KR20180121206A - Photosensitive resin composition, black photosensitive resin layer using the same and color filter - Google Patents

Abstract

Provided is a photosensitive resin composition, a black photosensitive resin film manufactured using the photosensitive resin composition, and a color filter comprising the black photosensitive resin film, wherein the photosensitive resin composition comprises: (A) a cardo binder resin having an acid value of 120-130 mgKOH/g and a weight average molecular weight of 4000-6000 g/mol; (B) a photopolymerizable monomer; (C) a photopolymerization initiator; (D) an organic black colorant; and (E) a solvent.

Description

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

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

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.

One embodiment is to provide a photosensitive resin composition which is excellent in step margin even at a low exposure amount and a short development time.

Another embodiment is to provide a black photosensitive resin film produced using the photosensitive resin composition.

Another embodiment is to provide a color filter comprising the black photosensitive resin film.

One embodiment includes (A) a cationic binder resin having an acid value of 120 mgKOH / g to 130 mgKOH / g and a weight average molecular weight of 4,000 g / mol to 6,000 g / mol; (B) a photopolymerizable monomer; (C) a photopolymerization initiator; (D) an organic black colorant; And (E) a solvent.

The organic black colorant may be a mixture of three or more different organic pigments.

The organic black colorant may be a mixture of a red pigment, a blue pigment and a violet pigment.

The red pigment may include a compound represented by the following general formula (1).

[Chemical Formula 1]

In Formula 1,

R ¹ and R ² are each independently a substituted or unsubstituted C1 to C10 alkyl group.

The blue pigment may include a compound represented by the following general formula (2).

(2)

In Formula 2,

R ³ to R ¹⁸ are each independently a hydrogen atom or a halogen atom.

The violet pigment may include a compound represented by the following formula (3).

(3)

The organic black colorant may comprise from 40% by weight to 50% by weight, from 30% by weight to 40% by weight and from 10% by weight to 20% by weight, respectively, of red pigment, blue pigment and violet pigment, based on the total amount of organic black colorant .

Wherein the photosensitive resin composition comprises (A) 1% by weight to 10% by weight of a cadmium-based binder resin, (B) 1 wt% to 10 wt% of a photopolymerizable monomer; (C) 0.1 to 5% by weight of a photopolymerization initiator; (D) 30% to 50% by weight of an organic black colorant; And (E) 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 provides a black photosensitive resin film produced using the photosensitive resin composition.

The black photosensitive resin film may be a black column spacer.

The black column spacer may include a main column spacer and a sub column spacer.

Another embodiment provides a color filter comprising the black photosensitive resin film.

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

The photosensitive resin composition according to an embodiment limits the acid value and the weight average molecular weight of the cadmium binder resin and at the same time contains the organic black colorant, thereby making it possible to manufacture a black column spacer having excellent step margins and processability and a color filter comprising the black column spacer have.

FIG. 1 is a view showing a main column spacer and a sub column spacer of a black column spacer, and a step difference therebetween.

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, " alkyl group " means a C1 to C20 alkyl group, " alkenyl group " means a C2 to C20 alkenyl group, " cycloalkenyl group " means a C3 to C20 cycloalkenyl group Quot; means a C3 to C20 heterocycloalkenyl group, " an aryl group " means a C6 to C20 aryl group, an " arylalkyl group " means a C6 to C20 arylalkyl group, Refers to a C 1 to C 20 alkylene group, "arylene group" refers to a C6 to C20 arylene group, "alkylarylene group" refers to a C6 to C20 alkylarylene group, "heteroarylene group" refers to a C3 to C20 hetero Quot; means an arylene group, and the " alkoxysilylene group " means a C1 to C20 alkoxysilylene group.

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, 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, a C1-C10 alkyl group, a C1- A C2 to C20 alkenyl group, a C2 to C20 alkynyl group, a C6 to C20 aryl group, a C3 to C20 cycloalkyl group, a C3 to C20 cycloalkenyl group, a C3 to C20 cycloalkynyl group, a C2 to C20 heterocycloalkyl group, a C2 to C20 heterocycloalkyl group, To C20 heterocycloalkenyl groups, C2 to C20 heterocycloalkynyl groups, C3 to C20 heteroaryl groups, or combinations thereof.

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

&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, an unsaturated bond includes not only multiple bonds between carbon-carbon atoms but also other molecules such as carbonyl bonds, azo bonds, and the like.

Unless otherwise defined in the chemical formulas in this specification, when no chemical bond is drawn at the position where the chemical bond should be drawn, it means that the hydrogen atom is bonded at the above position.

In the present specification, the cadmium resin means a resin in which at least one functional group selected from the group consisting of the following formulas (4-1) to (4-11) is contained in the main backbone of the resin.

Also, unless otherwise specified herein, " * " means the same or different atom or moiety connected to the formula.

The photosensitive resin composition according to one embodiment comprises (A) a cationic binder resin having an acid value of 120 mgKOH / g to 130 mgKOH / g and a weight average molecular weight of 4,000 g / mol to 6,000 g / mol; (B) a photopolymerizable monomer; (C) a photopolymerization initiator; (D) an organic black colorant; And (E) a solvent.

In general, cadmium binder resin is used as a binder resin in a photosensitive resin composition. In this case, there is a disadvantage that a break point (BP) gradually decreases with time and a stepwise change is very large when patterning a black column spacer. There is also a problem that the taper tends to be lowered.

In the case of a black column spacer, a step margin (MG step) between a main column spacer and a gate black matrix, a main column spacer and a sub column spacer column spacers, the tact time tends to be increased by applying a high exposure dose and a long developing time to secure a margin for the MS step (MS step margin), and the yield of the color filter including the black column spacer is lowered .

However, in the photosensitive resin composition according to one embodiment, a black column spacer pattern is implemented at a low exposure amount and a short developing time period by adjusting the acid value and the weight average molecular weight of the cadmium binder resin and using an organic black colorant as a black colorant , An excellent step margin and a fairness can be realized.

Each component will be described in detail below.

(A) Binder resin

The binder resin is a cadmium binder resin.

As described above, the use of a carcass binder resin in a composition for preparing a black matrix or a black column spacer generally decreases the break point (BP) with time, and thus the line width is reduced. In the case of the black column spacer, The height of the black matrix constituting the black column spacer tends to be lowered. In order to improve this, a method of excluding the use of a cadmium-based binder resin is usually used. However, when a general acrylic binder resin is used, fine patterning characteristics (fixation) are insufficient. In the case of a black column spacer, N-methyl pyrrolidine) due to lack of chemical resistance, such as the pattern is damaged side effects occur.

In order to minimize the above-mentioned side effects, an acrylic binder resin including an epoxy group rather than a cadmium binder resin may be used. In this case, the chemical resistance to NMP is improved and a disadvantage of using a cadmium binder resin alone Although the taper characteristics are also improved, the break point (BP) gradually increases with time, which causes a side effect in which the phenomenon occurs even though the development time is proper.

The photosensitive resin composition according to one embodiment can improve the step difference margin by using only the acid value and the weight average molecular weight of the cationic binder resin while using a cadmium binder resin as the binder resin.

The acid value of the cationic binder resin is 120 mgKOH / g to 130 mgKOH / g. The weight average molecular weight (measured by GPC) of the cationic binder resin is 4,000 g / mol to 6,000 g / mol. If the acid value and the weight average molecular weight of the cationic binder resin simultaneously satisfy the above range, a high step margin and excellent processability can be ensured even with a low exposure amount and a short development time period together with an organic black colorant to be described later, So that the tact time is reduced.

The cadmium binder resin may include a repeating unit represented by the following formula (4).

[Chemical Formula 4]

In Formula 4,

R ¹⁹ and R ²⁰ are each independently a hydrogen atom or a substituted or unsubstituted (meth) acryloyloxyalkyl group,

R ²¹ and R ²² are each independently a hydrogen atom, a halogen atom or a substituted or unsubstituted C1 to C20 alkyl group,

Z ¹ is a single bond, O, CO, SO ₂ , CR ²³ R ²⁴ , SiR ²⁵ R ²⁶ (wherein R ²³ to R ²⁶ are each independently a hydrogen atom or a substituted or unsubstituted C 1 to C 20 alkyl group) Is any one of the linking groups represented by the formulas (4-1) to (4-11)

[Formula 4-1]

[Formula 4-2]

[Formula 4-3]

[Formula 4-4]

[Formula 4-5]

(In the above Formula 4-5,

R ^a 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.

[Formula 4-6]

[Formula 4-7]

[Formula 4-8]

[Chemical Formula 4-9]

[Formula 4-10]

[Formula 4-11]

Z ² is an acid anhydride residue,

m1 and m2 are each independently an integer of 0 to 4;

The cadmium-based binder resin may include a functional group represented by the following formula (5) in at least one of the two terminals.

[Chemical Formula 5]

In Formula 5,

Z ³ may be represented by the following formulas (5-1) to (5-7).

[Formula 5-1]

(Wherein R ^b and R ^c are each independently a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, an ester group or an ether group)

[Formula 5-2]

[Formula 5-3]

[Formula 5-4]

[Formula 5-5]

Wherein R ^d is O, S, NH, a substituted or unsubstituted C1 to C20 alkylene group, a C1 to C20 alkylamine group, or a C2 to C20 alkenylamine group.

[Formula 5-6]

[Formula 5-7]

Examples of the cationic binder resin include fluorene-containing compounds such as 9,9-bis (4-oxiranylmethoxyphenyl) fluorene; Benzene tetracarboxylic dianhydride, naphthalene tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, benzophenone tetracarboxylic dianhydride, pyromellitic dianhydride, cyclobutanetetracarboxylic dianhydride, perylenetetracarboxylic dianhydride , Tetrahydrofuran tetracarboxylic acid dianhydride, tetrahydrophthalic anhydride and the like; Glycol compounds such as ethylene glycol, propylene glycol, and polyethylene glycol; Alcohol compounds such as methanol, ethanol, propanol, n-butanol, cyclohexanol and benzyl alcohol; Propylene glycol methyl ethyl acetate, and N-methyl pyrrolidone; Phosphorus compounds such as triphenylphosphine; And an amine or an ammonium salt compound such as tetramethylammonium chloride, tetraethylammonium bromide, benzyldiethylamine, triethylamine, tributylamine, benzyltriethylammonium chloride, or the like.

The cadmium-based binder resin may be contained in an amount of 1 to 10 wt% based on the total amount of the photosensitive resin composition. When the cadmium-based binder resin is contained within the above-mentioned range, the color filter is excellent in developability in the production of a color filter, and the cross-linkability is improved, whereby excellent surface smoothness can be obtained.

(D) a black colorant

The black colorant uses an organic black colorant.

The organic black colorant may be a mixture of three or more different organic pigments, such as a mixture of red pigment, blue pigment and violet pigment.

Since the black column spacer must be able to function as a black matrix and a column spacer, it must have a function of blocking light emitted from the backlight and a function of supporting the top plate and the bottom plate. In addition, the column spacer and the black matrix portion Should be clearly distinguished. However, when a black column spacer is implemented using an existing material such as an inorganic black pigment such as carbon black or an organic black pigment, since the light transmittance is low and only the film surface is cured, it is difficult to form a step.

However, according to one embodiment, an inorganic black pigment such as carbon black or an organic black pigment may be used singly as the organic black colorant, or a mixture of the inorganic black pigment and the organic black pigment may be used, By using a mixture of three or more different organic pigments, for example, a red pigment, a blue pigment and a violet pigment, it is possible to easily form a black column spacer step by raising the film transmittance together with a carcass binder resin having the above acid value and weight average molecular weight And can contribute to improving step margins and fairness.

For example, the red pigment may include a compound represented by the following formula (1).

[Chemical Formula 1]

In Formula 1,

R ¹ and R ² are each independently a substituted or unsubstituted C1 to C10 alkyl group.

For example, R ¹ and R ² each independently may be a methyl group.

Generally, in the case of a black column spacer, a polyimide film is formed thereon, and therefore, it is required that the polyimide film has excellent solvent resistance to NMP which is a solvent of polyimide. By using the compound represented by the above formula (1) as the red pigment, for example, it is possible to easily control the content-releasing property, for example, the releasability to NMP can do.

The black colorant may include 40% by weight to 50% by weight, 30% by weight to 40% by weight and 10% by weight to 20% by weight of red pigment, blue pigment and violet pigment, respectively, relative to the total amount of black colorant.

The blue pigment may include a phthalocyanine compound. For example, the blue pigment may be a phthalocyanine compound.

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

(2)

In Formula 2,

R ³ to R ¹⁸ are each independently a hydrogen atom or a halogen atom.

For example, R ³ to R ¹⁸ may all be hydrogen atoms.

The violet pigment may comprise a perylene compound. For example, the violet pigment may be represented by the following formula (3).

(3)

A dispersing agent may be used together to disperse the pigment. Specifically, the pigment may be surface-treated in advance with a dispersant, or a dispersant may be added to the pigment together with the pigment when the 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 adducts, alcohol alkylene oxide adducts, sulfonic acid esters, sulfonic acid salts, carboxylic acid esters, Alkylamido alkylene oxide adducts, and alkylamines. These may be used singly or in combination of two or more thereof.

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 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.

Specifically, the pigment may be used in the form of a pigment dispersion including the dispersant and a solvent described later, and the pigment dispersion may include a solid pigment, a dispersant, and a solvent. The solid pigment may be contained in an amount of 5 to 20% by weight, for example 8 to 15% by weight based on the total weight of the pigment dispersion.

The organic black colorant may be included in an amount of 30% by weight to 50% by weight, for example, 35% by weight to 45% by weight based on the total amount of the photosensitive resin composition. When the organic black colorant is contained within the above range, the coloring effect and developing performance are excellent.

(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.

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 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.

(C) Light curing Initiator

As the photopolymerization initiator, a benzophenone-based compound, a thioxanthone-based compound, a benzoin-based compound, a triazine-based compound, an oxime-based compound, an acetophenone-based compound, an oxime-based compound or a combination thereof may be used.

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-methylthioxanthone, isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 2- Chlorothioxanthone 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) -Dimethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4'-methoxynaphthyl) -4,6-bis (trichloromethyl) (Trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) (Trichloromethyl) -6-styryl-s-triazine, 2- (naphtho-1-yl) - 4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphthol-1-yl) (Trichloromethyl) -6- (4-methoxystyryl) -s-triazine, 2- [4 (trifluoromethyl) - (4-ethylphenyl) -phenyl] -4,6-bis (trichloromethyl) -1,3,5-triazine.

Examples of the oxime compounds include O-acyloxime compounds, 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione, 1- -1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone, O-ethoxycarbonyl-a-oxyamino-1-phenylpropan- 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.

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

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

The photopolymerization initiator may be used in combination with a photosensitizer that generates a chemical reaction by absorbing light to be in an excited state and transferring its energy.

Examples of the photosensitizer include tetraethylene glycol bis-3-mercaptopropionate, pentaerythritol tetrakis-3-mercaptopropionate, dipentaerythritol tetrakis-3-mercaptopropionate and the like .

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, it is possible to obtain sufficient reliability due to sufficient curing during exposure in the pattern formation step, to have excellent heat resistance, light resistance and chemical resistance, excellent resolution and adhesion, It is possible to prevent the transmittance from being lowered.

(E) Solvent

The solvent may be a mixture of the cationic binder resin, the organic black colorant, the photopolymerizable monomer, and the photopolymerization initiator, but not reacting with the photopolymerizable monomer.

Examples of the solvent 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 monomethyl ether, ethylene glycol monoethyl ether and ethylene glycol dimethyl ether (EDM); 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 esters such as methyl lactate and ethyl lactate; Oxyacetic acid alkyl esters such as methyl oxyacetate, ethyl oxyacetate and butyl oxyacetate; Alkoxyacetic acid alkyl esters such as methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, and ethyl ethoxyacetate; 3-oxypropionic acid alkyl esters such as methyl 3-oxypropionate and ethyl 3-oxypropionate; 3-alkoxypropionic acid alkyl esters such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate and methyl 3-ethoxypropionate; 2-oxypropionic acid alkyl esters such as methyl 2-oxypropionate, ethyl 2-oxypropionate and propyl 2-oxypropionate; 2-alkoxypropionic acid alkyl esters such as methyl 2-methoxypropionate, ethyl 2-methoxypropionate, ethyl 2-ethoxypropionate and methyl 2-ethoxypropionate; 2-methylpropionic acid esters such as methyl 2-oxy-2-methylpropionate and ethyl 2-oxy-2-methylpropionate, methyl 2-methoxy- Monooximonocarboxylic acid alkyl esters of 2-alkoxy-2-methylpropionic acid alkyls such as ethyl methyl propionate; Esters such as ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl hydroxyacetate and methyl 2-hydroxy-3-methylbutanoate; Ketone acid esters such as ethyl pyruvate, and the like, and also 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, And high boiling solvents such as ethyl acetate, diethyl oxalate, diethyl maleate,? -Butyrolactone, ethylene carbonate, propylene carbonate, and phenyl cellosolve acetate.

Among them, ketones such as cyclohexanone and the like are preferably used in consideration of compatibility and reactivity; Glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether and ethylene glycol diethyl ether; Ethylene glycol alkyl ether acetates such as ethyl cellosolve acetate; Esters such as ethyl 2-hydroxypropionate; Carbitols 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 30% by weight to 70% by weight based on the total amount of the photosensitive resin composition. When the solvent is included within the above range, the photosensitive resin composition has an appropriate viscosity, and thus the processability in the production of the black column spacer is excellent.

(F) Other additives

Meanwhile, 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.

The silane-based coupling agent may have a reactive substituent such as a vinyl group, a carboxyl group, a methacryloxy group, an isocyanate group, or an epoxy group in order to improve adhesion with a substrate.

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

The silane coupling agent may be included in an amount of 0.01 to 10 parts by weight based on 100 parts by weight of the photosensitive resin composition. When the silane coupling agent is included in the above range, the adhesion and storage stability are excellent.

The above-mentioned photosensitive resin composition may further contain a surfactant such as a fluorine-based surfactant for the purpose of improving coatability and preventing defect formation, if necessary.

The fluorine is a surfactant, the ^{BM Chemie社BM-1000 ®,} BM-1100 ® , and the like; Mecha Pack F 142D ^® , Copper F 172 ^® , Copper F 173 ^® , Copper F 183 ^® , Copper F 554 ^® and the like manufactured by Dainippon Ink & Chemicals Incorporated; Sumitomo M. (Note)社Pro rod FC-135 ^®, the same FC-170C ^®, copper FC-430 ^®, the same FC-431 ^®, and the like; Asahi Grass Co., Saffron S-112 ^® of社, such S-113 ^®, the same S-131 ^®, the same S-141 ^®, the same S-145 ^®, and the like; Toray Silicone ^® (Note)社SH-28PA, the same -190 ^®, may be used a fluorine-containing surfactants commercially available under the name such as copper ^{-193 ®, SZ-6032 ®,} SF-8428 ®.

The fluorine-based surfactant may be used in an amount of 0.001 part by weight to 5 parts by weight based on 100 parts by weight of the photosensitive resin composition. When the surfactant is contained within the above range, coating uniformity is ensured, no staining occurs, and wetting to an IZO substrate or a glass substrate is 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 black photosensitive resin film prepared by exposing, developing and curing the above-mentioned photosensitive resin composition.

The black photosensitive resin film may be a black column spacer.

The black column spacer may include a main column spacer and a sub column spacer.

The black photosensitive resin film production method is as follows.

(1) Coating and Film Formation Step

The photosensitive resin composition is coated on a substrate such as a glass substrate or an IZO substrate subjected to a predetermined pretreatment to a desired thickness by a spin or slit coating method, a roll coating method, a screen printing method, an applicator method or the like, Deg.] C to 100 [deg.] C for 1 minute to 10 minutes to remove the solvent to form a coating film.

(2) Exposure step

A full tone portion for implementing a half-tone portion and a main column spacer pattern for implementing a black matrix and a sub-column spacer pattern is formed on the coating film obtained above, And then an active line of 200 nm 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 differs depending on the kind of each component of the composition, the blending amount, and the dried film thickness, but is 500 mJ / cm ² (according to the 365 nm sensor) or less when high pressure mercury lamp is used.

(3) Development step

As a developing method, an unnecessary portion is dissolved and removed by using an alkaline aqueous solution as the developing solution after the above-mentioned exposure step, so that only the exposed portion is left to form a pattern and BP (Break Point) is measured.

(4) Post-treatment step

There is a post-heating process for obtaining an image pattern obtained by development in the above process, in terms of heat resistance, light resistance, adhesion, crack resistance, chemical resistance, high strength and storage stability. For example, after development, it may be heated in a convection oven at 250 ° C for 1 hour.

Another embodiment provides a color filter comprising the black photosensitive resin film.

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.

( Example )

(Preparation of photosensitive resin composition)

Example  One, Example  2, Comparative Example  1 to Comparative Example  7, Reference example  1 and Reference example  2

The photosensitive resin composition according to Example 1, Example 2, Comparative Example 1 to Comparative Example 7, Reference Example 1 and Reference Example 2 was prepared with the compositions shown in Tables 1 and 2 below using the following components.

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, an organic 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) Binder resin

(KBR101-S6, 120 mgKOH / g, 4,120 g / mol, Gyeongin Yang Co., Ltd.)

(A-2) Cathode binder resin (KBR101-S1, 130 mgKOH / g, 5,500 g / mol,

(A-3) Cathode binder resin (KBR101, 100 mgKOH / g, 4,140 g / mol,

(KBR101-LA, 91 mgKOH / g, 4,211 g / mol, manufactured by Gyeongin Yang Co., Ltd.)

(A-5) Cathode binder resin (KBR101-HW, 95 mgKOH / g, 7,241 g / mol,

(A-6) Cathode binder resin (KBR101-S2, 110 mgKOH / g, 5,500 g / mol,

(KBR101-S3, 140 mgKOH / g, 4,200 g / mol, manufactured by Gyeongin Yang Co., Ltd.) (A-7)

(KBR101-S4, 120 mgKOH / g, 7,251 g / mol, manufactured by Gyeongin Yang Co., Ltd.)

(KBR101-S5, 130 mgKOH / g, 7,254 g / mol, Gyeongin Yang Co., Ltd.)

(B) Photopolymerization  Monomer

Dipentaerythritol hexa (meth) acrylate (DPHA, sartomer)

(C) Light curing Initiator

OXE02, BASF Corporation,

(D) Organic black colorant

(D-1) C.I. Millbase dispersion with Red pigment 179 (SAKATA)

(D-2) C.I. Blue pigment 15: 6 with millbase dispersion (SAKATA Inc.)

(D-3) C.I. Millbase dispersion with Violet pigment 29 (SAKATA Inc.)

(D-4) Carbon black mill base (CI-M-120) dispersion (SAKATA)

(D-5) Millbase dispersion containing Organic Black Pigment (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

γ-glycidoxypropyltrimethoxysilane (S-510, Chisso)

(Unit: g) Kinds Example 1 Example 2 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 (A) Binder resin A-1 3.7 - - - - - - - - A-2 - 3.7 - - - - - - - A-3 - - 3.7 - - - - - - A-4 - - - 3.7 - - - - - A-5 - - - - 3.7 - - - - A-6 - - - - - 3.7 - - - A-7 - - - - - - 3.7 - - A-8 - - - - - - - 3.7 - A-9 - - - - - - - - 3.7 (B) a photopolymerizable monomer 3.7 3.7 3.7 3.7 3.7 3.7 3.7 3.7 3.7 (C) a photopolymerization initiator 0.402 0.402 0.402 0.402 0.402 0.402 0.402 0.402 0.402 (D) Organic black colorant D-1 16.9259 16.9259 16.9259 16.9259 16.9259 16.9259 16.9259 16.9259 16.9259 D-2 13.8131 13.8131 13.8131 13.8131 13.8131 13.8131 13.8131 13.8131 13.8131 D-3 6.5157 6.5157 6.5157 6.5157 6.5157 6.5157 6.5157 6.5157 6.5157 D-4 - - - - - - - - - D-5 - - - - - - - - - (E) Solvent E-1 38.4901 38.4901 38.4901 38.4901 38.4901 38.4901 38.4901 38.4901 38.4901 E-2 16.4 16.4 16.4 16.4 16.4 16.4 16.4 16.4 16.4 (F) Other additives 0.0532 0.0532 0.0532 0.0532 0.0532 0.0532 0.0532 0.0532 0.0532

(Unit: g) Kinds Reference Example 1 Reference Example 2 (A) Binder resin A-1 3.7 3.7 (B) a photopolymerizable monomer 3.7 3.7 (C) a photopolymerization initiator 0.402 0.402 (D) Organic black colorant D-1 - - D-2 - - D-3 - - D-4 37.2547 - D-5 - 37.2547 (E) Solvent E-1 38.4901 38.4901 E-2 16.4 16.4 (F) Other additives 0.0532 0.0532

(evaluation)

Step  margin

The photosensitive resin composition of Example 1, Example 2, Comparative Examples 1 to 7, and Reference Example 1 and Reference Example 2 was subjected to coating, exposure, development and post-baking, and the steps of the black column spacer pattern of the patterned specimen (3-D profiler; nanoview, nanosystem, Inc.), and the results are shown in Tables 3 to 6. < tb > < TABLE >

Exposure dose (mJ) Development time (sec) Step difference (占 퐉) between the main column spacer and the sub column spacer Example 1 40 50 1.5 70 1.2 90 0.9 110 0.55 130 0.25 150 0 Example 2 40 35 1.6 50 1.3 65 One 80 0.7 100 0.3 120 0

Exposure dose (mJ) Development time (sec) Step difference (占 퐉) between the main column spacer and the sub column spacer Comparative Example 1 40 150 2.5 250 One 350 0 Comparative Example 2 40 200 2.5 300 One 400 0 Comparative Example 3 40 250 2.5 350 1.7 450 1.2

Exposure dose (mJ) Development time (sec) Step difference (占 퐉) between the main column spacer and the sub column spacer Comparative Example 4 40 150 2.6 250 1.1 350 0 Comparative Example 5 40 20 1.6 30 One 40 0 Comparative Example 6 40 120 2.5 220 One 330 0

Exposure dose (mJ) Development time (sec) Step difference (占 퐉) between the main column spacer and the sub column spacer Comparative Example 7 40 90 2.5 190 One 290 0 Reference Example 1 40 60 2.5 80 2 100 1.5 120 One 140 0.5 160 0 Reference Example 2 40 60 2.5 80 1.9 100 1.4 120 0.9 140 0.45 160 0

It can be seen from the Tables 3 to 6 that the use of the photosensitive resin composition according to one embodiment makes it possible to produce a black photosensitive resin film, for example, a black column spacer having excellent step margin even at a low exposure amount and a short developing time.

Specifically, the step in the present description means a step between the main column spacer and the sub column spacer. For example, when the height of the main column spacer is 3 占 퐉 and the height of the sub column spacer is 1.5 占 퐉 to 2 占 퐉, The step difference is from 1 to 1.5 [micro] m) can be regarded as excellent in the step difference margin. The longer the development time interval for maintaining the step, the better the tact time is, and the development time period can not be extended unconditionally. Therefore, when three conditions (1) the step is in the range of 1 탆 to 1.5 탆, 2) the development time period in which the step of 1 탆 to 1.5 탆 is maintained is 30 seconds or more, and ③ the process time is within 100 sec ) Should satisfy both step margin and fairness.

The photosensitive resin compositions according to Comparative Examples 1 to 4, Comparative Example 6, Comparative Example 7, and Reference Example 1 and Reference Example 2 satisfied the conditions 1 and 2 above but did not satisfy the conditions 3 and 3, 5 satisfies the above conditions (1) and (3), but it can be confirmed that the above condition (2) is not satisfied. On the other hand, the photosensitive resin compositions according to Examples 1 and 2 can be confirmed to satisfy all of the conditions (1), (2) and (3) above.

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 (13)

(A) a cationic binder resin having an acid value of 120 mgKOH / g to 130 mgKOH / g and a weight average molecular weight of 4,000 g / mol to 6,000 g / mol;
(B) a photopolymerizable monomer;
(C) a photopolymerization initiator;
(D) an organic black colorant; And
(E) Solvent
.
The method according to claim 1,
Wherein the organic black colorant is a mixture of three or more different organic pigments.
3. The method of claim 2,
Wherein the organic black colorant is a mixture of a red pigment, a blue pigment, and a violet pigment.
The method of claim 3,
Wherein the red pigment comprises a compound represented by the following Formula 1:
[Chemical Formula 1]

In Formula 1,
R ¹ and R ² are each independently a substituted or unsubstituted C1 to C10 alkyl group.
The method of claim 3,
Wherein the blue pigment comprises a compound represented by the following Formula 2:
(2)

In Formula 2,
R ³ to R ¹⁸ are each independently a hydrogen atom or a halogen atom.
The method of claim 3,
Wherein the violet pigment comprises a compound represented by the following formula (3).
(3)

The method of claim 3,
Wherein the organic black colorant comprises 40 to 50 wt%, 30 to 40 wt% and 10 to 20 wt% of a red pigment, a blue pigment and a violet pigment, respectively, based on the total amount of the organic black colorant Composition.
The method according to claim 1,
The photosensitive resin composition preferably contains, relative to the total amount of the photosensitive resin composition,
(A) 1% to 10% by weight of a cadmium-based binder resin;
(B) 1 wt% to 10 wt% of a photopolymerizable monomer;
(C) 0.1 to 5% by weight of a photopolymerization initiator;
(D) 30% to 50% by weight of an organic black colorant; And
(E) Residue of solvent
.
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 black photosensitive resin film produced by using the photosensitive resin composition of any one of claims 1 to 9.
11. The method of claim 10,
The black photosensitive resin film is a black column spacer.
12. The method of claim 11,
The black column spacer includes a main column spacer and a sub column spacer.
A color filter comprising the black photosensitive resin film of claim 10.

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