KR101824326B1 - Photosensitive resin composition, color filter, liquid crystal display device, oxime ester, and photopolymerization initiator - Google Patents

Abstract

[PROBLEMS] To provide a photosensitive resin composition excellent in sensitivity and hardly colored by heating, a color filter using the same, and a display device. A photopolymerization initiator used in the above-mentioned photosensitive resin composition and an oxime ester compound used as the photopolymerization initiator.
[MEANS FOR SOLVING PROBLEMS] In a photosensitive resin composition comprising (A) a photopolymerizable compound and (B) a photopolymerization initiator, an oxime ester compound represented by the following general formula (1) is used as the photopolymerization initiator (B). In the general formula (1), R ¹ is a group selected from the group consisting of monovalent organic groups, amino groups, halogens, nitro groups and cyano groups, m is an integer of 0 to 4, p is 0 or 1, R ² is a phenyl group having or without a substituent, or a carbazolyl group having or without a substituent, and R ³ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

Description

TECHNICAL FIELD [0001] The present invention relates to a photosensitive resin composition, a color filter and a display device using the same, an oxime ester compound, and a photopolymerization initiator. BACKGROUND ART < RTI ID = 0.0 >

The present invention relates to a photosensitive resin composition, a color filter and a display device using the same, an oxime ester compound and a photopolymerization initiator.

A display device such as a liquid crystal display display has a structure in which a liquid crystal layer is sandwiched between two substrates on opposite sides of which electrodes are formed. A color filter including pixel regions of respective colors of red (R), green (G), and blue (B) is formed on the inner side of one substrate. In this color filter, a black matrix is usually formed so as to divide each pixel region such as red, green, and blue.

Generally, color filters are manufactured by lithography. That is, first, a black photosensitive resin composition is coated on a substrate and dried, followed by exposure and development to form a black matrix. Next, coating, drying, exposure, and development are repeated for each photosensitive resin composition of each color such as red, green, and blue to form a pixel area of each color at a specific position to produce a color filter.

The black matrix is a pattern made of a photosensitive resin composition containing a light-shielding agent. By suppressing light leakage from each pixel region, the black matrix contributes to improvement of contrast in a display device and good color development. As described above, the black matrix formed in the first stage of the color filter fabrication as described above has a role of forming recesses for embedding the photosensitive resin composition for coloring each pixel region thereafter and forming pixel regions of respective colors at specific positions I am in charge.

In recent years, attempts have been made to improve the contrast of an image to be displayed on a liquid crystal display by improving the light shielding property by the black matrix in the manufacture of a liquid crystal display. To this end, it is necessary to incorporate a large amount of a light shielding agent into the photosensitive resin composition for forming the black matrix. However, when a large amount of the light-shielding agent is contained in the photosensitive resin composition, light for curing the photosensitive resin composition hardly reaches the bottom of the film when the film of the photosensitive resin composition coated on the substrate is exposed, Resulting in poor curing due to a remarkable decrease in sensitivity of the cured product.

The photosensitive resin composition is cured by polymerizing a photopolymerizable compound contained in the photosensitive resin composition by the action of a photopolymerization initiator contained as a part of the component. Therefore, it is known that the sensitivity of the photosensitive resin composition is influenced by the type of the photopolymerization initiator contained therein. In addition, in recent years, as the number of production of liquid crystal display displays increases, the production amount of color filters also increases. From the viewpoint of further improvement of productivity, a photosensitive resin composition of high sensitivity capable of forming a pattern with a low exposure dose is desired. In such a situation, Patent Document 1 discloses various compounds such as oxime ester compounds as a photopolymerization initiator capable of improving the sensitivity of the photosensitive resin composition. Specifically, in the examples described in Patent Document 1, the compounds represented by the following Structural Formulas (a) to (d) are disclosed.

Japanese Patent Application Laid-Open No. 2009-134289

By using the compounds represented by the structural formulas (a) to (d) as a photopolymerization initiator, a highly sensitive photosensitive resin composition can be produced. However, the number of production of liquid crystal displays and the like is rapidly increasing, and a photosensitive resin composition which is further improved in sensitivity than the photosensitive resin composition using the compound described in Patent Document 1 is required.

The present invention has been made in view of the above circumstances, and it is an object of the present invention to provide a photosensitive resin composition excellent in sensitivity, and a color filter and a display device using the same. It is another object of the present invention to provide a photopolymerization initiator used in the above-mentioned photosensitive resin composition and an oxime ester compound used as the photopolymerization initiator.

The present inventors have found that a photosensitive resin composition having excellent sensitivity can be obtained by using the oxime ester compound having a specific structure as the photopolymerization initiator (B) in the photosensitive resin composition comprising the photopolymerizable compound (A) and the photopolymerization initiator (B) The present invention has been completed. Specifically, the present invention provides the following.

A first aspect of the present invention is a photosensitive resin composition comprising (A) a photopolymerizable compound and (B) a photopolymerization initiator, wherein the photopolymerization initiator (B) comprises an oxime ester compound represented by the following general formula (1).

(Wherein R ¹ is a monovalent organic group, an amino group, a halogen, a nitro group and a cyano group, m is an integer of 0 to 4, p is 0 or 1, R ² is a substituent Or a carbazolyl group having or without a substituent, and R ³ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

A second aspect of the present invention is a color filter formed using a photosensitive resin composition further comprising (C) a colorant among the photosensitive resin compositions related to the first aspect.

A third aspect of the present invention is a display device in which a color filter related to the second aspect is used.

A fourth aspect of the present invention is an oxime ester compound represented by the following general formula (1).

(Wherein R ¹ is a monovalent organic group, an amino group, a halogen, a nitro group and a cyano group, m is an integer of 0 to 4, p is 0 or 1, R ² is a substituent Or a carbazolyl group having or without a substituent, and R ³ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

A fifth aspect of the present invention is a photopolymerization initiator comprising an oxime ester compound according to the fourth aspect.

According to the present invention, a photosensitive resin composition having excellent sensitivity, a color filter using the same, and a display device can be provided. According to the present invention, a photopolymerization initiator used in the above-mentioned photosensitive resin composition and an oxime ester compound used as the photopolymerization initiator can be provided.

[Photosensitive resin composition]

The photosensitive resin composition according to the present invention contains at least a photopolymerizable compound (A) and a photopolymerization initiator (B). Hereinafter, each component contained in the photosensitive resin composition of the present invention will be described in detail.

≪ (A) Photopolymerizable compound >

The photopolymerizable compound (A) contained in the photosensitive resin composition according to the present invention is not particularly limited, and conventionally known photopolymerizable compounds can be used. Among them, a resin or monomer having an ethylenic unsaturated group is preferable, and a combination thereof is more preferable. By combining a resin having an ethylenic unsaturated group and a monomer having an ethylenic unsaturated group, it is possible to improve the curability of the photosensitive resin composition and facilitate pattern formation.

[Resin Having Ethylenic Unsaturated Group]

Examples of the resin having an ethylenic unsaturated group include (meth) acrylic acid, maleic acid, fumaric acid monomethyl, fumaric acid monoethyl, 2-hydroxyethyl (meth) acrylate, ethylene glycol monomethyl ether (Meth) acrylates such as ethylene glycol monoethyl ether (meth) acrylate, glycerol (meth) acrylate, (meth) acrylamide, acrylonitrile, methacrylonitrile, (Meth) acrylate, diethyleneglycol di (meth) acrylate, triethyleneglycol di (meth) acrylate, diethyleneglycol di (Meth) acrylate, propylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, propylene glycol di Acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, (Meth) acrylate, 1,6-hexanediol di (meth) acrylate, and cargo epoxy diacrylate; a polyester prepolymer obtained by condensing a polyhydric alcohol with a monobasic acid or a polybasic acid (Meth) acrylate obtained by reacting a polyol with a compound having two isocyanate groups and then reacting with (meth) acrylic acid, a bisphenol A type epoxy resin, a bisphenol A type epoxy resin, F type epoxy resin, bisphenol S type epoxy resin, phenol or cresol novolak type epoxy resin Epoxy resins such as epoxy resins, alicyclic epoxy resins, dihydroxybenzene type epoxy resins, and the like, as well as epoxy resins such as epoxy resins, epoxy resins, epoxy resins, And epoxy (meth) acrylate resins obtained by reacting a resin with (meth) acrylic acid. A resin obtained by reacting an epoxy (meth) acrylate resin with a polybasic acid anhydride can be suitably used. In the present specification, "(meth) acrylic" means "acrylic or methacrylic".

As the resin having an ethylenic unsaturated group, a resin obtained by reacting a reaction product of an epoxy compound and an unsaturated group-containing carboxylic acid compound with a polybasic acid anhydride can be suitably used.

Among them, a compound represented by the following general formula (a1) is preferable. The compound represented by the general formula (a1) is preferable in view of its high photocurability.

In the general formula (a1), X represents a group represented by the following general formula (a2).

In the general formula (a2), R ^1a independently represents a hydrogen atom, a hydrocarbon group of 1 to 6 carbon atoms or a halogen atom, R ^2a independently represents a hydrogen atom or a methyl group, W represents a single bond, (a3). In the general formulas (a2) and (a3), " * " means the terminal end of the bond of a divalent group.

In the general formula (a1), Y represents a residue other than an acid anhydride group (-CO-O-CO-) from a dicarboxylic acid anhydride. Examples of the dicarboxylic acid anhydride include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyl and methylene tetrahydrophthalic anhydride, chlorendic anhydride, methyltetrahydrophthalic anhydride, And glutaric acid.

In the general formula (a1), Z represents a residue other than the two acid anhydride groups in the tetracarboxylic acid dianhydride. Examples of the tetracarboxylic acid dianhydride include pyromellitic anhydride, benzophenonetetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, biphenyl ether tetracarboxylic dianhydride, and the like. In the general formula (a1), a represents an integer of 0 to 20.

The acid value of the resin having an ethylenic unsaturated group is preferably 10 to 150 mgKOH / g, more preferably 70 to 110 mgKOH / g, in terms of resin solid content. When the acid value is 10 mgKOH / g or more, sufficient solubility in a developing solution can be obtained, which is preferable. The acid value of 150 mgKOH / g or less is preferable because sufficient curability can be obtained and the surface property can be improved.

The mass average molecular weight of the resin having an ethylenic unsaturated group is preferably from 1,000 to 40,000, more preferably from 2,000 to 30,000. By setting the mass average molecular weight to 1000 or more, good heat resistance and film strength can be obtained, which is preferable. The weight average molecular weight is preferably 40,000 or less, because good developability can be obtained.

[Monomer having an ethylenically unsaturated group]

Monomers having an ethylenic unsaturated group include monofunctional monomers and polyfunctional monomers. Hereinafter, monofunctional monomers and multifunctional monomers will be described in order.

Examples of the monofunctional monomer include (meth) acrylamide, methylol (meth) acrylamide, methoxymethyl (meth) acrylamide, ethoxymethyl (meth) acrylamide, propoxymethyl (meth) acrylamide, butoxymethoxy (Meth) acrylic acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, maleic anhydride, maleic anhydride, Methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, (Meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-hydroxyethyl ) Acrylate, 2-phenoxy-2-hydroxypropyl (meth) (Meth) acrylate, glycerin mono (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, dimethylamino (meth) acrylate, glycidyl (Meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, and half . These monofunctional monomers may be used alone, or two or more monofunctional monomers may be used in combination.

Examples of the polyfunctional monomer include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (Meth) acrylate, butylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexane glycol di (Meth) acrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri ) Acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol Bis (4- (meth) acryloxypolyethoxyphenyl) propane, 2,2-bis (4- (meth) acryloxy diethoxyphenyl) propane, (Meth) acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, diethylene glycol diglycidyl ether di (Meth) acrylate, glycerin triacrylate, glycerin polyglycidyl ether poly (meth) acrylate, urethane (meth) acrylate (i.e., tolylene diisocyanate), trimethylhexamethylene diisocyanate A reaction product of hexamethylene diisocyanate and 2-hydroxyethyl (meth) acrylate, a reaction product of methylene bis (meth) acrylamide, (meth) acrylamide methylene ether, polyhydric alcohol and N-methylol And the like can be a polyfunctional monomer or triacrylate formal and the like. These multifunctional monomers may be used alone, or two or more of them may be used in combination.

The content of the photopolymerizable compound as the component (A) is preferably 10 to 99.9 parts by mass based on 100 parts by mass of the total solid content of the photosensitive resin composition. When the content of the component (A) is 10 parts by mass or more based on 100 parts by mass of the total amount of the solid components, sufficient heat resistance and chemical resistance of the formed pattern can be expected.

<(B) Photopolymerization initiator>

The photosensitive resin composition according to the present invention contains an oxime ester compound having the following structure as a photopolymerization initiator. By using an oxime ester compound having a structure represented by the following general formula (1) as a photopolymerization initiator, the photosensitive resin composition can be made excellent in sensitivity.

(Wherein R ¹ is a monovalent organic group, an amino group, a halogen, a nitro group and a cyano group, m is an integer of 0 to 4, p is 0 or 1, R ² is a substituent A substituted or unsubstituted phenyl group or a substituted or unsubstituted carbazolyl group and R ³ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms)

In the general formula ^(1), R 1 is not particularly limited within a range that does not inhibit the object of the present invention, it is suitably selected from a variety of organic groups. Preferred examples of the organic group R ¹ include an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic acyl group, an alkoxycarbonyl group, a saturated aliphatic acyloxy group, a phenyl group having or without a substituent, A phenoxy group, a benzoyl group having or without a substituent, a phenoxycarbonyl group having a substituent, a benzoyloxy group having a substituent, a phenylalkyl group having a substituent, a naphthyl group having a substituent, A naphthoyl group having or not having a substituent, a naphthoyl group having or not having a substituent, a naphthoxycarbonyl group having a substituent, a naphthoyloxy group having a substituent, a naphthylalkyl group having a substituent , A heterocyclyl group having or without a substituent, an amino group, an amino group substituted with an organic group of 1 or 2, A morpholin-1-yl group, a piperazin-1-yl group, a halogen atom, a nitro group, and a cyano group. When m is an integer of 2 to 4, R ¹ may be the same or different. The carbon number of the substituent does not include the carbon number of the substituent having the substituent.

When R ¹ is an alkyl group, the number of carbon atoms is preferably from 1 to 20, and more preferably from 1 to 6 carbon atoms. When R ¹ is an alkyl group, it may be a straight chain or branched chain. Specific examples of when R ¹ is an alkyl group include methyl group, ethyl group, n- propyl group, isopropyl group, n- butyl group, isobutyl group, sec- butyl group, tert- butyl group, n- pentyl group, an isopentyl group , n-hexyl, n-heptyl, n-octyl, isooctyl, sec-octyl, tert-octyl, n-nonyl, isononyl, n- Decyl group and isodecyl group. When R ¹ is an alkyl group, the alkyl group may contain an ether bond (-O-) in the carbon chain. Examples of the alkyl group having an ether bond in the carbon chain include a methoxyethyl group, an ethoxyethyl group, a methoxyethoxyethyl group, an ethoxyethoxyethyl group, a propyloxyethoxyethyl group, and a methoxypropyl group.

When R ¹ is an alkoxy group, the number of carbon atoms is preferably from 1 to 20, and more preferably from 1 to 6 carbon atoms. When R ¹ is an alkoxy group, it may be a straight chain or branched chain. Specific examples of when R ¹ is an alkoxy group include methoxy, ethoxy, n-propyloxy, isopropyloxy, n-butyloxy, isobutyloxy, sec- n-pentyloxy group, isopentyloxy group, sec-pentyloxy group, tert-pentyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, isooctyloxy group, , tert-octyloxy group, n-nonyloxy group, isononyloxy group, n-decyloxy group and isodecyloxy group. When R ¹ is an alkoxy group, the alkoxy group may contain an ether bond (-O-) in the carbon chain. Examples of the alkoxy group having an ether bond in the carbon chain include a methoxyethoxy group, an ethoxyethoxy group, a methoxyethoxyethoxy group, an ethoxyethoxyethoxy group, a propoxyoxyethoxyethoxy group and a methoxy Propyloxy group and the like.

When R ¹ is a cycloalkyl group or a cycloalkoxy group, the number of carbon atoms is preferably from 3 to 10, and more preferably from 3 to 6 carbon atoms. Concrete examples of the case where R ¹ is a cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group and a cyclooctyl group. Specific examples of when R ¹ is a cycloalkoxy group include a cyclopropyloxy group, a cyclobutyloxy group, a cyclopentyloxy group, a cyclohexyloxy group, a cycloheptyloxy group, and a cyclooctyloxy group.

When R ¹ is a saturated aliphatic acyl group or a saturated aliphatic acyloxy group, the number of carbon atoms is preferably from 2 to 20, and more preferably from 2 to 7 carbon atoms. Specific examples of when R ¹ is a saturated aliphatic acyl group include acetyl group, propanoyl group, n-butanoyl group, 2-methylpropanoyl group, n-pentanoyl group, heptanoyl group, n-octanoyl group, n-nonanoyl group, n-decanoyl group, n-undecanoyl group, n-dodecanoyl group, Pentadecanoyl group, and n-hexadecanoyl group. Specific examples of when R ¹ is a saturated aliphatic acyloxy group include acetyloxy, propanoyloxy, n-butanoyloxy, 2-methylpropanoyloxy, n-pentanoyloxy, N-hexanoyloxy group, n-heptanoyloxy group, n-octanoyloxy group, n-nonanoyloxy group, n-decanoyloxy group, n-undecanoyloxy group, n-dodecanoyloxy group, n -Tridecanoyloxy group, n-tetradecanoyloxy group, n-pentadecanoyloxy group, and n-hexadecanoyloxy group.

When R ¹ is an alkoxycarbonyl group, the number of carbon atoms is preferably 2 to 20, and more preferably 2 to 7 carbon atoms. Specific examples of when R ¹ is an alkoxycarbonyl group include a methoxycarbonyl group, ethoxycarbonyl group, n-propyloxycarbonyl group, isopropyloxycarbonyl group, n-butyloxycarbonyl group, isobutyloxycarbonyl group, sec-butyloxycarbonyl group, Sec-pentyloxycarbonyl group, tert-pentyloxycarbonyl group, n-hexyloxycarbonyl group, n-heptyloxycarbonyl group, n-octyloxycarbonyl group, isooctyloxycarbonyl group, sec An octyloxycarbonyl group, a tert-octyloxycarbonyl group, an n-nonyloxycarbonyl group, an isononyloxycarbonyl group, a n-decyloxycarbonyl group and an isodecyloxycarbonyl group.

When R ¹ is a phenylalkyl group, the number of carbon atoms is preferably 7 to 20, more preferably 7 to 10 carbon atoms. When R ¹ is a naphthylalkyl group, the number of carbon atoms is preferably from 11 to 20, and more preferably from 11 to 14 carbon atoms. Specific examples of when R ¹ is a phenylalkyl group include a benzyl group, a 2-phenylethyl group, a 3-phenylpropyl group and a 4-phenylbutyl group. Specific examples of when R ¹ is a naphthylalkyl group include? -Naphthylmethyl,? -Naphthylmethyl, 2- (? -Naphthyl) ethyl and 2- (? - naphthyl) ethyl groups. When R ¹ is a phenylalkyl group or a naphthylalkyl group, R ¹ may further have a substituent on the phenyl or naphthyl group.

When R ¹ is a heterocyclyl group, the heterocyclyl group may be a 5-membered or 6-membered monocyclic ring containing one or more N, S or O, or a heterocyclyl group in which the monocyclic ring is condensed with a benzene ring . And when the heterocyclyl group is a condensed ring, the number of rings is 3. Examples of the heterocycle constituting the heterocyclyl group include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, Benzothiazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, triphenylphosphine, benzothiophene, indole, isoindole, indolidine, benzoimidazole, Rhenazine, cinnoline and quinoxaline. When R ¹ is a heterocyclyl group, the heterocyclyl group may further have a substituent.

When R ¹ is an amino group substituted with 1 or 2 organic groups, preferred examples of the organic group include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a saturated aliphatic acyl group having 2 to 20 carbon atoms, A substituted or unsubstituted benzoyl group, a substituted or unsubstituted C 7 -C 20 phenylalkyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted naphthoyl group, a substituted or unsubstituted A naphthylalkyl group having from 11 to 20 carbon atoms and a heterocyclyl group which have no substituent. Specific examples of these preferred organic groups are the same as R &lt; ¹ &gt;. Specific examples of the amino group substituted with 1 or 2 organic groups include a methylamino group, ethylamino group, diethylamino group, n-propylamino group, di-n-propylamino group, isopropylamino group, n-butylamino group, , n-pentylamino group, n-hexylamino group, n-heptylamino group, n-octylamino group, n-nonylamino group, n-decylamino group, phenylamino group, naphthylamino group, acetylamino group, N-hexanoylamino group, n-heptanoylamino group, n-octanoylamino group, n-decanoylamino group, benzoylamino group, a-naphthoylamino group and? -Naphthoylamino group have.

Examples of the substituent in the case where the phenyl group, naphthyl group and heterocyclyl group contained in R ¹ have a substituent include an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a saturated aliphatic acyl group having 2 to 7 carbon atoms, A saturated aliphatic acyloxy group having 2 to 7 carbon atoms, a monoalkylamino group having an alkyl group having 1 to 6 carbon atoms, a dialkylamino group having an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, -1-yl group, a halogen atom, a nitro group, and a cyano group. When the phenyl group, naphthyl group and heterocyclyl group contained in R ¹ further have a substituent, the number of the substituent is not limited within the range not hindering the object of the present invention, but is preferably 1 to 4. When the phenyl group, naphthyl group and heterocyclyl group contained in R ¹ have plural substituents, a plurality of substituents may be the same or different.

From the viewpoint that R ¹ is chemically stable, the steric hindrance is small, and the oxime ester compound is easy to synthesize, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and a saturated aliphatic acyl group having 2 to 7 carbon atoms , Alkyl of 1 to 6 carbon atoms is more preferable, and methyl group is particularly preferable.

Where the R ¹ are bonded to the phenyl group for the phenyl group to the combined R ^1, the position of the bond position of the hand in position 1, and the methyl groups of the main skeleton of the phenyl group and the oxime ester compound in the case of a two-position, The fourth position or the fifth position is preferable, and the fifth position is more preferable. M is preferably an integer of 0 to 3, more preferably an integer of 0 to 2, and particularly preferably 0 or 1.

R ² is a phenyl group with or without a substituent or a carbazolyl group with or without a substituent. When R ² is a carbazolyl group having or without a substituent, the nitrogen atom on the carbazolyl group may be substituted with an alkyl group having 1 to 6 carbon atoms.

In R ² , the substituent of the phenyl group or carbazolyl group is not particularly limited within the scope of not impairing the object of the present invention. Examples of preferable substituents having a phenyl group or carbazolyl group on the carbon atom include those having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a cycloalkoxy group having 3 to 10 carbon atoms , A saturated aliphatic acyl group having 2 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, a saturated aliphatic acyloxy group having 2 to 20 carbon atoms, a phenyl group having or without a substituent, a phenoxy group having a substituent, A phenylthio group having or without a substituent, a benzoyl group having or without a substituent, a phenoxycarbonyl group having a substituent, a benzoyloxy group having a substituent, a phenylalkyl group having 7 to 20 carbon atoms, A naphthyl group having or not having a substituent, a naphtho group having or not having a substituent, a naphthoyl group having a substituent, a naphtho group having or without a substituent A naphthoyloxy group having or without substituent (s), a naphthylalkyl group having or without substituent (s) having 11 to 20 carbon atoms, a heterocyclyl group having or without substituent (s), a heterocyclylcarbonyl group having or without substituent , An amino group, an amino group substituted with an organic group of 1 or 2, a morpholin-1-yl group, a piperazin-1-yl group, a halogen atom, a nitro group and a cyano group.

When R ² is a carbazolyl group, examples of preferable substituent groups having or not having a carbazolyl group on a nitrogen atom include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a saturated aliphatic acyl group having 2 to 20 carbon atoms , An alkoxycarbonyl group having 2 to 20 carbon atoms, a phenyl group having or without a substituent, a benzoyl group having or without a substituent, a phenoxycarbonyl group having a substituent, a phenylalkyl group having 7 to 20 carbon atoms, A naphthoyl group having or without a substituent, a naphthoyl group having or without a substituent, a naphthocycarbonyl group having a substituent, a naphthylalkyl group having a substituent having or having no substituent, a naphthylalkyl group having a substituent, A heterocyclyl group, and a heterocyclylcarbonyl group having or without a substituent. Among these substituents, an alkyl group having 1 to 20 carbon atoms is preferable, an alkyl group having 1 to 6 carbon atoms is more preferable, and an ethyl group is particularly preferable.

Specific examples of the substituent having or not having a phenyl group or a carbazolyl group include an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic acyl group, an alkoxycarbonyl group, a saturated aliphatic acyloxy group, a phenyl An alkyl group, a naphthylalkyl group with or without a substituent, a heterocyclyl group with or without a substituent, and an amino group substituted with 1 or 2 organic groups are the same as R ¹ .

Examples of the substituent in the case where the phenyl group, naphthyl group and heterocyclyl group contained in the substituent of the phenyl group or the carbazolyl group in R ² further have a substituent include an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, A saturated aliphatic acyl group having 2 to 7 carbon atoms, an alkoxycarbonyl group having 2 to 7 carbon atoms, a saturated aliphatic acyloxy group having 2 to 7 carbon atoms, a phenyl group, a naphthyl group, a benzoyl group, a naphthoyl group, an alkyl group having 1 to 6 carbon atoms, A monoalkylamino group having an alkyl group having 1 to 6 carbon atoms, a dialkylamino group having an alkyl group having 1 to 6 carbon atoms, a dialkylamino group having an alkyl group having 1 to 6 carbon atoms, a benzoyl group substituted with a group selected from the group consisting of a hydrogen atom, A morpholin-1-yl group, a piperazin-1-yl group, a halogen, a nitro group, and a cyano group. When the phenyl group, the naphthyl group and the heterocyclyl group contained in the substituent of the phenyl group or the carbazolyl group further have a substituent, the number of the substituent is not limited to the range not hindering the object of the present invention, but is preferably 1 to 4 Do. When the phenyl group, the naphthyl group and the heterocyclyl group have a plurality of substituents, the plurality of substituents may be the same or different.

Among R ² , a group represented by the following general formula (2) or (3) is preferable, a group represented by the following general formula (2) is more preferable, and a group represented by the following general formula (2) , A group in which A is S is particularly preferable.

(R ⁴ is a group selected from the group consisting of a monovalent organic group, an amino group, a halogen, a nitro group and a cyano group, A is S or O, and n is an integer of 0 to 4)

(R ⁵ and R ⁶ are each a monovalent organic group)

In the case of forming a pattern using a photosensitive resin composition, the pattern tends to be colored by heating in a post-baking step at the time of pattern formation. However, in the case where the oxime ester compound represented by the general formula (1) is used as the photopolymerization initiator (B) as the photopolymerization initiator in the photosensitive resin composition, in which R ² is a group represented by the general formula (2) and A is S, The coloring of the pattern can be suppressed.

When R &lt; ⁴ &gt; in the general formula (2) is an organic group, various organic groups can be selected within the range not hindering the object of the present invention. In the general formula (2), R ⁴ is an organic group, and examples thereof include an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a saturated aliphatic acyl group having 2 to 7 carbon atoms, an alkoxycarbonyl group having 2 to 7 carbon atoms, A saturated aliphatic acyloxy group having 2 to 7 carbon atoms, a phenyl group, a naphthyl group, a benzoyl group, a naphthoyl group, an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazin- A monoalkylamino group having an alkyl group having 1 to 6 carbon atoms, a dialkylamino group having an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazin-1-yl group, And cyano group.

R ⁴ is preferably a benzoyl group substituted by a group selected from the group consisting of a benzoyl group, a naphthoyl group, an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazin-1-yl group and a phenyl group; , A benzoyl group, a naphthoyl group, a 2-methylphenylcarbonyl group, a 4- (piperazin-1-yl) phenylcarbonyl group and a 4- (phenyl) phenylcarbonyl group are more preferable.

In the general formula (2), n is preferably an integer of 0 to 3, more preferably an integer of 0 to 2, and particularly preferably 0 or 1. when n is 1, the binding position of R ⁴ is preferably in the para position relative to the bonding hands of the phenyl group which R ⁴ is bonded in combination with a sulfur atom.

R ⁵ in the general formula (3) can be selected from various organic groups within the range not hindering the object of the present invention. Preferable examples of R ⁵ include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a saturated aliphatic acyl group having 2 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, a phenyl group having or without a substituent, A phenoxycarbonyl group having or without a substituent, a phenylalkyl group having 7 to 20 carbon atoms having a substituent, a naphthyl group having a substituent, a naphthoyl group having a substituent, a substituent , A naphthylalkyl group having or without substituent (s) having 11 to 20 carbon atoms, a heterocyclyl group having or without substituent (s), and a heterocyclylcarbonyl group having or without substituent .

R ⁵ is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and particularly preferably an ethyl group.

R ⁶ in the general formula (3) is not particularly limited within the range not impairing the object of the present invention, and can be selected from various organic groups. Specific examples of the group represented by R ⁶ include an alkyl group having 1 to 20 carbon atoms, a phenyl group having or without a substituent, a naphthyl group having or without a substituent, and a heterocyclyl group having a substituent. As R ⁶ , among these groups, a phenyl group having or without a substituent is more preferable, and a 2-methylphenyl group is particularly preferable.

When the phenyl group, naphthyl group and heterocyclyl group contained in R ⁴ , R ⁵ or R ⁶ have a substituent, examples of the substituent include an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a saturated group having 2 to 7 carbon atoms An aliphatic acyl group, an alkoxycarbonyl group having 2 to 7 carbon atoms, a saturated aliphatic acyloxy group having 2 to 7 carbon atoms, a monoalkylamino group having an alkyl group having 1 to 6 carbon atoms, a dialkylamino group having an alkyl group having 1 to 6 carbon atoms, A 1-yl group, a piperazin-1-yl group, a halogen atom, a nitro group, and a cyano group. When the phenyl group, naphthyl group and heterocyclyl group contained in R ⁴ , R ⁵ or R ⁶ further have a substituent, the number of the substituent is not limited as long as it does not impair the object of the present invention, but is preferably 1 to 4 Do. When the phenyl group, naphthyl group and heterocyclyl group contained in R ⁴ , R ⁵ or R ⁶ have plural substituents, plural substituents may be the same or different.

R ³ in the general formula (1) is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. As R ³ , a methyl group or an ethyl group is preferable, and a methyl group is more preferable.

The oxime ester compound represented by the general formula (1) can be synthesized according to the following Scheme 1 when p is 0, for example. Specifically, an aromatic compound represented by the following general formula (1-1) is acylated by a Friedel-Crafts reaction using a halocarbonyl compound represented by the following general formula (1-2) To obtain a ketone compound represented by the formula (1-3), oxime the resulting ketone compound (1-3) with hydroxylamine to obtain an oxime compound represented by the general formula (1-4) -4) and an acid anhydride ((R ₃ CO) ₂ O) represented by the following general formula (1-5) or an acid halide (R ₃ COHal, Hal represented by the general formula (1-6) ) Is reacted to obtain an oxime ester compound represented by the following general formula (1-7). Hal in the general formula (1-2) below is halogen, and the following general formulas (1-1), (1-2), (1-3), (1-4) , R ¹ , R ² , R ³ and m are the same as in the general formula (1).

<Scheme 1>

The oxime ester compound represented by the general formula (1) can be synthesized according to the following scheme 2 when p is 1, for example. Specifically, a ketone compound represented by the following general formula (2-1) is reacted with an acetic acid ester represented by the following general formula (2-2) (RONO, R is an alkyl group having 1 to 6 carbon atoms) in the presence of hydrochloric acid to obtain The ketooxime compound represented by the following general formula (2-3) and the acid anhydride ((R ₃ CO) ₂ (2-2)) represented by the following general formula (2-4) O) or an acid halide (R ₃ COHal, Hal is halogen) represented by the following general formula (2-5) can be reacted to obtain an oxime ester compound represented by the following general formula (2-6). R ¹ , R ² , R ³ and m in the general formulas (2-1), (2-3), (2-4), (2-5) (1).

<Scheme 2>

When the oxime ester compound represented by the general formula (1) is a compound wherein p is 1, R ¹ is a methyl group, and R ¹ is bonded to a para position with respect to a methyl group bonded to a benzene ring to which R ¹ is bonded, The compound represented by the following general formula (2-7) can also be synthesized by oximation and acylation in the same manner as in Scheme 1. In the following general formula (2-7), R ² is the same as in the general formula (1).

Among the oxime ester compounds represented by the general formula (1), particularly preferred compounds are the following PI-1 to PI-42.

The photosensitive resin composition may contain, if necessary, a photopolymerization initiator other than the oxime ester compound represented by the general formula (1). Specific examples of the other photopolymerization initiator include 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- [4- (2-hydroxyethoxy) 2-methylpropan-1-one, 1- (4-isopropylphenyl) -2-hydroxy- 2-methylpropan-1-one, 2,2-dimethoxy-1,2-diphenylethan-1-one, bis (4-dimethylaminophenyl) 2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, ethanone, 1- (9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] Dimethylamino benzoic acid, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, butyl 4-dimethylaminobenzoate, 4-dimethylamino-2-ethylhexylbenzoic acid, 4 - Dimethylamino-2-isoamyl Ben Benzyl-β-methoxyethyl acetal, benzyl dimethyl ketal, 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, methyl o-benzoylbenzoate, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 1-chloro-4-propoxyoxanthone, thioxanthene, 2-chlorothioxanthene, 2,4- But are not limited to, oxanethene, 2-methylthioxanthene, 2-isopropylthioxanthene, 2-ethyl anthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-diphenylanthraquinone, azobisisobutyl 2-mercaptobenzooxazole, 2-mercaptobenzothiazole, 2- (o-chlorophenyl) -4,5-diphenylsulfone, 2- (O-chlorophenyl) -4,5-di (methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer , 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer, 2- (p-methoxyphenyl) -4,5-diphenylimidazole dimer, 2,4,5 - triaryl (I. E., Michler's ketone), 4,4'-bisdiethylaminobenzophenone (i.e., 4,4'-bisdiethylaminobenzophenone, Ethylhexyl ketone), 4,4'-dichlorobenzophenone, 3,3-dimethyl-4-methoxybenzophenone, benzyl, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, Benzoin isobutyl ether, benzoin butyl ether, acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloro Acetophenone, p-tert-butyl acetophenone, p-dimethylaminoacetophenone, p-tert-butyltrichloroacetophenone, p-tert-butyldichloroacetophenone,?,? -Dichloro- Thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, dibenzosuberone, pentyl-4-dimethylaminobenzoate, 9- (9-acridinyl) pentane, 1,3-bis- (9-acridinyl) propane, p- (Trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, 2- [2- (Trichloromethyl) -s-triazine, 2- [2- (furan-2-yl) ethenyl] -4,6-bis 2-methylphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (Trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) - (trichloromethyl) -s-triazine, 2- (4-n-butoxyphenyl) -4,6-bis Trichloromethyl) -s-triazine, 2,4-bis-trichloromethyl-6- (3-bromo-4-methoxy) phenyl- 6- (2-bromo-4-methoxy) phenyl-s- 2,4-bis trichloromethyl-6- (3-bromo-4-methoxy) styrylphenyl-s-triazine, 2,4- Bromo-4-methoxy) styrylphenyl-s-triazine. Among them, it is particularly preferable to use a photopolymerization initiator of oxime type in terms of sensitivity. These photopolymerization initiators may be used alone or in combination of two or more.

When the photosensitive resin composition contains a photopolymerization initiator other than the oxime ester compound represented by the general formula (1), the content of the other photopolymerizable compound is not particularly limited within the range not hindering the object of the present invention. In this case, the content of the other photopolymerization initiator is typically 50 mass% or less, more preferably 30 mass% or less, and particularly preferably 10 mass% or less, based on the total amount of the photopolymerization initiator contained in the photosensitive resin composition.

The content of the photopolymerization initiator as the component (B) is preferably from 0.1 to 50 parts by mass, more preferably from 1 to 45 parts by mass, based on 100 parts by mass of the total amount of the solid components of the photosensitive resin composition. Within the above range, sufficient heat resistance and chemical resistance can be obtained, and the coating film forming ability can be improved to suppress the photo-curing failure.

&Lt; (C) Colorant &gt;

The photosensitive resin composition according to the present invention may further contain (C) a colorant. The photosensitive resin composition is preferably used for forming a color filter of a liquid crystal display, for example, by including a colorant as the component (C). Further, the photosensitive resin composition according to the present invention is preferably used for forming a black matrix in a color filter of a display device, for example, by including a light-shielding agent as a coloring agent.

The colorant (C) contained in the photosensitive resin composition according to the present invention is not particularly limited. For example, a color index (CI) (published by The Society of Dyers and Colourists) is classified into a pigment It is preferable to use a compound, specifically, one having a color index (CI) number given below.

Examples of yellow pigments that can be preferably used include C.I. Pigment Yellow 1 (hereinafter referred to as &quot; CI Pigment Yellow &quot; is the same and only the numbers are described below), 3,11,12,13,14,15,16,17,20,24,31,35,55,60 , 61, 65, 71, 73, 74, 81, 83, 86, 93, 95, 97, 98, 99, 100, 101, 104, 106, 108, 109, , 120, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 166, 167, 168, .

Examples of orange pigments that can be preferably used include C.I. Pigment Orange 1 (hereinafter, &quot; CI Pigment Orange &quot; is the same and only the numbers are described), 5,13,14,16,17,24,34,36,38,40,43,46,49,51 , 55, 59, 61, 63, 64, 71, and 73, respectively.

Examples of purple pigments which can be preferably used include C.I. Pigment Violet 1 (hereinafter, "C.I. Pigment Violet" is the same and only the numbers are described below), 19, 23, 29, 30, 32, 36, 37, 38, 39, 40 and 50.

Examples of red pigments which can be preferably used include C.I. 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 14, 15, 16 (hereinafter, the same reference numerals are used for "CI Pigment Red" 48: 3, 48: 4, 49: 1, 49: 1, 48, : 2, 50: 1, 52: 1, 53: 1, 57, 57: 1, 57: 2, 58: 2, 58: 4, 60: 1, 63: : 1, 83, 88, 90: 1, 97, 101, 102, 104, 105, 106, 108, 112, 113, 114, 122, 123, 144, 146, 149, 150, 151, 155, 166, 168 171, 172, 174, 175, 176, 177, 178, 179, 180, 185, 187, 188, 190, 192, 193, 194, 202, 206, 207, 208, 209, 215, 216, 217 , 220, 223, 224, 226, 227, 228, 240, 242, 243, 245, 254, 255, 264 and 265.

Examples of blue pigments which can be preferably used include C.I. 15, 15: 3, 15: 6, 16, 22, 60, 64, and 66 (hereinafter, .

Examples of pigments of other colors which can be preferably used include C.I. Pigment Green 7, C.I. Pigment Green 36, C.I. Green pigments such as Pigment Green 37, C.I. Pigment Brown 23, C.I. Pigment Brown 25, C.I. Pigment Brown 26, C.I. Brown pigments such as Pigment Brown 28, C.I. Pigment Black 1, C.I. Pigment Black 7 and the like.

When a colorant is used as the light shielding agent, it is preferable to use a black pigment as the light shielding agent. Examples of the black pigments include carbon black, titanium black, metal oxides such as copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium and silver, complex oxides, metal sulfides, metal sulfates or metal carbonates, And various pigments. Among these, it is preferable to use carbon black having high light shielding properties.

As the carbon black, known carbon black such as channel black, furnace black, thermal black and lamp black can be used, but it is preferable to use channel black excellent in light shielding property. Resin-coated carbon black may also be used.

Resin-coated carbon black has a lower electrical conductivity than carbon black without resin coating. Therefore, when the resin-coated carbon black is used as a black matrix of a liquid crystal display element such as a liquid crystal display, it is possible to provide a low- Can be manufactured.

In order to adjust the color tone of the carbon black, the above organic pigment may be suitably added as an auxiliary pigment.

In order to uniformly disperse the colorant in the photosensitive resin composition, a dispersant may be further used. As such a dispersing agent, it is preferable to use a polymeric dispersant of a polyethylene imine type, a urethane resin type or an acrylic resin type. Particularly, when carbon black is used as the colorant, it is preferable to use an acrylic resin-based dispersant as the dispersant.

The inorganic pigments and the organic pigments may be used alone or in combination of two or more. When used in combination, the organic pigments are preferably used in an amount of from 10 to 80 parts by mass per 100 parts by mass of the total amount of the inorganic pigments and the organic pigments, And more preferably in the range of 20 to 40 parts by mass.

The amount of the coloring agent to be used in the photosensitive resin composition may be appropriately determined depending on the use of the photosensitive resin composition. For example, the amount is preferably 5 to 70 parts by mass, more preferably 25 to 60 parts by mass relative to 100 parts by mass of the total amount of solid components of the photosensitive resin composition More preferable. By setting the thickness within the above range, a black matrix or each colored layer can be formed with a desired pattern, which is preferable.

In particular, when forming a black matrix using a photosensitive resin composition, it is preferable to adjust the amount of the light-shielding agent in the photosensitive resin composition so that the OD value per 1 탆 coat of the black matrix is 4 or more. When the OD value per 1 m of the coating film in the black matrix is 4 or more, sufficient display contrast can be obtained when the black matrix is used for a black matrix of a liquid crystal display.

The colorant is preferably added to the photosensitive resin composition after preparing a dispersion in which the colorant is dispersed at a suitable concentration using a dispersant.

&Lt; Other components &gt;

Various additives may be added to the photosensitive resin composition according to the present invention as necessary. Specifically, examples thereof include a solvent, a sensitizer, a curing accelerator, a photo-crosslinking agent, a photosensitizer, a dispersing aid, a filler, an adhesion promoter, an antioxidant, an ultraviolet absorber, an aggregation inhibitor, a thermal polymerization inhibitor, a defoaming agent and a surfactant.

Examples of the solvent used in the photosensitive resin composition according to the present invention include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol mono Methyl ethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, Propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene Glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, (Poly) alkylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol (Poly) alkylene glycol monoalkyl ether acetates such as monomethyl ether acetate and propylene glycol monoethyl ether acetate; and (meth) acrylic acid esters such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether and tetrahydrofuran Other ethers include ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone and 3-heptanone, alkyl lactates such as methyl 2-hydroxypropionate and ethyl 2-hydroxypropionate, Ethyl 2-methylpropionate, methyl 3-methoxypropionate, 3-methoxy Methyl propionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, 3-methoxybutyl propionate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-pentyl formate, isopentyl acetate, n-butyl propionate, ethyl butyrate Other esters such as ethyl acetate, n-butyl acetate, isopropyl n-butyl acetate, isopropyl n-butyl acetate, isopropyl n-butyl acetate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, Aromatic amines such as N-methylpyrrolidone, N, N-dimethylformamide and N, N-dimethylacetamide. These solvents may be used alone or in combination of two or more.

Among these solvents, propylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, 3- Methoxybutyl acetate is preferred because it exhibits excellent solubility in the above-mentioned components (A) and (B), and in that the dispersibility of the aforementioned component (C) can be improved. Propylene glycol monomethyl ether acetate , 3-methoxybutyl acetate is particularly preferred. The solvent may be appropriately determined depending on the use of the photosensitive resin composition, and for example, about 50 to 900 parts by mass relative to 100 parts by mass of the total solid content of the photosensitive resin composition.

Examples of the thermal polymerization inhibitor used in the photosensitive resin composition according to the present invention include hydroquinone, hydroquinone monoethyl ether, and the like. Examples of the antifoaming agent include silicon compounds and fluorine compounds, and surfactants include anionic compounds, cationic compounds, and nonionic compounds.

[Method for preparing photosensitive resin composition]

The photosensitive resin composition according to the present invention is prepared by mixing all of the above components with a stirrer. Further, it may be filtered using a filter so that the prepared photosensitive resin composition becomes uniform.

[Pattern formation method]

To form a pattern using the photosensitive resin composition of the present invention, a non-contact type coating device such as a roll coater, a reverse coater, a bar coater, or a contact transfer type coating device or a spinner (rotary coating device) The photosensitive resin composition is applied.

Next, the applied photosensitive resin composition is dried to form a coating film. The drying method is not particularly limited and includes, for example, (1) a method of drying on a hot plate at a temperature of 80 to 120 ° C, preferably 90 to 100 ° C for 60 to 120 seconds, (2) (3) a method of removing the solvent by putting it in a warm air heater or an infrared heater for several minutes to several hours, and the like.

Next, the coating film is partially exposed by irradiating active energy rays such as ultraviolet rays and excimer laser rays through a negative type mask. The amount of energy ray to be irradiated varies depending on the composition of the photosensitive resin composition, but is preferably about 30 to 2000 mJ / cm 2, for example. As described above, when the photosensitive resin composition according to the present invention is used, the productivity of the liquid crystal display panel can be improved because the sensitivity is excellent.

Next, the exposed film is developed with a developing solution to be patterned into a desired shape. The developing method is not particularly limited, and for example, a dipping method, a spraying method, or the like can be used. Examples of the developing solution include organic ones such as monoethanolamine, diethanolamine and triethanolamine, and aqueous solutions such as sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia and quaternary ammonium salts.

Next, post-baking is preferably performed at about 200 to 250 DEG C with respect to the pattern after development.

The pattern thus formed can be suitably used, for example, as a pixel or a black matrix of a color filter in a display device such as a liquid crystal display or the like. Such a color filter or a display device using the color filter is also one of the present invention.

Example

Hereinafter, the present invention will be described in more detail with reference to examples, but the scope of the present invention is not limited to these examples.

In the Examples and Comparative Examples relating to the photosensitive resin composition, the following PI-A to PI-O compounds were used as a photopolymerization initiator.

[Synthesis of photopolymerization initiator (oxime ester compound)] [

Hereinafter, the synthesis of PI-A to PI-H will be described with reference to Synthesis Examples 1 to 8.

[ Synthetic example  One]

(23.12 mmol) of 2- (2,5-dimethylphenyl) -1- [4- (phenylsulfanyl) phenyl] ethane- 1,2-dione, 2.93 g (42.16 mmol) of hydroxylamine hydrochloride, (41.01 mmol) of the amine were mixed with 64.00 g of ethanol and reacted at 75 DEG C to 80 DEG C for 3 hours. The reaction solution was evaporated, ethyl acetate was added, the mixture was washed with brine, dried over anhydrous magnesium sulfate and evaporated to obtain 2- (2,5-dimethylphenyl) 2- (N-hydroxyimino) -1- [4- Phenylsulfanyl) phenyl] ethan-1-one. 8.35 g of the resulting 2- (2,5-dimethylphenyl) -2- (N-hydroxyimino) -1- [4- (phenylsulfanyl) phenyl] ethan- mmol) to obtain 6.30 g of an oxime ester compound having the structure of PI-A. The measurement results of 1 H-NMR of the oxime ester compound having the structure of the obtained PI-A were as follows.

^{1 H-NMR (600MHz, CDCl} 3) δ: 8.14 (d, J = 9.0Hz, 3H), 7.58-7.55 (m, 2H), 7.46-7.42 (m, 3H), 7.26 (d, J = 6.6Hz 2H), 7.19-7.15 (m, 2H), 7.03 (s, IH), 2.34 (s, 3H)

[ Synthetic example  2]

8.00 g of 2- (2,5-dimethylphenyl) -1- [4- (phenylsulfanyl) phenyl] ethane- Nitrophenylsulfanyl) phenyl] ethane-1,2-dione was changed to 10.01 g in the same manner as in Synthesis Example 1. 5.40 g of an oxime ester compound having a PI-B structure was obtained.

[ Synthetic example  3]

8.00 g of 2- (2,5-dimethylphenyl) -1- [4- (phenylsulfanyl) phenyl] ethane- Benzoylphenylsulfanyl) phenyl] ethane-1,2-dione was changed to 9.85 g in the same manner as in Synthesis Example 1, 7.19 g of an oxime ester compound having a PI-C structure was obtained.

[ Synthetic example  4]

8.00 g of 2- (2,5-dimethylphenyl) -1- [4- (phenylsulfanyl) phenyl] ethane- 4-β-naphthoylphenylsulfanyl) phenyl] ethane-1,2-dione was changed to 11.0 g, to obtain 6.11 g of oxime ester compound having the structure of PI-D.

[ Synthetic example  5]

8.00 g of 2- (2,5-dimethylphenyl) -1- [4- (phenylsulfanyl) phenyl] ethane- 6.56 g of an oxime ester compound having the structure of PI-E was obtained in the same manner as in Synthesis Example 1, except that 10.17 g of {4- [2-methylbenzoyl] phenyl} sulfanyl) phenyl] ethane-1,2-dione was used.

[ Synthetic example  6]

8.00 g of 2- (2,5-dimethylphenyl) -1- [4- (phenylsulfanyl) phenyl] ethane- The oxime ester of the structure of PI-F was synthesized in the same manner as in Synthesis Example 1, except that 11.49 g of {4- [4-morpholin-1-yl-benzoyl] phenyl} sulfanyl) phenyl] ethane- 4.78 g of a compound was obtained.

[ Synthetic example  7]

8.00 g of 2- (2,5-dimethylphenyl) -1- [4- (phenylsulfanyl) phenyl] ethane- 9.11 g of an oxime ester compound having the structure of PI-G was obtained in the same manner as in Synthesis Example 1 except that the amount of the compound was changed to 11.60 g of {4- [4-phenylbenzoyl] phenyl} sulfanyl) phenyl] ethane-1,2-dione.

[ Synthetic example  8]

8.00 g of 2- (2,5-dimethylphenyl) -1- [4- (phenylsulfanyl) phenyl] ethane- ) Phenyl] ethane-1,2-dione was changed to 7.68 g in the same manner as in Synthesis Example 1. 6.25 g of an oxime ester compound having a PI-H structure was obtained.

[ Example  1 to 13, and Comparative Example  1 to 13]

20 parts by mass of the photopolymerization initiator shown in Table 1, 30 parts by mass of Resin A (solid content: 55% by mass, solvent: 3-methoxybutyl acetate), 30 parts by mass of dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., , 100 parts by mass of a pigment liquid of the amount shown in Table 1 (manufactured by Tokyo Ohka Kogyo Co., Ltd., each solid content of 23% by mass and pigment content of 15% by mass) (60% by mass) and propylene glycol monomethyl acetate (40% by mass) were mixed and then filtered through a membrane filter having a pore diameter of 5 占 퐉 to prepare a photosensitive resin composition. In addition, the extinction coefficients of the photopolymerization initiators PI-A to PI-N were all equal. The solid content concentration in the photosensitive resin composition was adjusted to 15 mass% by adjusting the amount of the mixed solvent.

The resin A used in the preparation of the photosensitive resin composition was prepared in accordance with the following prescription.

235 g of bisphenol fluorene type epoxy resin (epoxy equivalent 235), 110 mg of tetramethylammonium chloride, 100 mg of 2,6-di-tert-butyl-4-methylphenol and 72.0 g of acrylic acid were placed in a 500 ml four- , And the mixture was heated and dissolved at 90 to 100 ° C while blowing air at a rate of 25 ml / min. Then, the temperature of the solution was gradually elevated while the solution was cloudy, and the solution was heated to 120 DEG C to be completely dissolved. At this time, the solution gradually became a transparent point group, but stirring was continued. During this time, the acid value was measured and the heating and stirring were continued until the concentration was less than 1.0 mg KOH / g. It took 12 hours to reach the target price. The mixture was then cooled to room temperature to obtain a bisphenol fluorene-type epoxy acrylate represented by the following structural formula (a4) which was colorless transparent and solid.

Subsequently, 600 g of 3-methoxybutyl acetate was added to 307.0 g of the bisphenol fluorene epoxy acrylate thus obtained, and then 80.5 g of benzophenonetetracarboxylic dianhydride and 1 g of tetraethylammonium bromide were mixed and slowly heated And reacted at 110 to 115 ° C for 4 hours. After confirming disappearance of the acid anhydride group, 38.0 g of 1,2,3,6-tetrahydrophthalic anhydride was mixed and reacted at 90 ° C for 6 hours to obtain a resin A. The disappearance of the acid anhydride group was confirmed by IR spectrum. This resin A corresponds to the compound represented by the aforementioned general formula (a1).

In Examples 1 to 13 and Comparative Examples 1 to 13, the following pigments were used as colorants.

R177: C.I. Pigment Red 177

R242: C.I. Pigment Red 242

G36: C.I. Pigment Green 36

B156: C.I. Pigment Blue 156

Y150: C.I. Pigment Yellow 150

V23: C.I. Pigment Violet 23

Photosensitive resin compositions of Examples 1 to 13 and Comparative Examples 1 to 13 were subjected to sensitivity evaluation, post-baking color evaluation, contrast ratio evaluation, and development tact evaluation according to the following methods. Table 1 shows the evaluation results of the respective photosensitive resin compositions.

[Sensitivity evaluation]

Sensitivities of the photosensitive resin compositions of Examples 1 to 13 and Comparative Examples 1 to 13 were evaluated in the following procedure.

First, the photosensitive resin composition was spin-coated on a glass substrate (10 cm x 10 cm) and heated at 90 占 폚 for 120 seconds to form a 1.0 占 퐉 coating film on the surface of the glass substrate. Thereafter, the coating film was exposed at an exposure amount of 90, 100, 120, 200, 300, or 1000 mJ / cm 2 (Gap 200 μm) using a mirror projection aligner (product name: TME-150RTO, Topcon Co., Ltd.). The exposed film was developed with a 0.04 mass% KOH aqueous solution of 26 占 폚 for 30 to 50 seconds, and then the dimensions of the patterning portion at each exposure amount were measured with an optical microscope, and the exposure amount at which a predetermined pattern size was obtained was measured. Cm &lt; 2 &gt;). The values of the sensitivities (exposure amounts) of the respective photosensitive resin compositions are shown in Table 1.

[Evaluation of coloring]

Each of the photosensitive resin compositions of Examples 1 to 13 and Comparative Examples 1 to 13 was subjected to coloring evaluation in the following procedure.

First, the photosensitive resin composition was spin-coated on a glass substrate (10 cm x 10 cm) and heated at 90 占 폚 for 120 seconds to form a 1.0 占 퐉 coating film on the surface of the glass substrate. Thereafter, using an exposure amount (exposure amount of 90 to 1000 mJ / cm 2, Gap of 200 m) corresponding to the sensitivity shown in Table 1 measured by the above sensitivity evaluation using a mirror projection aligner (product name: TME-150RTO, The coated film was exposed. The exposed film was developed with 0.04 mass% KOH aqueous solution at 26 占 폚 for 30 to 50 seconds, and post-baked at 230 占 폚 for 30 minutes. The coating film before and after the post-baking was measured with an instant multi-photometer system (MCPD-3000, manufactured by Otsuka Electronics Co., Ltd.) as a difference in transmittance in the wavelength region of 380 nm to 780 nm as? Y. The values of? Y are shown in Table 1. The smaller the absolute value of? Y, the less the coloring.

[Evaluation of contrast ratio]

The photosensitive resin composition was spin-coated on a glass substrate in the same manner as in the sensitivity evaluation, heated at 90 占 폚 for 120 seconds, and post-baked to form a coating film of a photosensitive resin composition having a thickness of 1.0 占 퐉. A glass substrate on which a coating film was formed between two polarizing plates was placed so that the luminance of the polarizing plate in parallel with the luminance was measured with a luminance measuring apparatus (product name: CT-1, manufactured by Hoffan Electric Co., Ltd.) The contrast ratio CR was obtained.

[Development tact]

For each of the photosensitive resin compositions of Examples 1 to 13 and Comparative Examples 1 to 13, development tact evaluation was carried out in the following procedure.

First, the photosensitive resin composition was spin-coated on a glass substrate (10 cm x 10 cm) and heated at 90 占 폚 for 120 seconds to form a 1.0 占 퐉 coating film on the surface of the glass substrate. Thereafter, using an exposure amount (exposure amount of 90 to 1000 mJ / cm 2, Gap of 200 m) corresponding to the sensitivity shown in Table 1 measured by the above sensitivity evaluation using a mirror projection aligner (product name: TME-150RTO, The coated film was exposed. The values of the exposure amounts of the respective photosensitive resin compositions are shown in Table 1. The exposed film was developed with a 0.04% by mass KOH aqueous solution of 26 ° C for 30,40, and 50 seconds, and the coated photosensitive resin composition was dissolved in development for 30 seconds in good developing tact and good for 40 to 50 seconds in development tact. Good &quot; was evaluated as &quot; Good &quot;, and defective was evaluated as Good. The evaluation results are shown in Table 1.

According to Table 1, the photosensitive resin compositions of Examples 1 to 13 containing the oxime ester compound represented by the general formula (1) as a photopolymerization initiator can form a pattern at a low exposure amount of 80 to 100 mJ / cm 2, . Although the ease of coloring during post-baking differs depending on the type of pigment, according to the comparison between the examples and the comparative examples, the oxime ester compound represented by the general formula (1) was used as a photopolymerization initiator, It can be seen that the coloring due to the heating at the time of post-baking can be suppressed to be equal to or less than that of the post-baking, so that the contrast ratio can be improved. Further, according to Table 1, it is found that the photosensitive resin compositions of Examples 1 to 13 containing the oxime ester compound represented by the general formula (1) as a photopolymerization initiator have short development tact and excellent developing property.

Claims (10)

(A) a photopolymerizable compound and (B) a photopolymerization initiator,
(B) a step of coating a photosensitive resin composition containing an oxime ester compound represented by the following general formula (1) on a substrate to form a coating film;
A step of exposing the coating film,
And developing the coated film after the exposure.

(R ¹ is a group selected from the group consisting of a monovalent organic group, an amino group, a halogen, a nitro group and a cyano group,
m is an integer of 0 to 4,
p is 0 or 1,
R ³ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms,
When p is 0,
R ² represents a phenyl group which may have a substituent, or a group represented by the following general formula (3):

&Lt; / RTI &gt;
R ⁵ is a monovalent organic group,
R ⁶ is a group selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, a phenyl group which may have a substituent, and a heterocyclyl group which may have a substituent,
However, R ⁶ is not a group represented by the following general formula (4)

R ²¹ represents a hydrogen atom, an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a phenyl group, a phenyl group (having an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, An alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an amino group, an alkylamino group having 1 to 8 carbon atoms or a dialkylamino group), or a naphthyl group Substituted &lt; / RTI &gt;
R ²² and R ²³ each represent a hydrogen atom, an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a halogen group, a phenyl group, a phenyl group (an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, An alkylamino group having 1 to 8 carbon atoms or a dialkylamino group having 1 to 8 carbon atoms), a naphthyl group (an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an amino group, Or a dialkylamino group), an anthryl group, a pyridyl group, a benzofuryl group or a benzothienyl group,
Ar ¹ is selected from the group consisting of phenylene, biphenylene, pyridylene, naphthylene, anthrylene, thienylene, furylene, 2,5-pyrrolidiyl, 4,4'- - represents a dill,
n1 represents 0 or 1,
However, under the condition that n1 is zero, and when Ar is phenylene, naphthylene or thienylene a, R ²¹ and R ²² is not a methyl group or an ethyl group, and R ²³ is not a methyl group or a phenyl group,
When p is 1,
R ² is a phenyl group which may have a substituent or a carbazolyl group which may have a substituent,
The nitrogen atom in the carbazolyl group is not substituted by a group represented by the following general formula (5)

R ¹⁰ to R ¹⁴ each independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, a haloalkyl group, a substituted or unsubstituted alkylsulfinyl group, a substituted or unsubstituted arylsulfinyl group, a substituted or unsubstituted alkylsulfonyl group, An unsubstituted arylsulfonyl group, or a substituted or unsubstituted acyl group, but all of R ¹⁰ to R ¹⁴ are not simultaneously hydrogen atoms,
R ² is not a group represented by the following general formula (6)

R ²¹ represents a hydrogen atom, an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a phenyl group, a phenyl group (having an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, An alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an amino group, an alkylamino group having 1 to 8 carbon atoms, or a dialkylamino group), or a naphthyl group , &Lt; / RTI &gt;
R ²² and R ²³ each represent a hydrogen atom, an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a halogen group, a phenyl group, a phenyl group (an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, An alkylamino group having 1 to 8 carbon atoms or a dialkylamino group having 1 to 8 carbon atoms), a naphthyl group (an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an amino group, Or a dialkylamino group), an anthryl group, a pyridyl group, a benzofuryl group or a benzothienyl group,
Ar ² represents a bond or an alkylene, a vinylene, a phenylene, a biphenylene, a pyridylene, a naphthylene, an anthrylene, a thienylene, a furylene, a 2,5- '-Stilbene-diyl or 4,2'-styrene-diyl,
n1 represents 0 or 1,
Provided that when R ²¹ and R ²² are not a methyl group or an ethyl group and R ²³ is not a methyl group or a phenyl group, when n 1 is 0 and Ar ² is a bond, phenylene, naphthylene or thienylene,
The carbazolyl group does not form a benzocarbazolyl group together with the substituent which binds to the carbazolyl group. The method according to claim 1,
When p is 0, R ² is a group represented by the following general formula (2) or a group represented by the general formula (3)
Wherein when p is 1, R ² is a group represented by the following general formula (2) or a group represented by the following general formula (7).

(Wherein R ⁴ is a monovalent organic group, an amino group, a halogen, a nitro group and a cyano group, A is S or O, and n is an integer of 0 to 4)

(R ⁷ and R ⁸ are each a monovalent organic group) The method of claim 2,
Wherein R ² is a group represented by the formula (2), and A is S. (A) a photopolymerizable compound and (B) a photopolymerization initiator,
(B) a step of coating a photosensitive resin composition containing an oxime ester compound represented by the following general formula (1) on a substrate to form a coating film;
A step of exposing the coating film,
And developing the coated film after the exposure.

(R ¹ is a group selected from the group consisting of a monovalent organic group, an amino group, a halogen, a nitro group and a cyano group,
m is an integer of 0 to 4,
p is 0 or 1,
R ² is a group represented by the following general formula (2):

(R ⁴ is a monovalent organic group, an amino group, a halogen, a nitro group and a cyano group, A is S, and n is an integer of 0 to 4)
Lt; 2 &gt;
R ³ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.) The method according to any one of claims 1 to 4,
(C) a colorant. The method of claim 5,
Wherein the colorant (C) is a light shielding agent. A color filter formed by the pattern forming method of claim 5. A black matrix formed by the pattern forming method of claim 6. A display device using the color filter of claim 7. A display device according to claim 8, wherein the black matrix is used.