KR20180117939A - Photosensitive resin composition, photosensitive resin layer using the same and color filter - Google Patents

Abstract

The present invention provides a photosensitive resin composition having excellent reliability on chemical resistance and liquid crystal elution, a photosensitive resin layer manufactured by using the same and a color filter including the photosensitive resin layer. The photosensitive resin composition comprises: (A) a black colorant including a red pigment, a blue pigment and a violet pigment; (B) a binder resin; (C) a photopolymerizable monomer; (D) a photopolymerizable initiator; and (E) a solvent. The blue pigment includes a phthalocyanine-based compound having a β type crystal and a phthalocyanine-based compound having a ε type crystal.

Description

TECHNICAL FIELD [0001] The present invention relates to a photosensitive resin composition, a photosensitive resin film and a color filter using the same. BACKGROUND ART < RTI ID = 0.0 >

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

The photosensitive resin composition is an indispensable material for the production of display devices such as color filters, liquid crystal display materials, organic light emitting devices, and display panel materials. For example, a color filter such as a color liquid crystal display requires a black matrix at a boundary portion between coloring layers such as red, green, and blue in order to enhance display contrast and coloring effect, The black matrix is mainly formed of a photosensitive resin composition.

Recently, efforts have been made to use the black matrix material as a column spacer supporting between two TFTs and a C / F substrate existing between the liquid crystal layers, and the column spacer is referred to as a black column spacer.

In the case of the black column spacer, the step of the pattern must be formed due to the difference in the transmittance of the photomask, and at the same time, not only the compressive displacement, the elastic recovery rate and the breaking strength which are functions of the column spacer but also the light- Should be high enough. In addition, since the column spacer and the black matrix layer are formed at the same time, the step height of the column spacer with a high height and the relatively low black matrix must be realized by using a half tone mask. Since the black column spacer is a layer that directly contacts the liquid crystal, unlike a general black matrix, a reliability characteristic capable of minimizing liquid crystal contamination is required, and the chemical resistance of the solution for the solvent and rework of the upper layer polyimide Is also essential.

However, the conventional photosensitive resin composition for a black column spacer still has a problem that the development period is appropriate and the content of the polyimide solvent is poor.

Therefore, studies for developing a photosensitive resin composition for a black column spacer taking such characteristics into consideration have continued.

An embodiment of the present invention is to provide a photosensitive resin composition excellent in chemical resistance and reliability regarding liquid crystal elution.

Another embodiment of the present invention is to provide a photosensitive resin film produced using the photosensitive resin composition.

Another embodiment of the present invention is to provide a color filter comprising the photosensitive resin film.

One embodiment of the present invention is a composition comprising (A) a black colorant comprising a red pigment, a blue pigment and a violet pigment; (B) a binder resin; (C) a photopolymerizable monomer; (D) a photopolymerization initiator; And (E) a solvent, wherein the blue pigment comprises a phthalocyanine-based compound having a beta (beta) -type crystal and a phthalocyanine-based compound having an epsilon-type crystal.

The phthalocyanine compound having the? -Form crystal may be contained in an amount of not less than the content of the phthalocyanine compound having the? -Type crystal.

The phthalocyanine compound having the? -Form crystal may be contained in an amount larger than that of the phthalocyanine compound having the? -Form crystal.

The phthalocyanine-based compound having the? -Form crystal is preferably a C.I. Pigment B15: 3, C.I. Pigment B15: 4, or a combination thereof.

The phthalocyanine compound having the? -Type crystal is preferably a C.I. Pigment B15: 6.

The red pigment may be at least one selected from the group consisting of pyrrolopyrrole-dione pigments, perylene pigments, anthraquinone pigments, dianthraquinone pigments, azo pigments, diazo pigments, quinacridone pigments, Pigments, anthracene-based pigments, or combinations thereof.

The red pigment may be represented by the following formula (1).

[Chemical Formula 1]

In Formula 1,

R ¹ to R ⁴ are each independently a hydrogen atom, a halogen atom or a substituted or unsubstituted C1 to C10 alkyl group,

n1 and n2 are each independently an integer of 1 to 5;

The violet pigment may be represented by the following formula (2).

(2)

The black colorant may further comprise an orange pigment, a yellow pigment or a combination thereof.

The binder resin may include a cadmium binder resin.

Wherein the photosensitive resin composition comprises 1 to 15% by weight of the black colorant (A) relative to the total amount of the photosensitive resin composition; 1 to 10% by weight of the binder resin (B); 0.1 to 10% by weight of the (C) photopolymerizable monomer; 0.1 to 5% by weight of the photopolymerization initiator (D); And (E) the solvent balance.

The photosensitive resin composition may further include additives such as malonic acid, 3-amino-1,2-propanediol, a silane coupling agent, a leveling agent, a fluorine surfactant, a radical polymerization initiator, or a combination thereof.

Another embodiment of the present invention provides a photosensitive resin film produced using the photosensitive resin composition.

The photosensitive resin film may be a black column spacer.

Another embodiment of the present invention provides a color filter comprising the photosensitive resin film.

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

By using the photosensitive resin composition according to one embodiment, a black column spacer having excellent chemical resistance and reliability in liquid crystal and a color filter including the same can be realized.

Fig. 1 is a graph of absorbance according to Examples 1 to 3 and Comparative Example 1. Fig.

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 in the compound is replaced by a halogen atom (F, Cl, Br, I), a hydroxy 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 acid anhydride, an amide group, an azo group, an azido group, an amidino group, a hydrazino group, a hydrazino group, a carbonyl group, , A C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C2 to C20 alkynyl group, a C6 to C30 aryl group, a C3 to C20 cycloalkyl group, a C3 to C20 cycloalkenyl group, a C3 to C20 cycloalkynyl group, An alkyl group, a C2 to C20 heterocycloalkenyl group, a C2 to C20 heterocycloalkynyl group, or a combination thereof.

Unless otherwise stated, the terms "heterocycloalkyl", "heterocycloalkenyl", "heterocycloalkynyl" and "heterocycloalkylene" refer to cycloalkyl, cycloalkenyl, cycloalkynyl, and cycloalkyl Means that at least one heteroatom of N, O, S or P is present in the ring compound of the ring.

As used herein, unless otherwise specified, "(meth) acrylate" means that both "acrylate" and "methacrylate" are possible.

The black column spacer has a function of a light-shielding portion having a sufficiently high optical density (OD) and a column spacer for maintaining a cell gap. Various black coloring agents are applied to the formation of the black column spacer, and black color is mixed by mixing a coloring agent showing various colors such as a red pigment, an orange pigment, a yellow pigment, a blue pigment, and a violet pigment to increase a step margin, .

However, in order to obtain a sufficient optical density (OD) in the case of a black column spacer, a phthalocyanine blue pigment must be used. Of these, blue pigments having an ε (Epsilon) type crystal most commonly used are liquid crystals Which is a major cause of problems in liquid crystal driving. However, according to one embodiment, it is possible to use a blue pigment having a crystal form β (beta) having a stable crystal form rather than an ε (Epsilon) type crystal, to provide a black column spacer having excellent solvent resistance to NMP and high reliability in liquid crystal .

Each component will be described in detail below.

(A) a black colorant

The photosensitive resin composition according to one embodiment includes a black colorant including a red pigment, a blue pigment, and a violet pigment.

The blue pigment includes a phthalocyanine-based compound such as a copper-phthalocyanine-based compound in order to ensure a sufficient optical density, and the copper-phthalocyanine-based compound is a copper-phthalocyanine-based compound having a? -Form crystal and a copper- Based compound.

In general, when pigments showing various colors are mixed to realize black, a copper-phthalocyanine compound having an epsilon type crystal is used as a blue pigment, but a metal ion (Cu ) Is a main cause of liquid crystal contamination, and there is a problem that liquid crystal driving failure occurs. The photosensitive resin composition according to one embodiment can improve the chemical resistance and reliability in the liquid crystal by using a copper-phthalocyanine compound having a? -Form crystal together with a copper-phthalocyanine compound having an? -Form crystal as the blue pigment, solving the problem of lowering the reliability due to liquid crystal contamination caused by using only the copper-phthalocyanine compound having the epsilon type crystal. The copper-phthalocyanine compound having a? -form crystal has a structure more stable than that of a copper-phthalocyanine compound having an? -type crystal, so that the phase transition to the organic solvent is not so good and the copper-phthalocyanine compound having an? when used in combination with a copper-phthalocyanine compound having a? -form crystal, high reliability in a liquid crystal can be achieved through controlling the content of the liquid crystal. That is, conventionally, even though a phthalocyanine compound is used as a blue pigment in a mixed black colorant, a phthalocyanine compound having an epsilon type crystal or a phthalocyanine compound having a beta crystal was used alone, In the embodiment, these problems are solved by mixing them.

Specifically, the phthalocyanine compound having the? -Form crystal may be contained in an amount of not less than the content of the phthalocyanine compound having the? -Type crystal. More specifically, the phthalocyanine-based compound having the? -Form crystal can be contained in a larger amount than the phthalocyanine-based compound having the? -Type crystal. In this case, the chemical resistance and the reliability in the liquid crystal can be further improved.

For example, the phthalocyanine-based compound having the? -Form crystal is preferably a C.I. Pigment B15: 3, C.I. Pigment B15: 4, or a combination thereof.

For example, the phthalocyanine-based compound having the? -Type crystal is preferably a C.I. Pigment B15: 6.

The red pigment may be at least one selected from the group consisting of pyrrolopyrrole-dione pigments, perylene pigments, anthraquinone pigments, dianthraquinone pigments, azo pigments, diazo pigments, quinacridone pigments, Pigments, anthracene-based pigments, or combinations thereof.

For example, the red pigment may be represented by the following formula (1).

[Chemical Formula 1]

In Formula 1,

R ¹ to R ⁴ are each independently a hydrogen atom, a halogen atom or a substituted or unsubstituted C1 to C10 alkyl group,

n1 and n2 are each independently an integer of 1 to 5;

For example, the violet pigment may be represented by the following formula (2).

(2)

When the black colorant contains the violet pigment, both the transmittance in the short wavelength region and the transmittance in the visible light region are lower than that in the case where the violet pigment is not included. In this case, It is possible to maximize the optical density, which is the intrinsic characteristic of the black column spacer, by reducing the transmittance in the visible light region while minimizing the transmittance loss in the short wavelength region.

The violet pigment may be contained in a smaller amount than the red pigment. In this case, compared with the case where the violet pigment is contained in a larger amount than the red pigment, the optical density can be increased while securing the transmittance in the short wavelength region.

The black colorant may further comprise an orange pigment, a yellow pigment or a combination thereof.

The pigments constituting the black colorant may be contained in the photosensitive resin composition in the form of a pigment dispersion. Such a pigment dispersion may be composed of a solid pigment and a solvent, a dispersing agent, a dispersing resin and the like.

The solid pigment may be present in the pigment dispersion in an amount ranging from 1% to 20%, such as 8% to 20%, such as 8% to 15%, such as 10% to 20% 15% by weight.

As the solvent, ethylene glycol acetate, ethyl cellosolve, propylene glycol methyl ether acetate, ethyl lactate, polyethylene glycol, cyclohexanone, propylene glycol methyl ether and the like can be used. Among them, propylene glycol methyl ether acetate is preferably used .

The dispersant helps to uniformly disperse the pigment in the dispersion, and any nonionic, anionic or cationic dispersant may be used. Specific examples thereof include polyalkylene glycols or esters thereof, polyoxyalkylene, polyhydric alcohol ester alkylene oxide adducts, alcohol alkylene oxide adducts, sulfonic acid esters, sulfonic acid salts, carboxylic acid esters, carboxylic acid salts, alkylamide alkylene oxide adducts Water, alkylamine, and the like. These may be used alone or in combination of two or more.

DISPERBYK-161, DISPERBYK-160, DISPERBYK-160, DISPERBYK-161, DISPERBYK-162, DISPERBYK-163, DISPERBYK-164, DISPERBYK-160, DISPERBYK-130, DISPERBYK- -166, DISPERBYK-170, DISPERBYK-171, DISPERBYK-182, DISPERBYK-2000, DISPERBYK-2001 and the like; EFKA-47, EFKA-47EA, EFKA-48, EFKA-49, EFKA-100, EFKA-400 and EFKA-450 of EFKA Chemical Co., Solsperse 5000, Solsperse 12000, Solsperse 13240, Solsperse 13940, Solsperse 17000, Solsperse 20000, Solsperse 24000GR, Solsperse 27000, Solsperse 28000 from Zeneka; Or Ajinomoto's PB711 and PB821.

The dispersant may be contained in an amount of 0.1 to 15% by weight based on the total amount of the photosensitive resin composition. When the dispersing agent is contained within the above range, the dispersibility of the composition is excellent, so that the stability, developability and patternability of the black column spacer are excellent.

The dispersion resin may use an acrylic resin containing a carboxyl group, which not only improves the stability of the pigment dispersion but also improves the patterning of pixels.

The pigment may be used by pretreatment using a water-soluble inorganic salt and a wetting agent. When the pigment is used by the pretreatment, the average particle diameter of the pigment can be made smaller.

The pretreatment may be performed by kneading the pigment with a water-soluble inorganic salt and a wetting agent, and filtering and washing the pigment obtained in the kneading step.

The kneading may be carried out at a temperature of 40 to 100 DEG C, and the filtration and washing may be performed by washing the inorganic salt with water, etc., followed by filtration.

Examples of the water-soluble inorganic salt include, but are not limited to, sodium chloride and potassium chloride. The wetting agent acts as a medium through which the pigment and the water-soluble inorganic salt are uniformly mixed to easily pulverize the pigment. Examples of the wetting agent include ethylene glycol monoethyl ether, propylene glycol monomethyl ether, diethylene glycol monomethyl ether and the like Alkylene glycol monoalkyl ethers; And alcohols such as ethanol, isopropanol, butanol, hexanol, cyclohexanol, ethylene glycol, diethylene glycol, polyethylene glycol, glycerin polyethylene glycol and the like. These may be used singly or in combination of two or more thereof.

The pigment after the kneading step may have an average particle diameter of 5 nm to 200 nm, for example, 5 nm to 150 nm. When the average particle diameter of the pigment is within the above range, the stability in the pigment dispersion is excellent and there is no fear of deterioration of the resolution of the pixels.

The black colorant may be contained in an amount of 1 to 15% by weight, for example, 5 to 10% by weight based on the pigment dispersion based on the total amount of the photosensitive resin composition. For example, the black colorant may be contained in an amount of 0.1 wt% to 5 wt%, for example, 0.15 wt% to 2.25 wt% based on the total amount of the photosensitive resin composition. When the black colorant is used within the above range, excellent blackness and reliability can be realized.

(B) binder resin

The photosensitive resin composition according to one embodiment includes a binder resin. The binder resin may include a cadmium binder resin. When a cationic binder resin is used, the heat resistance and chemical resistance of the photosensitive resin composition can be improved.

The weight average molecular weight of the cationic binder resin may be from 1,000 g / mol to 50,000 g / mol, and specifically from 3,000 g / mol to 35,000 g / mol. When the weight average molecular weight of the cationic binder resin is within the above range, excellent patterning and developability can be obtained in the production of a black column spacer.

The cadmium-based binder resin may be a compound containing a repeating unit represented by the following formula (3).

(3)

(3)

R ₂₄ to R ₂₇ are the same or different and each is 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 is 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 is a single bond, O, CO, SO ₂ , CR _b R _c , SiR _d R _e (wherein R _b to R _e are the same or different and are a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group Or a compound represented by any one of the following formulas (4) to (14)

Z ₂ is an acid anhydride residue or an acid anhydride residue.)

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

(7)

[Chemical Formula 8]

(In the formula (8)

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 9]

[Chemical formula 10]

(11)

[Chemical Formula 12]

[Chemical Formula 13]

[Chemical Formula 14]

The cationic binder resin can be specifically obtained by reacting a compound represented by the following formula (15) with a tetracarboxylic acid dianhydride.

[Chemical Formula 15]

The tetracarboxylic dianhydride may be an aromatic tetracarboxylic dianhydride. Examples of the aromatic tetracarboxylic dianhydride include pyromellitic 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'-biphenylether tetracarboxylic acid dianhydride, 3,3 ', 4,4'-diphenylsulfone tetracarboxylic 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 tetra Carboxylic acid dianhydride, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, and the like, but are not limited thereto.

The binder resin may be added to the total amount of the photosensitive resin composition 　 1 wt% to 10 wt%, such as 3 wt% to 8 wt%. When the binder resin is contained within the above range, the viscosity is appropriately maintained and the patterning property, the processability and the developing property are excellent in the production of the black column spacer.

(C) Photopolymerization  Monomer

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

By having the ethylenically unsaturated double bond, the photopolymerizable monomer can form a pattern having excellent heat resistance, light resistance and chemical resistance by causing sufficient polymerization during exposure in the pattern formation step.

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 di (Meth) acrylate, 1,6-hexanediol di (meth) acrylate, bisphenol A di (meth) acrylate, pentaerythritol di (meth) acrylate, (Meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol hexa (Meth) acrylate, dipentaerythritol hexa (meth) acrylate, bisphenol A epoxy (meth) acrylate, ethylene glycol monomethacrylate (Meth) acrylate, trimethylolpropane tri (meth) acrylate, tris (meth) acryloyloxyethyl phosphate, novolac epoxy (meth) acrylate and the like.

Examples of commercially available products of photopolymerizable monomers are 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 contained in an amount of 0.1 wt% to 10 wt%, for example, 1 wt% to 5 wt% with respect to the total amount of the photosensitive resin composition. When the photopolymerizable monomer is contained within the above range, the photopolymerizable monomer sufficiently cures upon exposure in the pattern forming step, and therefore, the photopolymerizable monomer is excellent in reliability and developability in an alkaline developer.

(D) Light curing Initiator

The photopolymerization initiator is a photopolymerization initiator generally used in a photosensitive resin composition. Examples of the photopolymerization initiator include an acetophenone compound, a benzophenone compound, a thioxanthone compound, a benzoin compound, a triazine compound, a oxime compound, Can be used.

Examples of the acetophenone compound include 2,2'-diethoxyacetophenone, 2,2'-dibutoxyacetophenone, 2-hydroxy-2-methylpropiophenone, pt-butyltrichloroacetophenone, Dichloroacetophenone, 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropane-1-one , And 2-dimethylamino-2- (4-methyl-benzyl) -1- (4-morpholin-4-yl-phenyl) -butan-1-one.

Examples of the benzophenone compound include benzophenone, benzoyl benzoic acid, 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-methylthioxanthone, isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 2- Orcanthon and the like can be used.

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 type compound include 2,4,6-trichloro-s-triazine, 2-phenyl 4,6-bis (trichloromethyl) -s- triazine, 2- (3 ', 4'-dimethoxy (Trichloromethyl) -s-triazine, 2- (4'-methoxynaphthyl) -4,6-bis (trichloromethyl) (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) Bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphtho-1-yl) -4,6- Bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphtho 1-yl) -4,6-bis 6-triazine, 2-4-trichloromethyl (4'-methoxystyryl) -6-triazine, and the like can be used.

Examples of the oxime compounds include O-acyloxime compounds such as 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione, 1- 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone, O-ethoxycarbonyl- Can be used. Specific examples of the O-acyloxime-based compound include 1,2-octanedione, 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholin- 2-oxime-O-benzoate, 1- (4-phenylsulfanylphenyl) -octane-1,2-dione -1-one oxime-O-acetate, 1- (4-phenylsulfanylphenyl) -butan-1-one oxime- O-acetate and the like can be used.

In addition to the above-described photopolymerization initiators, carbazole-based compounds, diketone compounds, sulfonium borate compounds, diazo compounds, imidazole-based compounds, fluorene-based compounds and the like can also be used as a photopolymerization initiator.

The photopolymerization initiator may be contained in an amount of 0.1 wt% to 5 wt%, for example, 0.1 wt% to 3 wt% with respect to the total amount of the photosensitive resin composition. When the photopolymerization initiator is contained within the above range, photopolymerization occurs sufficiently during exposure in the pattern formation process for the production of the black column spacer, so that the sensitivity is excellent and the transmittance is improved.

(E) Solvent

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 , N-methylpyrrolidone, dimethylsulfoxide, benzyl ethyl ether, dihexyl ether, acetylacetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, Ethyl, 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 50 to 90% by weight based on the total amount of the photosensitive resin composition. When the solvent is contained within the above range, the photosensitive resin composition is excellent in coating property and excellent flatness can be maintained in a film having a thickness of 3 m or more.

(F) Other additives

The above-mentioned photosensitive resin composition may contain at least one selected from the group consisting of malonic acid, malonic acid, and malonic acid, in order to prevent stains and spots upon application, to prevent leveling, 3-amino-1,2-propanediol; A silane-based coupling agent comprising a vinyl group or (meth) acryloxy group; Leveling agents; Fluorine surfactants; And other additives such as a radical polymerization initiator.

Examples of the silane coupling agent include trimethoxysilylbenzoic acid,? -Methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane,? -Isocyanatopropyltriethoxysilane,? -Glycidoxypropyltrimethoxysilane, and? - (3,4-epoxycyclohexyl) ethyltrimethoxysilane. These may be used singly or in combination of two or more.

Examples of the fluorine-based surfactant, BM Chemie BM-1000 ^® of社(four), BM-1100 ^®, and the like; Mecha Pack F 142D ^® , Copper F 172 ^® , Copper F 173 ^® , Copper F 183 ^® and the like manufactured by Dainippon Ink & Chemicals Incorporated; M. Sumitomo Co. Pro rod FC-135 ^® of社(g), the same FC-170C ^®, copper FC-430 ^®, the same FC-431 ^®, and the like; Asahi Grass (Note)社(G) Saffron S-112 ^®, the same S-113 ^®, the same S-131 ^®, the same S-141 ^®, the same S-145 ^® and the like; Toray silicone (Note) ^® SH-28PA of社(g), copper ^® -190, may be a commercially available product such as copper ^{-193 ®, SZ-6032 ®,} SF-8428 ®.

The other additives may be included in an amount of 0.01 to 10 parts by weight, for example, 0.01 to 5 parts by weight based on 100 parts by weight of the photosensitive resin composition. When the above-mentioned other additives are included within the above range, the adhesiveness and shelf life are excellent.

The photosensitive resin composition may contain a certain amount of other additives such as an antioxidant and a stabilizer within a range that does not impair the physical properties.

Another embodiment provides a photosensitive resin film produced using the above-described photosensitive resin composition. The method of producing the photosensitive resin film is as follows.

(1) Coating and Film Formation Step

The above-mentioned photosensitive resin composition is applied onto a predetermined pretreated substrate by a method such as spin or slit coat method, roll coating method, screen printing method, applicator method or the like to a desired thickness, for example, a thickness of 0.9 탆 to 4.0 탆 After coating, the solvent is removed by heating at a temperature of 70 ° C to 100 ° C for 1 minute to 10 minutes to form a coating film.

(2) Exposure step

In order to form a pattern necessary for the obtained coating film, a mask of a predetermined type (a mask composed of a mixture of a halftone portion for implementing a black matrix pattern and a full-tone portion for implementing a column spacer pattern) is irradiated and then an active line of 200 to 500 nm is irradiated.

As the light source used for the irradiation, a low pressure mercury lamp, a high pressure mercury lamp, an ultra high pressure mercury lamp, a metal halide lamp, an argon gas laser, and the like can be used.

The exposure dose varies depending on the kind of each component of the photosensitive resin composition, the blending amount, and the dried film thickness. For example, when a high pressure mercury lamp is used, the exposure dose is 500 mJ / cm ² (By a 365 nm sensor).

(3) Development step

Following the above exposure step, an unnecessary portion is dissolved and removed by using an alkaline aqueous solution as a developing solution, so that only the exposed portion is left to form an image pattern.

(4) Post-treatment step

The image pattern obtained by the above-described development can be cured by heating again or by active ray irradiation or the like in order to obtain a pattern excellent in terms of heat resistance, light resistance, adhesion, crack resistance, chemical resistance, high strength and storage stability.

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 photosensitive resin composition)

Example  1 to Example  3, Comparative Example  1 and Comparative Example  2

The photosensitive resin compositions according to Examples 1 to 3, Comparative Examples 1 and 2 were prepared using the following components as shown in Table 1 below.

Specifically, the content of the photopolymerization initiator was precisely measured, the solvent was then added, and the mixture was sufficiently stirred (more than 30 minutes) until the photopolymerization initiator was sufficiently dissolved. The binder resin and the photopolymerizable monomer were sequentially added thereto, followed by stirring for about 1 hour. Subsequently, a black colorant (pigment dispersion) was added, and other additives were added thereto, and finally the entire composition was stirred for 2 hours or more to prepare a photosensitive resin composition.

The specifications of each component used in the production of the photosensitive resin composition are as follows.

(A) a black colorant

(A-1) C.I. Blue pigment 15: 6 with millbase dispersion (15% solids) (SANYO)

(A-2) C.I. Blue pigment 15: 3 with millbase dispersion (15% solids) (SANYO)

(A-3) C.I. Violet pigment 29 millbase dispersion (solid content 15%) (SAKATA Inc.)

(A-4) C.I. Millbase dispersion with red pigment 254 (15% solids) (ENF company)

(A-5) Millbase dispersion with organic black pigment (solids content 15%) (BASF)

(B) binder resin

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

(C) Photopolymerization  Monomer

Dipentaerythritol hexa (meth) acrylate (DPHA, Japan Catalysts Co., Ltd.)

(D) Light curing Initiator

OXE01 (BASF)

(E) Solvent

(E-1) Propylene glycol monomethyl ether acetate (PGMEA, Sigma-aldrich)

(E-2) Ethylene glycol dimethyl ether (EDM, Sigma-aldrich)

(F) Other additives

Leveling agent (F-554, DIC)

(Unit: wt%) Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 (A) a black colorant (A-1) 0.753 1.506 2.259 3.012 - (A-2) 2.259 1.506 0.753 - - (A-3) 1.288 1.288 1.288 1.288 - (A-4) 3.365 3.365 3.365 3.365 - (A-5) - - - - 7.665 (B) binder resin 5.592 5.592 5.592 5.592 5.592 (C) a photopolymerizable monomer 2.978 2.978 2.978 2.978 2.978 (D) a photopolymerization initiator 0.180 0.180 0.180 0.180 0.180 (E) Solvent (E-1) 66.835 66.835 66.835 66.835 66.835 (E-2) 16.400 16.400 16.400 16.400 16.400 (F) Other additives 0.350 0.350 0.350 0.350 0.350

Evaluation 1: Elution property  Measure

(HPLC measurement)

The photosensitive resin compositions prepared in Examples 1 to 3 and Comparative Examples 1 and 2 were coated on a predetermined pretreated substrate to a thickness of 2.0 탆 and heated at 90 캜 for 4 minutes to remove the solvent Thereby forming a coating film. Subsequently, the photomask was placed on the coated film and the entire surface was exposed at 40 mJ. Then, the coated film was baked at 220 ° C for 25 minutes using convection oven. Then, the coating film sample was cut into a size of 1.5 cm * 3.0 cm and then immersed in a vial containing 10 g of NMP. The vial was maintained (left to stand) at 100 DEG C for 60 minutes, and only NMP was collected. The collected NMP (effluent) was filtered using a 0.2 탆 syringe filter, and the resultant was placed in an HPLC vial and subjected to HPLC. The results are shown in Table 2 below. The measurement conditions are as follows.

- Column: Shiseido, Capcell pak, MGII, 4.6 mm x 250 mm, C18, 5 m

- Flow rate: 1 mL / min

- Injection Volume: 10 μl

- Column Oven Temperature: 40 ° C

- Analysis time: 60 min

Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 area (%) 12,000 15,000 29,000 38,000 52,000

It can be seen from Table 2 that the amounts of organic elution are smaller than those of Comparative Example 1 and Comparative Example 2 in Examples 1 to 3 including a phthalocyanine compound having a? -Form crystal and a phthalocyanine compound having an? -Form crystal Can be confirmed. Furthermore, in the case of Examples 1 and 2 in which the content of the phthalocyanine compound having the? -Form crystal is equal to or more than the content of the phthalocyanine compound having the? -Form crystal, the amount of the organic elution decreased by 100% or more .

(UV-vis measurement)

The photosensitive resin composition prepared in Examples 1 to 3 and Comparative Example 1 was coated on a substrate to which a predetermined pretreatment was applied in a thickness of 2.0 탆 and heated at 90 캜 for 4 minutes to remove the solvent to form a coating film Respectively. Subsequently, the photomask was placed on the coated film and the entire surface was exposed at 40 mJ. Then, the coated film was baked at 220 ° C for 25 minutes using convection oven. Then, 0.2 g of the coating film sample was collected and immersed in a vial together with 10 g of liquid crystal. The vials were kept at 100 ° C. for 60 minutes. Only the liquid crystals were collected. The collected liquid crystals were measured for absorbance by an analytical instrument (Agilent Cary 5000 UV-vis-NIR) Respectively.

It can be seen from Fig. 1 that the peaks at 671 nm were decreased in Examples 1 to 3 containing a phthalocyanine compound having a? -Form crystal and a phthalocyanine compound having an? -Form crystal compared with Comparative Example 1. Furthermore, in Examples 1 and 2 in which the content of the phthalocyanine compound having the? -Form crystal is equal to or more than the content of the phthalocyanine compound having the? -Form crystal, peaks at 671 nm are significantly reduced Can be confirmed. The peak at 671 nm is a peak against the elution of Cu-phthalocyanine blue, and it can be confirmed that the photosensitive resin composition according to one embodiment has high reliability because the peak is reduced.

Evaluation 2: Measurement of VHR value

The photosensitive resin compositions prepared in Examples 1 to 3 and Comparative Examples 1 and 2 were coated on a glass substrate patterned with ITO to form a coating film. The formed coating film and the patterned ITO electrode were assembled with each other, pressed, injected with liquid crystal therebetween, and sealed to fabricate a sample device. VHR values (60 ° C, 10 Hz) were measured using these autonomous VHRM devices. The results are shown in Table 3 below.

VHR Value (%) Example 1 86.2 Example 2 76.4 Example 3 65.8 Comparative Example 1 60.1 Comparative Example 2 56.5

In the case of Examples 1 to 3 using the phthalocyanine compound having the? -Form crystal and the phthalocyanine compound having the? -Type crystal simultaneously as the blue pigment in the black colorant, the results of Comparative Example 1 and Comparative Example 2 It can be seen that the elution amount of the metal ions is remarkably reduced to prevent the defective liquid crystal, and the light shielding property is excellent.

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.

Claims (15)

(A) a black colorant including a red pigment, a blue pigment and a violet pigment;
(B) a binder resin;
(C) a photopolymerizable monomer;
(D) a photopolymerization initiator; And
(E) Solvent
Lt; / RTI >
Wherein the blue pigment comprises a phthalocyanine compound having a? -Form crystal and a phthalocyanine compound having an? -Type crystal.
The method according to claim 1,
Wherein the phthalocyanine compound having the? -Form crystal is contained in an amount of not less than the content of the phthalocyanine compound having the? -Type crystal.
3. The method of claim 2,
Wherein the phthalocyanine compound having the? -Form crystal is contained in an amount larger than that of the phthalocyanine compound having the? -Type crystal.
The method according to claim 1,
The above-mentioned phthalocyanine compound having a? -Form crystal includes CI Pigment B15: 3, CI Pigment B15: 4, or a combination thereof.
The method according to claim 1,
Wherein the phthalocyanine compound having the? -Type crystal comprises CI Pigment B15: 6.
The method according to claim 1,
The red pigment may be at least one selected from the group consisting of pyrrolopyrrole-dione pigments, perylene pigments, anthraquinone pigments, dianthraquinone pigments, azo pigments, diazo pigments, quinacridone pigments, A pigment, an anthracene-based pigment, or a combination thereof.
The method according to claim 6,
Wherein the red pigment is represented by the following Formula 1:
[Chemical Formula 1]

In Formula 1,
R ¹ to R ⁴ are each independently a hydrogen atom, a halogen atom or a substituted or unsubstituted C1 to C10 alkyl group,
n1 and n2 are each independently an integer of 1 to 5;
The method according to claim 1,
The violet pigment is a photosensitive resin composition represented by the following formula (2): < EMI ID =
(2)

The method according to claim 1,
Wherein the black colorant further comprises an orange pigment, a yellow pigment, or a combination thereof.
The method according to claim 1,
Wherein the binder resin comprises a cadmium-based binder resin.
The method according to claim 1,
The above-mentioned photosensitive resin composition is characterized in that the total amount of the photosensitive resin composition
1 to 15% by weight of the black colorant (A);
1 to 10% by weight of the binder resin (B);
0.1 to 10% by weight of the (C) photopolymerizable monomer;
0.1 to 5% by weight of the photopolymerization initiator (D); And
The amount of the solvent (E)
.
The method according to claim 1,
Wherein the photosensitive resin composition further comprises additives such as malonic acid, 3-amino-1,2-propanediol, a silane coupling agent, a leveling agent, a fluorine-based surfactant, a radical polymerization initiator or a combination thereof.
A photosensitive resin film produced by using the photosensitive resin composition of any one of claims 1 to 12.
14. The method of claim 13,
Wherein the photosensitive resin film is a black column spacer.
A color filter comprising the photosensitive resin film of claim 13.

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