KR20150001166A - Photosensitive resin composition and color filter using the same - Google Patents

Abstract

[화학식 2]

[화학식 3]

[화학식 4]

[화학식 5]

[화학식 6]

[화학식 7]

[화학식 8]

(상기 화학식 1 내지 8에서,　각 치환기는 명세서에 정의된 바와 같다.)(A) at least one repeating unit represented by the following formula (1), at least one repeating unit represented by the following formula (2), at least one repeating unit represented by the following formula (3), at least one repeating unit represented by the following formula , At least one repeating unit represented by the following formula (5), at least one repeating unit represented by the following formula (6), at least one repeating unit represented by the following formula (7), and at least one repeating unit represented by the following formula A binder resin containing an acrylic binder resin; (B) a photopolymerizable monomer; (C) a photopolymerization initiator; (D) a colorant; And (E) a solvent, and a color filter using the same.
[Chemical Formula 1]

(2)

(3)

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

(7)

[Chemical Formula 8]

(In the above Chemical Formulas 1 to 8, each substituent is as defined in the specification.)

Description

TECHNICAL FIELD [0001] The present invention relates to a photosensitive resin composition for a color filter, and a color filter using the same. BACKGROUND ART [0002]

The present invention relates to a photosensitive resin composition for a color filter and a color filter using the same.

A color filter is used for a liquid crystal display, an optical filter of a camera, and the like, and is manufactured by coating a fine area colored with three or more hues on a solid-state imaging element or a transparent substrate. Such a colored thin film is usually formed by a pigment dispersion method or the like.

The colored photosensitive resin composition used in the production of a color filter according to the pigment dispersion method generally comprises a binder resin, a photopolymerizable monomer, a photopolymerization initiator, a colorant, an epoxy resin, a solvent, and other additives. As the binder resin, for example, Japanese Patent Application Laid-Open Nos. 7-140654 and 10-254133 use a carboxyl group-containing acrylic copolymer.

In particular, recent color filter manufacturing processes are being produced in a continuous process capable of mass production. In recent years, color filters having excellent color characteristics, heat resistance, and the like have been required in accordance with high-quality specifications. In particular, attempts to improve pigments and dyes as colorants have been made to improve the luminance characteristics. However, there are limitations in improving the luminance characteristics through the improvement of pigments and dyes, which are colorants, and it is necessary to study the improvement of the luminance characteristics through improvement of other components other than the colorant.

An embodiment of the present invention is to provide a photosensitive resin composition for a color filter excellent in color characteristics and excellent in heat resistance and pattern processability by having a high luminance.

Another embodiment of the present invention is to provide a color filter using the photosensitive resin composition.

(A) at least one repeating unit represented by the following general formula (1), at least one repeating unit represented by the following general formula (2), at least one repeating unit represented by the following general formula (3) At least one repeating unit represented by the following formula (5), at least one repeating unit represented by the following formula (6), at least one repeating unit represented by the following formula (7), and at least one repeating unit represented by the following formula A binder resin comprising an acrylic binder resin containing a repeating unit represented by formula (8); (B) a photopolymerizable monomer; (C) a photopolymerization initiator; (D) a colorant; And (E) a solvent for a color filter.

[Chemical Formula 1]

(2)

(3)

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

(7)

[Chemical Formula 8]

(In the above Chemical Formulas 1 to 8,

R ¹ to R ⁷ , R ', and R "are each independently hydrogen or a substituted or unsubstituted C1 to C10 alkyl group,

L ¹ to L ⁶ are each independently a single bond or a substituted or unsubstituted C1 to C10 alkylene group,

S ¹ is a substituted or unsubstituted C7 to C30 cycloalkyl group or a substituted or unsubstituted C7 to C30 multibranched alkyl group,

S ² to S ⁴ are each independently hydrogen, halogen, a substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C1 to C10 alkoxy group,

S ⁵ is a substituted or unsubstituted C3 to C30 cycloalkyl group.)

In the acrylic binder resin, the repeating unit represented by Formula 1 is 4 mol% to 10 mol%, the repeating unit represented by Formula 2 is 4 mol% to 10 mol%, and the repeating unit represented by Formula 3 is 4 The repeating unit represented by the formula (4) is 10 mol% to 20 mol%, the repeating unit represented by the formula (5) is 10 mol% to 20 mol%, the repeating unit represented by the formula 5 mol% to 15 mol%, the repeating unit represented by the formula (7) is 15 mol% to 35 mol%, and the repeating unit represented by the formula (8) is 10 mol% to 20 mol%.

Wherein R ¹ to ^{R 3, R 5, R 6} , R ', R ", and S ⁴ may be each independently substituted or unsubstituted C1 to C6 alkyl ring, wherein R ^4, R ^7, S ^2, and S ³ may each independently be hydrogen, L ¹ to L ⁶ may be, independently of each other, a substituted or unsubstituted C1 to C6 alkylene group, and S ¹ is a substituted or unsubstituted C7 to C20 polycyclic alkyl group And S < ⁵ > may be a substituted or unsubstituted C3 to C10 cycloalkyl group.

The acrylic binder resin may include a structural unit represented by the following general formula (9).

[Chemical Formula 9]

(In the above formula (9)

a, b, c, d, e, f, g and h are each independently an integer of 1 or more.

The weight average molecular weight of the acrylic binder resin may be 6,000 to 15,000 g / mol.

The acid value of the acrylic binder resin may be 50 to 100 mgKOH / g.

The binder resin may further include a cadmium binder resin.

The colorant may comprise a dye, a pigment, or a combination thereof.

The photosensitive resin composition for color filters comprises (A) 1 to 40% by weight of the binder resin; (B) 1 wt% to 30 wt% of the photopolymerizable monomer; (C) 0.1 to 10% by weight of the photopolymerization initiator; (D) 1% to 40% by weight of the colorant; And (E) the solvent balance.

The photosensitive resin composition for a color filter comprises malonic acid; 3-amino-1,2-propanediol; A coupling agent comprising a vinyl group or (meth) acryloxy group; Leveling agents; Fluorine surfactants; And at least one additive selected from a radical polymerization initiator.

Another embodiment of the present invention provides a color filter using the photosensitive resin composition for a color filter.

Other details of the embodiments of the present invention are included in the following detailed description.

Since the photosensitive resin composition has high brightness and excellent color characteristics and heat resistance, it can be usefully used for a color filter.

1 is an optical microscope photograph showing CD and holes of a color filter pattern.

Hereinafter, embodiments of the present invention will be described in detail. However, it should be understood that the present invention is not limited thereto, and the present invention is only defined by the scope of the following claims.

Unless otherwise specified herein, "substituted" means that at least one hydrogen atom is replaced by a halogen atom (F, Cl, Br, I), a hydroxy group, a C1 to C20 alkoxy group, a nitro group, a cyano group, A thio group, an ester group, an ether group, a carboxyl group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphoric acid or a salt thereof, an amidino group, a hydrazino group, a hydrazino group, a carbonyl group, a carbamyl group, A cycloalkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, a cycloalkenyl group having 3 to 20 carbon atoms, a cycloalkynyl group having 3 to 20 carbon atoms, Substituted with a substituent of a C2 to C20 heterocycloalkyl group, a C2 to C20 heterocycloalkenyl group, a C2 to C20 heterocycloalkynyl group, a C3 to C30 heteroaryl group, or a combination thereof.

Also, unless otherwise specified herein, "hetero" means that at least one heteroatom of N, O, S and P is included in the ring group.

&Quot; (Meth) acrylic acid "refers to both" acrylic acid "and" methacrylic acid " "It means both are possible.

&Quot; Combination " as used herein, unless otherwise specified, means mixing or copolymerization.

Unless otherwise specified herein, " multi-ring alkyl group " means a fused ring in which two or more rings share at least one carbon-carbon bond.

In the chemical formulas described herein, " * " means the same or different atom or moiety connected to the chemical formula.

The photosensitive resin composition for a color filter according to an embodiment includes (A) a binder resin comprising an acrylic binder resin, (B) a photopolymerizable monomer, (C) a photopolymerization initiator, (D) a colorant, and .

Since the acrylic binder resin (A) contains the repeating units represented by the following formulas (1) to (8), it is possible to improve the brightness only by the characteristics of the binder resin without improving the coloring agent such as pigment or dye, Excellent process characteristics can be realized.

[Chemical Formula 1]

(2)

(3)

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

(7)

[Chemical Formula 8]

(In the above Chemical Formulas 1 to 8,

R ¹ to R ⁷ , R ', and R "are each independently hydrogen or a substituted or unsubstituted C1 to C10 alkyl group,

L ¹ to L ⁶ are each independently a single bond or a substituted or unsubstituted C1 to C10 alkylene group,

S ¹ is a substituted or unsubstituted C7 to C30 cycloalkyl group or a substituted or unsubstituted C7 to C30 multibranched alkyl group,

S ² to S ⁴ are each independently hydrogen, halogen, a substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C1 to C10 alkoxy group,

S ⁵ is a substituted or unsubstituted C3 to C30 cycloalkyl group.)

Each component will be described in detail below.

(A) Binder resin

Wherein the binder resin comprises at least one repeating unit represented by Formula 1, at least one repeating unit represented by Formula 2, at least one repeating unit represented by Formula 3, and at least one repeating unit represented by Formula 4 At least one repeating unit represented by Formula 5, at least one repeating unit represented by Formula 6, at least one repeating unit represented by Formula 7, and at least one repeating unit represented by Formula 8 , It is possible to realize a color filter having high luminance and high contrast ratio and excellent in developing property, heat resistance and pattern processability when used in a photosensitive resin composition for a color filter. The binder resin further includes the acrylic binder resin, thereby preventing the occurrence of yellowing of the binder resin.

In Formula 1 to Formula 8, R ¹ to R ³ , R ⁵ , R ⁶ , R ', R ", and S ⁴ may each independently be a substituted or unsubstituted C 1 to C 6 alkyl group, wherein R ^4, R ^7, S ² and S ³ each may be independently selected from hydrogen, the L ¹ to L ⁶ is independently may be an substituted or unsubstituted C1 to C6 alkylene group to each other, S ¹ is a substituted or An unsubstituted C7 to C20 polycyclic alkyl group, and S < ⁵ > may be a substituted or unsubstituted C3 to C10 cycloalkyl group.

For example, the multibranched alkyl group may comprise a bicyclo alkyl group. For example, the multiple ring alkyl group may be represented by the following formula a or b.

(A)

[Formula b]

In the above formulas (a) and (b), each of A ¹ to A ⁵ may independently be hydrogen, halogen, or a substituted or unsubstituted C1 to C10 alkyl group. For example, each of A ¹ to A ⁵ may independently be hydrogen, a methyl group, an ethyl group, a propyl group, or an isopropyl group.

For example, in the above Chemical Formulas 1 to 8, wherein R ¹ to ^{R 3, R 5, R 6} , R ', R ", and S ⁴ are the R ^4,, it may be each independently a group R ^7, S ² and S ³ each independently can be hydrogen, wherein the L ¹ to L ^3, L ^5, and L ⁶ may be ethylene date, independently of each other, the L ⁴ may methylene date, S ¹ has the formula c, and S < ⁵ > may be a cyclohexyl group.

(C)

In the acrylic binder resin, the repeating unit represented by Formula 1 is 4 mol% to 10 mol%, the repeating unit represented by Formula 2 is 4 mol% to 10 mol%, and the repeating unit represented by Formula 3 is 4 The repeating unit represented by the formula (4) is 10 mol% to 20 mol%, the repeating unit represented by the formula (5) is 10 mol% to 20 mol%, the repeating unit represented by the formula 5 mol% to 15 mol%, the repeating unit represented by the formula (7) is 15 mol% to 35 mol%, and the repeating unit represented by the formula (8) is 10 mol% to 20 mol%.

By containing each repeating unit in the above content range, the acrylic binder resin can realize a color filter having high brightness and high contrast ratio in the color filter composition and excellent in developing property, heat resistance, and pattern processability.

Each of the repeating units represented by the above formulas (1) to (8) is capable of forming a copolymer at random as well as in block and alternation.

The acrylic binder resin may specifically include a structural unit represented by the following formula (9).

[Chemical Formula 9]

In the above formula (9)

a, b, c, d, e, f, g, and h are each independently an integer of 1 or more.

The weight average molecular weight of the acrylic binder resin may be 6,000 to 1,5000 g / mol, and may be 9,000 to 11,000 g / mol. When the weight average molecular weight is in the above range, developability by an alkali developing solution can be improved.

The acid value of the acrylic binder resin may be 50 to 100 mgKOH / g, and specifically 60 to 80 mgKOH / g. When the acid value is within the above-mentioned range, the developability for an alkali developing solution is excellent and a color filter pattern can be easily formed.

The binder resin may further include an additional acrylic binder resin in addition to the acrylic binder resin. The additional acrylic binder resin may be any acrylic binder resin known in the art.

The binder resin may further include a cationic binder resin including a repeating unit represented by the following formula (10) together with the acrylic binder resin.

[Chemical formula 10]

(In the formula (10)

R ₂₄ To R < ₂₇ > are the same or different and each represents a hydrogen atom, a halogen atom, or a substituted or unsubstituted C1 to C20 alkyl group,

R ₂₈ and R ₂₉ are the same as or different from each other, and represent a hydrogen atom or -CH ₂ OR _a (R _a is a vinyl group, an acrylate group or a methacrylate group)

R ₃₀ are the same or different from each other and each represent a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, an acrylate group or a methacrylate group,

Z ₁ are the same or different and are a single bond, -O-, -CO-, -SO ₂ -, -CR _b R _c -, -SiR _d R _e - (wherein R _b to R _e are the same And is a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group), or a linking group represented by the following general formulas (11) to (21)

Z ₂ are the same or different from each other, and the acid dianhydride residue.

(11)

[Chemical Formula 12]

[Chemical Formula 13]

[Chemical Formula 14]

[Chemical Formula 15]

(In the above formula (15)

R _f is a hydrogen atom, an ethyl group, -C ₂ H ₄ Cl, -C ₂ H ₄ OH, -CH ₂ CH = CH ₂ , or a phenyl group.

[Chemical Formula 16]

[Chemical Formula 17]

[Chemical Formula 18]

[Chemical Formula 19]

[Chemical Formula 20]

[Chemical Formula 21]

The cadmium binder resin can be specifically obtained by reacting a compound represented by the following formula (22) with a tetracarboxylic acid dianhydride.

[Chemical Formula 22]

The tetracarboxylic dianhydride may be an aromatic tetracarboxylic dianhydride. Examples of the aromatic tetracarboxylic acid dianhydride include pyromellic acid dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 2,3,3', 4-biphenyltetracarboxylic dianhydride, 2 , 2 ', 3,3'-biphenyltetracarboxylic dianhydride, 3,3', 4,4'-benzophenonetetracarboxylic dianhydride, 3,3 ', 4,4'-biphenyl ether tetracarboxylic acid dianhydride , 3,3 ', 4,4'-diphenylsulfone tetracarboxylic acid dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 2, 3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,5,6-pyridine tetracarboxylic dianhydride, 3,4,9,10-perylene Tetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, and the like, but the present invention is not limited thereto.

The weight average molecular weight of the cationic binder resin may be from 1,000 to 20,000 g / mol, and specifically from 3,000 to 10,000 g / mol. When the weight average molecular weight of the cationic binder resin is within the above range, excellent patterning property and developability can be obtained in the production of a color filter.

The binder resin may be contained in an amount of 1 to 40% by weight based on the total amount of the photosensitive resin composition for a color filter, specifically 5 to 30% by weight.

The content of the acrylic binder resin containing the repeating units represented by the above formulas (1) to (8) in the binder resin may be at least 5 to 10% by weight. And may further comprise the additional acrylic binder resin and / or the cadmium binder resin in the remaining amount range excluding the above content.

When the binder resin is contained within the above range, the developability, the thickness uniformity, the surface roughness and the adhesiveness to an alkali developing solution can be improved, and a color filter having high brightness can be realized.

(B) Photopolymerization  Monomer

The photopolymerizable monomer may be a monofunctional or polyfunctional ester of (meth) acrylic acid having at least one ethylenically unsaturated double bond.

Since the photopolymerizable monomer has the ethylenically unsaturated double bond, sufficient polymerization is caused during exposure in the pattern formation step, whereby a pattern having excellent heat resistance, light resistance and chemical resistance can be formed.

Specific examples of the photopolymerizable monomer include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, neopentyl glycol Acrylate such as di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, bisphenol A di (meth) acrylate, pentaerythritol di (Meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol hexa (meth) acrylate, dipentaerythritol di Acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, bisphenol A epoxy (meth) acrylate, ethylene glycol There may be mentioned furnace methyl ether (meth) acrylate, trimethylolpropane tri (meth) acrylate, tris (meth) acryloyloxyethyl phosphate, novolak epoxy (meth) acrylate, and the like.

A commercially available product of the photopolymerizable monomer is exemplified as follows. The (meth) acrylic acid is one example of a polyfunctional ester, such as doah Gosei Kagaku Kogyo's (primary)社Aronix M-101 ^®, the same M-111 ^®, the same M-114 ^®; KAYARAD TC-110S ^® and TC-120S ^{® from} Nihon Kayaku Co., Ltd.; Osaka yukki the like Kagaku Kogyo (main)社of ^{V-158 ®, V-2311} ®. The (meth) transfer function of an example esters of acrylic acid are, doah Gosei Kagaku Kogyo (Note)社of Aronix M-210 ^®, copper or the like M-240 ^®, the same M-6200 ^®; KAYARAD HDDA ^® , HX-220 ^® and R-604 ^{® from} Nihon Kayaku Corporation; Osaka yukki the like Kagaku Kogyo Co., Ltd. of ^{社V-260 ®, V-} 312 ®, V-335 HP ®. Examples of the tri-functional ester of (meth) acrylic acid, doah Gosei Kagaku Kogyo (Note)社of Aronix M-309 ^®, the same M-400 ^®, the same M-405 ^®, the same M-450 ^®, Dong M -7100 ^® , copper M-8030 ^® , copper M-8060 ^® and the like; Nippon Kayaku (Note)社of KAYARAD TMPTA ^®, copper DPCA-20 ^{®, ®} copper -30, -60 ^® copper, copper ^® -120 and the like; Osaka yukki Kayaku high (primary)社of V-295 ^®, copper ^® -300, -360 ^® copper, copper -GPT ^®, copper -3PA ^®, and the like copper -400 ^®. These products may be used alone or in combination of two or more.

The photopolymerizable monomer may be treated with an acid anhydride to give better developing properties.

The photopolymerizable monomer may be included in an amount of about 1 to 30% by weight based on the total amount of the photosensitive resin composition for a color filter, and specifically about 5 to 10% by weight. When the photopolymerizable monomer is contained within the above range, the photopolymerizable monomer sufficiently cures upon exposure in the pattern formation step, is excellent in reliability, and is excellent in developability in an alkaline developer.

(C) Light curing Initiator

The photopolymerization initiator may be an acetophenone-based compound, a benzophenone-based compound, a thioxanthone-based compound, a benzoin-based compound, a triazine-based compound, or an oxime-based compound.

Examples of the acetophenone-based compound include 2,2'-diethoxyacetophenone, 2,2'-dibutoxyacetophenone, 2-hydroxy-2-methylpropiophenone, pt-butyltrichloroacetophenone, dichloro-4-phenoxyacetophenone, 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropanone, p-butyldichloroacetophenone, 1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one.

Examples of the benzophenone compound include benzophenone, benzoyl benzoic acid, methyl benzoyl benzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4,4'-bis (dimethylamino) benzophenone, '-Bis (diethylamino) benzophenone, 4,4'-dimethylaminobenzophenone, 4,4'-dichlorobenzophenone, and 3,3'-dimethyl-2-methoxybenzophenone.

Examples of the thioxanthone compound include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisobutyl Propyl thioxanthone and the like.

Examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and benzyl dimethyl ketal.

Examples of the triazine-based compound include 2,4,6-trichloro-s-triazine, 2-phenyl 4,6-bis (trichloromethyl) (Trichloromethyl) -s-triazine, 2- (4'-methoxynaphthyl) -4,6-bis (trichloromethyl) Bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) Bis (trichloromethyl) -s-triazine, bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphtho 1-yl) -4,6 -Bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphtho-1-yl) (Piperonyl) -6-triazine, and 2-4-trichloromethyl (4'-methoxystyryl) -6-triazine.

Examples of the oxime compounds include 2- (o-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione, 1- (o- Ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone.

The photopolymerization initiator may be a carbazole compound, a diketone compound, a sulfonium borate compound, a diazo compound, an imidazole compound, or a nonimidazole compound in addition to the above compounds.

The photopolymerization initiator may be included in an amount of about 0.1 to 10% by weight based on the total amount of the photosensitive resin composition for a color filter, and specifically about 0.1 to 5% by weight. When the photopolymerization initiator is contained within the above range, photopolymerization sufficiently occurs upon exposure in the pattern formation step, and the decrease of the transmittance due to the unreacted initiator can be prevented.

(D) Colorant

The colorant may be at least one selected from pigments and dyes.

Examples of the pigments include red pigments, blue pigments, green pigments, violet pigments, yellow pigments, cyanine pigments, magenta pigments, and black pigments.

Examples of the red pigments include perylene pigments, anthraquinone pigments, dianthraquinone pigments, azo pigments, diazo pigments, quinacridone pigments, and anthracene pigments. have. Specific examples of the red pigments include perylene pigments, quinacridone pigments, naphthol AS, siccone pigments, anthraquinone (sudan I, II, III, R), dianthraquinolide, Vis azo, benzopyran and the like.

Examples of the blue pigments include metal phthalocyanine pigments, indanthrone pigments, indophenol pigments, and the like. Specific examples of the blue pigments include phthalocyanine metal complexes such as copper phthalocyanine, chloro copper phthalocyanine, chloroal phthalocyanine, titanyl phthalocyanine, vanadinic acid phthalocyanine, magnesium phthalocyanine, zinc phthalocyanine, iron phthalocyanine and cobalt phthalocyanine.

As the green pigments, halogenated phthalocyanine pigments 　 And the like. Specific examples thereof include polychloro-copper phthalocyanine and polychlorobromophthalocyanine.

Examples of the violet pigment include dioxazine violet, first violet B, methyl violet, indanthrene brilliant violet, and the like.

Examples of the yellow pigments include tetrachloroisoindolinone pigments, hansa pigments, benzidine yellow pigments, and azo pigments. Examples of the yellow pigments include tetrachloroisoindolinone pigments, hansa pigments, benzidine yellow pigments, and azo pigments. Specific examples thereof include hansa yellow (10G, 5G, 3G, G, GR, A, RN, R), benzidine (G, GR), chrome yellow, permanent yellow (FGL, H10G, HR).

Examples of the cyanine pigment include metal-free phthalocyanine, merocyanine, and the like.

Examples of the magenta pigment include dimethyl quinacridone, thioindigo, and the like.

Examples of the black pigment include aniline black, perylene black, titanium black and carbon black.

A dispersing agent may be used together to disperse the pigment in the photosensitive resin composition for a color filter.

The pigment may be contained in the photosensitive resin composition for a color filter in the form of a dispersion. Examples of the pigment dispersion solvent include ethylene glycol acetate, ethylcellosolve, propylene glycol methyl ether acetate, ethyl lactate, polyethylene glycol, cyclohexanone , Propylene glycol methyl ether, and the like.

Specifically, the pigment may be surface-treated beforehand with a dispersant, or a dispersant may be added together with the pigment when the photosensitive resin composition is prepared.

As the dispersing agent, a nonionic dispersing agent, an anionic dispersing agent, a cationic dispersing agent and the like can be used. Specific examples of the dispersing agent include polyalkylene glycols and esters thereof, polyoxyalkylene, polyhydric alcohol ester alkylene oxide adduct, alcohol alkylene oxide adduct, sulfonic acid ester, sulfonic acid salt, carboxylic acid ester, carboxylic acid Salts, alkylamide alkylene oxide adducts, and alkylamines. These may be used singly or in combination of two or more.

The dispersing agent may be contained in an amount of 0.01 to 15% by weight based on the total amount of the photosensitive resin composition for a color filter. When the dispersing agent is contained within the above range, the dispersibility of the photosensitive resin composition for a color filter is excellent, so that excellent stability, developability and patternability can be obtained.

The average particle diameter of the pigment may be from 5 nm to 150 nm, and more specifically from 10 nm to 70 nm. When the average particle diameter of the pigment is within the above range, the contrast ratio can be realized while having excellent heat resistance and light resistance.

The dyes may be selected from, for example, direct dyes, acid dyes, basic dyes, acid mordant dyes, sulfide dyes, reducing dyes, azoic dyes, disperse dyes, reactive dyes, oxidation dyes, useful dyes, azo dyes, anthraquinone dyes, Dyes, rhodamine dyes, rylene dyes, azo cyanine dyes, or combinations thereof. The term " dyes "

The dye may be, for example, C.I. Acid violet 49, C.I. Basic violet 1, C.I. Basic violet 3, C.I. Basic violet 4, C.I. Basic violet 7, C.I. Basic violet 10, C.I. Basic violet 11, C.I. Basic violet 14, C.I. Basic violet 18, C.I. Basic Yellow 2, C.I. Basic Yellow 9, C.I. Basic Yellow 13, C.I. Basic Yellow 15, C.I. Basic Yellow 21, C.I. Basic Yellow 23, C.I. Basic Yellow 24, C.I. Basic Yellow 25, C.I. Basic Yellow 32, C.I. Basic Yellow 41, C.I. Basic Orange 2, C.I. Basic Orange 14, C.I. Basic Orange 22, C.I. Basic Orange 23, C.I. Basic orange 24, C.I. Basic orange 25, C.I. Basic Orange 30, C.I. Basic Orange 33, C.I. Basic Green 1, C.I. Basic Green 4, C.I. Basic Green 5, C.I. Acid Blue 7, C.I. Basic Blue 1, C.I. Basic Blue 3, C.I. Basic Blue 6, C.I. Basic Blue 9, C.I. Basic Blue 22, C.I. Basic Blue 41, C.I. Basic Blue 45, C.I. Basic Blue 47, C.I. Basic Blue 64, C.I. Basic Blue 66, C.I. Mordant blue 1, C.I. Basic Red 1, C.I. Basic Red 2, C.I. Basic Red 9, C.I. Basic Red 11 (Rhodamine S), C.I. Basic Red 14, C.I. Basic Red 17, C.I. Basic Red 18, C.I. Basic Red 22, C.I. Basic Red 23, C.I. Basic Red 24, C.I. Basic Red 25, C.I. Basic Red 27, C.I. Basic Red 29, C.I. Basic Red 30, C.I. Basic Red 39, C.I. Acid Red 52, C.I. Basic Brown 1, C.I. Basic Black 2 and so on.

The colorant may be included in an amount of about 1 to 40% by weight based on the total amount of the photosensitive resin composition for a color filter, for example, about 3 to 25% by weight. When the colorant is used within the above range, a high contrast ratio can be exhibited at the same color coordinates while having excellent color characteristics.

(E) Solvent

The solvent may be a material that is compatible with the binder resin, the photopolymerizable monomer, the photopolymerization initiator, and the colorant but does not react.

The solvent is not particularly limited, but specific examples thereof include alcohols such as methanol and ethanol; Ethers such as dichloroethyl ether, n-butyl ether, diisobutyl ether, methylphenyl ether and tetrahydrofuran; Glycol ethers such as ethylene glycol methyl ether, ethylene glycol ethyl ether and propylene glycol methyl ether; Cellosolve acetates such as methyl cellosolve acetate, ethyl cellosolve acetate and diethyl cellosolve acetate; Carbitols such as methylethylcarbitol, diethylcarbitol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether and diethylene glycol diethyl ether; Propylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate and propylene glycol propyl ether acetate; Aromatic hydrocarbons such as toluene and xylene; Ketones such as methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, methyl-n-propyl ketone, methyl- ; Saturated aliphatic monocarboxylic acid alkyl esters such as ethyl acetate, n-butyl acetate and isobutyl acetate; Lactic acid alkyl esters such as methyl lactate and ethyl lactate; Hydroxyacetic acid alkyl esters such as methylhydroxyacetate, ethylhydroxyacetate and butylhydroxyacetate; Alkoxyalkyl esters such as methoxy methyl acetate, methoxy ethyl acetate, methoxy butyl acetate, ethoxy methyl acetate, and ethoxy ethyl acetate; 3-hydroxypropionic acid alkyl esters such as methyl 3-hydroxypropionate and ethyl 3-hydroxypropionate; 3-alkoxypropionic acid alkyl esters such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate and methyl 3-ethoxypropionate; 2-hydroxypropionic acid alkyl esters such as methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate and propyl 2-hydroxypropionate; 2-alkoxypropionic acid alkyl esters such as methyl 2-methoxypropionate, ethyl 2-methoxypropionate, ethyl 2-ethoxypropionate and methyl 2-ethoxypropionate; 2-hydroxy-2-methylpropionic acid alkyl esters such as methyl 2-hydroxy-2-methylpropionate and ethyl 2-hydroxy-2-methylpropionate; 2-alkoxy-2-methylpropionic acid alkyl esters such as methyl 2-methoxy-2-methylpropionate and ethyl 2-ethoxy-2-methylpropionate; Esters such as 2-hydroxyethyl propionate, 2-hydroxy-2-methyl ethyl propionate, hydroxy ethyl acetate and methyl 2-hydroxy-3-methyl butanoate; Or ethyl pyruvate. Examples of the ketone acid esters include N-methylformamide, N, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N, N-dimethylacetamide Benzyl alcohol, benzoic acid, benzoic acid, benzoic acid, benzoic acid, benzoic acid, benzoic acid, benzoic acid, benzoic acid, Ethyl benzoate, diethyl oxalate, diethyl maleate,? -Butyrolactone, ethylene carbonate, propylene carbonate, phenyl cellosolve acetate, etc. These may be used alone or in combination of two or more.

In view of the miscibility and reactivity of the solvent, glycol ethers such as ethylene glycol monoethyl ether and the like; Ethylene glycol alkyl ether acetates such as ethyl cellosolve acetate; Esters such as 2-hydroxyethyl propionate; Diethylene glycol such as diethylene glycol monomethyl ether; Propylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate and propylene glycol propyl ether acetate can be used.

The solvent may be contained in an amount of 40 to 70% by weight based on the total amount of the photosensitive resin composition for a color filter. When the solvent is contained within the above range, the photosensitive resin composition for a color filter has an appropriate viscosity, and therefore, the color filter has excellent processability in the production of the color filter.

(F) Other additives

The photosensitive resin composition for a color filter may contain at least one selected from the group consisting of malonic acid, malonic acid, and malonic acid to prevent spots and spots upon application, to improve leveling performance, 3-amino-1,2-propanediol; A coupling agent comprising a vinyl group or (meth) acryloxy group; Leveling agents; Surfactants; And at least one additive selected from a radical polymerization initiator.

The additive can be easily adjusted according to desired properties.

The coupling agent may be a silane coupling agent. Examples of the silane coupling agent include trimethoxysilylbenzoic acid,? -Methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane and β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and these may be used singly or in combination of two or more Can be mixed and used.

The silane coupling agent may be used in an amount of 0.01 to 1 part by weight based on 100 parts by weight of the photosensitive resin composition for a color filter.

The photosensitive resin composition for a color filter may further contain a surfactant if necessary.

Examples of the surfactant include F-482, F-484, and F-478 of DIC Company, but are not limited thereto.

The amount of the surfactant is preferably 0.01 to 5% by weight, more preferably 0.1 to 2% by weight based on the total amount of the photosensitive resin composition. If it is out of the above range, a foreign matter may be generated after development, which is not preferable.

The photosensitive resin composition for a color filter according to one embodiment is an alkali developing type which is cured by irradiation of light and can be developed into an alkaline aqueous solution. When the photosensitive resin composition is laminated on a substrate and irradiated with an active ray to form a pattern necessary for the color filter, the photosensitive resin composition is reacted with light. The reacted site is less soluble in the solvent than the unreacted site, Are selectively soluble. The solution for removing the unexposed portions is called a developer, and there are two types of such developers, organic solvent type and alkali developing type. Among them, organic solvent type causes air pollution and is harmful to human body, so it is better to use alkali developing type in environmental aspect. The photosensitive resin composition for a color filter according to one embodiment can be used in an environmentally friendly manner since an alkali developing type developer can be used.

According to another embodiment of the present invention, there is provided a color filter manufactured using the above-described photosensitive resin composition for a color filter.

A method of manufacturing the color filter is as follows.

The above-mentioned photosensitive resin composition is coated on the glass substrate by a suitable method such as spin coating, roller coating, spray coating or the like to a thickness of 0.5 占 퐉 to 10 占 퐉, for example, to form a resin composition layer.

Then, light is irradiated to form a pattern necessary for the color filter on the substrate on which the resin composition layer is formed. As the light source used for the irradiation, UV, electron beam or X-ray can be used. For example, UV in the range of 190 nm to 450 nm, specifically 200 nm to 400 nm can be irradiated. A photoresist mask may be further used in the above irradiation step. After the step of irradiating in this manner, the resin composition layer irradiated with the light source is treated with a developing solution. At this time, the non-exposed portions in the resin composition layer are dissolved to form a pattern necessary for the color filter. By repeating such a process according to the number of necessary colors, a color filter having a desired pattern can be obtained. In addition, when the image pattern obtained by development in the above step is heated again or cured by actinic ray irradiation or the like, crack resistance, solvent resistance and the like can be improved.

Hereinafter, preferred embodiments of the present invention will be described. However, the following examples are only a preferred embodiment of the present invention, and the present invention is not limited by the following examples.

(Preparation of acrylic binder resin)

Manufacturing example  One

In a flask equipped with a cooling tube and a stirrer, 2 to 20 g of each of the repeating units represented by Chemical Formulas (1) to (8) were charged, and 1.6 g and 0.2 g of V-601 (photopolymerization initiator, WAKO) After dissolving, 75 g of a solvent was dropped in a flask maintained at 85 캜 for 3 hours under a nitrogen atmosphere, followed by polymerization and stirring for 3 hours, followed by cooling to room temperature. 2.4 g of MOI (2-isocyanatoethyl methacrylate) and 0.02 g of DBTDL (Dibutyltin dilaurate) were added to the compound cooled to room temperature, and the mixture was heated to 40 ° C and stirred for 16 hours to obtain a compound containing a structural unit represented by the following formula . The weight average molecular weight of the compound prepared above was 10200 g / mol and the acid value was 72 mgKOH / g.

[Chemical Formula 9]

(Wherein a = 5, b = 6, c = 19, d = 17, e = 13, f = 6, g = 19, h = 15).

(Preparation of Photosensitive Resin Composition for Color Filter)

Example  One, Example  2, Comparative Example  1, and Comparative Example  2

The following photopolymerization initiator was dissolved in the following solvent with the composition shown in Table 1, followed by stirring at room temperature for 2 hours. To the composition shown in Table 1, the following acrylic binder resin, cadmium binder resin, and the following photopolymerizable monomer were added and stirred at room temperature for 2 hours. In the composition shown in Table 1, the following pigments were added, and the mixture was stirred at room temperature for 1 hour. Then, the following surfactant and coupling agent were added and stirred at room temperature for 1 hour. The solution was filtered three times to remove impurities to prepare photosensitive resin compositions according to Example 1, Example 2, Comparative Example 1, and Comparative Example 2. The components used in the production of the photosensitive resin composition are as follows.

(A) Binder resin

(A-1) The acrylic binder resin prepared in Production Example 1 was used.

    (A-2) Acrylic binder resin (CRB-200H, SMS)

(A-3) Cadmium binder resin (V259ME, Shinil Chemical Co., Ltd.)

(B) a photopolymerizable monomer

    (B-1) a photopolymerizable monomer (dipentaerythritol hexaacrylate (DPHA))

(B-2) A photopolymerizable monomer (A-BPE-20, manufactured by SHIN-NAKAMURA CHEMICAL)

(C) a photopolymerization initiator

    (C-1) oxime compound (TPM-P07, manufactured by TAKOMA)

(C-2) oxime compound (CGI-124, manufactured by Ciba)

(D) Pigment

(D-1) pigment (SGTC49, SKC-HAAS)

(D-2) Pigment (SGTC52, SKC-HAAS)

    (D-3) Pigment (GJ1814, Sanyo)

(D-4) Pigment (LCY8252, ENF)

(E) Solvent

(E-1) propylene glycol monomethyl ether acetate (PGMEA) was used.

(E-2) propylene glycol methyl ether (PGME) was used.

(F) Additive

(F-1) surfactant (F-559, DIC)

(F-2) coupling agent (S-510, CHISSO)

(Unit: wt%) Example 1 Example 2 Comparative Example 1 Comparative Example 2 (A) Binder resin A-1 4.98 7.98 A-2 7.40 4.84 A-3 2.85 1.14 0.64 2.73 (B) a photopolymerizable monomer B-1 7.45 7.45 6.70 6.60 B-2
(Developability type) 0.50 0.50 (C) a photopolymerization initiator C-1 0.09 0.09 1.18 0.91 C-2 0.34 0.34 (D) Pigment D-1 19.98 19.98 18.04 22.44 D-2 14.41 14.41 D-3 11.48 D-4 12.17 (E) Solvent E-1 37.32 36.02 41.49 37.24 E-2 12.22 12.23 12.22 12.22 (F) Additive F-1 0.20 0.20 0.20 0.20 F-2 0.16 0.16 0.15 0.15 Total 100.00 100.00 100.00 100.00

Evaluation 1: Photosensitive resin composition for color filter Color characteristics  And heat resistance

The photosensitive resin composition of Example 1, Example 2, Comparative Example 1 and Comparative Example 2 was coated on a glass substrate using a coating machine (MIKASA), and then dried on a hot plate at 90 캜 to obtain a coating film Respectively. The obtained coating film was irradiated with light at an exposure dose of 50 mj / cm < ^{2 &} gt ;, followed by baking at 230 DEG C for 30 minutes in an oven condition. The color coordinates and the luminance were measured using a colorimeter (Otsuka, MCPD 3000) before and after the post bake (PSB), and the change values before and after the measurement were used to confirm the heat resistance characteristics. The results are shown in Tables 2 and 3 Respectively. The color coordinates (Gx) and luminance (Y) were calculated based on the color coordinate (Gy).

step Color coordinates (Gx) Color coordinates (Gy) Luminance (Y) Example 1 PSB I 0.2810 0.5675 64.12 After PSB 0.2801 0.5675 63.74 Example 2 PSB I 0.2809 0.5675 64.14 After PSB 0.2801 0.5675 63.75 Comparative Example 1 PSB I 0.2777 0.5675 63.05 After PSB 0.2775 0.5675 62.53 Comparative Example 2 PSB I 0.2808 0.5675 63.86 After PSB 0.2786 0.5675 63.15

Gx Y Example 1 -0.0008 -0.37 Example 2 -0.0008 -0.40 Comparative Example 1 -0.0002 -0.53 Comparative Example 2 -0.0021 -0.71

Table 2 and Table 3 show that the brightness of the photosensitive resin composition for a color filter is higher than that of Comparative Example 1 and Comparative Example 2 in Examples 1 and 2 using the acrylic binder resin according to one embodiment, It is understood that the difference in the value is small and excellent heat resistance is obtained.

Evaluation 2: Pattern fairness of color filter and Developability

Each of the photosensitive resin compositions according to Example 1, Example 2, Comparative Example 1 and Comparative Example 2 was coated on a glass substrate using a MIKASA instrument and dried on a hot plate at 90 캜 to obtain a coated film . The obtained coating film was irradiated with light at an exposure dose of 50 mJ / cm ² to prepare evaluation specimens. Thereafter, a KOH solution (Myung Ming Co.) was diluted with a developer, and development was carried out in the diluted solution, and the break point (BP) at which the pattern appeared was measured (at this time, the BP should be at least 40 seconds ). The developed pattern substrate was baked at 230 캜 for 30 minutes in an oven condition to form a pattern of CD 70 탆 and hole 40 탆. The results are shown in Table 4 below.

50 mJ / cm ² BP
(second) PSB I After PSB CD Hole CD Hole Example 1 74.52 35.01 75.02 34.44 28 Example 2 74.79 35.23 75.16 34.57 26 Comparative Example 1 74.56 35.18 75.56 34.54 40 Comparative Example 2 74.82 35.45 75.56 34.58 35

Referring to Table 4, in the case of Examples 1 and 2 in which no additional photopolymerizable monomer for improving developability was used, the color filter of Comparative Example 1 and Comparative Example 2 using the additional photopolymerizable monomer It can be seen that the pattern fairness is maintained equally. In addition, it can be seen that Examples 1 and 2 have a shorter BP than Comparative Examples 1 and 2 and are more excellent in developing property.

It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the present invention as defined by the following claims. As will be understood by those skilled in the art. It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive.

a: Pattern of CD (diameter)
b: hole size of the pattern

Claims (11)

(A) at least one repeating unit represented by the following formula (1), at least one repeating unit represented by the following formula (2), at least one repeating unit represented by the following formula (3), at least one repeating unit represented by the following formula , At least one repeating unit represented by the following formula (5), at least one repeating unit represented by the following formula (6), at least one repeating unit represented by the following formula (7), and at least one repeating unit represented by the following formula A binder resin containing an acrylic binder resin;
(B) a photopolymerizable monomer;
(C) a photopolymerization initiator;
(D) a colorant; And
(E) Solvent
A photosensitive resin composition for a color filter comprising:
[Chemical Formula 1]

(2)

(3)

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

(7)

[Chemical Formula 8]

In the above Chemical Formulas 1 to 8,
R ¹ to R ⁷ , R ', and R "are each independently hydrogen or a substituted or unsubstituted C1 to C10 alkyl group,
L ¹ to L ⁶ are each independently a single bond or a substituted or unsubstituted C1 to C10 alkylene group,
S ¹ is a substituted or unsubstituted C7 to C30 cycloalkyl group or a substituted or unsubstituted C7 to C30 multibranched alkyl group,
S ² to S ⁴ are each independently hydrogen, halogen, a substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C1 to C10 alkoxy group,
S ⁵ is a substituted or unsubstituted C3 to C30 cycloalkyl group.
The method according to claim 1,
In the acrylic binder resin, the repeating unit represented by Formula 1 is 4 mol% to 10 mol%, the repeating unit represented by Formula 2 is 4 mol% to 10 mol%, and the repeating unit represented by Formula 3 is 4 The repeating unit represented by the formula (4) is 10 mol% to 20 mol%, the repeating unit represented by the formula (5) is 10 mol% to 20 mol%, the repeating unit represented by the formula 5 to 15 mol% of the repeating unit represented by the formula (1), 15 to 35 mol% of the repeating unit represented by the formula (7), and 10 to 20 mol% Composition.
The method according to claim 1,
Wherein R ¹ to R ³ , R ⁵ , R ⁶ , R ', R "and S ⁴ are each independently a substituted or unsubstituted C 1 to C 6 alkyl group,
Wherein R ⁴ , R ⁷ , S ² , and S ³ are each independently hydrogen,
Wherein L ¹ to L ⁶ are independently a substituted or unsubstituted C1 to C6 alkylene group,
Wherein S < ¹ > is a substituted or unsubstituted C7 to C20 polyalkyl group,
And S ⁵ is a substituted or unsubstituted C3 to C10 cycloalkyl group.
The method according to claim 1,
The acrylic binder resin includes a structural unit represented by the following formula (9): < EMI ID =
[Chemical Formula 9]

In the above formula (9)
a, b, c, d, e, f, g, and h are each independently an integer of 1 or more.
The method according to claim 1,
Wherein the acrylic binder resin has a weight average molecular weight of 6,000 to 15,000 g / mol.
The method according to claim 1,
And the acid value of the acrylic binder resin is 50 to 100 mgKOH / g.
The method according to claim 1,
Wherein the binder resin further comprises a carcass binder resin.
The method according to claim 1,
Wherein the colorant comprises a dye, a pigment, or a combination thereof.
The method according to claim 1,
The photosensitive resin composition for a color filter
(A) 1 to 40% by weight of the binder resin;
(B) 1 to 30% by weight of the photopolymerizable monomer;
(C) 0.1 to 10% by weight of the photopolymerization initiator;
(D) 1 to 40% by weight of the colorant; And
(E) the solvent remaining amount
Wherein the photosensitive resin composition is a photosensitive resin composition for a color filter.
The method according to claim 1,
The photosensitive resin composition for a color filter comprises malonic acid; 3-amino-1,2-propanediol; A coupling agent comprising a vinyl group or (meth) acryloxy group; Leveling agents; Fluorine surfactants; And at least one additive selected from a radical polymerization initiator.
A color filter produced by using the photosensitive resin composition for a color filter according to any one of claims 1 to 10.

Images