TWI615678B - Photosensitive resin composition, black column spacer using the same, and color filter - Google Patents

Abstract

Provided is a photosensitive resin composition, a black columnar spacer manufactured by using the photosensitive resin composition, and a color filter including the black columnar spacer, the photosensitive resin composition comprising: (A) a colorant having a maximum transmittance at 360 nm to 410 nm; (B) a photopolymerization initiator having a maximum absorbance at 360 nm to 410 nm; (C) a photopolymerizable monomer; D) Solvent.

Description

Photosensitive resin composition, black column spacers and color filters using the same

[CROSS-REFERENCE TO RELATED APPLICATIONS] This application claims the priority and the benefit of the Korean Patent Application No. 10-2016-0027786, filed on March 8, 2016 in the Korean Intellectual Property Office, the Korean Patent Application The entire contents of this article are incorporated by reference.

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

It is necessary to use a photosensitive resin composition such as a color filter, a liquid crystal display material, an organic light emitting diode, or a display panel material in the display device. For example, a color filter such as a color liquid crystal display needs to have a black matrix at a boundary between colored layers such as red, green, blue, etc. to enhance display contrast or chromophore effect. Such a light blocking layer can be mainly formed of a photosensitive resin composition.

Recently, attempts have been made to use a black matrix material as a columnar spacer supporting two thin film transistor (TFT) and color filter (C/F) substrates having a liquid crystal layer therebetween, and such a column spacer is called Black columnar spacer.

The black columnar spacer selectively uses a pigment capable of increasing an optical density (OD) to obtain a light blocking property, but since the ultraviolet (UV) transmittance is also deteriorated, the black columnar spacer may Not conducive to light curing. In particular, the most commonly used pigment (carbon black) of the black columnar spacer has excellent light blocking properties, and the ultraviolet transmittance is 0 and thus has a disadvantage of deteriorating the process margin because only the surface occurs. Development was performed by curing without internal solidification performed only in the dark.

Therefore, research has been conducted on a photosensitive resin composition of a black columnar spacer which can solve the above disadvantages.

An embodiment provides a photosensitive resin composition capable of ensuring light blocking properties in a visible light region while ensuring transmittance in an ultraviolet (UV) region.

Another embodiment provides a black columnar spacer using the photosensitive resin composition.

Yet another embodiment provides a color filter including the black columnar spacer.

An embodiment provides a photosensitive resin composition comprising: (A) a colorant having a maximum transmittance at 360 nm to 410 nm; and (B) a photopolymerization initiator at 360 The maximum absorbance at meters to 410 nm; (C) photopolymerizable monomer; and (D) solvent.

The colorant can be a pigment, a dye, or a combination thereof.

The pigment may be an organic pigment.

The organic pigment may comprise a mixture of two or more selected from the group consisting of a red pigment, a green pigment, a blue pigment, and a yellow pigment.

The photopolymerization initiator may have a maximum absorbance at from 370 nm to 410 nm.

The photopolymerization initiator may be a lanthanide compound.

The photosensitive resin composition may further comprise a photopolymerization initiator having a maximum absorbance at 310 nm to 360 nm.

The photopolymerization initiator having a maximum absorbance at 310 nm to 360 nm may be a triazine compound or an acetophenone compound.

The photopolymerization initiator having a maximum absorbance at 360 nm to 410 nm and a photopolymerization initiator having a maximum absorbance at 310 nm to 360 nm may be contained in a weight ratio of 1:4 to 4:1.

The photopolymerization initiator having a maximum absorbance at 310 nm to 360 nm may be contained in an amount of from 0.01% by weight to 5% by weight based on the total amount of the photosensitive resin composition.

The photosensitive resin composition may further comprise (E) a binder resin.

The binder resin may include an acrylic binder resin, a card multi-adhesive resin, or a combination thereof.

The photosensitive resin composition may include: 5% by weight to 50% by weight of the coloring agent; and 0.1% by weight to 5% by weight of 360 nm to 410 nm, based on the total amount of the photosensitive resin composition The photopolymerization initiator having the maximum absorbance; 1% by weight to 10% by weight of the photopolymerizable monomer; 5% by weight to 20% by weight of the binder resin; and the balance of the solvent.

The photosensitive resin composition may further comprise the following additives: malonic acid, 3-amino-1,2-propanediol, decane-based coupling agent, leveling agent, fluorine-based surfactant, radical polymerization initiator or combination.

Another embodiment provides a black columnar spacer manufactured by exposing and developing the photosensitive resin composition.

Yet another embodiment provides a color filter including the black columnar spacer.

Other embodiments of the invention are included in the detailed description which follows.

The photosensitive resin composition according to an embodiment provides a black columnar spacer and a color filter including the black columnar spacer, the black column spacer having a light blocking property in a visible light region and having a process The margin, the color filter has a light blocking property in a visible light region and a light transmittance in an ultraviolet (UV) region due to a black colorant.

In the following, embodiments of the invention are explained in detail. However, the embodiments are exemplary, and the invention is not limited thereto, and the invention is defined by the scope of the claims.

In the present specification, when no definition is provided, "alkyl" means a C1 to C20 alkyl group, "alkenyl" means a C2 to C20 alkenyl group, and "cycloalkenyl" means a C3 to C20 cycloalkenyl group. "Heterocyclenyl" means C3 to C20 heterocycloalkenyl, the term "aryl" means C6 to C20 aryl, "arylalkyl" means C6 to C20 arylalkyl, "alkyl" Refers to C1 to C20 alkylene, "extended aryl" means C6 to C20 extended aryl, "alkyl extended aryl" means C6 to C20 alkyl extended aryl, "extended aryl" means C3 to C20 Heteroaryl, and "alkylalkoxy" means C1 to C20 alkoxy.

In the present specification, when a definition is not additionally provided, "substituted" means substitution of at least one hydrogen by a substituent: a halogen atom (F, Cl, Br, I), a hydroxyl group, a C1 to C20 alkoxy group, Nitro, cyano, amine, imido, azide, sulfhydryl, fluorenyl, fluorenyl, carbonyl, amine carbaryl, thiol, ester, ether, carboxyl or its salts, sulfonic acid Or a salt thereof, a phosphate group or a salt thereof, a C1 to C20 alkyl group, 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, C3 To C20 cycloalkynyl, C2 to C20 heterocycloalkyl, C2 to C20 heterocycloalkenyl, C2 to C20 heterocycloalkynyl, C3 to C20 heteroaryl or a combination thereof.

In the present specification, when a specific definition is not additionally provided, "hetero" means that at least one hetero atom selected from the group consisting of N, O, S, and P is contained in one functional group and the remainder is carbon.

In the present specification, "(meth)acrylate" means both "acrylate" and "methacrylate", and "(meth)acrylic" means "acrylic acid" when no specific definition is provided. And "methacrylic acid".

In the present specification, the term "combination" means mixing or copolymerization when a specific definition is not additionally provided.

In the present specification, when a specific definition is not additionally provided, the unsaturated bond includes a bond between other atoms, such as a carbonyl bond or an azo bond, and a multi-bond between carbon-carbon atoms.

In the present specification, a cardo-based resin refers to a resin containing at least one functional group selected from the chemical formula 1-1 to the chemical formula 1-11 in the skeleton.

In the present specification, when a specific definition is not additionally provided, the maximum transmittance and the maximum absorbance range refer to a region ranging from 300 nm to 700 nm, regardless of a range of less than 300 nm and a range of more than 700 nm.

In the present specification, when a specific definition is not additionally provided, "*" indicates a point connecting the same or different atoms or chemical formulas.

The photosensitive resin composition according to an embodiment comprises: (A) a colorant; (B) a photopolymerization initiator; (C) a photopolymerizable monomer; and (D) a solvent, wherein the colorant is at 360 nm The maximum transmittance is up to 410 nm, and the photopolymerization initiator has a maximum absorbance at 360 nm to 410 nm.

A photosensitive resin composition for a conventional black matrix or black columnar spacer contains a black pigment (for example, an inorganic pigment having a high optical density (for example, carbon black)) to achieve excellent light blocking properties. However, the black pigment (for example, carbon black) has improved light blocking properties but has a significantly reduced transmittance in the ultraviolet (UV) region, so the process margin cannot be increased.

However, the photosensitive resin composition according to an embodiment can provide a black columnar spacer having both photosensitive properties and light blocking properties by including coloring having a maximum transmittance at 360 nm to 410 nm. And a photopolymerization initiator having a maximum absorbance at 360 nm to 410 nm.

In the following, each component is specifically illustrated. ( A ) colorant

The colorant may contain a pigment, a dye, or a combination thereof, and has high transmittance in an ultraviolet (UV) region while having high light blocking properties in a visible light region.

For example, the colorant can have a maximum transmission at 300 nm to 410 nm (eg, 360 nm to 410 nm).

During the preparation of the photosensitive resin composition, when the coloring agent is used together with a photopolymerization initiator described later having a maximum absorbance at 300 nm to 410 nm (for example, 360 nm to 410 nm), in visible light The light blocking properties in the area are improved and at the same time the photocurability is improved.

For example, the colorant can be an organic pigment, a dye, or a combination thereof.

For example, the organic pigment may be a mixture of two or more selected from the group consisting of a red pigment, a green pigment, a blue pigment, and a yellow pigment. For example, the organic pigment may be a combination of a red pigment, a green pigment, and a blue pigment. For example, the organic pigment may be a combination of a red pigment, a blue pigment, and a yellow pigment.

When an inorganic pigment such as aniline black, phthalocyanine, titanium black, or carbon black is used as a coloring agent, excellent light blocking properties can be achieved, but process margin cannot be maximized because the surface is cured and the interior is not cured. Development is carried out.

The red pigment may be CI red pigment 179, CI red pigment 254, CI red pigment 255, CI red pigment 264, CI red pigment 270, CI red pigment 272, CI red pigment 177, CI red in the color index. Pigment 89 or the like, and the red pigment may be used singly or in the form of a mixture of two or more, but is not limited thereto.

The green pigment may be a halogen-substituted copper indigo pigment such as CI green pigment 59, CI green pigment 58, CI green pigment 36, CI green pigment 7, etc., and the green pigment may be used singly or in the form of a mixture of two or more. Use, but not limited to this.

The blue pigment may be a CI blue pigment 15:6 in a colorimetric index, a CI blue pigment 15:0, a CI blue pigment 15:1, a CI blue pigment 15:2, a CI blue pigment 15:3, CI blue pigment 15:4, CI blue pigment 15:5, CI blue pigment 15:6, CI blue pigment 16, and the blue pigment may be used alone or in the form of a mixture of two or more, but Not limited to this.

The yellow pigment may be an isoporphyrin pigment (for example, CI yellow pigment 139), a quinophthalone pigment (for example, CI yellow pigment 138), a nickel complex pigment (for example, CI yellow pigment 150, CI yellow) in the color index. Pigment 100) and the like, and the yellow pigment may be used singly or in the form of a mixture of two or more, but is not limited thereto.

When the colorant is a pigment, a dispersing agent may be used together with the pigment to disperse the pigment. Specifically, the pigment may be pretreated on the surface with a dispersing agent or added together with the dispersing agent to prepare a composition.

The dispersant may be a nonionic dispersant, an anionic dispersant, a cationic dispersant or the like. Specific examples of the dispersant may be a polyalkylene glycol and its ester, a polyalkylene oxide, a polyol ester alkylene oxide addition product, an alcohol alkylene oxide addition product, a sulfonate, a sulfonate, a carboxylate, a carboxylate The acid salt, the alkylguanamine alkylene oxide addition product, the alkylamine or the like, and the dispersing agents may be used singly or in the form of a mixture of two or more.

Commercially available examples of dispersants may include DISPERBYK-101, DISPERBYK-130, DISPERBYK-140, DISPERBYK-160, DISPERBYK-161, manufactured by BYK Co., Ltd. DISPERBYK-162, DISPERBYK-163, DISPERBYK-164, DISPERBYK-165, DISPERBYK-166, DISPERBYK-170, DISPERBYK-171, DISPERBYK-182, DISPERBYK-2000, DISPERBYK-2001; by EFKA Chemicals Co .) produced by EFKA-47, EFKA-47EA, EFKA-48, EFKA-49, EFKA-100, EFKA-400, EFKA-450; manufactured by Zeneka Co. Solsperse 5000, Solsperse 12000, Solsperse 13240, Solsperse 13940, Solsperse 17000, Solsperse 20000, Solsperse 24000 GR, Solsperse 27000, Solsperse 28000, etc.; or PB711, PB821, etc., manufactured by Ajinomoto Inc.

The dispersing agent may be contained in an amount of 0.1% by weight to 15% by weight based on the total amount of the photosensitive resin composition. When the dispersant in the range is contained, the composition has excellent stability, developability, and pattern forming ability due to improved dispersion properties during the production of the black columnar spacer.

The pigment can be pretreated with a water soluble inorganic salt and a wetting agent. When the pigment is pretreated, the average particle diameter of the pigment may become finer.

The pretreatment can be carried out by kneading the pigment with a water-soluble inorganic salt and a wetting agent and then filtering and washing the kneaded pigment.

The kneading can be performed at a temperature of 40 ° C to 100 ° C, and the filtration and washing can be performed by filtering the pigment after washing off the inorganic salt with water or the like.

Examples of the water-soluble inorganic salt may be sodium chloride, potassium chloride or the like, but are not limited thereto. The humectant allows the pigment to be uniformly mixed with the water-soluble inorganic salt and pulverized. Examples of the humectant include: alkylene glycol monoalkyl ethers such as ethylene glycol monoethyl ether, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, and the like; and alcohols such as ethanol, isopropanol, butanol, hexanol And cyclohexanol, ethylene glycol, diethylene glycol, polyethylene glycol, glycerol polyethylene glycol, and the like, and the humectants may be used singly or in the form of a mixture of two or more.

The kneaded pigment may have an average particle diameter ranging from 5 nm to 200 nm (for example, 5 nm to 150 nm). When the pigment has an average particle diameter within the range, the stability of the pigment dispersion can be improved, and the pixel resolution can be not deteriorated.

In particular, the pigment may be used in the form of a pigment dispersion comprising a dispersant and a solvent to be described later, and the pigment dispersion may comprise a solid pigment, a dispersant, and a solvent. The solid pigment may be contained in an amount of from 5% by weight to 20% by weight (for example, from 8% by weight to 15% by weight) based on the total amount of the pigment dispersion.

The colorant may be contained in an amount of 5 to 50% by weight (e.g., 5 to 45% by weight) based on the total amount of the photosensitive resin composition. When the coloring agent within the range is included, the coloring effect and development efficiency can be improved. ( B ) Photopolymerization initiator

The photopolymerization initiator has a maximum absorbance at 360 nm to 410 nm. For example, the photopolymerization initiator can have a maximum absorbance from 370 nm to 410 nm.

When a photopolymerization initiator is used together with the above colorant to prepare a photosensitive resin composition, the photosensitive resin composition can not only achieve black color but also internal solidification of the photosensitive resin composition, thereby maximizing process margin.

Further, the photosensitive resin composition according to an embodiment may further comprise a photopolymerization initiator having a maximum absorbance at 310 nm to 360 nm and a photopolymerization having a maximum absorbance at 360 nm to 410 nm. Starting agent.

The photopolymerization initiator having a maximum absorbance at 360 nm to 410 nm and a ratio of 310 nm to 360 may be contained in a weight ratio of 1:4 to 4:1 (for example, 1:3 to 3:1), respectively. A photopolymerization initiator with maximum absorbance under the nano. When a photopolymerization initiator having a maximum absorbance in a different range within the range of the weight ratio is contained, a wider wavelength can be used during exposure, thus promoting photocuring.

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

Examples of the benzophenone compound may be benzophenone, benzhydryl benzoate, methyl benzomethionate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated Benzophenone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-dimethylamine Benzobenzophenone, 4,4'-dichlorobenzophenone, 3,3'-dimethyl-2-methoxybenzophenone, and the like.

Examples of the thioxanthone-based compound may be thioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone , 2-chlorothioxanthone and the like.

Examples of the benzoin-based compound may be benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyl dimethyl ketal or the like.

Examples of the triazine-based compound may be 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(3', 4'-dimethoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4'-methoxynaphthyl)-4,6-bis(trichloro) Methyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-double (trichloromethyl)-s-triazine, 2-biphenyl-4,6-bis(trichloromethyl)-s-triazine, bis(trichloromethyl)-6-styryl-s -triazine, 2-(naphthol 1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphthol-1-yl)-4,6- Bis(trichloromethyl)-s-triazine, 2-4-bis(trichloromethyl)-6-piperidinyl-s-triazine, 2-4-bis(trichloromethyl)-6-( 4-methoxystyryl)-s-triazine, 2-[4-(4-ethylphenyl)-phenyl]-4,6-bis(trichloromethyl)-1,3,5 - Triazine and the like.

An example of the lanthanoid compound may be an O-mercapto lanthanide compound, 2-(O-benzylidene fluorenyl)-1-[4-(phenylthio)phenyl]-1,2-octanedione, 1 -(O-ethylhydrazinyl)-1-[9-ethyl-6-(2-methylbenzylidenyl)-9H-indazol-3-yl]ethanone, O-ethoxycarbonyl- Α-oxyamino-1-phenylpropan-1-one and the like. A specific example of the O-mercapto lanthanide compound may be 1,2-octanedione, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4- -Phenyl)-butan-1-one, 1-(4-phenylthiophenyl)-butane-1,2-dione-2-indole-O-benzoate, 1-(4- Phenylthiophenyl)-octane-1,2-dione-2-indole-O-benzoate, 1-(4-phenylthiophenyl)-oct-1-one oxime-O-B An acid ester, 1-(4-phenylthiophenyl)-butan-1-one oxime-O-acetate or the like.

For example, a photopolymerization initiator having a maximum absorbance at 360 nm to 410 nm may be a lanthanide compound. For example, the photopolymerization initiator having a maximum absorbance at 360 nm to 410 nm may be an O-mercapto lanthanide compound, but is not limited thereto.

Examples of the acetophenone-based compound may be 2,2'-diethoxyacetophenone, 2,2'-dibutoxyacetophenone, 2-hydroxy-2-methylpropiophenone, and a third butyl group. Trichloroacetophenone, p-tert-butyldichloroacetophenone, 4-chloroacetophenone, 2,2'-dichloro-4-phenoxyacetophenone, 2-methyl-1-( 4-(methylthio)phenyl)-2-morpholinylpropan-1-one, 2-benzyl-2-ethylamino-1-(4-morpholinylphenyl)-butyl- 1-ketone and the like.

For example, the photopolymerization initiator having a maximum absorbance at 310 nm to 360 nm may be a triazine compound or an acetophenone compound, but is not limited thereto.

The photopolymerization initiator may further contain an oxazole compound, a diketone compound, a lanthanum borate compound, an azide compound, an imidazole compound, a biimidazole compound or the like in addition to the above compound.

The photopolymerization initiator can be used together with a sensitizer capable of causing a chemical reaction by absorbing light and becoming excited and then transmitting its energy.

Examples of the sensitizer may be tetraethylene glycol bis-3-mercaptopropionate, pentaerythritol tetrakis-mercaptopropionate, dipentaerythritol tetrakis-mercaptopropionate or the like.

The photopolymerization initiator having a maximum absorbance at 360 nm to 410 nm may be contained in an amount of 0.1% by weight to 5% by weight (for example, 0.1% by weight to 3% by weight) based on the total amount of the photosensitive resin composition. And a photopolymerization initiator having a maximum absorbance at 310 nm to 360 nm in an amount of 0.01% by weight to 5% by weight (for example, 0.01% by weight to 3% by weight) based on the total amount of the photosensitive resin composition . For example, the photosensitive resin composition according to an embodiment contains 0.11% by weight to 10% by weight (for example, 0.11% by weight to 6% by weight) of a photopolymerization initiator. When the photopolymerization initiator in the range is contained, excellent reliability can be ensured due to sufficient curing during exposure in the pattern forming process, and the pattern can have excellent resolution and close contact properties as well as excellent heat resistance. It has light resistance and chemical resistance, and can prevent deterioration of transmittance due to a non-reactive starter. ( C ) photopolymerizable monomer

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

The photopolymerizable monomer has an ethylenically unsaturated double bond, and thus can cause sufficient polymerization during the exposure in the pattern forming process and form a pattern having excellent heat resistance, light resistance, and chemical resistance.

The photopolymerizable monomer may be, for example, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylic acid. Ester, neopentyl glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, bisphenol A di(A) Acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol hexa(meth)acrylate, dipentaerythritol di(meth)acrylate , dipentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, bisphenol A epoxy (meth) acrylate, ethylene glycol monomethyl ether ( Methyl) acrylate, trimethylolpropane tri(meth) acrylate, tris(meth) propylene decyl oxyphosphate, novolac epoxy (meth) acrylate or a combination thereof.

Commercially available examples of photopolymerizable monomers are as follows. Monofunctional (meth) acrylates may include: Aronix M-101 ^® , M-111 ^® , M-114 ^® (Toagosei Chemistry Industry Co., Ltd.); KAYARAD TC-110S ^® , TC-120S ^® (Nippon Kayaku Co., Ltd.); V-158 ^® , V-2311 ^® (Osaka Organic) Chemical Ind., Ltd.)). Examples of difunctional (meth) acrylates may include: Aronix M-210 ^® , M-240 ^® , M-6200 ^® (East Asia Synthetic Chemical Co., Ltd.), KAYARAD HDDA ^® , HX-220 ^® , R-604 ^® ( Nippon Kayaku Co., Ltd.), V-260 ^® , V-312 ^® , V-335 HP ^® (Osaka Organic Chemical Co., Ltd.), etc. Examples of trifunctional (meth) acrylates may include: Aronix M-309 ^® , M-400 ^® , M-405 ^® , M-450 ^® , M-7100 ^® , M-8030 ^® , M-8060 ^® (East Asia Synthetic Chemical Co., Ltd.), KAYARAD TMPTA ^® , DPCA-20 ^® , DPCA-30 ^® , DPCA-60 ^® , DPCA-120 ^® (Nippon Chemical Co., Ltd.), V-295 ^® , V-300 ^® , V-360 ^® , V-GPT ^® , V-3PA ^® , V-400 ^® (Osaka Yuki Kayaku Kogyo Co. Ltd.). These products may be used singly or in the form of a mixture of two or more.

The photopolymerizable monomer can be treated with an acid anhydride to improve developability.

The photopolymerizable monomer may be contained in an amount of from 1% by weight to 10% by weight (for example, from 1% by weight to 8% by weight) based on the total amount of the photosensitive resin composition. When the photopolymerizable monomer in the range is contained, the reactive unsaturated compound is sufficiently cured during the exposure in the pattern forming process, and has excellent reliability, so that it can be formed to have excellent heat resistance and light resistance. A pattern that is chemically resistant and also has excellent resolution and close contact properties. ( E ) binder resin

The photosensitive resin composition according to an embodiment may further comprise a binder resin. For example, the binder resin may include a cardo-based adhesive resin, an acrylic-based adhesive resin, or a combination thereof.

When the binder resin in the photosensitive resin composition is a cardo-based binder resin, the composition has excellent developability and sensitivity during photocuring, and thus has a fine pattern forming ability. When a cardo-based adhesive resin is used, the reliability of the black columnar spacer can be ensured.

The card multi-adhesive resin may contain a repeating unit represented by Chemical Formula 1. [Chemical Formula 1]

[化學式1-2]

[化學式1-3]

[化學式1-4]

[化學式1-5]

在化學式1-5中， R^a 為氫原子、乙基、C₂ H₄ Cl、C₂ H₄ OH、CH₂ CH=CH₂ 或苯基。 [化學式1-6]

[化學式1-7]

[化學式1-8]

[化學式1-9]

[化學式1-10]

[化學式1-11]

In Chemical Formula 1, R ¹¹ and R ^{12 are} independently a hydrogen atom or a substituted or unsubstituted (meth) acryloxyalkyl group, and R ¹³ and R ^{14 are} independently a hydrogen atom, a halogen atom, or a a substituted or unsubstituted C1 to C20 alkyl group, and Z ^{1 is} selected from the group consisting of a single bond, O, CO, SO ₂ , CR ⁷ R ⁸ , SiR ⁹ R ¹⁰ (wherein R ⁷ to R ^{10 are} independently a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group) or a linking group represented by one of Chemical Formula 1-1 to Chemical Formula 1-11, [Chemical Formula 1-1]

[Chemical Formula 1-2]

[Chemical Formula 1-3]

[Chemical Formula 1-4]

[Chemical Formula 1-5]

In Chemical Formula 1-5, 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. [Chemical Formula 1-6]

[Chemical Formula 1-7]

[Chemical Formula 1-8]

[Chemical Formula 1-9]

[Chemical Formula 1-10]

[Chemical Formula 1-11]

Z ² is an acid anhydride residue, and m1 and m2 are independently an integer ranging from 0 to 4.

在化學式2中， Z³ 由化學式2-1至化學式2-7表示。 [化學式2-1]

在化學式2-1中，R^b 及R^c 獨立地為氫原子、經取代或未經取代的C1至C20烷基、酯基或醚基。 [化學式2-2]

[化學式2-3]

[化學式2-4]

[化學式2-5]

在化學式2-5中，R^d 為O、S、NH、經取代或未經取代的C1至C20伸烷基、C1至C20烷基胺基或C2至C20烯基胺基。 [化學式2-6]

[化學式2-7]

The card multi-adhesive resin may contain a functional group represented by Chemical Formula 2 at at least one of the two ends. [Chemical Formula 2]

In Chemical Formula 2, Z ^{3 is} represented by Chemical Formula 2-1 to Chemical Formula 2-7. [Chemical Formula 2-1]

In Chemical Formula 2-1, R ^b and R ^{c are} independently a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, an ester group or an ether group. [Chemical Formula 2-2]

[Chemical Formula 2-3]

[Chemical Formula 2-4]

[Chemical Formula 2-5]

In Chemical Formula 2-5, R ^d is O, S, NH, a substituted or unsubstituted C1 to C20 alkyl group, a C1 to C20 alkylamino group or a C2 to C20 alkenylamino group. [Chemical Formula 2-6]

[Chemical Formula 2-7]

The cardo-based resin can be prepared, for example, by mixing at least two of the following compounds: a ruthenium-containing compound such as 9,9-bis(4-oxecyclopropylmethoxyphenyl)anthracene or the like; an acid anhydride compound, For example, pyromellitic dianhydride, naphthalene tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, benzophenone tetracarboxylic dianhydride, pyromellitic dianhydride, cyclobutane tetracarboxylic dianhydride, perylenetetracarboxylic dianhydride , tetrahydrofuran tetracarboxylic dianhydride, tetrahydrophthalic anhydride, etc.; diol compounds, such as ethylene glycol, propylene glycol, polyethylene glycol, etc.; alcohol compounds, such as methanol, ethanol, propanol, n-butanol, cyclohexane Alcohol, benzyl alcohol, etc.; solvent-based compounds such as propylene glycol methyl ethyl acetate, N-methylpyrrolidone, etc.; phosphorus compounds such as triphenylphosphine; and amine or ammonium salt compounds such as tetramethyl chloride Ammonium, tetraethylammonium bromide, benzyldiethylamine, triethylamine, tributylamine, benzyltriethylammonium chloride, and the like.

The card multi-adhesive resin may have a weight average molecular weight of from 500 g/m to 50,000 g/mole (for example, from 1,000 g/m to 30,000 g/mole). When the card multi-adhesive resin has a weight average molecular weight within the range, a pattern can be well formed during the production of the black columnar spacer without residue and the film thickness is not lost during development.

The cardo-based binder resin may be contained in an amount of from 5% by weight to 20% by weight (for example, from 5% by weight to 15% by weight) based on the total amount of the photosensitive resin composition. When the card multi-adhesive resin in the range is contained, excellent sensitivity, developability, resolution, and pattern linearity can be obtained.

The acrylic binder resin is a copolymer of a first ethylenically unsaturated monomer and a second ethylenically unsaturated monomer copolymerizable therewith, and is a resin containing at least one acrylic repeating unit.

The first ethylenically unsaturated monomer is an ethylenically unsaturated monomer comprising at least one carboxyl group. Examples of the monomer include (meth)acrylic acid, maleic acid, itaconic acid, fumaric acid, or a combination thereof.

The first ethylenically unsaturated monomer may be included in an amount of from 5% by weight to 50% by weight (for example, from 10% by weight to 40% by weight) based on the total of the acrylic binder resin.

The diene unsaturated monomer may be an aromatic vinyl compound such as styrene, α-methylstyrene, vinyltoluene, vinylbenzyl methyl ether or the like; an unsaturated carboxylic acid ester compound such as (A) Methyl acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, benzene (meth) acrylate Methyl ester, cyclohexyl (meth)acrylate, phenyl (meth)acrylate, etc.; aminoalkyl ester of unsaturated carboxylic acid, such as 2-aminoethyl (meth)acrylate, (meth)acrylic acid 2-dimethylaminoethyl ester or the like; a vinyl carboxylate compound such as vinyl acetate, vinyl benzoate or the like; an unsaturated carboxylic acid glycidyl ester compound such as glycidyl (meth)acrylate; A vinyl cyanide compound such as (meth)acrylonitrile or the like; an unsaturated guanamine compound such as (meth)acrylamide or the like. These may be used singly or in the form of a mixture of two or more.

Specific examples of the acrylic adhesive resin may be acrylic acid/benzyl methacrylate copolymer, methacrylic acid/benzyl methacrylate copolymer, methacrylic acid/benzyl methacrylate/styrene copolymer, Methyl methacrylate / benzyl methacrylate / 2-hydroxyethyl methacrylate copolymer, methacrylic acid / benzyl methacrylate / styrene / 2-hydroxyethyl methacrylate copolymer, etc. It is not limited thereto, and these may be used alone or in the form of a mixture of two or more.

The acrylic adhesive resin may be contained in an amount of from 1% by weight to 20% by weight (for example, from 1% by weight to 15% by weight, for example, from 1% by weight to 10% by weight) based on the total amount of the photosensitive resin composition. When the acrylic adhesive resin in the range is contained, excellent sensitivity, developability, resolution, and pattern linearity can be achieved.

On the other hand, the photosensitive resin composition according to an embodiment may contain only a cardo-based adhesive resin as a binder resin, and may not contain an acrylic-based binder resin. ( D ) solvent

The solvent is a material which is compatible with a color former, a photopolymerization initiator, a photopolymerizable monomer, and a binder resin but does not react with a color former, a photopolymerization initiator, a photopolymerizable monomer, and a binder resin.

Examples of the solvent may include an alcohol such as methanol, ethanol, etc.; an ether such as dichloroethyl ether, n-butyl ether, diisoamyl ether, methylphenyl ether, tetrahydrofuran or the like; a glycol ether such as ethylene glycol monomethyl ether, Ethylene glycol monoethyl ether, ethylene glycol dimethyl ether (EDM), etc.; cellosolve acetate, such as methyl cellosolve acetate, ethyl cellosolve B Ethyl acetate (ethyl cellosolve acetate), diethyl cellosolve acetate, etc.; carbitol, such as methyl ethyl carbitol, diethyl carbitol, diethylene glycol monomethyl Ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ether, diethylene glycol diethyl ether, etc.; propylene glycol alkyl ether acetate, such as propylene glycol methyl ether acetate, propylene glycol Ether acetate or the like; aromatic hydrocarbons such as toluene, xylene, etc.; ketones such as methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, methyl n-propyl ketone, methyl positive Butyl ketone, methyl n-amyl ketone, 2-heptanone, etc.; saturated aliphatic monocarboxylic acid alkyl ester, for example Ethyl acetate, n-butyl acetate, isobutyl acetate, etc.; lactate esters such as methyl lactate, ethyl lactate, etc.; alkyl oxyacetate, such as methyl oxyacetate, ethyl oxyacetate, oxygen Butyl acetate and the like; alkyl alkoxyacetate, such as methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc. An alkyl 3-oxopropionate such as methyl 3-oxypropionate, ethyl 3-oxypropionate or the like; an alkyl 3-alkoxypropionate such as 3-methoxypropionic acid Methyl ester, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, etc.; alkyl 2-oxopropionate, such as 2-oxypropane Methyl ester, ethyl 2-oxypropionate, propyl 2-oxypropionate, etc.; alkyl 2-alkoxypropionate, such as methyl 2-methoxypropionate, 2-methoxy Ethyl propionate, ethyl 2-ethoxypropionate, methyl 2-ethoxypropionate, etc.; 2-oxy-2-methylpropionate, such as 2-oxy-2-methylpropane Methyl ester, 2-oxy-2-methylpropionic acid ethyl ester, etc.; 2-alkoxy-2-methylpropionic acid alkyl ester of monooxymonocarboxylic acid alkyl ester, examples Such as methyl 2-methoxy-2-methylpropanoate, ethyl 2-ethoxy-2-methylpropionate, etc.; esters, such as 2-hydroxyethyl propionate, 2-hydroxy-2 propionate - methyl ethyl ester, hydroxyethyl acetate, 2-hydroxy-3-methyl methyl butyrate, etc.; keto esters such as ethyl pyruvate. In addition, high boiling solvents such as N-methylformamide, N,N-dimethylformamide, N-methylformamide, N-methylacetamide, N,N-di can also be used. Methylacetamide, N-methylpyrrolidone, dimethyl hydrazine, benzyl ethyl ether, dihexyl ether, acetamidine, isophorone, hexanoic acid, octanoic acid, 1-octanol, 1 - decyl alcohol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethyl carbonate, propyl carbonate, benzene Cellulose acetate and the like.

In view of miscibility and reactivity, a glycol ether such as ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether or the like; ethylene glycol alkyl ether acetate, for example, may be preferably used. Ethyl cellosolve acetate, etc.; esters, such as 2-hydroxyethyl propionate; carbitol, such as diethylene glycol monomethyl ether; propylene glycol alkyl ether acetate, such as propylene glycol methyl ether Acid ester, propylene glycol propyl ether acetate, and the like.

The solvent is used in the balance (for example, 30% by weight to 90% by weight, for example, 40% by weight to 85% by weight) based on the total amount of the photosensitive resin composition. When the solvent in the range is contained, the photosensitive resin composition may have an appropriate viscosity, thereby improving the coating characteristics of the black columnar spacer. ( F ) other additives

The photosensitive resin composition may further comprise the following additives: malonic acid; 3-amino-1,2-propanediol; decane-based coupling agent; leveling agent; fluorine-based surfactant; radical polymerization initiator; .

The decane coupling agent may have the following reactive substituents to improve the intimate contact properties with the substrate: vinyl, carboxyl, methacryloxy, isocyanate, epoxy, and the like.

Examples of the decane coupling agent may include trimethoxydecyl benzoic acid, γ-methyl propylene methoxy propyl trimethoxy decane, vinyl triethoxy decane, vinyl trimethoxy decane, γ-isocyanate. Propyltriethoxydecane, γ-glycidoxypropyltrimethoxydecane, β-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, and the like. These may be used singly or in the form of a mixture of two or more.

The decane-based coupling agent may be contained in an amount of from 0.01 part by weight to 10 parts by weight based on 100 parts by weight of the photosensitive resin composition. When the decane-based coupling agent in the range is contained, the close contact property, the storage property, and the like can be improved.

The photosensitive resin composition may further contain a surfactant (for example, a fluorine-based surfactant) to improve coating properties and prevent defects if necessary.

Examples of the fluorine-based surfactant may be commercially available fluorine-based surfactants such as BM-1000 ^® and BM-1100 ^® (BM Chemie Inc.); MEGAFACE F 142D ^® , F 172 ^® , F 173 ^® , F 183 ^® and F 554 ^® (Dainippon Ink Kagaku Kogyo Co., Ltd.); FULORAD FC-135 ^® , FULORAD FC-170C ^® , FULORAD FC-430 ^® and FULORAD FC- 431 ^® (Sumitomo 3M Co., Ltd.); SURFLON S-112 ^® , SURFLON S-113 ^® , SURFLON S-131 ^® , SURFLON S-141 ^® and SURFLON S- 145 ^® (Asahi Glass Co., Ltd.); and SH-28PA ^® , SH-190 ^® , SH-193 ^® , SZ-6032 ^® and SF-8428 ^® (Toray Ketone Limited) Toray Silicone Co., Ltd.).

The fluorine-based surfactant may be used in an amount of from 0.001 part by weight to 5 parts by weight based on 100 parts by weight of the photosensitive resin composition. When the surfactant in the range is contained, excellent wetting and coating uniformity on the IZO substrate or the glass substrate can be ensured without staining.

Further, the photosensitive resin composition may contain other additives (for example, an antioxidant, a stabilizer, etc.) in a predetermined amount unless other additives deteriorate the properties of the photosensitive resin composition.

Another embodiment provides a black columnar spacer manufactured by exposing, developing, and curing a photosensitive resin composition.

The pattern in the black columnar spacer may have a taper angle of less than or equal to 5° (eg, less than or equal to 5° and greater than or equal to 60°).

A method of manufacturing a black columnar spacer is as follows. (1) Coating and film formation

Coating the photosensitive resin composition onto a substrate (for example, a glass substrate or an IZO substrate) subjected to a predetermined pretreatment by a spin coating or slit coating method, a roll coating method, a screen printing method, a coater method, or the like The photosensitive resin composition is heated by a vacuum dry (VCD) process at 70 ° C to 100 ° C for 1 minute to 10 minutes to remove the solvent, thereby forming a photosensitive resin film. (2) exposure

The photosensitive resin film is patterned by: arranging a mask composed of a half tone portion for achieving a black matrix pattern and a full tone for achieving a columnar spacer pattern, and then Irradiating actinic ray ranging from 200 nm to 500 nm. Irradiation is performed by using, for example, a mercury lamp having a low pressure, a high pressure, or an ultrahigh pressure, a metal halide lamp, an argon laser, or the like. Depending on the situation, X-rays, electron beams, etc. may also be used.

When a high pressure mercury lamp is used, the exposure process uses, for example, a light dose of 500 mJ/cm 2 or less than 500 mJ/cm 2 (using a 365 nm sensor). However, the light dose may vary depending on the kind of each component, the combination ratio thereof, and the dry film thickness. (3) Development

After the exposure process, the exposed film is developed using an alkaline aqueous solution by dissolving and removing excess portions other than the exposed portion to form a pattern. (4) Post processing

The developed image pattern can be post-heated to achieve excellent quality in terms of heat resistance, light resistance, close contact properties, crack resistance, chemical resistance, high strength, storage stability, and the like.

Another embodiment provides a color filter comprising a black columnar spacer.

In the following, illustrative examples of the invention are set forth. However, the examples are not to be construed as limiting the scope of the invention in any way. (Example) (Preparation of photosensitive resin composition) Example 1

（在表1中，NCI831在380奈米下具有最大吸光度（如在圖1中所示），而TEB在345奈米下具有最大吸光度（如在圖2中所示）） （在表1中，著色劑在400奈米下具有最大透射率（如在圖4中所示）） （在表1中，以顏料分散液的總量計，以15重量%的量包含顏料固體）實例 2 The photopolymerization initiator was dissolved in the solvent in the composition provided in Table 1, and the solution was stirred at room temperature for 2 hours. Subsequently, a binder resin and a photopolymerizable monomer were added thereto, and the mixture was stirred again for 2 hours at room temperature. Then, a coloring agent was added thereto, the mixture was stirred at room temperature for 1 hour, a decane coupling agent was added thereto as another additive, and the obtained mixture was stirred at room temperature for 1 hour. The resulting solution was filtered three times to remove impurities, thereby preparing a photosensitive resin composition according to Example 1. (Table 1) (Unit: gram)

(In Table 1, NCI831 has maximum absorbance at 380 nm (as shown in Figure 1), while TEB has maximum absorbance at 345 nm (as shown in Figure 2)) (in Table 1) The colorant has a maximum transmittance at 400 nm (as shown in Fig. 4)) (In Table 1, the pigment solid is contained in an amount of 15% by weight based on the total amount of the pigment dispersion) Example 2

（在表2中，NCI831在380奈米下具有最大吸光度，而TEB在345奈米下具有最大吸光度） （在表2中，著色劑在400奈米下具有最大透射率（如在表5中所示）） （在表2中，以顏料分散液的總量計，以10重量%的量包含顏料固體）實例 3 A photosensitive resin composition according to Example 2 was prepared according to the same method as Example 1 except that the following components were used to have the composition shown in Table 2. (Table 2) (Unit: gram)

(In Table 2, NCI831 has maximum absorbance at 380 nm, while TEB has maximum absorbance at 345 nm) (In Table 2, the colorant has maximum transmittance at 400 nm (as in Table 5). Shown)) (In Table 2, pigment solids are contained in an amount of 10% by weight based on the total amount of the pigment dispersion) Example 3

（在表3中，NCI831在380奈米下具有最大吸光度，而TEB在345奈米下具有最大吸光度） （在表3中，著色劑在400奈米下具有最大透射率） （在表3中，以顏料分散液的總量計，以10重量%的量包含顏料固體）實例 4 The photosensitive resin composition according to Example 3 was prepared according to the same method as Example 1 except that the following components were used to have the composition shown in Table 3. (Table 3) (Unit: gram)

(In Table 3, NCI831 has maximum absorbance at 380 nm, while TEB has maximum absorbance at 345 nm) (in Table 3, the colorant has maximum transmittance at 400 nm) (in Table 3) , including pigment solids in an amount of 10% by weight based on the total amount of the pigment dispersion) Example 4

（在表4中，NCI831在380奈米下具有最大吸光度，而TEB在345奈米下具有最大吸光度） （在表4中，著色劑在400奈米下具有最大透射率） （在表4中，以顏料分散液的總量計，以10重量%的量包含顏料固體）實例 5 The photosensitive resin composition according to Example 4 was prepared according to the same method as Example 1 except that the following components were used to have the composition shown in Table 4. (Table 4) (Unit: gram)

(In Table 4, NCI831 has maximum absorbance at 380 nm, while TEB has maximum absorbance at 345 nm) (in Table 4, the colorant has maximum transmittance at 400 nm) (in Table 4) , including pigment solids in an amount of 10% by weight based on the total amount of the pigment dispersion) Example 5

（在表5中，NCI831在380奈米下具有最大吸光度，而TEB在345奈米下具有最大吸光度） （在表5中，著色劑在400奈米下具有最大透射率） （在表5中，以顏料分散液的總量計，以10重量%的量包含顏料固體）實例 6 The photosensitive resin composition according to Example 5 was prepared according to the same method as Example 1 except that the following components were used to have the composition shown in Table 5. (Table 5) (Unit: gram)

(In Table 5, NCI831 has maximum absorbance at 380 nm, while TEB has maximum absorbance at 345 nm) (in Table 5, the colorant has maximum transmittance at 400 nm) (in Table 5) , including pigment solids in an amount of 10% by weight based on the total amount of the pigment dispersion) Example 6

（在表6中，NCI831在380奈米下具有最大吸光度，而TEB在345奈米下具有最大吸光度） （在表6中，著色劑在400奈米下具有最大透射率） （在表6中，以顏料分散液的總量計，以10重量%的量包含顏料固體。）比較例 1 The photosensitive resin composition according to Example 6 was prepared according to the same method as Example 1 except that the following components were used to have the composition shown in Table 6. (Table 6) (Unit: gram)

(In Table 6, NCI831 has maximum absorbance at 380 nm, while TEB has maximum absorbance at 345 nm) (in Table 6, the colorant has maximum transmittance at 400 nm) (in Table 6) The pigment solid was contained in an amount of 10% by weight based on the total amount of the pigment dispersion.) Comparative Example 1

（在表7中，TEB在345奈米下具有最大吸光度） （在表7中，著色劑在400奈米下具有最大透射率） （在表7中，以顏料分散液的總量計，以10重量%的量包含顏料固體）比較例 2 The photosensitive resin composition according to Comparative Example 1 was prepared according to the same method as Example 1 except that the following components were used to have the composition shown in Table 7. (Table 7) (Unit: gram)

(In Table 7, TEB has maximum absorbance at 345 nm) (In Table 7, the colorant has maximum transmittance at 400 nm) (in Table 7, based on the total amount of pigment dispersion, 10% by weight of the amount contains the pigment solid) Comparative Example 2

（在表8中，OXE01在260奈米及330奈米下具有最大吸光度（如在圖3中所示），而TEB在345奈米下具有最大吸光度） （在表8中，著色劑在400奈米下具有最大透射率） （在表8中，以顏料分散液的總量計，以10重量%的量包含顏料固體）比較例 3 The photosensitive resin composition according to Comparative Example 2 was prepared according to the same method as Example 1 except that the following components were used to have the composition shown in Table 8. (Table 8) (Unit: gram)

(In Table 8, OXE01 has maximum absorbance at 260 nm and 330 nm (as shown in Figure 3), while TEB has maximum absorbance at 345 nm) (in Table 8, the colorant is at 400) The maximum transmittance under the nanometer (in Table 8, the pigment solid is contained in an amount of 10% by weight based on the total amount of the pigment dispersion) Comparative Example 3

（在表9中，NCI831在380奈米下具有最大吸光度，而TEB在345奈米下具有最大吸光度） （在表9中，以顏料分散液的總量計，以15重量%的量包含顏料固體）（評估） 評估：顯影裕度 A photosensitive resin composition according to Comparative Example 3 was prepared according to the same method as Example 1 except that the following components were used to have the composition shown in Table 9. (Table 9) (Unit: gram)

(In Table 9, NCI831 has the maximum absorbance at 380 nm, and TEB has the maximum absorbance at 345 nm) (In Table 9, the pigment is contained in an amount of 15% by weight based on the total amount of the pigment dispersion. Solid) (Evaluation) Assessment: Development Margin

（在表10中，擋光區域中的顯影裕度指示半色調區域的在10秒的顯影時間內變化的厚度）The photosensitive resin compositions according to Examples 1 to 6 and Comparative Examples 1 to 3 were respectively coated, exposed (by using a halftone mask), developed, and post-baked to obtain a patterned sample. And Table 10 shows the slope change of the step thickness of the 10 μm pattern of the light barrier layer of the column spacer pattern in the development time of 10 seconds, wherein the thickness is by using a non-contact type thickness gauge (Three-dimensional (3-D) profiler) measurement. (Table 10)

(In Table 10, the development margin in the light blocking area indicates the thickness of the halftone area which varies within a development time of 10 seconds)

Referring to Table 10, a photosensitive resin composition comprising a color former having a maximum transmittance at 360 nm to 410 nm and a photopolymerization initiator having a maximum absorbance at 360 nm to 410 nm is shown: The photosensitive resin composition not containing the colorant has an excellent development margin in the light blocking region despite having the same central exposure amount. Further, the photosensitive resin composition containing the colorant and the photopolymerization initiator in a weight ratio of 1:4 to 4:1 (for example, 1:3 to 3:1), respectively, is shown as: The weight of 4 to 4:1 (for example, 1:3 to 3:1) has an excellent development margin in the light blocking region as compared with the photosensitive resin composition containing the coloring agent and the photopolymerization initiator.

Although the present invention has been described in connection with the exemplary embodiments of the present invention, it is understood that the invention is not to be construed as limited Various finishes and equivalent configurations. Therefore, the above embodiments are to be considered as illustrative and not restrictive.

no

Fig. 1 is a graph showing changes in absorbance of a photopolymerization initiator (NCI831) according to wavelength. Fig. 2 is a graph showing changes in absorbance of a photopolymerization initiator (TEB) depending on wavelength. Fig. 3 is a graph showing changes in absorbance of a photopolymerization initiator (OXE01) according to wavelength. 4 is a graph showing changes in transmittance of a pigment dispersion containing 849R, 100Y, and 614B depending on wavelength. Fig. 5 is a graph showing changes in transmittance of a coloring agent containing a pigment dispersion liquid containing 849R, 100Y, and 614B and a dye according to wavelength.

Claims (11)

A photosensitive resin composition comprising: (A) a colorant having a maximum transmittance at 360 nm to 410 nm; (B) a lanthanide photopolymerization initiator and a triazine-based photopolymerization initiator, wherein The lanthanide photopolymerization initiator has a maximum absorbance at 360 nm to 410 nm, and the triazine-based photopolymerization initiator has a maximum absorbance at 310 nm to 360 nm; (C) Photopolymerizable a monomer; and (D) a solvent; and (E) a binder resin, which is contained in an amount of from 0.01 nm to 360 nm in an amount of from 0.01% by weight to 5% by weight based on the total amount of the photosensitive resin composition The triazine-based photopolymerization initiator having the maximum absorbance. The photosensitive resin composition according to claim 1, wherein the colorant is a pigment, a dye, or a combination thereof. The photosensitive resin composition according to claim 2, wherein the pigment is an organic pigment. The photosensitive resin composition according to claim 3, wherein the organic pigment comprises a mixture of two or more selected from the group consisting of a red pigment, a green pigment, a blue pigment, and a yellow pigment. The photosensitive resin composition according to claim 1, wherein the photopolymerization initiator has a maximum absorbance at from 370 nm to 410 nm. The photosensitive resin composition according to claim 1, wherein the oxime-based photopolymerization initiator having a maximum absorbance at 360 nm to 410 nm is contained in a weight ratio of 1:4 to 4:1. And the triazine-based photopolymerization initiator having a maximum absorbance at 310 nm to 360 nm. The photosensitive resin composition according to claim 1, wherein the binder resin comprises an acrylic binder resin, a cardo binder resin, or a combination thereof. The photosensitive resin composition according to claim 1, wherein the photosensitive resin composition comprises: 5% by weight to 50% by weight of the coloring agent based on the total amount of the photosensitive resin composition; From 0% by weight to 5% by weight of the photopolymerization initiator having a maximum absorbance at 360 nm to 410 nm; 1% by weight to 10% by weight of the photopolymerizable monomer; 5% by weight to 20% by weight The binder resin; and the balance of the solvent. The photosensitive resin composition according to claim 1, wherein the photosensitive resin composition further comprises the following additives: malonic acid, 3-amino-1,2-propanediol, decane coupling agent, leveling agent A fluorine-based surfactant, a radical polymerization initiator, or a combination thereof. A black columnar spacer is produced by exposing and developing a photosensitive resin composition as described in any one of the above-mentioned claims. A color filter comprising the black columnar spacer as described in claim 10 of the patent application.