KR101869205B1 - Photosensitive resin composition, and pattern formed therefrom, color filter comprising thereof and liquid crystal display device comprigin the color filter - Google Patents

Abstract

An object of the present invention is to provide a colored photosensitive resin composition having high optical density and excellent reliability. The present invention relates to a colored photosensitive resin composition, a pattern layer to be formed, a color filter including the same, and a liquid crystal display device including the same. The colored photosensitive resin composition comprises: a colorant; an alkali-soluble resin; a polymerizable compound; a photopolymerization initiator; and a solvent, wherein the colorant comprises a green colorant, an orange colorant, and a purple colorant.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a colored photosensitive resin composition, a pattern layer formed therefrom, a color filter including the same, and a liquid crystal display device including the same. BACKGROUND ART [0002]

The present invention relates to a colored photosensitive resin composition, a pattern layer formed therefrom, a color filter including the same, and a liquid crystal display device including the same.

Display is becoming the most common means of information delivery in modern society. Therefore, a liquid crystal display (LCD) is one of widely used flat panel display devices, and a thin film transistor substrate having a pixel electrode and a color filter substrate having a common electrode formed thereon Facing each other and a liquid crystal layer interposed therebetween. In such a liquid crystal display device, a voltage is applied to the pixel electrode and the common electrode to rearrange the liquid crystal molecules in the liquid crystal layer, thereby displaying an image by adjusting the amount of light transmitted through the liquid crystal layer. The organic light emitting display (OLED) that is attracted attention as a next generation display is advantageous in the development of a flexible display because it uses a self-luminous element without using a liquid crystal as described above.

Generally, in a display element such as a thin film transistor (TFT) type liquid crystal display element or an organic EL (electroluminescent) element, a patterned electrode protecting film, a planarizing film, an insulating film, and the like are provided. As a material for forming these films, a photosensitive resin composition having a feature that the number of processes for obtaining a desired pattern shape is small and has sufficient flatness is widely used in the photosensitive resin composition from the past.

On the other hand, a composition using a blue coloring agent, carbon black and / or organic black has been known in the prior art photosensitive resin composition in order to improve the optical properties. In Korean Patent Laid-Open No. 10-2014-0096423, a colored photosensitive resin composition However, this method has a limitation in increasing the light shielding property. In order to increase the light shielding property, a method of increasing the content of a pigment such as carbon black having a high shielding property is used. However, when the carbon black content is increased, the relative dielectric constant is remarkably increased, There is a problem that the process yield is lowered due to the decrease of the near-infrared transmittance, and the use amount of the pigment is limited. Also, in the case of the organic black, as the addition amount is increased, the reliability is lowered, such as the elution problem with respect to the NMP solvent, so that the use amount of the organic black is inevitably limited. Accordingly, it is necessary to increase the amount of the coloring agent except for the black coloring agent in a large amount. However, when the amount of the coloring agent of the red coloring agent is excessively increased by the red coloring (red, orange, violet, yellow, The light-shielding layer formed by the conventional technique has a problem that a problem such as a reddish phenomenon can not be solved. Further, when the content of the colorant is simply increased, the proportion of the cured component is reduced, thereby causing a problem of reliability and deterioration of process characteristics.

Korean Laid-Open Publication No. 10-2014-0096423

The present invention is to provide a colored photosensitive resin composition having high optical density and excellent reliability while improving the above-mentioned problems.

The present invention also provides a color filter manufactured using the colored photosensitive resin composition.

The present invention also provides a display device including the color filter.

The present invention relates to a colorant; Alkali-soluble resins; Polymerizable compounds; Photopolymerization initiator; And a solvent, wherein the coloring photosensitive resin composition comprises:

Wherein the colorant comprises an orange colorant and a purple colorant and a green colorant having a complementary relationship with the colorant.

The present invention also provides a pattern layer formed from the above-mentioned colored photosensitive resin composition.

The present invention also provides a color filter comprising the above-described pattern layer.

Further, the present invention provides a liquid crystal display device including the color filter described above.

The present invention provides a colored photosensitive resin composition in which the reddish phenomenon is improved by using a green colorant having a complementary relationship with orange and / or purple colorants.

In addition, the present invention solves the above-mentioned problem of reddish phenomenon, so that it is possible to add a coloring agent having a purple color system excellent in light-shielding property, thereby lowering the overall pigment content and improving the process characteristics and reliability by increasing the curing component .

Further, the present invention provides a photosensitive resin composition having improved optical density and NMP elution problem and having excellent reliability effect.

The present invention also provides a pattern layer having excellent shielding properties and excellent reliability, including the colored photosensitive resin composition, a color filter including the same, and a liquid crystal display device.

FIG. 1 is a photograph showing whether or not a reddish phenomenon has occurred. FIG. 1A and FIG. 1B in which Reddish phenomenon occurs are for Comparative Example 2 and Comparative Example 4, and FIG. 1C is for Example 1.

Hereinafter, embodiments of the present invention will be described in detail so that those skilled in the art can easily carry out the present invention.

The colored photosensitive resin composition of the present invention has a high optical density and is improved in NMP eluting material to provide a colored photosensitive resin composition having excellent reliability, a pattern spacer made of the same, a black matrix and / or a black column spacer A color filter including the same, and a liquid crystal display device including the same.

Further, the colored photosensitive resin composition of the present invention can more preferably provide a black photosensitive resin composition.

coloring agent

In the present invention, the colorant is included for realizing a high optical density. When the pigments of different colors are used in combination, the combination of colors is not particularly limited. However, from the viewpoint of light shielding property, 950 nm transmittance, A combination of a green pigment, an orange pigment and a purple pigment may be preferable from the viewpoints of high optical density and excellent reliability. By including the colorant, it is possible to minimize the occurrence of the phenomenon of reduction in shielding property or reddish phenomenon while increasing the optical density.

As the green colorant, C.I. Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55, 58, From the viewpoint of light shielding, CI Pigment Green 7, 36, 54, 58, 59, and more preferably, C.I. It is more preferable to include the pigment green 54.

As the orange colorant, C.I. Pigment Orange 1, 2, 5, 13, 16, 17, 19, 20, 21, 22, 23, 24, 34, 36, 38, 39, 43, 46, 48, 49, 61, 62, 64, 65 , 67, 69, 70, 71, 72, 73, 74, 75, 77, 78 and 79. From the viewpoint of light- Pigment Orange 38, 43, 64, 71, 72, and C.I. Pigment Orange 64 is more preferable.

As the purple colorant, C.I. Pigment Violet 1, 1: 1, 2, 2: 2, 3, 3: 1, 3: 3, 5, 5: 1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32 , 37, 39, 42, 44, 47, 49, 50, and the like, Pigment Violet 19, 23, and 29, and it is preferable that C.I. It is more preferable to include Pigment Violet 23, 29.

In addition, the colored photosensitive resin composition of the present invention may further contain a black coloring agent to adjust optical characteristics. The black colorant may be appropriately selected from inorganic or organic pigments. Examples of usable black colorants include carbon black, atelieren black, lamp black, black black, graphite, iron black, aniline black, cyanine black, titanium black, rhammet black and perylene black. The organic pigments may be used alone or in combination. The content of the carbon black may be 0 to 13%, more preferably 4 to 10%, in the solid content. In addition, organic black among the black pigments may be added, preferably 3 to 25% by weight based on the solid content. If the organic black is less than 3% in the solid content of the colorant, the optical density may be ineffective. If it exceeds 25%, the product reliability may be affected. In the present invention, the black colorant may be mixed with a black oil / inorganic pigment as the case may be.

The coloring agent may be contained in an amount of 20 to 55% by weight based on the total solid content of the colored photosensitive resin composition, more preferably 23 to 50% by weight. When the content of the colorant is within the above range, sufficient shielding ability, that is, high optical density (OD) can be exhibited, and sufficient pattern formation is possible. The ratio of the pigment component may be changed according to the thickness of the light-shielding layer formed from the colored photosensitive resin composition or the light-shielding ratio.

Alkali-soluble resin

In the present invention, an alkali-soluble resin usually makes the non-exposed portion of the photosensitive resin layer formed using the photosensitive resin composition alkali-soluble and can also act as a dispersion medium for the pigment. The alkali-soluble resin may be selected from a variety of polymers used in the applicable application fields. A binder resin containing an epoxy group may be more preferable. This is because the alkali-soluble resin containing the epoxy group may affect the reliability improvement of the coating film due to thermal curing. The molecular weight of the alkali-soluble resin used may be in the range of 3,000 to 40,000 and preferably in the range of 5,000 to 30,000. In addition, the acid value of the alkali-soluble resin is preferably in the range of 50 to 200 mgKOH / g based on the solid content. When the acid value of the alkali resin satisfies the above-described range, there is an advantage that the developability against the alkali development is excellent, the occurrence of the residue is suppressed, and the adhesion of the pattern and the leveling property of the pattern are improved.

The alkali-soluble resin may be contained in an amount of 20 to 45% by weight based on the total solid content of the colored photosensitive resin composition, more preferably 25 to 40% by weight. When the content of the alkali-soluble resin is within the above range, it is preferable from the viewpoint that the developing property, the residual film ratio and the dispersibility of the coloring agent are improved and the performance of the coloring agent can be excellently expressed.

Photopolymerizable compound

The photopolymerizable compound of the present invention contains an unsaturated bond and undergoes a photoreaction with the photoinitiator to form a photosensitive resin layer. The polymerizable compound to be used in the present invention includes a commonly used (meth) acrylate in a functional group When the composition contains an unsaturated group and is photosensitive, there is no limitation in use.

Specific examples of the photopolymerizable compound include ethylene glycol diacrylate, triethylene glycol diacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, pentaerythritol diacrylate, But are not limited to, glycol acrylate, glycol acrylate, glycol acrylate, glycol acrylate, lithol acrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, dipentaerythritol diacrylate, dipentaerythritol triacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate , Bisphenol A diacrylate, trimethylolpropane triacrylate, novolak epoxy acrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, and the like. . The above-mentioned photopolymerizable compounds may be used alone or in combination of two or more thereof.

The photopolymerizable compound may be included in the total solid content of the colored photosensitive resin composition in an amount of 5 to 50% by weight, more preferably 10 to 40% by weight. When the content of the photopolymerizable compound is within the above range, So that a good pattern property can be formed.

Photopolymerization initiator

The photopolymerization initiator of the present invention initiates a radical reaction of the photosensitive resin composition to cause curing and improve the sensitivity. The photopolymerization initiator is a photopolymerization initiator generally used in a photosensitive resin composition, and oxime, acetophenone, benzophenone, triazine, thioxanthone, benzoin, and imidazole compounds can be used.

Oximeimino-1-phenylpropan-1-one and the like, and more preferable examples of the oxime-based compounds include OXE01 and OXE02 of BASF Corporation, which are commercially available products.

Examples of the acetophenone compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 2- 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1- Methyl [4- (1-methylvinyl) phenyl] propane-1-one, 2-benzyl-2-dimethylamino- 2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, and the like. In addition, photopolymerization initiators other than the acetophenone-based photopolymerization initiator may be used in combination. Photopolymerization initiators other than acetophenone-based photopolymerization initiators include active radical generators, sensitizers, and acid generators that generate active radicals upon irradiation with light. Examples of the active radical generator include benzoin-based compounds, benzophenone-based compounds, thioxanthone-based compounds, and triazine-based compounds. Examples of the benzoin-based compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoisobutyl ether and the like. Examples of the benzophenone-based compound include benzophenone, methyl o-benzoylbenzoate, 4-phenylphenazine, 4-benzoyl-4'-methyldiphenylsulfide, 3,3 ', 4,4'-tetra t-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, and the like. Examples of the thioxanthone compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1- Propanedioxanthone, and the like. Examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) (Trichloromethyl) -6- (4-methoxystyryl) -1,3,5-triazine, 2,4-bis Azine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) ethenyl] -1,3,5-triazine, 2,4- Yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino- Methylphenyl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5 -Triazine, and the like . Examples of the active radical generator include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,2-bis (o-chlorophenyl) -4,4 ', 5,5'-tetra Phenyl-1,2'-biimidazole, 10-butyl-2-chloroacridone, 2-ethyl anthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, methyl phenylglyoxylate, Compounds and the like can be used. Examples of the acid generator include 4-hydroxyphenyldimethylsulfonium p-toluene sulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluene sulfone 4-acetoxyphenylmethylbenzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate, diphenyliodonium p-toluenesulfonate, Diphenyl iodonium hexafluoroantimonate and the like, and nitrobenzyl tosylates, benzoin tosylates and the like. Also, as the active radical generator, there are compounds which generate an acid at the same time as an active radical, and for example, a triazine-based photopolymerization initiator is also used as an acid generator.

The photopolymerization initiator may be contained in an amount of 0.1 to 40% by weight, preferably 1 to 30% by weight based on the total weight of the solid content in the colored photosensitive resin. When the photopolymerization initiator is contained within the above range, the pattern formation becomes favorable, the colored photosensitive resin composition becomes highly sensitive, and the strength of the pixel portion formed by using the composition and the smoothness on the surface of the pixel portion tend to be favorable, Do.

Further, in the present invention, a photopolymerization initiator may be used. The photopolymerization initiator is sometimes used in combination with a photopolymerization initiator and is a compound used for promoting the polymerization of the photopolymerizable compound initiated by the photopolymerization initiator. Examples of the photopolymerization initiator include an amine compound, an alkoxyanthracene compound, a thioxanthone compound, a carboxylic acid compound, and a sulfonic acid compound.

 Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylamino benzoate Ethyl (4-dimethylaminobenzoic acid), 2-ethylhexyl 4-dimethylaminobenzoate, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzphenone Amino) benzophenone, and 4,4'-bis (ethylmethylamino) benzophenone. Of these, 4,4'-bis (diethylamino) benzophenone is preferable. Examples of the alkoxyanthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene And the like. Examples of the thioxanthone compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1- Propanedioxanthone, and the like. These photopolymerization initiators (D) may be used singly or in combination of two or more thereof. Commercially available photopolymerization initiators may be used as the photopolymerization initiator. Commercially available photopolymerization initiators include, for example, trade names "EAB-F" (manufactured by Hodogaya Chemical Industry Co., Ltd.) and the like.

 When these photopolymerization initiators are used, the amount of the photopolymerization initiator is usually 10 moles or less, preferably 0.01 to 5 moles per mole of the photopolymerization initiator. Within the above range, the sensitivity of the colored photosensitive resin composition becomes higher, and the productivity of the color filter formed using the composition tends to be improved, which is preferable.

solvent

The solvent contained in the colored photosensitive resin composition of the present invention is not particularly limited and various organic solvents used in the field of the colored photosensitive resin composition can be used. Specific examples of the solvent include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether and ethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, Diethylene glycol dialkyl ethers such as diethylene glycol dipropyl ether and diethylene glycol dibutyl ether, ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, Alkylene glycol alkyl ether acetates such as propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate and methoxypentyl acetate, aromatic hydrocarbons such as benzene, toluene, xylene and mesitylene , Ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone and cyclohexanone, alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol and glycerin, Ethyl and methyl 3-methoxypropionate, and cyclic esters such as? -Butyrolactone. Among the above-mentioned solvents, an organic solvent having a boiling point of 100 to 200 ° C in the solvent is preferably used from the viewpoint of coatability and dryness, more preferably an alkylene glycol alkyl ether acetate, a ketone, a 3-ethoxypropionic acid Ethyl, and 3-methoxypropionate, and more preferred examples thereof include propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, ethyl 3-ethoxypropionate, 3- Methyl propoxypropionate, and the like. These solvents may be used alone or in admixture of two or more, or mixed with organic solvents having different boiling points.

The content of the solvent in the colored photosensitive resin composition of the present invention may be 60 to 90% by weight, preferably 65 to 85% by weight, based on the total weight of the colored photosensitive resin composition containing the colored photosensitive resin composition. When the content of the solvent is within the above range, it is preferable that the leveling property and the coating property are good and curing is easy.

additive

The blue photosensitive resin composition of the colored pattern layer according to the present invention may further contain an additive such as a silane coupling agent and a surfactant in order to improve the coating property and the adhesive property as required.

The silane coupling agent for improving adhesion to a substrate may include a silane coupling agent having a reactive substituent selected from the group consisting of a carboxyl group, a methacryloyl group, an isocyanate group, an epoxy group, and a combination thereof. Examples of the silane coupling agent include trimethoxysilylbenzoic acid,? -Methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane,? -Isocyanatepropyltriethoxysilane, r-glycidoxypropyl Trimethoxysilane, and? - (3,4-epoxycyclohexyl) ethyltrimethoxysilane. These may be used alone or in combination of two or more.

The surfactant may be further added to improve coatability. Specifically, fluorine surfactants such as BM-1000, BM-1100 (BM Chemie) and Proride FC-135 / FC-170C / FC-430 (Sumitomo 3M Co.) can be used.

The additive can be suitably added and used by those skilled in the art within a range not hindering the effect of the present invention. For example, the additive may be used in an amount of 0.05 to 10 parts by weight, preferably 0.1 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the total of the colored photosensitive resin composition.

The colored photosensitive resin composition according to the present invention can be produced, for example, by the following method. The colorant is mixed with a solvent and dispersed. If necessary, a dispersant may be further used, and some or all of the alkali-soluble resin may be blended. The remaining amount of the alkali-soluble resin, the photopolymerizable compound, the photopolymerization initiator, other components to be used if necessary, and, if necessary, the additional solvent are further added to the obtained dispersion (hereinafter, also referred to as mill base) To obtain a desired colored photosensitive resin composition.

Column spacer , Black matrix and / or black column Spacer  Included Pattern layer , A color filter and a liquid crystal display

The color filter according to the present invention has advantages of minimizing NMP elution and having high optical density and excellent reliability and shielding property by including green, orange, and purple coloring agents, without adding an excessive amount of black coloring agent to the colored photosensitive resin composition. The color filter includes a substrate and a pattern layer formed on the substrate.

The substrate may be the substrate of the color filter itself, or may be a portion where a color filter is placed on a display device or the like, and is not particularly limited. The substrate may be glass, silicon (Si), silicon oxide (SiOx), or a polymer substrate. The polymer substrate may be polyethersulfone (PES) or polycarbonate (PC).

The pattern layer may include a column spacer, a black matrix and / or a black column spacer as a layer containing a cured product of the colored photosensitive resin composition of the present invention.

The column spacer, the black matrix, and / or the black column spacer according to the present invention include the green, orange, and purple coloring agents without the excessive addition of the black colorant to the colored photosensitive resin composition, thereby minimizing the elution of NMP, And has an excellent shielding property.

 The pattern layer may be a layer formed by applying the above-mentioned colored photosensitive resin composition and exposing, developing, and thermosetting in a predetermined pattern, and the pattern layer may be formed by performing a method commonly known in the art.

In still another embodiment of the present invention, the color filter may further include at least one selected from the group consisting of a red pattern layer and a green pattern layer.

The color filter including the substrate and the pattern layer as described above may further include a partition wall formed between the respective patterns, and may further include a black matrix, but is not limited thereto.

Another aspect of the present invention relates to a liquid crystal display device including the color filter described above. In short, the liquid crystal display device according to the present invention may include a color filter including a pattern layer containing a cured product of the above-mentioned colored photosensitive resin composition.

The color filter of the present invention is applicable not only to a general liquid crystal display device but also to various image display devices such as an electroluminescence display device, a plasma display device, and a field emission display device.

When the liquid crystal display device includes the color filter including the pattern layer according to the present invention, there is an advantage that the shielding property and the reliability are excellent. The colored photosensitive resin composition included in the color filter according to the present invention minimizes the reddish phenomenon by including a green coloring agent in addition to orange and purple coloring agents. Thus, a color filter including the photosensitive resin composition and a liquid crystal display device There is an advantage of excellent color reproduction.

Hereinafter, the present invention will be described in detail by way of examples to illustrate the present invention. However, the embodiments according to the present disclosure can be modified in various other forms, and the scope of the present specification is not construed as being limited to the above-described embodiments. Embodiments of the present disclosure are provided to more fully describe the present disclosure to those of ordinary skill in the art. In the following, "% " and " part " representing the content are by weight unless otherwise specified.

Manufacturing example : Preparation of binder resin (B)

277 g of methoxybutyl acetate was added to a 1-liter separable flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen inlet tube, and the mixture was heated to 80 DEG C, and 3,4-epoxytricyclo [5.2. (50: 50 (molar ratio)) of 3,4-epoxytricyclo [5.2.1.0,2,6] decane-8-yl acrylate , A mixed solution obtained by dissolving 301 g of the compound represented by the formula (11), Ra '= H], 49 g of methacrylic acid and 23 g of azobisdimethyl valeronitrile in 350 g of methoxybutyl acetate was added dropwise over 5 hours , And further aged for 3 hours to obtain a copolymer solution (solid content (NV) 35.0% by weight). The obtained copolymer had an acid value (dry) of 69.8 KOH mg / g, a weight average molecular weight (Mw) of 12,300 and a dispersion degree (Mw / Mn) of 2.1.

Example  1 to 7 and Comparative Example  1 to 4: Preparation of colored photosensitive resin composition

The colored photosensitive resin compositions of Examples 1 to 7 and Comparative Examples 1 to 4 were prepared according to the composition shown in Table 1 below.

[Table 1]

Binder resin (B): See Production Example

Monomer (M): DPHA (Nippon Kayaku Co., Ltd.)

Photopolymerization initiator (PI): 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -ethanone- 1- (O- acetyloxime) (Irgacure OXE- four)

Additive (D1): F554 (DIC)

Additive (D2): Sol Spurs 5000 (manufactured by Lubrisol)

Solvent (S): Propylene glycol monomethyl ether acetate (PGMEA)

Fabrication of Substrate

A 5 cm x 5 cm glass substrate (Corning) was cleaned with a neutral detergent and water and dried. Each of the colored photosensitive resin compositions prepared in Example 1 and Comparative Example was spin-coated on the glass substrate to a final film thickness of 3.0 占 퐉, prebaked at 80 to 120 占 폚 and dried for 1 to 2 minutes to prepare a solvent Respectively. Then, exposure was performed at an exposure amount of 25 to 35 mJ / cm ² to form a pattern, and an unexposed area was removed using an aqueous alkaline solution. Followed by baking at 200 to 250 DEG C for 10 to 30 minutes to prepare a colored substrate.

Experimental Example  One. Optical property  evaluation

Based on the substrate manufacturing standards as described above, optical characteristics are evaluated with a substrate made to be coated with a black photosensitive resin on the entire surface without a pattern. UV-vis (UV-2550, manufactured by Shimadzu) is used. In the evaluation of optical characteristics, the optical density was measured at 400 to 650 nm, and the near-infrared (near-IR) area was measured at 950 nm. The optical density meter (361T, X- rite) to measure the transmittance at a center wavelength of 510 nm, and optical density to a thickness of 1 mu m was determined. The specific evaluation criteria are as follows, and the evaluation results are shown in Table 2 below.

[Evaluation standard]

1. Optical characteristics (optical density, transmittance at 950 nm)

(1) Optical density and transmittance in a wavelength range of 400 to 650 nm

?: Excellent, 0.05% or less

Good: more than 0.05T% to less than 0.1T%

?: Insufficient, more than 0.1T% to less than 0.2T%

X: deteriorated, exceeding 0.2T%

(2) 950 nm transmittance

◎: Excellent, 18T% or more

Good: 15T% or more to less than 18T%

△: insufficient, 12T% or more to less than 15T%

X: worse, less than 12T%

Experimental Example  2. Reliability Evaluation

A substrate is manufactured so that a black photosensitive resin is applied to the entire surface without a pattern, on the basis of the above substrate manufacturing standards. It is cut into a size of 3 x 3 cm, immersed in NMP solvent, and heated at 100 캜 for 60 minutes. Thereafter, only the NMP solvent is extracted, and the degree of elution in the NMP solvent is measured using an UV-vis spectrometer, and the absorbance is expressed as an integral value of 400 to 700 nm. Specific evaluation criteria are as follows, and the measurement results are shown in Table 2 below.

[Evaluation standard]

Reliability (NMP elution reliability): 400 to 700 nm Abs integral value

Excellent ◎ = less than 5

Good ○ = 5 to 8

Lack of △ = 8 ~ 12

Worse than X = 12

Experimental Example  3. Evaluation of Reddish phenomenon

On the basis of the above substrate production, a substrate is prepared so that the colored photosensitive resin is coated on the entire surface without patterning and the film thickness after curing is 3.0 占 퐉. The LED lamp (brightness temperature range of 5500 ~ 6000K) with 1000cd / m2 brightness was placed on the back of the substrate, and the color was visually or photographed.

1000cd / m2 Luminance (LED)

[Table 2]

It was confirmed that the substrates prepared in Examples 1 to 7 which are the colored photosensitive resin compositions of the present invention had high optical density and excellent optical properties as well as excellent reliability. In addition, in Examples 1 to 7 of the present invention, it was confirmed in FIG. 1 that shielding is excellent and reddish phenomenon does not occur. On the other hand, it was confirmed that the optical characteristics (950 nm light transmittance, reddish phenomenon) and reliability were poor as in Comparative Examples 1 to 4 when an excessive amount of organic black or carbon black was added to improve the optical density or the blue coloring agent instead of the green coloring agent.

Claims (12)

coloring agent; Alkali-soluble resins; Photopolymerizable compounds; Photopolymerization initiator; And a solvent, wherein the coloring photosensitive resin composition comprises:
Wherein the colorant comprises an orange colorant and a purple colorant, and CI Pigment Green 54 which is a green colorant in a complementary relationship with the orange colorant and the purple colorant. The method according to claim 1,
The orange colorant may be selected from the group consisting of CI Pigment Orange 1, 2, 5, 13, 16, 17, 19, 20, 21, 22, 23, 24, 34, 36, 38, 39, 43, 46, 48, At least one member selected from the group consisting of 62, 64, 65, 67, 69, 70, 71, 72, 73, 74, 75, 77,
The purple colorant is selected from the group consisting of CI Pigment Violet 1, 1: 1, 2, 2: 2, 3, 3: 1, 3: 3, 5, 5: 1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49 and 50. The colored photosensitive resin composition according to claim 1, The method according to claim 1,
Wherein the coloring agent further comprises a black coloring agent. The method of claim 3,
Wherein the black colorant includes at least one selected from the group consisting of carbon black, atteylene black, lamp black, main black, graphite, iron black, aniline black, cyanine black, titanium black, , Colored photosensitive resin composition. The method according to claim 1,
Wherein the alkali-soluble resin comprises an epoxy group. The method according to claim 1,
Wherein the photopolymerization initiator includes at least one selected from the group consisting of acetophenone, benzophenone, triazine, thioxanthone, oxime, benzoin and nonimidazole compounds. Composition. The colored photosensitive resin composition according to claim 1, wherein the photosensitive resin composition further comprises an additive The method according to claim 1,
20 to 55% by weight of a colorant relative to the total solid content of the colored photosensitive resin composition; 20 to 45% by weight of an alkali-soluble resin; 10 to 40% by weight of photopolymerizable compound; 0.1 to 40% by weight of a photopolymerization initiator, and 60 to 90% by weight of a solvent based on the total amount of the colored photosensitive resin composition. A pattern layer made of the photosensitive resin composition of claim 1. The pattern layer according to claim 9, wherein the pattern layer is at least one selected from the group consisting of a column spacer, a black matrix and a black column spacer. A color filter comprising the patterned layer of claim 9. A liquid crystal display device comprising the color filter of claim 11.

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