KR101274384B1 - A blue colored photosensitive resin composition, the color filter and the liquid crystal display device employing the same - Google Patents

Abstract

The present invention provides a photopolymerization initiator (A), a hindered phenol-based antioxidant (B), a binder resin (C), a photopolymerizable compound (D), a coloring material (E) and at least one or more oxime ester polymerization initiators. As a blue photosensitive resin composition containing a solvent (F), it provides a blue photosensitive resin composition, a color filter, and a liquid crystal display device which have high sensitivity and show high brightness characteristics.

Blue photosensitive resin composition, color filter, liquid crystal display device, oxime photoinitiator, hindered phenolic antioxidant

Description

A blue colored photosensitive resin composition, the color filter and the liquid crystal display device employing the same}

The present invention relates to a high sensitivity, high brightness blue photosensitive resin composition, a color filter and a liquid crystal display device using the same.

Color filters are widely used in imaging devices, liquid crystal displays (LCDs), and the like, and their application ranges are rapidly expanding. The color filter used for a color liquid crystal display device, an image pick-up element, etc. normally spin-coats and slit-coats the coloring photosensitive resin composition containing the pigment corresponding to each color of red, green, and blue on the board | substrate with which the black matrix was patterned. After coating uniformly, an operation of exposing and developing a coating film formed by heating and drying (hereinafter sometimes referred to as preliminary firing) and further curing by heat (hereinafter sometimes referred to as postfiring) as necessary is performed for each color. It is manufactured by forming the pixel of each color repeatedly.

As such colored photosensitive resin composition, the composition containing a photopolymerizable compound and a photoinitiator together with a pigment and binder resin is used abundantly, and the photosensitive resin composition containing a black pigment is used also for black matrix formation.

As a method for shortening the process time, which is a major issue of the recent color filter production technology, the colored photosensitive resin composition is required to have a colored photosensitive resin composition excellent in equivalent sensitivity and pattern precision even with a small exposure amount (high sensitivity). However, in order to achieve high sensitivity, examples of the use of triazine-based and halomethyl oxazole compounds as high-sensitivity initiators have been disclosed, but this has a problem of significantly lowering luminance when using blue pigments.

An object of the present invention is to provide a highly sensitive, high brightness blue photosensitive resin composition.

Still another object of the present invention is to provide a high brightness and high quality color filter and a liquid crystal display device including the same.

The present invention for achieving the above object,

A photopolymerization initiator (A), a hindered phenol-based antioxidant (B), a binder resin (C), a photopolymerizable compound (D), and a coloring material (E) containing an oxime ester polymerization initiator represented by the formula (1) or (2). And a blue photosensitive resin composition comprising a solvent (F):

≪ Formula 1 >

<Formula 2>

In Formula 1 and Formula 2, R1, R2, and R3 are each independently a hydrogen atom, R, OR, COR, SR, CONRR 'or CN, and R and R' are an alkyl group having 1 to 8 carbon atoms and a carbon atom number An aryl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 13 carbon atoms, or a 5 to 7 membered heterocyclic group, which are substituted or unsubstituted with a halogen atom or a heterocyclic group, wherein R and R 'together form a ring; Can be formed.

R4, R5, R6 and R7 each independently represent a hydrogen atom, a halogen atom or an alkyl group having 1 to 8 carbon atoms, R8 represents an alkyl group having 1 to 10 carbon atoms, and Y1, Y2 and Y3 each independently represent an oxygen atom or Sulfur atom is represented, X represents a halogen atom or an alkyl group having 1 to 8 carbon atoms.

For another object of the present invention,

The present invention provides a color filter comprising a color layer formed by exposing and developing the blue photosensitive resin composition according to the present invention in a predetermined pattern.

For another object of the present invention,

The present invention provides a liquid crystal display device including the color filter according to the present invention.

The blue photosensitive resin composition according to the present invention exhibits high sensitivity performance when forming a pixel, and thus can produce a high quality color filter having a good pattern shape even at a low exposure dose and excellent in straightness, especially in blue, high color purity and high brightness. It is possible to provide a high quality color filter having excellent color characteristics and a liquid crystal display device including the same.

The present invention is described in more detail below. This is for the purpose of illustration and should not be construed as limiting the scope of the invention.

The present invention provides a photopolymerization initiator (A), a hindered phenol-based antioxidant (B), a binder resin (C), a photopolymerizable compound (D), containing at least one or more oxime ester photopolymerization initiators of the general formula (1) or (2), A blue photosensitive resin composition containing a coloring material (E) and a solvent (F) is provided.

&Lt; Formula 1 >

<Formula 2>

In Formula 1 and Formula 2, R1, R2, and R3 are each independently a hydrogen atom, R, OR, COR, SR, CONRR 'or CN, and R and R' are an alkyl group having 1 to 8 carbon atoms and a carbon atom number An aryl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 13 carbon atoms, or a 5 to 7 membered heterocyclic group, which are substituted or unsubstituted with a halogen atom or a heterocyclic group, wherein R and R 'together form a ring; Can be formed.

R4, R5, R6 and R7 each independently represent a hydrogen atom, a halogen atom or an alkyl group having 1 to 8 carbon atoms, R8 represents an alkyl group having 1 to 10 carbon atoms, and Y1, Y2 and Y3 each independently represent an oxygen atom or Sulfur atom is represented, X represents a halogen atom or an alkyl group having 1 to 8 carbon atoms.

The photopolymerization initiator (A) may further include a polymerization initiator other than the polymerization initiator of the general formula (1) or the general formula (2), but the polymerization initiator of the general formula (1) or the general formula (2) is included in an amount of 15 parts by mass or more based on 100 parts by mass of the total polymerization initiator. desirable. More preferably, the amount of 20 to 70 parts by mass is excellent in sensitivity and reliability even at a low exposure amount, so that surface defects do not occur in the pixel portion, the flatness of the base surface is excellent, and good taper and straightness without pattern loss. It can be secured.

It is preferable that the said blue photosensitive resin composition contains a photoinitiator (A) in 0.01-30 mass parts, More preferably, it is 0.1-25 mass parts with respect to 100 mass parts of total solids. It should be included in this content range, it is preferable because the high sensitivity to shorten the exposure time to improve the productivity, and also to maintain a high resolution.

It is preferable that the said blue photosensitive resin composition contains 0.01-25 mass parts of said antioxidants (B) with respect to 100 mass parts of total solids, More preferably, it is 0.1-21 mass parts.

In particular, it is preferable that antioxidant (B) is 5-75 mass parts with respect to 100 mass parts of said all photoinitiators (A), More preferably, 15-70 mass parts is contained. When the antioxidant (B) is included relatively less, not only the brightness is poor, but also the shape and straightness of the taper are not good. In addition, if a large amount is added, there is a problem that the sensitivity is lowered to achieve the purpose of shortening the process time.

It is preferable that the said blue photosensitive resin composition contains the said binder resin (C) in 10-80 mass parts, Preferably it is 20-70 mass parts with respect to 100 mass parts of total solids. A pattern can be formed in it being the said range, and since it is a tendency for the resolution and the residual film rate to improve, it is preferable.

It is preferable that the said blue photosensitive resin composition contains the said photopolymerizable compound (D) in 1-80 mass parts with respect to 100 mass parts of total solids.

If the photopolymerizable compound (D) is within the above range, the strength and smoothness of the pixel portion tend to be good, and thus it is preferable.

As for the said blue photosensitive resin composition, with respect to 100 mass parts of total solids, the said coloring material (E) is 3-60 mass parts, Preferably it can be contained in 5-50 mass parts. If the content of the coloring material (E) is in the above-described range, the color density of the pixel is sufficient even when a thin film is formed, and since the omission property of the non-pixel portion at the time of development does not decrease, a residue tends to occur, which is preferable.

<Photoinitiator (A)>

The photopolymerization initiator (A) according to the present invention includes an oxime ester photopolymerization initiator of Formula 1 or Formula 2.

&Lt; Formula 1 >

<Formula 2>

In Formula 1 and Formula 2, R1, R2, and R3 are each independently a hydrogen atom, R, OR, COR, SR, CONRR 'or CN, and R and R' are an alkyl group having 1 to 8 carbon atoms and a carbon atom number An aryl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 13 carbon atoms, or a 5 to 7 membered heterocyclic group, which are substituted or unsubstituted with a halogen atom or a heterocyclic group, wherein R and R 'together form a ring; Can be formed.

R4, R5, R6 and R7 each independently represent a hydrogen atom, a halogen atom or an alkyl group having 1 to 8 carbon atoms, R8 represents an alkyl group having 1 to 10 carbon atoms, and Y1, Y2 and Y3 each independently represent an oxygen atom or Sulfur atom is represented, X represents a halogen atom or an alkyl group having 1 to 8 carbon atoms.

In addition, the present invention may further include a photopolymerization initiator other than the oxime ester photopolymerization initiator of Formula 1 or Formula 2, and as these photopolymerization initiators, for example, acetophenone compounds, biimidazole compounds, and oximes At least one compound selected from the group consisting of compounds.

As said acetophenone type compound, 2-methyl-1- (4-methylthiophenyl) -2-morpholino propane- 1-one, diethoxy acetophenone, 2-hydroxy-2-methyl- is mentioned, for example. 1-phenylpropane-1-one, benzyldimethyl ketal, 2-hydroxy-1- [4- (2-hydroxyethoxy) phenyl] -2-methylpropan-1-one, 1-hydroxycyclohexylphenyl Ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propane And oligomers of -1-ones. As an acetophenone type compound, the compound represented by following formula (4) is mentioned, for example:

&Lt; Formula 4 >

In the above <Formula 4>, R1 to R4 are each independently substituted or unsubstituted by a hydrogen atom, a halogen atom, a hydroxyl group, a phenyl group unsubstituted or substituted with an alkyl group having 1 to 12 carbon atoms, an alkyl group having 1 to 12 carbon atoms Or a naphthyl group unsubstituted or substituted by a benzyl group or an alkyl group having 1 to 12 carbon atoms.

Specific examples of the compound represented by the above <Formula 4> 2-methyl-2-amino (4-morpholinophenyl) ethane-1-one, 2-ethyl-2-amino (4-morpholinophenyl) ethane -1-one, 2-propyl-2-amino (4-morpholinophenyl) ethan-1-one, 2-butyl-2-amino (4-morpholinophenyl) ethan-1-one, 2-methyl 2-amino (4-morpholinophenyl) propane-1-one, 2-methyl-2-amino (4-morpholinophenyl) butan-1-one, 2-ethyl-2-amino (4-mor Polynophenyl) propane-1-one, 2-ethyl-2-amino (4-morpholinophenyl) butan-1-one, 2-methyl-2-methylamino (4-morpholinophenyl) propane-1 -One, 2-methyl-2-dimethylamino (4-morpholinophenyl) propan-1-one, 2-methyl-2-diethylamino (4-morpholinophenyl) propan-1-one, etc. are mentioned. Can be.

As said biimidazole compound, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'- tetraphenyl biimidazole, 2,2'-bis (2,3-, for example) Dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (alkoxyphenyl) biimi Dazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetra (trialkoxyphenyl) biimidazole, phenyl group at 4,4', 5,5 'position And imidazole compounds substituted with a boalkoxy group. Among them, 2,2'bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3-dichlorophenyl) -4,4', 5,5'-tetraphenylbiimidazole is preferably used.

As said oxime compound, 0-ethoxycarbonyl- (alpha)-oxyimino- 1-phenyl propane- 1-one of following <formula 5>, etc. are mentioned, for example.

&Lt; Formula 5 >

Further, as long as the effect of the present invention is not impaired, other photopolymerization initiators generally used in this field may be further used in combination. Examples of other photopolymerization initiators include benzoin-based compounds, benzophenone-based compounds, thioxanthone-based compounds, and anthracene-based compounds. These may be used alone or in combination of two or more.

As said benzoin type compound, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, etc. are mentioned, for example.

Examples of the benzophenone compound include benzophenone, methyl 0-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3 ', 4,4'-tetra tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, and the like.

Examples of the thioxanthone compound include 2-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4- .

Examples of the anthracene-based compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, and the like. Can be mentioned.

Other examples include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, phenylclyoxylic acid Methyl, titanocene compounds and the like can be mentioned as other photopolymerization initiators.

In addition, a photopolymerization initiator having a group capable of chain transfer may be used. As the photopolymerization initiator, for example, those described in Japanese Patent Publication (A) No. 2002-544205 can be cited.

Moreover, when photopolymerization start adjuvant (A-1) is used together with a photoinitiator (A), since the coloring photosensitive resin composition containing these becomes more sensitive and the productivity at the time of forming a color filter using this composition is preferable, it is preferable. .

The amount of the photopolymerization initiation assistant (A-1) to be used is usually 0.1 to 50 parts by mass, preferably 1 to 40 parts by mass with respect to 100 parts by mass of the total photosensitive resin composition. Moreover, when the usage-amount of a photoinitiator auxiliary (A-1) exists in the said range, since the sensitivity of a coloring photosensitive resin composition becomes higher and the productivity of the color filter formed using this composition tends to improve, it is preferable.

As the photopolymerization initiation auxiliary (A-1), an amine compound or a carboxylic acid compound is preferably used.

Specific examples of the amine compound include aliphatic amine compounds such as triethanolamine, methyldiethanolamine and triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoic acid and 4-dimethylaminobenzoic acid 2-ethylhexyl, 2-dimethylaminoethyl benzoate, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzophenone (common name: Mihiler ketone), 4,4'-bis (diethylamino Aromatic amine compounds, such as benzophenone, are mentioned. As the amine compound, an aromatic amine compound is preferably used.

Specific examples of the carboxylic acid compound include phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid and dichloro And aromatic heteroacetic acids such as phenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, and naphthoxyacetic acid.

Antioxidant (B)

Examples of the antioxidant (B) are generally 2-t-butylphenol, 2,6-di-t-butylphenol, 2,4-di-t-butylphenol, 2-sec-butylphenol, 2 , 6-di-sec-butylphenol, 2,4-di-sec-butylphenol, 2-isopropylphenol, 2,6-diisopropylphenol, 2,4-diisopropylphenol, 2-t-octyl Phenol, 2,6-di-t-octylphenol, 2,4-di-t-octylphenol, 2-cyclopentylphenol, 2,6-dicyclopentylphenol, 2,4-dicyclopentylphenol, 2- t-butyl-p-cresol, 2,6-di-t-amylphenol, 2,4-di-t-amylphenol, 6-t-butyl-o-cresol, 2,6-di-t- Dodecylphenol, 2,4-di-t-dodecylphenol, 2-sec-butyl-p-cresol, 2,6-di-t-octylphenol, 2,4-di-t-octylphenol, 6 -sec-butyl-o-cresol, 2-t-octyl-p-cresol, 2-t-dodecyl-p-cresol, 2-t-butyl-6-isopropylphenol, 6-t-octyl -o-cresol, 6-t-dodecyl-o-cresol, 4,4'-butylidenebis (3-methyl-6-t-butylphenol), octadecyl-3- (3,5-di -t-butyl-4-hydroxyphenyl) propionate, 4,4'-butylidenebis (6-tetra-butyl-3-methyl Nol), 4,4'-thio-bis (3-methyl-6-t-butylphenol), triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) prop Cypionate], 1,6-hexanediol-bis- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], pentaerythritol-tetrakis [3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate], 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl ) Benzene, 2,6-di-t-butyl-4-ethylphenol, 2,2'-methylenebis (4-methyl-6-t-butylphenol), 1,1,3-tris (2-methyl- 4-hydroxy-5-t-butylphenyl) butane, 1,3,5-tris (4-hydroxybenzyl) benzene and tetrakis [methylene-3- (3,5'-di-t-butyl-4 '-Hydroxyphenyl propionate)] methane, and the like, and these may be used alone or in combination of two or more.

More preferably, the antioxidant (B) is more preferably the antioxidant of the formula (3) in terms of brightness or straightness.

<Formula 3>

In the above formula, R1, R2, R3, R4 and R5 are independently a linear and cyclic alkyl group having 1 to 10 carbon atoms or hydrogen.

 <Binder Resin (C)>

The binder resin (C) contained in the blue photosensitive resin composition of the present invention can be used as long as it is a polymer that acts as a binder resin for the coloring material (E) and is soluble in the alkaline developer used in the developing step for producing the color filter. have.

The binder resin (C) may be, for example, a copolymer of a carboxyl group-containing monomer and another monomer copolymerizable with the monomer.

As said carboxyl group-containing monomer, For example, unsaturated monocarboxylic acid, unsaturated carboxylic acid, such as unsaturated polyhydric carboxylic acid which has one or more carboxyl groups in molecules, such as unsaturated dicarboxylic acid and unsaturated tricarboxylic acid, etc. are mentioned. Can be mentioned.

Examples of the unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, crotonic acid,? -Chloroacrylic acid, cinnamic acid, and the like.

Examples of the unsaturated dicarboxylic acid include maleic acid, fumaric acid, itaconic acid, citraconic acid, and mesaconic acid.

The unsaturated polycarboxylic acid may be an acid anhydride, and specific examples thereof include maleic anhydride, itaconic anhydride, citraconic anhydride and the like.

In addition, the unsaturated polyhydric carboxylic acid may be mono (2-methacryloyloxyalkyl) ester thereof, for example, succinic mono (2-acryloyloxyethyl), succinic acid mono (2-methacryloyloxy Ethyl), mono (2-acryloyloxyethyl) phthalate, mono (2-methacryloyloxyethyl) phthalate, and the like.

The unsaturated polyhydric carboxylic acid may be mono (meth) acrylate of the sock end dicarboxy polymer, and examples thereof include ω-carboxypolycaprolactone monoacrylate and ω-carboxypolycaprolactone monomethacrylate. have.

These carboxyl group-containing monomers may be used alone or in combination of two or more.

As another monomer copolymerizable with the said carboxyl group-containing monomer, For example, styrene, (alpha) -methylstyrene, o-vinyl toluene, m-vinyl toluene, p-vinyl toluene, p-chloro styrene, o-methoxy styrene, m-meth Oxy styrene, p-methoxy styrene, o-vinyl benzyl methyl ether, m-vinyl benzyl methyl ether, p-vinyl benzyl methyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p- Aromatic vinyl compounds such as vinyl benzyl glycidyl ether and indene;

Methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, i-propyl acrylate, i-propyl methacrylate, n-butyl acrylate, n-butyl methacrylate, i-butyl acrylate, i-butyl methacrylate, sec-butyl acrylate, sec-butyl methacrylate, t-butyl acrylate, t-butyl methacrylate, 2-hydroxy Ethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2-hydroxy Hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, 3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, allyl Acrylate, allyl methacrylate, benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, phenyl acrylate, phenyl methacrylate, 2-methoxyethyl acrylate, 2-methoxyethyl Methacrylate, 2-phenoxyethyl acrylate, 2-phenoxyethyl methacrylate, methoxydiethylene glycol acrylate, methoxydiethylene glycol methacrylate, methoxytriethylene glycol acrylate, methoxytriethylene glycol meth Methacrylate, methoxy propylene glycol acrylate, methoxy propylene glycol methacrylate, methoxy dipropylene glycol acrylate, methoxy dipropylene glycol methacrylate, isobornyl acrylate, isobornyl methacrylate, dicyclopentadier Nylacrylate, dicyclopentadiethyl methacrylate, 2-hydroxy-3-phenoxy Unsaturated carboxylic acid esters such as propyl acrylate, 2-hydroxy-3-phenoxypropyl methacrylate, glycerol monoacrylate, and glycerol monomethacrylate;

2-aminoethyl acrylate, 2-aminoethyl methacrylate, 2-dimethylamino ethyl acrylate, 2-dimethylaminoethyl methacrylate, 2-aminopropyl acrylate, 2-aminopropyl methacrylate, 2- Unsaturation such as dimethylaminopropyl acrylate, 2-dimethylaminopropyl methacrylate, 3-aminopropyl acrylate, 3-aminopropyl methacrylate, 3-dimethylaminopropyl acrylate and 3-dimethylaminopropyl methacrylate Carboxylic acid aminoalkyl esters;

Unsaturated carboxylic acid glycidyl esters such as glycidyl acrylate and glycidyl methacrylate;

Carboxylic acid vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate and vinyl benzoate;

Unsaturated ethers such as vinyl methyl ether, vinyl ethyl ether and allyl glycidyl ether;

Vinyl cyanide compounds such as acrylonitrile, methacrylonitrile,? -Chloroacrylonitrile, and vinylidene cyanide;

Unsaturated amides such as acrylamide, methacrylamide,? -Chloroacrylamide, N-2-hydroxyethyl acrylamide and N-2-hydroxyethyl methacrylamide;

Maleimide, N-phenylmaleimide. Unsaturated imides such as N-cyclohexylmaleimide;

Aliphatic conjugated dienes such as 1,3-butadiene, isoprene and chloroprene;

Monoacryloyl group or monomethacryloyl group at the terminal of the polymer molecular chain of polystyrene, polymethyl acrylate, polymethyl methacrylate, poly-n-butyl acrylate, poly-n-butyl methacrylate, polysiloxane The macromonomer which has, etc. are mentioned. These monomers may be used alone or in combination of two or more.

Content of the carboxyl group-containing monomeric unit in the said binder resin (C) is 10-50 mass% normally by mass fraction, Preferably it is 15-40 mass%, More preferably, it is 25-40 mass%. When content of a carboxyl group-containing monomeric unit is 10-50 mass%, since the solubility to a developing solution is favorable and there exists a tendency for the pattern at the time of image development to be formed correctly, it is preferable.

Examples of the binder resin include (meth) acrylic acid / methyl (meth) acrylate copolymer, (meth) acrylic acid / benzyl (meth) acrylate copolymer, (meth) acrylic acid / 2-hydroxyethyl (Meth) acrylate / polymethyl (meth) acrylate copolymer, a (meth) acrylic acid / methyl (meth) acrylate / polymethyl (meth) acrylate macromonomer Acrylic acid / benzyl (meth) acrylate / polymethyl (meth) acrylate macromonomer copolymer, (meth) acrylic acid / benzyl (meth) acrylate / polystyrene macromonomer copolymer, (Meth) acrylic acid / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / polystyrene macromonomer copolymer, Rimethyl (meth) acrylate macromonomer copolymer, (meth) acrylic acid / styrene / benzyl (meth) acrylate / N-phenylmaleimide copolymer, (meth) acrylic acid / succinic acid mono (2-acryloyloxy) / Styrene / benzyl (meth) acrylate / N-phenylmaleimide copolymer, (meth) acrylic acid / succinic acid mono (2-acryloyloxyethyl) / styrene / allyl (meth) acrylate / N-phenylmaleimide copolymer And (meth) acrylic acid / benzyl (meth) acrylate / N-phenylmaleimide / styrene / glycerol mono (meth) acrylate copolymer.

Of these, (meth) acrylic acid / benzyl (meth) acrylate copolymer, (meth) acrylic acid / benzyl (meth) acrylate / styrene copolymer, (meth) acrylic acid / methyl / Methyl (meth) acrylate / styrene copolymer is preferably used.

The binder resin of the present invention has an acid value in the range of 20 to 200 (KOH mg / g). When the acid value is in the above range, the solubility in the developer is improved, the non-exposed portion is easily dissolved and the sensitivity is increased, and as a result, the pattern of the exposed portion remains during development, thereby improving the film remaining ratio. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide necessary for neutralizing 1 g of the acrylic polymer, and can be generally determined by titration using an aqueous solution of potassium hydroxide.

Also, the polystyrene reduced weight average molecular weight (hereinafter, simply referred to as 'weight average molecular weight') measured by gel permeation chromatography (GPC; tetrahydrofuran as an eluting solvent) is 3,000 to 200,000, preferably 5,000 to 100,000. Alkali-soluble resins are preferred. When the molecular weight is within the above range, the hardness of the coating film is improved, the residual film ratio is high, the solubility of the non-exposed portion in the developer is excellent, and the resolution tends to be improved.

<Photopolymerizable compound (D)>

The photopolymerizable compound (D) contained in the blue photosensitive resin composition of this invention is a compound which can superpose | polymerize by the action of light and the photoinitiator mentioned later, and can contain a monofunctional monomer, a bifunctional monomer, and another polyfunctional monomer. have

Specific examples of the monofunctional monomers include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate, and N-vinyl py. A ralidone etc. are mentioned.

As a specific example of the said bifunctional monomer, 1, 6- hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and triethylene glycol di (meth) acrylate And bis (acryloyloxyethyl) ether of bisphenol A, 3-methylpentanediol di (meth) acrylate, and the like.

Specific examples of other polyfunctional monomers include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, and dipentaerythritol penta (meth) acrylate, di Pentaerythritol hexa (meth) acrylate etc. are mentioned.

Of these, multifunctional monomers having two or more functional groups are preferably used.

<Coloring material (E)>

It is preferable that the coloring material (E) used by this invention is an organic pigment or inorganic pigment normally used for a pigment dispersion resist as a pigment normally. If necessary, dyes may be used and are included in the present invention.

Specific examples of the organic pigment and inorganic pigment include compounds classified as pigments in the Color Index (published by The society of Dyers and Colorists), and more specifically, pigments having the following color index (CI) numbers. Although these are mentioned, It is not necessarily limited to these.

C.I. Pigment Violet 14, 19, 23, 29, 32, 33, 36, 37 and 38

C.I. Pigment Blue 15 (15: 3, 15: 4, 15: 6, etc.), 21, 28, 60, 64, and 76

These coloring materials (E) can be used individually or in combination of 2 or more types, respectively.

<Solvent (F)>

The solvent (F) contained in the blue photosensitive resin composition of this invention is not restrict | limited, The various organic solvents used in the field of colored photosensitive resin composition can be used. Content of the solvent (F) in the blue photosensitive resin composition of this invention is 60-90 mass% normally with a mass fraction with respect to the whole blue photosensitive resin composition containing it, Preferably it is 70-85 mass%. If the content of the solvent (F) is in the range of 60 to 90% by mass based on the above-mentioned reference, it is applied with a coating device such as a roll coater, spin coater, slit and spin coater, slit coater (sometimes referred to as die coater), inkjet, or the like. It is preferable because the coating property tends to be good at the time.

Specific examples thereof include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene. Diethylene glycol dialkyl ethers such as glycol dipropyl ether and diethylene glycol dibutyl ether, ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, and propylene glycol Monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate, methoxypentyl acetate, alkylene glycol alkyl ether acetates, aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene, methyl ethyl ketone, acetone, methyl Ketones such as amyl ketone, methyl isobutyl ketone, cyclohexanone, alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, glycerin, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, etc. And cyclic esters such as γ-butyrolactone.

Among the solvents described above, organic solvents having a boiling point of 100 to 200 ° C in the solvents are preferable in terms of coating properties and drying properties, and more preferably alkylene glycol alkyl ether acetates, ketones and 3-ethoxypropionic acid. Ester, such as ethyl and 3-methoxy propionate, is mentioned, More preferably, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, 3-ethoxy propionate, 3-methoxy Methyl oxypropionate etc. are mentioned.

These solvents (F) can be used individually or in mixture of 2 or more types, respectively.

In the coloring photosensitive resin composition of this invention, it is also possible to add additives, such as a filler, another high molecular compound, a pigment dispersing agent, an adhesion promoter, a ultraviolet absorber, and an aggregation preventing material, as needed.

Specific examples of the filler include glass, silica, alumina and the like.

Specific examples of other high molecular compounds include curable resins such as epoxy resins and maleimide resins, thermoplastic resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ethers, polyfluoroalkyl acrylates, polyesters, polyurethanes, and the like. have.

As the pigment dispersant, commercially available surfactants can be used, and examples thereof include surfactants such as silicone, fluorine, ester, cationic, anionic, nonionic, and amphoteric surfactants. These may be used alone or in combination of two or more. As said surfactant, For example, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyethylene glycol diester, sorbitan fatty acid ester, fatty acid modified polyester, tertiary amine modified polyurethane, Polyethyleneimines and the like, and other trade names include KP (manufactured by Shin-Etsu Chemical Co., Ltd.), POLYFLOW (manufactured by Kyoeisha Chemical Co., Ltd.), EFTOP (manufactured by Tochem Products), Mega MEGAFAC (made by Dainippon Ink & Chemicals Co., Ltd.), Florad (made by Sumitomo 3M Co., Ltd.), Asahi guard, Suflon (above, manufactured by Asahi Glass Co., Ltd.), Sol SLSPERSE (made by Genka Corporation), EFKA (made by EFKA Chemicals), PB 821 (made by Ajinomoto Co., Ltd.), etc. are mentioned.

As the adhesion promoter, for example, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2 -(3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyl Trimethoxysilane etc. are mentioned.

Specific examples of the ultraviolet absorber include 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzothiazole and alkoxybenzophenone.

Specific examples of the aggregation inhibitor include sodium polyacrylate and the like.

The blue photosensitive resin composition of this invention can be manufactured by the following method, for example. The coloring material (E) is mixed with the solvent (F) in advance and dispersed using a bead mill or the like until the average particle diameter of the coloring material becomes about 0.2 탆 or less. At this time, a pigment dispersant may be used if necessary, and some or all of the binder resin (C) may be blended. In the resulting dispersion (hereinafter sometimes referred to as mill base), the remainder of the binder resin (C), the polyfunctional additive, the photopolymerizable compound (D) and the photopolymerization initiator (A), other components used as necessary, Therefore, further solvent is further added so that it may become a predetermined concentration, and a desired blue photosensitive resin composition is obtained.

Hereinafter, the pattern formation method of the blue photosensitive resin composition which concerns on this invention is demonstrated.

The pattern forming method of the blue photosensitive resin composition according to the present invention comprises the steps of applying the above-described blue photosensitive resin composition on a substrate, selectively exposing a portion of the blue photosensitive resin composition, and the blue photosensitive resin composition Removing the exposed or non-exposed areas.

As an example, it can apply | coat on a base material as follows, and perform a photocuring and image development to form a pattern, and can be used as a colored pixel (colored image).

First, the composition is applied onto a substrate (not limited, usually glass or silicon wafer) or a layer containing solids of the colored photosensitive resin composition formed first and preliminarily dried to remove volatile components such as solvents to obtain a smooth coating film. . The thickness of the coating film at this time is usually about 0.5 mu m to 4 mu m. Ultraviolet rays are applied to a specific region through a mask to obtain a desired pattern on the thus obtained coating film. At this time, it is preferable to use apparatuses, such as a mask aligner and a stepper, so that a parallel light beam may be irradiated uniformly to the whole exposure part, and a mask and a board | substrate will be correctly aligned. Thereafter, the coated film after curing is brought into contact with the aqueous alkaline solution to dissolve and expose the non-exposed region, thereby making it possible to produce a desired pattern. After image development, after-drying for about 10 to 60 minutes can be performed at 120-230 degreeC as needed.

The developing solution used for image development after patterned exposure is the aqueous solution containing an alkaline compound and surfactant normally.

The alkaline compound may be either an inorganic or organic alkaline compound.

Specific examples of the inorganic alkaline compound include sodium hydroxide, potassium hydroxide, disodium hydrogen phosphate, sodium dihydrogen phosphate, ammonium dihydrogen phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, sodium silicate, potassium silicate, sodium carbonate, Potassium hydrogen carbonate, sodium borate, potassium borate, and ammonia.

Specific examples of the organic alkaline compound include tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoiso Propylamine, diisopropylamine, ethanolamine, and the like. These inorganic and organic alkaline compounds may be used alone or in combination of two or more.

The preferable concentration of the alkaline compound in the alkali developing solution is in the range of 0.01 to 10 mass%, more preferably 0.03 to 5 mass%.

The surfactant in the alkaline developer may be any of a nonionic surfactant, an anionic surfactant or a cationic surfactant.

Specific examples of the non-ionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene aryl ether, polyoxyethylene alkyl aryl ether, other polyoxyethylene derivatives, oxyethylene / oxypropylene block copolymers, sorbitan fatty acid esters, poly Oxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, glycerin fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene alkyl amine and the like.

Specific examples of the anionic surfactants include higher alcohol sulfate ester salts such as sodium lauryl alcohol sulfate and sodium oleyl alcohol sulfate, alkyl sulfates such as sodium lauryl sulfate and ammonium lauryl sulfate, sodium dodecylbenzenesulfonate, Alkyl aryl sulfonates, such as sodium dodecyl naphthalene sulfonate, etc. are mentioned.

Specific examples of the cationic surfactant include amine salts such as stearylamine hydrochloride and lauryl trimethylammonium chloride, or quaternary ammonium salts.

These surfactants may be used alone or in combination of two or more.

The concentration of the surfactant in the alkaline developer is usually 0.01 to 10% by mass, preferably 0.05 to 8% by mass, more preferably 0.1 to 5% by mass.

Hereinafter, the color filter according to the present invention will be described.

The color filter according to the present invention is characterized in that it comprises a color layer formed by exposing and developing the above-described blue photosensitive resin composition in a predetermined pattern.

The pattern formation method of a coloring photosensitive resin composition is based on the above-mentioned, and detailed description is abbreviate | omitted. As described above, a pixel or a black matrix corresponding to the color of the coloring material in the photosensitive resin composition is obtained through application of the colored photosensitive resin solution, drying, patterned exposure to the resulting dry coating film, and development. The color filter can be obtained by repeating such an operation by the number of colors required for the color filter. The construction and manufacturing method of the color filter are well known in the art, and a detailed description thereof will be omitted.

The color filter manufactured using the blue photosensitive resin composition of this invention has little in-plane film thickness difference, For example, it can make in-plane film thickness difference 0.15 micrometer or less, Furthermore, 0.05 micrometer or less with the film thickness of 0.5-4 micrometers. . Therefore, the color filter obtained in this way is excellent in smoothness, and it can manufacture a liquid crystal display device and an image pick-up element of outstanding quality by high yield by assembling this to a color liquid crystal display device and an image pick-up element.

The present invention includes a liquid crystal display device having the color filter described above.

The liquid crystal display of the present invention includes a configuration known in the art except for the color filter described above. That is, all liquid crystal display devices to which the color filter of the present invention can be applied are included in the present invention. For example, a transmissive liquid crystal display device in which a counter electrode substrate having a thin film transistor (TFT element), a pixel electrode, and an alignment layer are faced at predetermined intervals and a liquid crystal material is injected into the gap portion to form a liquid crystal layer . There is also a reflective liquid crystal display device in which a reflective layer is provided between the substrate of the color filter and the colored layer.

As another example, a liquid crystal display including a TFT (Thin Film Transistor) substrate joined on a transparent electrode of a color filter and a backlight fixed at a position where the TFT substrate overlaps the color filter. The TFT substrate includes an outer frame made of light-proof resin surrounding a peripheral surface of a color filter, a liquid crystal layer made of nematic liquid crystals imposed in the outer frame, and a plurality of pixel electrodes provided for each region of the liquid crystal layer. , A transparent glass substrate on which the pixel electrode is formed, and a polarizing plate formed on the exposed surface of the transparent glass substrate.

The polarizing plate has a polarization direction perpendicular to the polarizing direction and is made of an organic material such as polyvinyl alcohol. Each of the plurality of pixel electrodes is connected to a plurality of thin film transistors formed on a glass substrate of a TFT substrate. If a predetermined potential difference is applied to a specific pixel electrode, a predetermined voltage is applied between the specific pixel electrode and the transparent electrode. Accordingly, the electric field formed according to the voltage changes the orientation of the region corresponding to the specific pixel electrode of the liquid crystal layer.

Example

Hereinafter, the present invention will be described in more detail with reference to examples. However, the embodiments of the present invention described below are illustrative only and the scope of the present invention is not limited to these embodiments. It is intended that the scope of the invention be indicated by the appended claims and include all changes that come within the meaning and range of equivalency of the claims which follow. Hereinafter, the present invention will be described in more detail with reference to examples, but it is needless to say that the present invention is not limited to the examples. In the following Examples and Comparative Examples, "%" and "part" representing the content are on a mass basis unless otherwise specified.

Example 1-8, Comparative Example 1-7

The components shown in Table 1 and Table 2 were mixed and dissolved to prepare a photopolymerizable composition.

Example One 2 3 4 5 6 7 8 (E-1) 2.228 2.228 2.228 2.228 2.228 2.228 2.228 2.228 (E-2) 0.248 0.248 0.248 0.248 0.248 0.248 0.248 0.248 (C-1) 5.076 4.995 4.916 4.916 4.916 4.767 4.628 4.767 (D-1) 4.537 4.455 4.377 4.377 4.377 4.228 4.089 4.228 (A-1) 0.907 0.891 0.875 0.875 0.875 0.846 0.818 (A-2) 0.363 0.356 0.350 0.350 0.350 0.338 0.327 (A-3) 0.907 0.891 0.875 0.875 0.846 0.818 2.029 (A-4) 0.875 (A-5) (A-6) [B-1] 0.218 0.428 0.630 0.630 1.015 1.374 1.015 [B-2] 0.630 (F-1) 34.000 34.000 34.000 34.000 34.000 34.000 34.000 34.000 (F-2) 51.000 51.000 51.000 51.000 51.000 51.000 51.000 51.000 (G-1) 0.063 0.063 0.063 0.063 0.063 0.063 0.063 0.063 (G-2) 0.454 0.446 0.438 0.438 0.438 0.423 0.409 0.423

Comparative example One 2 3 4 5 6 7 (E-1) 2.228 2.228 2.228 2.228 2.228 2.228 2.228 (E-2) 0.248 0.248 0.248 0.248 0.248 0.248 0.248 (C-1) 5.161 5.161 4.995 5.161 4.995 5.161 4.995 (D-1) 4.621 4.621 4.455 4.621 4.455 4.621 4.455 (A-1) 0.924 1.479 1.426 0.924 0.891 0.924 0.891 (A-2) 0.370 0.739 0.713 0.370 0.356 0.370 0.356 (A-3) 0.924 (A-4) (A-5) 0.924 0.891 (A-6) 0.924 0.891 [B-1] 0.428 0.428 0.428 [B-2] (F-1) 34.000 34.000 34.000 34.000 34.000 34.000 34.000 (F-2) 51.000 51.000 51.000 51.000 51.000 51.000 51.000 (G-1) 0.063 0.063 0.063 0.063 0.063 0.063 0.063 (G-2) 0.462 0.462 0.446 0.462 0.446 0.462 0.446

(A-1) 2-Benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one [Irgacure 369; Manufactured by Ciba Specialty Chemical)

(A-2) 4,4'-bis (diethylamino) benzophenone [EAB-F; Manufactured by Hodogaya Chemical Co., Ltd.]

(E) -1- (1- (6- (4 - ((2,2-dimethyl-1,3-dioxolan-4-yl) methoxy) -2-methylbenzoyl) -9- 9,9-dihydro-4aH-carbazol-3-yl) ethylideneaminooxy) ethanone [N-1919 <

(A-4) 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime) [IRGACURE ^® OXE02 <Ciba Specialty Chemicals>]

(A-5) 1,2-octanedione 1- [4- (phenylthio) phenyl] -2- (O-benzoyloxime) [IRGACURE ^? OXE01 <Manufacturer: Ciba Specialty Chemicals>]

(A-6) trichloromethyltriazine

(B-1) 4,4'-butylidenebis (6-tetra-butyl-3-methylphenol) (Sumitomo Chemical-BBM-S)

(B-2) Octadecyl 3- (3,5-di-tert-butyl-4-hydroxyphenol) propionate

(C-1) Copolymer of methacrylic acid and benzyl methacrylate (the ratio of the methacrylic acid unit and the benzyl methacrylate unit is 25:75 in molar ratio, the acid value is 82, the weight average molecular weight in terms of polystyrene is 28,000)

(D-1) dipentaerythritol hexaacrylate

(E-1) C.I. Pigment Blue 15: 6

(E-2) C.I. Pigment Violet 23

(F-1) ethyl 3-ethoxypropionate

(F-2) Propylene Glycol Monomethyl Ether Acetate

(G-1) methacryloxypropyl trimethoxysilane

(G-2) epoxy resin (SUMI-EPOXY ESCN-195XL)

The blue photosensitive resin compositions for color filters of Examples 1 to 8 and Comparative Examples 1 to 7 were coated on a glass substrate by spin coating, and then placed on a heating plate and maintained at a temperature of 100 ° C. for 3 minutes to form a thin film. Subsequently, an interval of 100 μm and an exposure dose of 80 mJ / cm 2 was irradiated on the thin film with a photomask for changing the transmittance stepwise in a range of 1 to 100%, and a test having a line / space pattern from 1 μm to 100 μm The photomask was put on, and 200 micrometers, 40mJ / cm <2> of exposure amounts, and 20mJ / cm <2> were investigated for the space | interval with a test photomask.

In this case, a 1kw high-pressure mercury lamp containing all g, h, and i rays was used, and no special optical filter was used. The UV-irradiated thin film was developed for 80 seconds using a spray developer in a KOH aqueous solution developing solution of pH 12.5. The thin plate coated with glass was washed with distilled water, dried by blowing nitrogen gas, and heated in a heating oven at 220 ° C. for 20 minutes. The pattern shape (film) thickness of the color filter obtained through this was 1.5 micrometers.

Sensitivity, brightness reduction, taper, and pattern straightness were evaluated for the color filters prepared with the colored photosensitive resin compositions for color filters of Examples 1 to 8 and Comparative Examples 1 to 7, and the results are shown in Table 3 below. As shown.

Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Sensitivity * 1 (mJ / cm ² ) 14.4 (○) 16 (○) 20 (○) 20 (○) 20 (○) 24 (△) 32 (△) 20 (○) Luminance reduction * 2 △ ○ ○ ○ ○ ○ ○ △ Taper shape * 3 ○ ○ ○ ○ ○ ○ ○ ○ Straightness * 4 ○ ○ ○ ○ ○ ○ ○ ○

Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 Sensitivity * 1 (mJ / cm ² ) 9.6 (○) 40 (△) X 40 (△) 48 (X) 24 (△) 48 (X) Luminance reduction * 2 X ○ ○ X X ○ ○ Taper shape * 3 ○ × × × × × × Straightness * 4 ○ × × × × × ×

* 1: The minimum required exposure dose required to form a pattern without surface roughness even when developed,

○: no surface roughness at 20 mJ or less

△: 20 mJ or more 40 mJ or less

X: more than 40mJ

* 2: change in luminance (Y) relative to target (target)

○: △ Y ≥ 0 relative to the target (target)

△: 0> △ Y ≥ -0.3

X: △ Y <-0.3

* 3: The shape of the pixel surface was observed using SEM (10,000 magnification).

○: Good pattern profile

X: Pattern profile is bad

* 4: The shape of the pixel surface was observed using SEM (10,000 magnification).

(Circle): The straightness deviation of a pattern edge part is 1 micrometer or less

X: deviation of linearity of pattern edge is over 1㎛

As a result of evaluating the color filter prepared from the blue photosensitive resin composition for color filters of Examples 1 to 8 and Comparative Examples 1 to 7, the oxime ester polymerization initiator represented by Formula 1 or Formula 2 was an essential component, and a hindered system. Although the composition of Examples 1 to 8 using the antioxidant does not use the oxime ester polymerization initiator represented by the formula (1) or (2) as an essential ingredient, or as an essential ingredient, compared to the composition without using the hindered antioxidant It was confirmed that the sensitivity, luminance reduction, taper and pattern straightness were excellent.

Claims (7)

A photopolymerization initiator (A), a hindered phenol-based antioxidant (B), a binder resin (C), a photopolymerizable compound (D), and a coloring material (E) containing an oxime ester polymerization initiator represented by the formula (1) or (2). And solvent (F), The antioxidant (B) is a blue photosensitive resin composition, characterized in that the antioxidant of the formula (3). &Lt; Formula 1 >

<Formula 2>

(In Formula 1, Formula 2, R1, R2, R3 are each independently a hydrogen atom, R, OR, COR, SR, CONRR 'or CN, R and R' is an alkyl group having 1 to 8 carbon atoms, carbon source An aryl group having 6 to 12 embroidery, an aralkyl group having 7 to 13 carbon atoms, or a 5 to 7 membered heterocyclic group, and these are substituted or unsubstituted with a halogen atom or a 5 to 7 membered heterocyclic group, among which R and R 'Can form a ring together, R4, R5, R6 and R7 each independently represent a hydrogen atom, a halogen atom or an alkyl group having 1 to 8 carbon atoms, R8 represents an alkyl group having 1 to 10 carbon atoms, and Y1, Y2 and Y3 each independently represent an oxygen atom or A sulfur atom, X represents a halogen atom or an alkyl group having 1 to 8 carbon atoms.) <Formula 3>

(Wherein, R1, R2, R3, R4 and R5 are independently a linear and cyclic alkyl group or hydrogen of 1 to 10 carbon atoms.) The method of claim 1, The photoinitiator (A) further comprises a polymerization initiator other than the polymerization initiator of the formula (1) or formula (2), wherein the polymerization initiator of the formula (1) or formula (2) is contained 15 parts by mass or more based on 100 parts by mass of the total polymerization initiator A blue photosensitive resin composition characterized by the above-mentioned. The method of claim 1, The photopolymerization initiator (A) further comprises a polymerization initiator other than the polymerization initiator of the formula (1) or (2), wherein the polymerization initiator of the formula (1) or (2) is 20 parts by mass to 70 parts by mass with respect to 100 parts by mass of the entire polymerization initiator. Blue photosensitive resin composition characterized by being included. The method of claim 1, Said antioxidant (B) is contained in 5-75 mass parts with respect to 100 mass parts of said photoinitiators (A), The blue photosensitive resin composition characterized by the above-mentioned. delete The color filter formed by exposing and developing the blue photosensitive resin composition of any one of Claims 1-4 in a predetermined pattern, The color filter characterized by the above-mentioned. A liquid crystal display device comprising the color filter of claim 6.