ink repellants 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, relative to 100 parts by mass of the ethylenically unsaturated compound . These inorganic compounds may 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 such as BYK series of Big Chem products can be used. Particularly, a polymer dispersing agent comprising a polyester having a basic functional group, a polyether or a polyurethane, a functional group having a nitrogen atom as a basic functional group and having a nitrogen atom is an amine and / or a quaternary salt thereof and has an amine value of 1 to 100 mg KOH / g is preferably used.

As the chain transfer agent or sensitizer, a sulfur atom-containing compound is generally used. 3-mercaptopropionic acid, N- (2-mercaptopropionyl) glycine, 2-mercapto nicotinic acid, 3-mercaptopropionic acid, 3-mercaptopropionic acid and the like are exemplified by thioglycolic acid, thioferric acid, thiosalicylic acid, 2- mercaptopropionic acid, - [N- (2-mercaptoethyl) amino] propionic acid, N- (3-mercaptopropionyl) alanine, 2-mercaptoethanol Mercaptoethanesulfonic acid, dodecyl (4-methylthio) phenyl ether, 2-mercaptoethanol, 3-mercapto-1,2-propanediol, 1-mercapto- 3-mercapto-2-butanol, mercaptophenol, 2-mercaptoethylamine, 2-mercaptoimidazole, 2-mercaptobenzoimidazole, 2- (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), and the like, which are known in the art, such as 2-mercaptobenzothiazole, mercaptoacetic acid, trimethylolpropane tris Mercapto compounds, disulfide compounds obtained by oxidizing the mercapto compounds, alkyl iodide compounds such as iodoacetic acid, iodopropionic acid, 2-iodoethanol, 2-iodoethanesulfonic acid and 3-iodopropanesulfonic acid, trimethylolpropane tris (3 -Mercaptoisobutyrate), butanediol bis (3-mercaptoisobutylate), hexanedithiol, decanedithiol, 1,4-dimethylmercaptobenzene, butanediol bis-thiouropionate, butanediol bis- Propylene glycol monobutyl ether, propylene glycol monobutyl ether, propylene glycol monobutyl ether, propylene glycol monobutyl ether, propylene glycol monobutyl ether, propylene glycol monobutyrate, ethylene glycol bistioglycolate, trimethylolpropane tristhioglycolate, butanediol bistyphosphate, trimethylolpropane tristhiopropionate, trimethylolpropane tristhioglycolate, , Pentaerythritol tetrakisthioglycolate, trishydroxyetilide Aliphatic polyfunctional thiol compounds such as stearoyl phonate, diethyl thioxanthone, diisopropyl thioxanthone, the following compound No. C1 and trimercapto propionic acid tris (2-hydroxyethyl) isocyanurate, And the products made by Denko Corporation, such as Carbens MT BD1, PE1, and NR1.

Examples of the surfactant include fluorine surfactants such as perfluoroalkylphosphoric acid esters and perfluoroalkylcarboxylic acid salts, anionic surfactants such as higher fatty acid alkali salts, alkylsulfonates and alkylsulfates, higher amine halides, Cationic surfactants such as 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, and silicone surfactants Surfactants may be used, and they may be used in combination.

As the silane coupling agent, for example, a silane coupling agent available from Shin-Etsu Chemical Co., Ltd. can be used. Among them, an isocyanate group, a methacryloyl group or an epoxy group such as KBE-9007, KBM-502 and KBE- A silane coupling agent is preferably used.

Examples of the melamine compound include an active methylol group (CH ₂ OH group) in a nitrogen compound such as (poly) methylol melamine, (poly) methylol glycoluril, (poly) methylolbenzoguanamine, (poly) (At least two) of all or some of them are alkyl-etherified.

Here, examples of the alkyl group constituting the alkyl ether include a methyl group, an ethyl group, and a butyl group, and they may be the same or different. In addition, the methylol group which is not alkyl-etherified may self-condense within one molecule, or may condense between two molecules, resulting in formation of an oligomer component.

Specifically, hexamethoxymethylmelamine, hexabutoxymethylmelamine, tetramethoxymethylglycoluril, tetrabutoxymethylglycoluril and the like can be used.

Of these, alkyl etherified melamines such as hexamethoxymethyl melamine and hexabutoxymethyl melamine are preferred.

As the leveling agent, a commercially available product can be used. As a leveling agent for a commercial product, for example, BYK-300, BYK-301, BYK-302, BYK-306, BYK-307, BYK-310, BYK- BYK-323, BYK-325, BYK-330, BYK-331, BYK-333, BYK-337, BYK-341, BYK-344, BYK- 349, BYK-370, BYK-375, BYK-377, BYK-UV3500, BYK-UV3510, BYK-UV3570, BYK-340, BYK-3550, BYK-SILCLEAN3700, BYK-SILCLEAN3720, BYK-DYNWET800 Polyflux No.3, Polyflow No.50HF, Polyflow No.54, Polyflow No.64HF, Polyflow No.75, Polyflow No.77, Polyflow No.85HF, Polyflow No 90, Granol 400, Granol 420, Granol 440, Granol 450, Granol B-1484, < RTI ID = 0.0 & FZ-2122, FZ-2122 and FZ-2123 (manufactured by Dow Corning Toray Industries, Inc.), L-7001, L-7002, L-7006, 56ADDITIVE, 57ADDITIVE, 67ADDITIVE, 8032ADDITIVE, FZ- And the like.

The latent additive is inert in the room temperature, light exposure process, and prebake process, and is heated at a temperature of 100 to 250 ° C or in the presence of an acid / base catalyst to be heated at 80 to 200 ° C, will be. Examples of effects obtained by activation include oxidation prevention, ultraviolet absorption, antifouling property, recoatability, and adhesion.

As the latent additive, those described in WO2014 / 021023 can be preferably used.

As the above-mentioned latent additive, a commercially available product can be used. For example, Adeka AcuLites GPA-5001 and the like can be mentioned.

In the polymerizable composition and the colored polymerizable composition of the present invention, the amount of the ethylenically unsaturated compound, the oxime ester compound of the present invention, and optional components other than the coloring material (excluding the above polymer, inorganic compound, coloring material and solvent) Is suitably selected according to the purpose of use and is not particularly limited, but is preferably 50 parts by mass or less based on 100 parts by mass of the ethylenically unsaturated compound.

The polymerizable composition and the colored polymerizable composition of the present invention can be used as a photocurable paint or varnish; Photocurable adhesive; Printing ink; Dental compositions; Photoresists for electronics; Electroplating resist; Etching resist; Solder resist; And a resist for forming a structure in a manufacturing process of an LCD; A composition for enclosing electrical and electronic components; Solder resist; Magnetic recording material; A plating mask; An etching mask; A material for producing a three-dimensional object with stereolithography; A decolorizing material for an image recording material; A decolorizing material for an image recording material using microcapsules; Photoresist materials for printed wiring boards; Photoresist materials for UV and visible laser direct imaging systems; And can be used for various applications such as a photoresist material or a protective film used for forming a dielectric layer in successive lamination of a printed circuit board, and there is no particular limitation on its use.

The polymerizable composition and the colored polymerizable composition of the present invention can be used for the purpose of forming a spacer for a liquid crystal display panel and for forming a projection for a vertical alignment type liquid crystal display element. And is particularly useful as a polymerizable composition and a colored polymerizable composition for simultaneously forming protrusions and spacers for vertically aligned liquid crystal display elements.

The above liquid crystal display panel spacer may be formed by (1) forming a coating film (coating film) of the polymerizable composition of the present invention on a substrate, (2) irradiating 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 film after exposure, and (5) a step of heating the coating film after development.

The polymerizable composition and the colored polymerizable composition of the present invention to which an ink repellent agent is added are useful as a barrier rib forming resin composition for an ink jet system. The composition is used for a color filter, and particularly, And is preferably used for a filter partition wall. As the ink repellent agent, a composition comprising 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 photosensitive paste composition by containing an inorganic material (inorganic compound). The photosensitive paste composition is used to form a fired pattern such as a barrier rib 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 the colored polymerizable composition of the present invention can be produced by a known means such as a spin coater, a roll coater, a bar coater, a die coater, a curtain coater, various printing, , Paper, plastic, or the like. Further, the film may be once transferred onto a supporting substrate such as a film, and then transferred onto another supporting substrate.

Examples of the light source of the energy ray used for curing the polymerizable composition or the colored polymerizable composition of the present invention include an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a medium pressure mercury lamp, a low pressure mercury lamp, a mercury vapor arc, Energy rays such as electromagnetic wave energy having a wavelength of 2000 to 7000 angstroms, electron beams, X-rays, and radiation obtained from metal halide lamps, fluorescent lamps, tungsten lamps, excimer lamps, sterilizing lights, light emitting diodes and CRT light sources Mercury vapor arc, carbon arc, xenon arc, etc., which emit light with a wavelength of 300 to 450 nm, are preferably used.

Further, by using the laser light for the exposure light source, the laser direct imaging method for forming an image directly 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 positional accuracy can be improved. As the laser beam used in the laser direct imaging 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 to emit light in the infrared region from visible light such as a YAG laser. In the case of using these lasers, the polymerizable composition and the colored polymerizable composition of the present invention are added with a sensitizing dye which absorbs the corresponding infrared region from visible.

The cured product obtained from the polymerizable composition or the colored polymerizable composition of the present invention may be a printed substrate; A color filter in a liquid crystal display element of color display such as a color TV, a PC monitor, a portable information terminal, and a digital camera; A color filter of a CCD image sensor; An electrode material for a plasma display panel; Powder coating; Printing plates; Magnetic recording material; Micro machine parts; Waveguides; Optical switch; Color test system; Glass fiber cable coating; Image recording material; Microelectronic circuits; Decolorizing material; A protective film; Insulating film; Optical elements, and the like, and there is no particular limitation on the use thereof.

Example

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.

The preparation of Compound No. 1 and its intermediates is shown below.

<Step 1; Preparation 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. Subsequently, 111.1 g (681 mmol) of 2-bromothiophene was added dropwise, and the mixture was added at 20 占 폚 or lower. After completion of dropwise addition, reaction was carried out at 17 캜 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 dropwise addition, the temperature was raised to 60 占 폚 and the reaction was carried out for 22 hours.

After completion of the reaction, the reaction mixture was cooled to 30 ° C, 10% hydrochloric acid was added dropwise, and the mixture was stirred until the remaining magnesium dissolved. After completion of the stirring, ethyl acetate was added to separate oil and water. After the separation of oil and water, washing with water was carried out four times, and a de-solvent was carried out to obtain 124.1 g of the following intermediate 1A in a yield of 97.1%.

<Step 2; Preparation of intermediate 1B >

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 in a nitrogen atmosphere 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 캜, and 120.4 g of toluene was added thereto to separate. The mixture was treated with hydrochloric acid, washed three times with water, and then concentrated to obtain 54.8 g of a crude product. Thereafter, 167.1 g of toluene was added, and the mixture was dissolved by heating at 50 占 폚. Then, 104.8 g of ethanol and 51.4 g of hexane were further added thereto. The mixture was cooled to 5 占 폚 and stirred for 1 hour and then filtered to obtain the following intermediate 1B in an amount of 28.6 g 71.4%.

<Step 3; Preparation of intermediate 1C >

27.4 g (90 mmol) of Intermediate 1B synthesized above was added to 194.0 g of EDC in a nitrogen atmosphere, dissolved at room temperature, and then added with zinc chloride, followed by cooling. Next, 22.0 g (135 mmol) of octanoyl chloride was added dropwise at 5 占 폚 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 the oil and water were separated, treated with hydrochloric acid, and treated in the order of sodium chloride aqueous solution and saturated brine three times to desolvate. 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; Preparation of intermediate 1D >

7.5 g (17 mmol) of Intermediate 1C was added to 24.0 g of pyridine, and after stirring and dissolution, 2.4 g (34 mmol) of hydroxylamine hydrochloride was added, and the mixture was heated to 60 캜 and reacted for 2 hours. After completion of the reaction, washing with water was carried out three times to remove the solvent. The crude product (9.7 g) was subjected to column chromatography with 40 times of silica gel to obtain 3.3 g of Intermediate 1D shown below at a yield of 42.3%.

<Step 4; Preparation of compound No. 1 >

0.7 g (2 mmol) of Intermediate 1D was added to 4.1 g of DMF, and after stirring and dissolution, 0.5 g (4.7 mmol) of acetic anhydride and one piece of sodium acetate were added and reacted at 40 ° C for 4 hours. After completion of the reaction, washing with water was carried out three times to remove the solvent. The crude product (0.7 g) was subjected to column chromatography at 40 × on silica gel to obtain Compound No. 1 in an amount of 0.4 g and a yield of 50.6%.

The preparation of Compound No. 2 and its intermediates is shown below.

<Step 1; Preparation of intermediate 2A >

After adding 80.0 g (1200 mmol) of aluminum chloride to 365.0 g of EDC at 0 占 폚, 97.6 g (1200 mmol) of n-octanoyl chloride was added dropwise at 2 占 폚 or lower to make it uniform. An EDC solution obtained by dissolving 58.6 g of indole in 292.9 g of EDC was added dropwise at 2 ° C or lower, and the mixture was 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 waxy solid. Methanol was added to the precipitated waxy solid, and after heating and dissolution, water was added dropwise, and the precipitate was filtered and dried. The crude product (116.5 g) was purified by column chromatography with silica gel 60 times to obtain 31.0 g, and then crystallized from 60-fold amount of methanol to obtain 12.6 g of Intermediate 2A shown below.

<Step 2; Preparation 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 and reacted at 130 ° C for 3 hours. The reaction solution was cooled to 45 ° C, ion-exchanged water and hydrochloric acid were added thereto, and the mixture was filtered. The filtrate was dissolved in ethyl acetate, washed with ion-exchanged water, and then desolvated. The crude product of the desolvation was purified by a mixed solvent of ethyl acetate, isopropyl alcohol and hexane, filtered, and dried to obtain 12.5 g of the following intermediate 2B.

<Step 3; Preparation of Compound No. 2 >

(20 mmol) of 35% hydrochloric acid was added dropwise, followed by addition of 8.3 g (80 mmol) of isobutyl nitrite, and the mixture was stirred at room temperature for 24 hours Lt; / RTI &gt; 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 and desolvation was carried out to obtain 13.1 g of Compound No. 2.

Production of Comparative Compound No. 1 and its intermediates is shown below.

<Step 1; Preparation of intermediate 1a >

(4 mmol) of copper iodide, 0.9 g (8 mmol) of cyclohexane diamine (cis-trans mixture), 8.5 g (40 mmol) of tripotassium phosphate, 6.4 g of 3-acetylindole, Were mixed and stirred at room temperature. 8.2 g (40 mmol) of iodobenzene was added dropwise thereto. After completion of the dropwise addition, the mixture was heated and stirred at an oil bath temperature of 135 占 폚 for 18 hours to carry out the reaction. After completion of the reaction, the reaction mixture was cooled to room temperature. The reaction solution was poured into 150 g of ion-exchanged water and 200 g of toluene was added to separate the oil and water from the separated solution. After washing the organic layer three times, white insoluble material was observed, so that it was filtered with a Kiriyama lot. The filtrate was dried over anhydrous sodium sulfate and desolvated to obtain 6.3 g of the following intermediate 1a in a yield of 67%.

<Step 2; Preparation of intermediate 1b >

(20 mmol) of Intermediate 1a, 1.7 g (24 mmol) of hydroxylamine hydrochloride, 25.0 g of DMF and 1.9 g (24 mmol) of pyridine were mixed and reacted at an oil bath temperature of 80 ° C for 6 hours. After completion of the reaction, the reaction mixture was cooled to room temperature. The reaction mixture was poured into 150 g of ion exchange water and 200 g of ethyl acetate was added to separate oil and water from the separated liquid. The organic layer was washed with water three times, dried over anhydrous sodium sulfate, and then desolvated. The crude product was dispersed and washed with 150 g of hexane, and then dried to obtain 4.0 g of the following intermediate 1b in a yield of 81%.

<Step 3; Preparation of Comparative Compound No. 1>

2.8 g (10 mmol) of 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 to the mixture on an ice bath at 5 ° C . After raising the temperature to room temperature, the reaction was carried out with stirring for 8 hours. The reaction solution was poured into 100 g of ion-exchanged water, and 150 g of ethyl acetate was added thereto, and separation of oil and water was carried out 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 to crystallize, and the crystals were collected by filtration and dried to obtain 2.6 g of the following Comparative Compound No. 1 as pale yellow crystals in a yield of 82%.

The preparation of Comparative Compound No. 2 and its intermediates is shown below.

<Step 1; Preparation 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 stirring was carried out at 5 DEG C on an ice bath. 7.8 g (55 mmol) of methyl iodide was added dropwise thereto. After completion of the dropwise addition, the reaction was carried out at room temperature for 8 hours with stirring. After completion of the reaction, the reaction mixture was cooled to room temperature. The reaction mixture was poured into 150 g of ion-exchanged water, and 200 g of ethyl acetate was added to separate oil and water from the separated liquid. The organic layer was washed with water three times, dried over anhydrous sodium sulfate, and then desolvated. The crude product was subjected to column chromatography to obtain 4.0 g of Intermediate 2a shown below at a yield of 51%.

<Step 2; Preparation of intermediate 2b >

3.1 g (20 mmol) of Intermediate 2a and 39.6 g of 1,2-dichloroethane were mixed and stirred at 3 째 C on an ice bath. 3.3 g (24 mmol) of zinc chloride was added thereto. Thereafter, 1.9 g (24 mmol) of acetyl chloride was added dropwise at 10 DEG C or lower. After completion of dropwise addition, the mixture was heated to room temperature and 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. 100 g of chloroform was added to the solution, and the solution was transferred to a separating lot to separate oil and water. The organic layer was washed with water three times, dried over anhydrous sodium sulfate, and then desolvated. The crude product was subjected to column chromatography to obtain 2.5 g of the following intermediate 2b in a yield of 68%.

<Step 3; Preparation of intermediate 2c >

2.0 g (10 mmol) of Intermediate 2b and 0.8 g (12 mmol) of hydroxylamine hydrochloride were added to DMF (10.7 g), and the mixture was heated and stirred at 80 ° C for 5 hours to carry out the reaction. After completion of the reaction, the reaction mixture was cooled to room temperature. The reaction solution was poured into 100 g of ion-exchanged water, and 150 g of ethyl acetate was added thereto, and separation of oil and water was carried out 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 dispersed and washed with 150 g of hexane, and dried to obtain 2.0 g of the following intermediate 2c in 94% yield.

<Step 4; Preparation of Comparative Compound No. 2>

1.7 g (8 mmol) of Intermediate 2c and 0.1 g (1 mol) of sodium acetate were added to DMF (5.6 g), and 1.2 g (12 mmol) of acetic anhydride was added dropwise to the ice bath at 5 占 폚. After the temperature was raised to room temperature, stirring was performed for 6 hours. Precipitated white crystals were collected by filtration. The obtained crystals were dispersively washed with ion-exchanged water and methanol, and dried to obtain 0.8 g of the following comparative compound No. 2 as white crystals in a yield of 43%.

The results of the analysis of the oxime ester compound 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)

The solubility of Compound No. 1, Compound No. 2, Comparative Compound No. 1, Comparative Compound No. 2, and Comparative Compound No. 3 below at room temperature in PGMEA, PGM and cyclohexanone (CHN) was evaluated . , And those obtained by dissolving them in an amount of less than 10 wt% were rated &quot; DELTA &quot;, and those having a solubility of less than 3 wt% were evaluated as &amp; cir &amp;

From Table 4, the oxime ester compound of the present invention has high solubility in solvents. It is apparent that the solubility in an ether ester solvent represented by PGMEA is high.

Therefore, when the oxime ester compound of the present invention is used as a polymerization initiator of a polymerizable composition, since a wide range of solvents and raw materials can be selected, the degree of freedom of compounding is high, precipitation of oxime ester compound hardly occurs during storage, The storage stability of the composition is excellent and useful.

[Examples 3 and 4 and Comparative Examples 4 to 6] Preparation of polymerizable composition

The following components were prepared in accordance with the formulation shown in Table 5 to obtain polymerizable compositions (Examples 3 and 4 and Comparative Examples 4 to 6). The numbers in the tables indicate the mass parts. Compound No. 1, Compound No. 2, Comparative Compound No. 1, Comparative Compound No. 2 and Comparative Compound No. 3 were used alone as polymerization initiators.

The symbols of the respective components in the tables indicate 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 (ethylenically unsaturated compound having an acid group; manufactured by Showa Denko Co., Ltd.)

B-2 Aronix M-450 (ethylenically unsaturated compound: manufactured by Toagosei Co., Ltd.)

C-1 PGMEA (solvent)

D-1 KBE-403 (silane coupling agent; available from Shin-Etsu Chemical Co., Ltd.)

D-2 FZ-2122 (leveling agent; manufactured by Toray Dow Corning)

D-3 Adeka Cools GPA-5001 (potential additive; ADEKA product)

[Evaluation Examples 3 and 4 and Comparative Evaluation Examples 4 to 6]

The polymerizable composition was evaluated for sensitivity and transparency by the following methods. The results are shown in Table 6.

(Transparency)

The above polymerizable composition was spin-coated on a glass substrate (500 rpm, 2 seconds, 900 rpm, 5 seconds) and prebaked at 90 캜 for 90 seconds using a hot plate. A 100 mJ / cm2 exposure was performed using a high-pressure mercury lamp as a light source, and post-baking was performed at 230 deg. C for 30 minutes using an oven. The transmittance at 380 nm and 400 nm was measured using a spectrophotometer. A transmittance of 400 nm or more was 95% or more, and a transmittance of 380 nm was 92% or more was rated as?, And satisfying only one of them was rated as?.

(Sensitivity)

The polymerizable composition was spin-coated on a glass substrate (500 rpm, 2 seconds, 900 rpm, 5 seconds) and prebaked at 90 캜 for 90 seconds using a hot plate. And exposed at a dose of 20 mJ / cm2 to 1000 mJ / cm2. Thereafter, development was carried out using a basic developer for 27 to 28 seconds.

The cured film remained on the glass substrate after development in an exposure of less than 100 mJ / cm &lt; 2 &gt; was evaluated as?, And the cured film remained on the glass substrate at not less than 100 mJ / cm2 and not more than 1000 mJ / And those not remaining were rated as x.

From the [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 polymer composition and a highly transparent cured product can be obtained. Among the oxime ester compounds of the present invention, compounds having a structure represented by Compound No. 2 are particularly preferred because of higher sensitivity.

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

The oxime ester compound of the present invention is useful as a polymerization initiator with high sensitivity used in a polymerizable composition.

Claims (8)

An 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 ) A group represented by the following general formula (II), a hydrogen atom, a halogen atom, a nitro group, a nitrile group, a cyano group, a hydroxyl group, a carboxyl group, a formyl group, a 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 represent a hydrocarbon group having 1 to 20 carbon atoms or a heterocyclic ring-containing group having 2 to 20 carbon atoms,
The hydrogen atom of a hydrocarbon group having 1 to 20 carbon atoms or a heterocyclic ring-containing group having 2 to 20 carbon atoms represented by R ¹³ , R ¹⁴ and R ¹⁵ is a group represented by the following formula (II), a nitrile group, a halogen A hydroxyl group, an amino group, a carboxyl group, a methacryloyl group, an acryloyl group, an epoxy group, a vinyl group, a vinyl ether group, a mercapto group, an isocyanate group or a heterocyclic ring containing group, and R ^The methylene group in the hydrocarbon group of 2 to 20 carbon atoms or the heterocyclic ring-containing group of 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-,
R ¹⁶ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms,
R ¹¹ and R ¹² 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 ring-containing group having 2 to 20 carbon atoms,
The hydrogen atom of the hydrocarbon group having 1 to 20 carbon atoms or the heterocyclic ring-containing group having 2 to 20 carbon atoms represented by R ¹¹ and R ¹² is preferably a halogen atom, a nitro group, a cyano group, a hydroxyl group, an amino group, a carboxyl group, An acryloyl group, an epoxy group, a vinyl group, a vinyl ether group, a mercapto group, an isocyanate group, or a heterocyclic ring-containing group, a hydrocarbon group having 1 to 20 carbon atoms represented by R ¹¹ and R ¹² , in methylene group-containing heterocyclic atoms, 2 to 20 groups -O-, -CO-, -COO-, -OCO-, -NR 17 -, -NR 17 CO-, -S-, -SO 2 -, - SCO- or -COS-,
R ¹⁷ represents a hydrogen atom or 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 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 are combined to form a ring However,
and 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 ring-containing group having 2 to 20 carbon atoms,
The hydrogen atom of a hydrocarbon group having 1 to 20 carbon atoms or a heterocyclic ring-containing group having 2 to 20 carbon atoms represented by R ²¹ and R ²² is preferably a halogen atom, a nitro group, a cyano group, a hydroxyl group, an amino group, a carboxyl group, An alkoxy group, an acryloyl group, an epoxy group, a vinyl group, a vinyl ether group, a mercapto group, an isocyanate group or a heterocyclic ring-containing group, and a hydrocarbon group having 1 to 20 carbon atoms represented by R ²¹ and R ²² , The methylene group in the heterocyclic containing group having 2 to 20 atoms is preferably -O-, -CO-, -COO-, -OCO-, -NR ²³ -, -NR ²³ CO-, -S-, -SO ₂ -, - SCO- or -COS-,
R ²³ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms,
and n represents 0 or 1.) The method 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). 3. The method according to claim 1 or 2,
An oxime ester compound 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 according to claim 4 and an ethylenically unsaturated compound. A colored polymerizable composition comprising the polymerizable composition according to claim 5 and a colorant. 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.