KR20170075641A - Colored photosensitive resin composition, color filter, image display device, and method for manufacturing the color filter - Google Patents

Abstract

The present invention relates to a photosensitive resin composition comprising (A) at least one colorant selected from the group consisting of (A) an alkali-soluble resin, (C) a photopolymerizable compound, (D) a photopolymerization initiator, (E) a polyfunctional thiol compound, ;
Wherein the colorant (A) comprises at least one selected from CI Pigment Green 59, 62, and 63, and at least one selected from pigments and dyes, a color produced using the colored photosensitive resin composition A filter, an image display device including the color filter, and a method of manufacturing a color filter.

Description

TECHNICAL FIELD [0001] The present invention relates to a colored photosensitive resin composition, a color filter manufactured using the same, an image display device, and a manufacturing method of a color filter. BACKGROUND ART [0002]

The present invention relates to a colored photosensitive resin composition, a color filter manufactured using the same, an image display device, and a method of manufacturing a color filter.

Color filters are widely used for various display devices such as an image pickup device and a liquid crystal display device (LCD), and their application range is rapidly expanding. The color filter used in the image pickup device, the liquid crystal display device, and the like may be a color pattern of three colors of red, green, and blue, or may be a color pattern of yellow, magenta, Cyan).

The coloring pattern of each of the color filters is generally formed using a colored photosensitive resin composition comprising a coloring agent such as pigment or dye, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent. The coloring pattern processing using the colored photosensitive resin composition is usually performed by a lithography process.

In recent years, various display devices including a solid-state image sensor such as a digital camera and a color filter for a liquid crystal display (LCD) have been required to have high brightness and high coloring property in order to improve the processability and quality, It is not satisfied.

For example, Korean Laid-Open Patent Application No. 2013-0134494 discloses C. I. Pigment Green 7 and C.I. Discloses a resin composition using Pigment Yellow 185, but has a drawback that it can not simultaneously satisfy both high luminance and high coloring property.

In the colored photosensitive resin composition, the heat resistance suppresses the occurrence of yellowing in a high temperature process, thereby maintaining high brightness even in a high temperature process, preventing development unevenness in the washing process, . Therefore, the heat resistance is a property that is very importantly required for improving the reliability of the colored photosensitive resin composition.

However, conventional techniques do not sufficiently satisfy the heat resistance required in the colored photosensitive resin composition.

Korea Patent Publication No. 2013-0134494

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems of the prior art,

A colored photosensitive resin composition which is excellent in heat resistance to prevent the occurrence of yellowing in a high temperature process and thereby maintains high brightness, prevents development unevenness in the washing process, and easily adjusts the taper angle of the color filter pixel coating film And to provide the above objects.

In addition, it is excellent in adhesion, maintains adhesiveness between a substrate and a resist even in a low-temperature firing step, prevents peeling of a coating film, improves the reliability of a panel in which a color filter and a TFT are adhered to each other, And does not generate a residual film or a residue after the exposure.

Another object is to provide a colored photosensitive resin composition excellent in luminance and coloring property and having high sensitivity.

Another object of the present invention is to provide a color filter including the colored photosensitive resin composition and an image display device including the same.

It is another object of the present invention to provide a method for producing a color filter using the above-mentioned colored photosensitive resin composition.

According to the present invention,

At least one selected from the group consisting of (A) a colorant, (B) an alkali-soluble resin, (C) a photopolymerizable compound, (D) a photopolymerization initiator, (E) a polyfunctional thiol compound and a silicone compound, and (F) ;

The colorant (A) is a colorant. Pigment Green 59, 62 and 63, and at least one pigment selected from the group consisting of pigments and dyes.

In addition,

There is provided a color filter including a coloring pattern made of the colored photosensitive resin composition.

In addition,

And an image display device including the color filter.

In addition,

And a step of forming a colored pattern by a low temperature baking process at 80 to 180 캜 using the colored photosensitive resin composition.

The colored photosensitive resin composition of the present invention is excellent in heat resistance to prevent the occurrence of yellowing in a high temperature process and thereby to maintain a high brightness. In addition, since the contact angle of the coating film against deionized water (DI) So that it is easy to adjust the taper angle of the color filter pixel coating film, and it is possible to easily solve the tapered step of the color pattern.

In addition, the colored photosensitive resin composition of the present invention is excellent in adhesion, and in particular, even in a low-temperature firing step, adhesion between the substrate and the resist is maintained to prevent peeling of the coating film and high temperature and high humidity Thereby preventing the occurrence of after-images and providing no residual film or residue after development.

Further, the colored photosensitive resin composition of the present invention has excellent brightness and coloring property and provides excellent sensitivity.

Further, the image display device of the present invention includes a color filter manufactured using the above-mentioned colored photosensitive resin composition, thus providing a high-resolution image.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. G58 or G7 is used as the colorant.

The present invention

At least one selected from the group consisting of (A) a colorant, (B) an alkali-soluble resin, (C) a photopolymerizable compound, (D) a photopolymerization initiator, (E) a polyfunctional thiol compound and a silicone compound, and (F) ;

The colorant (A) is a colorant. Pigment Green 59, 62 and 63, and at least one pigment selected from the group consisting of pigments and dyes.

Hereinafter, the colored photosensitive resin composition of the present invention will be described in detail for each component.

(A) Colorant

The colorant may be C.I. Pigment Green 59, 62 and 63, and at least one pigment selected from pigments and dyes.

(a1) pigment

The C.I. Pigment Green 59 has a characteristic comprising a compound represented by the following general formula (1). The compound represented by the following formula (1) has a structure of ZnPc (Zinc Phthalocyanine). When the colorant of the present invention includes a compound represented by the following formula (1), there is an advantage of high color reproduction.

[Chemical Formula 1]

In Formula 1, A ¹ to A ¹⁶ are each independently Cl, Br, or H, 1 to 6 of A ¹ to A ¹⁶ are H, 0 to 5 are Cl, and 5 to 13 are Br;

More preferably 1 to 6 are H, 0 to 5 are Cl, and 7 to 13 are Br;

More preferably 2 to 5 may be H, 0 to 3 may be Cl, and 8 to 13 may be Br. In this case, the effect of the present invention is advantageously maximized.

C.I. Pigment Green 58 (G58) has an advantage of high brightness, but in order to realize high coloring property, the pigment content is increased. When the pigment is contained in a large amount in the composition, the development is poor and the pattern formed by the composition And sensitivity may be lowered.

However, by using the pigment containing the compound represented by the formula (1) as a coloring agent, it is possible to design a resist of a color reproduction even if the content of the pigment is small. Pigment Green 59 may be the compound represented by Formula 1 itself.

The C.I. Pigment greens 62 and 63 can provide the same effects as in FIG. The C.I. Pigment Green 59 may be those manufactured by DIC Corporation of Japan, and C.I. Pigment greens 62 and 63 may be those manufactured by Toyoki Ink Corporation.

On the other hand, C.I. When Pigment Green 7 (G7) is included in the resin composition, it can exhibit high coloring property even if the pigment content is decreased, which is advantageous for use, but there is a problem of low luminance. However, the Pigment Green 59 contained in the colored photosensitive resin composition of the present invention contains C.I. Exhibits a transmission spectrum and color coordinates similar to those of Pigment Green 7, but also functions to exhibit excellent luminance included in the colored photosensitive resin composition. As can be seen in FIG. 1, the Pigment Green 59 has a C.I. Similar to Pigment Green 7, it has a transmission spectrum at a wavelength of 400 nm to 610 nm.

In the present specification, Tmax means the wavelength at which the transmittance of the pigment is maximum, and T50% means the wavelength at which the pigment transmittance is 50% or more of the maximum value.

In an embodiment of the present invention, the Tmax of the Pigment Green 59 may be 500 to 530 nm, which is preferable in terms of excellent coloring.

In another embodiment of the present invention, the T50% of the Pigment Green 59 may be in the range of 445 to 580 nm, which is preferable in terms of excellent coloring property.

The C.I. Pigment Green 59, 62 and 63 is preferably contained in an amount of 0.05 to 30% by weight, more preferably 0.05 to 25% by weight, based on the total weight of the solid components in the colored photosensitive resin composition of the present invention , More preferably from 0.05 to 20% by weight. When the compound of formula (1) is contained within the above range, it is preferable that the compound of the formula (1) is excellent in colorability and can express a high-brightness resist.

The coloring agent according to the present invention is a colorant. Pigment Green 59, 62, and 63, a pigment that is commonly used in the art as a component capable of expressing a color such as red, green, or blue so that a pattern having a desired color can be produced And dyes, and may be manufactured in the form of a mill base.

The C.I. Pigment Green 59, 62, and 63, and at least one pigment selected from the group consisting of pigments and dyes is preferably 1: 0.050 to 1: 18.0, more preferably 1: 0.1 to 1: 9, Preferably in a weight ratio of 1: 0.2 to 1: 4. If it is contained in the above-mentioned weight ratio, it is advantageous because it has advantages of high coloring property and high brightness, and has an advantage of improving process margin and sensitivity.

In this case, C.I. Pigment Green 59, 62 and 63 may have a color coordinate of x = 0.1 to 0.35 when y = 0.6 or more in the XYZ color system.

The pigments include organic pigments and inorganic pigments, which may be used alone or in combination of two or more. The use of an organic pigment may be more preferable in view of excellent heat resistance and color development. The organic pigment may be a synthetic pigment or a natural pigment.

The organic pigment may optionally be rosin treated; Surface treatment using a pigment derivative in which an acidic group or a basic group is introduced; Graft treatment on the surface of a pigment using a polymer compound or the like; Microparticulation treatment by sulfuric acid microparticle formation method or the like; Or cleaning treatment with an organic solvent or water to remove impurities; .

Examples of the inorganic pigments include metal compounds such as metal oxides and metal complex salts, and inorganic salts of barium sulfate (extender pigments). More specifically, the metal compounds include iron, cobalt, aluminum, cadmium, lead, , Oxides or complex metal oxides of metals such as magnesium, chromium, zinc, antimony and carbon black.

Specific examples of the pigment include compounds classified as pigments in the Color Index (The Society of Dyers and Colors), more specifically, the following color index (CI) numbers , But the present invention is not limited thereto. One or more kinds selected from them may be covalently dispersed using an alkali-soluble resin, a dispersing agent, or the like so as to match the desired chromaticity.

C.I. Specific examples of pigment yellow include C.I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 129, 137, 138 , 139, 147, 148, 150, 153, 154, 166, 173, 180, 185, 194 and 214;

C.I. Specific examples of pigment oranges include C.I. Pigment Orange 13, 31, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71 and 73;

C.I. Specific examples of Pigment Red include C.I. Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264 and 265 Have;

C.I. Specific examples of the pigment blue include C.I. Pigment Blue 15: 3, 15: 4, 15: 6, 16, 22, 28, 60 and the like;

C.I. Specific examples of pigment violet include C.I. Pigment Violet 14, 19, 23, 29, 32, 177 and the like,

C.I. Specific examples of pigment greens include C.I. Pigment Green 7, 36, 58 and the like

Among the pigments exemplified above, preferred is C.I. Pigment Yellow 138, C.I. Pigment Yellow 129, C.I. Pigment Yellow 150, C.I. Pigment < RTI ID = 0.0 > 185 < / RTI >

(a2) Dye

The dyes that can be included in the colorant of the present invention can be used without limitation as long as they are soluble or dispersible in an organic solvent. It is preferable to use a dye which has solubility in an organic solvent and can ensure reliability such as solubility in an alkali developing solution, heat resistance and solvent resistance. In the case of a dye having no solubility in an organic solvent, it may be dispersed and used.

The dye may be at least one selected from an acidic dye having an acidic group such as a sulfonic acid or a carboxylic acid, a salt of an acidic dye and a nitrogen-containing compound, a sulfonamide derivative of an acidic dye or the like, and derivatives thereof. In addition, azo dyes, xanthan dyes, phthalocyanine acid dyes and derivatives thereof may be selected.

The dye is preferably a compound classified as a dye in the color index (published by The Society of Dyers and Colourists), or a known dye described in a dyeing note (coloring yarn).

Specific examples of the dye include,

C.I. Solvent Yellow (Solvent Yellow) No. 2, C.I. Solvent Yellow No. 14, C.I. Solvent Yellow No. 16, C.I. Solvent Yellow No. 33, C.I. Solvent Yellow No. 34, C.I. Solvent Yellow No. 44, C.I. Solvent Yellow No. 56, C.I. Solvent Yellow No. 82, C.I. Solvent Yellow No. 93, C.I. Solvent Yellow No. 94, C.I. Solvent Yellow No. 98, C.I. Solvent Yellow No. 116, C.I. Solvent Yellow No. 135;

C.I. Solvent Orange (Solvent Orange) No. 1, C.I. Solvent Orange No. 3, C.I. Solvent Orange No. 7, C.I. Solvent Orange No. 63;

C.I. Solvent Red (Solvent Red) No. 1, C.I. Solvent Red No. 2, C.I. Solvent Red No. 3, C.I. Solvent Red No. 8, C.I. Solvent Red No. 18, C.I. Solvent Red No. 23, C.I. Solvent Red No. 24, C.I. Solvent Red No. 27, C.I. Solvent Red No. 35, C.I. Solvent Red No. 43, C.I. Solvent Red No. 45, C.I. Solvent Red No. 48, C.I. Solvent Red No. 49, C.I. Solvent Red 91: 1, C.I. Solvent Red No. 119, C.I. Solvent Red No. 135, C.I. Solvent Red No. 140, C.I. Solvent Red No. 196, C.I. Solvent Red No. 197;

C.I. Solvent Violet (Solvent Purple) No. 8, C.I. Solvent Purple No. 9, C.I. Solvent Purple No. 13, C.I. Solvent Purple No. 26, C.I. Solvent Purple No. 28, C.I. Solvent Purple No. 31, C.I. Solvent Purple No. 59;

C.I. Solvent Blue (Solvent Blue) No. 4, C.I. Solvent Blue No. 5, C.I. Solvent Blue No. 25, C.I. Solvent Blue No. 35, C.I. Solvent Blue No. 36, C.I. Solvent Blue No. 38, C.I. Solvent Blue No. 70;

C.I. Solvent Green (Solvent Green) No. 3, C.I. Solvent Green No. 5, C.I. Solvent Green No. 7, and the like.

The colorant (A) may be contained in an amount of 5 to 70% by weight, more preferably 10 to 50% by weight based on the total weight of the solid content in the colored photosensitive resin composition. If the content of the colorant is less than 5% by weight, the color-separating ability of the formed pattern may be deteriorated. If the content of the colorant exceeds 70% by weight, the lithographic performance may deteriorate,

In the present invention, the solid content in the colored photosensitive resin composition means the total content of the remaining components excluding the solvent from the colored photosensitive resin composition.

(B) an alkali-soluble resin

The alkali-soluble resin contained in the colored photosensitive resin composition of the present invention is a component that imparts solubility to the alkali developing solution used in the developing process. In the present invention, the alkali-soluble resin is not particularly limited, but is preferably a copolymer of a monomer having a carboxyl group and another monomer copolymerizable therewith.

The monomer having a carboxyl group is not particularly limited, and specific examples thereof include monocarboxylic acids such as acrylic acid, methacrylic acid and crotonic acid; Dicarboxylic acids such as fumaric acid, mesaconic acid and itaconic acid; Mono (meth) acrylates of a polymer having a carboxyl group and a hydroxyl group at both ends such as? -Carboxypolycaprolactone mono (meth) acrylate, and acrylic acid and methacrylic acid are more preferable. One or more of these can be selected and used.

The other copolymerizable monomer is not particularly limited as long as it is a monomer having a carbon-carbon unsaturated bond, and specific examples thereof include aromatic vinyl compounds such as styrene,? -Methylstyrene and vinyltoluene; Acrylates such as methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, benzyl acrylate, Unsaturated carboxylate compounds such as acrylate; Unsaturated aminoalkyl carboxylate compounds such as aminoethyl acrylate; Unsaturated glycidyl carboxylate compounds such as glycidyl methacrylate; Vinyl carboxylate compounds such as vinyl acetate and vinyl propionate; Vinyl cyanide compounds such as acrylonitrile, methacrylonitrile and? -Chloroacrylonitrile; 3-methyl-3-acryloxymethyloxetane, 3-methyl-3-acryloxymethyloxetane, 3-methyl-3-methacryloxymethyloxetane, Methyl-3-acryloxyethyl oxetane, 3-methyl-3-acryloxyethyl oxetane, 3-methyl-3-methacryloxyethyl oxetane, Unsaturated oxetanecarboxylate compounds, and the like. These monomers may be used alone or in combination of two or more.

According to the present invention, the molecular weight distribution of the alkali-soluble resin, that is, the weight average molecular weight (weight average molecular weight (Mw) / number average molecular weight (Mn)) relative to the number average molecular weight is preferably 1.5 to 6.0, more preferably 1.8 To 4.0 is preferable from the viewpoint of developability.

The acid value of the alkali-soluble resin is preferably 30 to 170 mgKOH / g, more preferably 50 to 150 mgKOH / g, based on the solid content. When the acid value of the alkali-soluble resin is less than 30 mgKOH / g, it is difficult to ensure a sufficient developing rate of the colored photosensitive resin composition. When the acid value exceeds 170 mgKOH / g, the adhesion with the substrate is reduced, There is a problem in compatibility with the coloring agent, so that the coloring agent in the colored photosensitive resin composition is precipitated, the storage stability of the colored photosensitive resin composition is lowered, and the viscosity is increased, which is not preferable.

The alkali-soluble resin (B) is preferably contained in an amount of 5 to 85% by weight, more preferably 10 to 70% by weight based on the total weight of the solid content in the colored photosensitive resin composition. When the content of the alkali-soluble resin is within the above range, solubility in a developing solution is sufficient, so that development residue does not easily occur on the substrate of the non-pixel portion, and film reduction of the pixel portion of the exposure portion is prevented at the time of development, It is preferable since the missing part of the part tends to be good

(C) Photopolymerization  compound

The photopolymerizable compound contained in the colored photosensitive resin composition of the present invention is a compound that can be polymerized by an active radical or an acid generated from a photopolymerization initiator (D) which will be described later by light irradiation and which can be polymerized by the action of a photopolymerization initiator It is not particularly limited as long as it is a compound. Preferably, monofunctional monomers, bifunctional monomers or trifunctional or more polyfunctional monomers can be used, and at least one monomer selected therefrom can be used.

Specific examples of the monofunctional monomer include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate or N- Examples of commercially available products include Aronix M-101 (Toagosei), KAYARAD TC-110S (Nippon Kayaku), and Viscot 158 (Osaka Yuki Kagaku Kogyo). It is not.

Specific examples of the bifunctional monomer include 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (Acryloyloxyethyl) ether of bisphenol A, 3-methylpentanediol di (meth) acrylate, propylene glycol dimethacrylate, urethane (meth) acrylate, AH-600, AT-1, and K-KAARAD HDDA (Nippon Kayaku), Viscoat 260 (Osaka Yuki Kagaku Kogyo Co., Ltd.) 600 or UA-306H (manufactured by Kyoeisha Chemical Co., Ltd.), but the present invention is not limited thereto.

Specific examples of the polyfunctional photopolymerizable compound having three or more functional groups include trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate (Meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol diacrylate, dipentaerythritol triacrylate, dipentaerythritol penta (Meth) acrylate, propoxylated dipentaerythritol hexa (meth) acrylate, and dipentaerythritol hexa (meth) acrylate. Commercially available products include Aronix M -309, TO-1382 (Toagosei), KAYARAD TMPTA, KAYARAD DPHA or KAYARAD DPHA-40H (Nippon Kayaku). .

Among the photopolymerizable compounds exemplified above, it is more preferable to use a multifunctional monomer having three or more functional groups. Since the (meth) acrylates and the urethane (meth) acrylates have excellent polymerizability and can improve the strength, desirable.

The photopolymerizable compound (C) is contained in an amount of 5 to 45% by weight, more preferably 10 to 35% by weight based on the total weight of the solid content of the colored photosensitive resin composition. When the photopolymerizable compound is contained within the above range, the strength and smoothness of the pixel portion are favorable, which is preferable.

(D) Light curing Initiator

The photopolymerization initiator can be used without limitation as long as it can polymerize the photopolymerizable compound. Preferably, the photopolymerization initiator is selected from the group consisting of an acetophenone compound, a benzophenone compound, a triazole compound, Based compound may be one or more compounds selected from the group consisting of acyclic compounds, non-imidazole-based compounds, oxime compounds and thioxanthone compounds.

Specific examples of the acetophenone-based compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 2-hydroxy- 1- [4- 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one, 2-methylcyclohexyl phenyl ketone, 2-methyl-1- [4- (1-methylvinyl) phenyl] propane-1-one 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one.

Specific examples of the benzophenone compound include benzophenone, methyl 0-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3 ', 4,4'- -Butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, and the like.

Specific examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6 - (4-methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, (Trichloromethyl) -6- [2- (5-methylfuran-2- (4-methoxystyryl) -1,3,5-triazine, Yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan- , 2,4- (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine, 2,4- ) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine.

Specific examples of the imidazole compound include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbimidazole, 2,2'-bis (2,3- Phenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (alkoxyphenyl) , 2,2'-bis (2,6-dichlorophenyl) -4,4 ', 5,5'-tetra (trialkoxyphenyl) 4 ', 5,5'-tetraphenyl-1,2'-biimidazole, or an imidazole compound in which the phenyl group at the 4,4', 5,5 'position is substituted by a carboalkoxy group .

More preferably, it is selected from the group consisting of 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3- , 4 ', 5,5'-tetraphenylbiimidazole, 2,2-bis (2,6-dichlorophenyl) -4,4', 5,5'-tetraphenyl- And the like.

Specific examples of the oxime compounds include o-ethoxycarbonyl-? -Oxyimino-1-phenylpropan-1-one and the like, and commercially available products may be OXE01 and OXE02 of BASF.

Specific examples of the thioxanthone compound include 2-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4- .

The content of the photopolymerization initiator (D) is preferably 0.1 to 40% by weight, more preferably 1 to 30% by weight based on the total weight of the solid components in the colored photosensitive resin composition. When the photopolymerization initiator is contained in the above range, the colored photosensitive resin composition is highly sensitized and the exposure time is shortened, so that productivity is improved and high resolution can be maintained. The strength of the pixel portion formed using the composition, So that the surface smoothness of the part becomes good.

(E) Multifunctional Thiol  At least one compound selected from a compound and a silicone compound

It is preferable that at least one selected from the polyfunctional thiol compound and the silicone compound is contained in an amount of 0.1 to 8% by weight based on the total weight of the solid content contained in the composition.

If less than 0.1% by weight of the polyfunctional thiol compound and / or the silicone compound is contained, the effect of maintaining the brightness at high temperature is not exhibited, the water repellency against DI is lowered and the unevenness may remain, The pattern may be short-circuited, and the reliability of the panel in which the color filter and the TFT are adhered may be influenced and a residual image may be generated. If it exceeds 5% by weight, the taper of the colored photosensitive resin composition coat may be attracted, which may make it difficult to form an accurate pattern, and a residual film or residue may be formed after development.

< Multifunctional Thiol  Compound &gt;

The polyfunctional thiol compound may be a mercapto compound as illustrated below. The mercapto compound may be selected from the group consisting of 4-mercaptohydrocinnamic acid, 4-mercaptobenzoic acid, thiosalicylic acid, 3,4-dimeroxybenzenethiol (3, 4-Dime thoxybenzenethiol, 3-Ethoxybenzenethiol, 4-Hydroxybenzenethiol, 3-Methoxybenzenethiol, 2-Hydroxybenzenethiol (2 Hydroxybenzenethiol, 4-methoxybenzenethiol, 3-hydroxybenzenethiol, 2-methoxybenzenethiol, methyl thiosalicylate, , 2,3,5,6-tetrafluoro-4-mercaptobenzoic acid, 2-mercaptobenzothiazole, 1,4-bis (3 -Mercaptopropionic acid, methyl 3-mercaptopropionate, 2-ethylhexyl 3-mercaptoate, 3-mercaptopropionate, Mercaptopropionate, n-octyl 3-mercaptopropionate, methoxybutyl 3-mercaptopropionate, stearyl 3-mercaptopropionate, 3-Mercaptopropionate), trimethylolpropane tris (3-mercaptopropionate), tris [3-mercaptopropionyloxy) -ethyl] (3-Mercaptopropionyloxy) -isocyanurate, pentaerythritol tetrakis (3-mercaptopropionate), tetraethylene glycol bis (3-mercaptopropionate) (3-mercaptopropionate), and dipentaerythritol hexakis (3-mercaptopropionate). The polyether polyol may be at least one selected from the group consisting of polyoxyethylene (polyoxyethylene / polyoxyethylene / polyoxyethylene / polyoxyethylene / There .

The polyfunctional thiol compound is preferably a polyfunctional thiol compound selected from the group consisting of trimethylolpropanetris (3-mercaptopropionate) and pentaerythritol hexakis (3-mercaptopropionate) represented by the following general formulas (2) ) [Pentaerythritol tetrakis (3-mercaptopropionate)].

(2)

(3)

The polyfunctional thiol compound may be contained in an amount of 0.1 to 5% by weight, more preferably 0.3 to 5% by weight based on the total weight of the solid content in the colored photosensitive resin composition. When the polyfunctional thiol compound is contained in the above range, the effect of maintaining the luminance at high temperature is excellent, the water repellency against DI in the wash zone after the development is excellent, and there is no unevenness, and the angle of the taper To provide the effect of dropping.

When the content is less than 0.1% by weight, the effect of maintaining the luminance at high temperature is not exhibited, the water repellency against DI is reduced and the unevenness remains. If the content exceeds 5% by weight, the taper of the colored photosensitive resin composition film is attracted , Accurate pattern formation may become difficult.

The colored photosensitive resin composition containing the polyfunctional thiol compound is excellent in heat resistance to prevent the occurrence of yellowing in a high temperature process and thereby to maintain a high brightness. In addition, the contact angle of the coating film with respect to DI water It is advantageous in preventing development unevenness, and it is possible to easily adjust the taper angle of the color filter pixel coating film, thereby making it easy to solve the tapered step of the color pattern.

&Lt; Silicon compound &

The silicone compound used in the present invention is added to improve the adhesion between the substrate and the resin film. As the substrate, a glass or plastic substrate can be used, and the colored photosensitive resin composition of the present invention can be more preferably used particularly when a plastic substrate is used.

That is, a plastic substrate such as polyethylene terephthalate can be used as a substrate of a flexible display. Since the substrate is elongated or shrunk during firing, the function as a display is impaired and the firing process is required to be lowered. However, in the case of a conventional colored photosensitive resin composition, if the temperature of the post-baking process is lowered in order to reduce the deformation of the substrate, the adhesion between the substrate and the resist decreases and the reliability (chemical resistance) . Furthermore, the reliability of the panel fabricated by bonding the color filter substrate and the TFT substrate to each other is affected, thereby causing a problem of afterimage.

However, when the colored photosensitive resin composition of the present invention containing the silicone compound is used, very good adhesion can be maintained even at low temperature baking, and thus it can be very usefully used for a plastic substrate.

The silicone compound may be represented by the following Formula 4:

 [Chemical Formula 4]

Wherein R1 and R2 are each independently selected from the group consisting of a glycidyl group, a (meth) acryloyl group, an aminopropyl group, a mercaptopropyl group, a cyano propyl group, a vinyl group, and an isocyanatopropyl group And R 2 is a hydrogen atom, a methyl group, an ethyl group or a hydroxy group, n is an integer of 1 to 20, and n is an integer of 1 to 3. The organic functional group is selected from the group consisting of a halogen atom, Lt; / RTI &gt;

It is more preferable that R1 is (meth) acryloyl group, though not limited thereto.

The silicone compound represented by Formula 4 may have a cage-type structure or a ladder-type structure prepared through a sol-gel process, or may be a mixture of these structures.

Particularly, when the cage-type structure and the ladder-type structure are mixed, a more preferable effect is provided.

Wherein the silicone compound is selected from the group consisting of vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3- aminopropylmethyldimethoxysilane, N- Aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4 -Epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, methacryloxymethyltriethoxysilane, methacryl 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, - acryloxypropyl trichlorosilane, etc., alone or in combination of two or more, - gel process.

Of these compounds, methacryloxymethyltriethoxysilane, methacryloxymethyltrimethoxysilane, 3-methacryloxypropyltrichlorosilane, methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane Acryloxypropyltrimethoxysilane, 3-acryloxypropyltrichlorosilane, and more preferably 3-methacryloxypropyltrimethoxysilane from a sol-gel process.

The silicone compound is preferably contained in an amount of 0.1 to 3% by weight, more preferably 0.3 to 2% by weight based on the total weight of the solid content in the colored photosensitive resin composition. If the content of the silicone compound is less than 0.1% by weight, adhesion between the substrate and the resist may be insufficient, resulting in a short circuit of the pattern. In addition, the reliability of the panel in which the color filter and the TFT are bonded affects the afterimage. If it exceeds 3 parts by weight, a residual film or residue may occur after development.

The colored photosensitive resin composition containing the silicone compound is excellent in adhesion, and can keep the adhesiveness between the substrate and the resist even when subjected to a low-temperature firing step to prevent peeling of the coating film. In addition, It is possible to improve the reliability in high humidity and not to cause after-images, and to provide an effect that no residual film or residue is generated after development.

(F) Solvent

The solvent used for dissolving other components of the colored photosensitive resin composition of the present invention is not particularly limited as long as it is a solvent used in a conventional colored photosensitive resin composition and may be used in the form of an ether, an aromatic hydrocarbon, a ketone, an alcohol Esters, amides and the like can be preferably 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 dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether and diethylene glycol dibutyl ether; Alkylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate; Alkylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate, 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; Esters such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate; cyclic esters such as? -Butyrolactone; Amides such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone.

An example thereof is ethyl 3-ethoxypropionate.

Among the solvents exemplified above, organic solvents having a boiling point of preferably 100 to 200 are preferable in view of the coating property and dry surface, more preferably alkylene glycol alkyl ether acetates, ketones, ethyl 3-ethoxypropionate , And methyl 3-methoxypropionate. More preferred are esters such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, ethyl 3-ethoxypropionate, 3-methoxypropionic acid Methyl and the like. These solvents may be used alone or in combination of two or more.

The content of the solvent (F) may be 40 to 90 wt%, preferably 40 to 80 wt%, based on the total weight of the colored photosensitive resin composition. When the solvent is contained in the above-described range, the coating property can be improved when applied by a coating device such as a roll coater, a spin coater, a slit and spin coater, a slit coater (sometimes referred to as a die coater), or an ink jet.

(G) Additive

The colored photosensitive resin composition of the present invention may further contain additives such as other polymer compounds, a curing agent, a surfactant, an adhesion promoter, an antioxidant, an anti-aggregation agent, and a pigment dispersant, if necessary.

Specific examples of the other polymer compound include a curable resin such as epoxy resin and maleimide resin, a thermoplastic resin such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, polyester, polyurethane and the like .

The curable resin is used for deep curing and for increasing mechanical strength. Specific examples of the curable resin include an epoxy compound, a polyfunctional isocyanate compound, a melamine compound, and an oxetane compound.

Specific examples of the epoxy compound in the curing agent include bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol F epoxy resin, hydrogenated bisphenol F epoxy resin, novolak epoxy resin, other aromatic epoxy resin, alicyclic epoxy resin Alicyclic or aromatic epoxy compounds, butadiene (co) polymeric epoxides and isoprene (co) polymers other than the brominated derivatives, epoxy resins and brominated derivatives of these epoxy resins, glycidyl ester resins, glycidyl amine resins, (Co) polymer epoxides, glycidyl (meth) acrylate (co) polymers, triglycidyl isocyanurate, and the like;

Specific examples of the oxetane compound include carbonate bisoxetane, xylene bisoxetane, adipate bisoxetane, terephthalate bisoxetane, and cyclohexanedicarboxylic acid bisoxetane.

The curing resin may be used in combination with a curing resin in combination with a curing auxiliary compound capable of ring-opening polymerization of the epoxy group of the epoxy compound and the oxetane skeleton of the oxetane compound. The curing assistant compound includes, for example, polyvalent carboxylic acids, polyvalent carboxylic anhydrides, and acid generators. The polyvalent carboxylic acid anhydrides may be those commercially available as an epoxy resin curing agent. Specific examples of the above-mentioned epoxy resin curing agent include epoxy resin curing agents such as epoxy resins, epoxy resins, epoxy resins, epoxy resins, epoxy resins, epoxy resins, Manufactured by Japan Ehwa Co., Ltd.). The curing agents exemplified above may be used alone or in combination of two or more.

The surfactant may be used to further improve film-forming properties of the photosensitive resin composition, and a fluorine-based surfactant or a silicone-based surfactant may be preferably used.

Examples of the silicone surfactant include DC3PA, DC7PA, SH11PA, SH21PA and SH8400 from Dow Corning Toray Silicone Co., Ltd. and TSF-4440, TSF-4300, TSF-4445, TSF-4446 and TSF-4460 , And TSF-4452. Examples of the fluorine-based surfactant include Megapis F-470, F-471, F-475, F-482 and F-489 commercially available from Dainippon Ink and Chemicals, Incorporated. The above-exemplified surfactants may be used alone or in combination of two or more.

The surfactant may be contained in an amount of usually 0.01 to 5% by weight, preferably 0.1 to 3% by weight based on the total weight of the solid content in the colored photosensitive resin composition.

As the adhesion promoter, silane compounds are preferable, and specific examples thereof include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3- Aminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, Propylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-chloropropyltrimethoxysilane, 3- Silane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatepropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, and the like. The adhesion promoters exemplified above may be used alone or in combination of two or more.

 The adhesion promoter may be contained in an amount of usually 0.01 to 10% by weight, preferably 0.05 to 2% by weight based on the total weight of the solid content in the colored photosensitive resin composition.

Specific examples of the antioxidant include 2-tert-butyl-6- (3- tert -butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, 2- [1- Butylphenyl) ethyl] -4,6-di-tert-pentylphenylacrylate, 6- [3- (3- tert -butyl-4-hydroxy- ] - 2,4,8,10-tetra-tert-butyldibenz [d, f] [1,3,2] dioxaphosphepin, 3,9-bis [2- {3- Butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, 2,2'-methylenebis 4-methylphenol), 4,4'-butylidenebis (6-tert-butyl-3-methylphenol), 4,4'-thiobis (2-tert- butyl- Phenol), 2,2'-thiobis (6-tert-butyl-4-methylphenol), dilauryl 3,3'-thiodipropionate, dimyristyl 3,3'-thiodipropionate, Distearyl 3,3'-thiodipropionate, pentaerythrityl tetrakis (3-laurylthiopropionate), 1,3,5-tris (3,5- Dihydroxybenzyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, 3,3 ', 3 " - (mesitylene-2,4,6-triyl) tri-p-cresol, pentaerythritol tetrakis [3- (3 Butylphenyl) propionate], 2,6-di-tert-butyl-4-methylphenol and 2,2'-thiobis (4-methyl-6-t -Butylphenol), 2,6-di-t-butyl-4-methylphenol and the like.

Specific examples of the anti-aggregation agent include sodium polyacrylate and the like.

The pigment dispersant is added to maintain the deagglomeration and stability of the pigment, and any of those generally used in the art can be used without limitation. An acrylate-based dispersant (hereinafter also referred to as an &quot; acrylic dispersant &quot;) containing butyl methacrylate (BMA) or N, N-dimethylaminoethyl methacrylate (DMAEMA) may be used. Dispersing BYK-2000, DISPER BYK-2001, DISPER BYK-2070, DISPER BYK-2150 and DISPER BYK LPN-6919 are examples of commercially available acrylate dispersants. The acrylic dispersants exemplified above may be used alone or in combination of two or more.

As the pigment dispersant, other resin type pigment dispersants other than the acrylic dispersant may be used.

Examples of the other resin type pigment dispersants include polycarboxylic acid esters represented by polyurethanes and polyacrylates, unsaturated polyamides, polycarboxylic acids, (partial) amine salts of polycarboxylic acids, polycarboxylic acids An alkylamine salt of a polycarboxylic acid, a polysiloxane, a long chain polyaminoamide phosphate salt, an ester of a hydroxyl group-containing polycarboxylic acid and a modified product thereof, or a polyester having a free carboxyl group and a poly An amide formed by the reaction of an alkyleneimine) or a salt thereof; Soluble resin or water-soluble polymer compound such as (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylate ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol or polyvinylpyrrolidone; Polyester; Modified polyacrylates; Adducts of ethylene oxide / propylene oxide, and phosphate esters.

DISPER BYK-161, DISPER BYK-162, DISPER BYK-163, DISPER BYK-160, DISPER BYK-160, and DISPER BYK-160 , DISPER BYK-166, DISPER BYK-171, DISPER BYK-182, DISPER BYK-184; EFKA-4060, EFKA-4060, EFKA-4055, EFKA-4055, EFKA-4055, EFKA-4020, EFKA-4015, EFKA-4060, EFKA- 4330, EFKA-4400, EFKA-4406, EFKA-4510, EFKA-4800; SOLSPERS-24000, SOLSPERS-32550, NBZ-4204/10 from Lubirzol; Hinoact T-6000, Hinoact T-7000, Hinoact T-8000; available from Kawaken Fine Chemicals; AJISPUR PB-821, Ajisper PB-822, Ajisper PB-823 manufactured by Ajinomoto; FLORENE DOPA-17HF, fluorene DOPA-15BHF, fluorene DOPA-33, and fluorene DOPA-44 are trade names of Kyoeisha Chemical Co.,

The pigment dispersant is preferably contained in an amount of 5 to 60 parts by weight, more preferably 10 to 50 parts by weight, based on 100 parts by weight of the solid content of the pigment (a1). If the content of the pigment dispersant is less than 5 parts by weight, it may be difficult to atomize the pigment or gelation after dispersion. If the content of the pigment dispersant is more than 60 parts by weight, the viscosity may be increased.

In addition,

A color filter made of the colored photosensitive resin composition, and an image display device including the color filter.

An image display apparatus of the present invention includes a color filter of the present invention including a substrate and a color layer. The image display apparatus includes a configuration known to those skilled in the art, except that the color filter is provided.

In addition,

And a step of forming a colored pattern by a low-temperature baking process at 80 to 180 캜 using the colored photosensitive resin composition of the present invention.

According to the above manufacturing method, adhesion of the base material and the resist is maintained even at a low temperature firing step, so that peeling of the coating film is prevented, and reliability in high temperature and high humidity of the panel in which the color filter and the TFT are adhered is improved.

A method of preparing the photosensitive resin composition of the present invention will be described as follows.

First, the pigment (a1) in the colorant (A) is mixed with the solvent (F) and dispersed using a bead mill or the like until the average particle diameter of the pigment becomes about 0.2 μm or less. At this time, if necessary, part or all of the alkali-soluble resin (B) may be dissolved or dispersed by mixing with some or all of (F) the solvent.

(B) an alkali-soluble resin, (C) a photopolymerizable compound, (D) a photopolymerization initiator, (E) a polyfunctional thiol compound and a silicone compound, and (F) To prepare a colored photosensitive resin composition according to the present invention.

Hereinafter, the present invention will be described in more detail with reference to examples. However, the embodiments of the present invention described below are illustrative, and the scope of the present invention is not limited to these embodiments.

In the following Examples and Comparative Examples, "%" and "part" representing the content are based on weight unless otherwise specified.

Synthetic example  1: Synthesis of Silicone Compound

80 ml of 3-methacryloxypropyltrimethoxysilane (MTMS: GE-Toshiba A-174) was placed in a reaction vessel equipped with a stirrer, a thermometer and a pH meter, and 5 ml of a malonic acid aqueous solution having a pH of 2.5 was mixed with 15 ml of methanol Was placed in a dropping funnel, and a mixed solution of methanol and malonic acid aqueous solution was added dropwise at room temperature over 30 minutes while stirring the reaction vessel. After completion of dropwise addition, the mixture was stirred for 2 hours while keeping the temperature at room temperature. After stirring for 2 hours, the solvent was removed under reduced pressure. Distilled water remaining with anhydrous magnesium sulfate was dehydrated and anhydrous magnesium sulfate was filtered off. In the above process, the finally obtained silicone compound is present in the form of a silicone sol which is a colorless viscous liquid exhibiting optimum performance for enhancing adhesion. One specific example of the above hydrolysis and condensation polymerization reaction can be represented by the following reaction formula.

[Reaction Scheme 1]

Synthetic example  2: Synthesis of Silicone Compound

In the same manner as in Synthesis Example 1 except that 3-methacryloxypropyltrimethoxysilane was changed to 3-glycidoxypropyltrimethoxysilane (GPTMS: GE-Toshiba A-187) in Synthesis Example 1, Compounds were synthesized.

Synthetic example  3: Synthesis of Silicone Compound

A silicone compound was synthesized in the same manner as in Synthesis Example 1 except that 3-methacryloxypropyltrimethoxysilane was changed to vinyltrimethoxysilane (VTMS: GE-Toshiba A-171).

Example  1 to 13 and Comparative Example  1 to 13: Preparation of colored photosensitive resin composition

The components shown in Tables 1 to 3 were mixed at the composition ratios to prepare colored photosensitive resin compositions.

division Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 (A) Colorant A-1 2.84 - 1.988 - - - - 2.84 2.84 2.84 4.9 A-2 - 2.84 1.988 2.15 - - - - - A-3 - - 0.852 0.852 0.92 3.4 - - - - - A-4 - - - - - 2.84 - - - - A-5 2.83 - - - A-6 2.83 2.83 - 2.6 3.3 2.83 2.83 2.83 2.83 1.8 A-7 - - 2.83 - - - - - - - - (B) an alkali-soluble resin B-1 4.1 4.1 4.1 4.18 4.14 3.07 4.1 4.04 4.2 4.25 3.07 (C) Photopolymerizable compound C-1 2.2 2.2 2.2 2.32 2.3 2.2 2.2 2.06 2.45 2.38 2.2 (D) a photopolymerization initiator D-1 1.2 1.2 1.2 1.24 1.3 1.2 1.2 1.1 1.25 1.47 1.2 (E) Multifunctional thiol compound E-1 0.6 0 0.4 0.0 0.36 0.6 0.4 0.7 0.008 0.0 0.6 E-2 0.0 0.6 0.2 0.36 0.0 0.0 0.2 0.2 0.006 0.0 0.0 (F) Solvent F-1 70.0 70 70 70 70 70 70 70 70 70 70 F-2 15 15 15 15 15 15 15 15 15 15 15 (G) Additive G-1 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 G-2 1.17 1.17 1.17 1.17 1.17 1.17 1.17 1.17 1.17 1.17 1.17 G-3 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 Sum 100 100 100 100 100 100 100 100 100 100 100

(Unit: wt%)

division Example 6 Example 7 Example 8 Example 9 Example 10 Example 11 Example 12 Example 13 The colorant (A) A-1 2.84 - 1.988 - - 2.84 2.84 2.84 A-2 - 2.84 1.988 2.15 - - A-3 - - 0.852 0.852 0.92 - - A-4 - - - - - - A-5 2.83 - A-6 2.83 2.83 - 2.6 2.83 2.83 2.83 A-7 - - 2.83 - - - - The alkali-soluble resin (B) B-1 4.15 4.15 4.05 4.15 4.15 4.15 4.15 4.15 The photopolymerizable compound (C) C-1 2.3 2.3 2.25 2.3 2.3 2.3 2.3 2.44 Photopolymerization initiator (D) D-1 1.34 1.34 1.34 1.34 1.34 1.34 1.34 1.34 The silicone compound (F) E-3 0.27 0 0.42 0.11 0.05 0 0 0 E-4 0 0.15 0 0 0 0.27 0 0.13 E-5 0 0.12 0 0.16 0.22 0 0.27 0 E-6 0 0 0 0 0 0 0 0 E-7 0 0 0 0 0 0 0 0 E-8 0 0 0 0 0 0 0 0 Solvent (G) F-1 70.0 70 70 70 70 70.0 70.0 70.0 F-2 15 15 15 15 15 15 15 15 Additive (E) G-1 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 G-2 1.22 1.22 1.22 1.22 1.22 1.22 1.22 1.22 Sum 100 100 100 100 100 100 100 100

(Unit: wt%)

division Comparative Example 7 Comparative Example 8 Comparative Example 9 Comparative Example 10 Comparative Example 11 Comparative Example 12 Comparative Example 13 (A) Colorant A-1 2.84 2.84 2.84 - 2.84 2.84 4.6 A-2 - - - - - - - A-3 - - - - - - - A-4 - - - 2.84 - - - A-5 - A-6 2.83 2.83 2.83 2.83 2.83 2.83 2.1 A-7 - - - - - - - (B) an alkali-soluble resin B-1 4.15 4.15 4.15 4.15 3.96 4.25 3.6 (C) Photopolymerizable compound C-1 2.3 2.3 2.3 2.3 2.11 2.47 1.82 (D) a photopolymerization initiator D-1 1.34 1.34 1.34 1.34 1.34 1.34 1.34 (E) Silicone compound E-3 0 0 0 0.27 0.65 0 0.27 E-4 0 0 0 0 0 0 0 E-5 0 0 0 0 0 0 0 E-6 0.27 0 0 0 0 0 0 E-7 0 0.27 0 0 0 0 0 E-8 0 0 0.27 0 0 0 0 Solvent (F) F-1 70 70 70 70 70 70 70 F-2 15 15 15 15 15 15 15 (G) Additive G-1 0.05 0.05 0.05 0.05 0.05 0.05 0.05 G-2 1.22 1.22 1.22 1.22 1.22 1.22 1.22 Sum 100 100 100 100 100 100 100

(Unit: wt%)

The ingredients used in Tables 1 to 3 are as follows:

A-1: 2 of Cl, 9 of Br, 5 of H (Tmax: 515 nm, T50%: 450 to 575 nm) (manufactured by DIC Corporation)

A-2: 3 of Cl, 8 of Br, 5 of H (Tmax: 510 nm, T50%: 445 to 570 nm)

A-3: G58 (the central atom of the structure represented by the formula (1) is Zn and A1 to A16 are H: 0 to 1, Cl: 0 to 1, Br: 14 to 16)

A-4: G7 (in the structure of formula (1), the central atom is Cu, A1 to A16 are H: 0 to 2, Cl: 14 to 16 mixture)

A-5: Y129 (manufacturer: DIC)

A-6: Y138 (manufacturer: BASF)

A-7: Y185 (manufactured by BS Corporation)

B-1: methacrylic acid: benzyl methacrylate = 31: 69 (molar ratio),

A copolymer of methacrylic acid and benzyl methacrylate having a weight average molecular weight of 30,000 and an acid value of 105 mgKOH / g

C-1: dipentaerythritol hexaacrylate (KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.)

D-1: OXE-01 (manufactured by Ciba)

E-1: TMMP [Trimethylolpropanetris (3mercaptopropionate)] (manufactured by Sakai Kagaku Co., Ltd.)

E-2: PEMP [Pentaerythritol tetrakis-3mercaptopropionate] (manufactured by Sakai Kagaku Co., Ltd.)

E-3: Synthesis Example 1

E-4: Synthesis Example 2

E-5: Synthesis Example 3

E-6: 3-methacryloxypropyltrimethoxysilane

E-7: 3-glycidoxypropyltrimethoxysilane

E-8: Vinyltrimethoxysilane

F-1: Propylene glycol monomethyl ether acetate

F-2: Ethyl 3-ethoxypropionate

G-1: Silicone surfactant (SH-8400)

G-2: Acrylic pigment dispersant (DISPER BYK-2001, manufactured by BYK)

G-3: adhesion promoter (3-methacryloxypropyltrimethoxysilane)

Test Example  1: Evaluation of physical properties of colored photosensitive resin composition

Color filters were prepared using the colored photosensitive resin compositions prepared in the following Examples 1 to 13 and Comparative Examples 1 to 13.

Each of the colored photosensitive resin compositions was coated on a glass substrate by a spin coating method, and then placed on a heating plate and held at a temperature of 100 for 3 minutes to form a thin film. Subsequently, a test photomask having a pattern for changing the transmittance in the range of 1 to 100% to a step-like pattern and a line / space pattern of 1 to 50 m was placed on the thin film and the distance between the test photomask and the test photomask was set to 100 m. Respectively. At this time, the ultraviolet light source was irradiated with a high pressure mercury lamp of 1 KW containing g, h and i lines at an illuminance of 100 mJ / cm 2, and no special optical filter was used. The thin film irradiated with ultraviolet rays was immersed in a KOH aqueous solution of pH 10.5 for 2 minutes to develop. The glass plate coated with the thin film was washed with distilled water, dried by blowing nitrogen gas, and heated in a 220 oven for 1 hour to prepare a color filter. The film thickness of the color filter prepared above was 2.0 mu m.

(Brightness), reliability (heat resistance and chemical resistance), development unevenness, taper angle, residual test, and PCT test of the color filter were measured and evaluated as follows, and the results are shown in Tables 4 and 5.

&Lt; Measurement of spectral (luminance)

The luminance and chromaticity coordinates were measured using a microscopic spectrophotometer (Model No. OSP-SP2000, Olympus).

Luminance criterion

○: Suitable for more than 47.0

X: Not satisfactory as less than 47.0

<Reliability - Heat resistance>

The substrate prepared as described above was left in an oven at 230 ° C. for 2 hours, and the color change (E * ab) was measured. At this time, the color characteristics before and after the heat resistance evaluation are confirmed by using a microscopic spectrophotometer (Model No. OSP-SP2000, Olympus).

The CIE color coordinate values before and after the evaluation were respectively measured and evaluated using the following equation (1) and evaluated according to the following evaluation criteria.

[Equation 1]

? E * ab = [(L *) ² + (a *) ² + (b *) ² ] 1/2

In the above equation (1), E * ab represents a color change, L * represents a lightness difference, a * represents a color difference between red and green, and b * represents a color difference between yellow and blue.

?:? E * ab = 2.0 or less

Δ: ΔE * ab = 2.0 or more and less than 3.0

×: ΔE * ab exceeding 3.0.

<Reliability - Chemical resistance>

The substrate prepared by the above-mentioned experimental method was immersed in NMP (N-methyl-2-pyrrolidone) solution for 30 minutes, and color change (E * ab) was measured.

At this time, color characteristics before and after immersion in NMP were confirmed by using a microscopic spectrophotometer (Model No. OSP-SP2000, Olympus).

The CIE color coordinate values before and after the evaluation were respectively measured and evaluated using the following equation (2) and evaluated according to the following evaluation criteria.

&Quot; (2) &quot;

? E * ab = [(L *) ² + (a *) ² + (b *) ² ] 1/2

In the above equation (1), E * ab represents a color change, L * represents a lightness difference, a * represents a color difference between red and green, and b * represents a color difference between yellow and blue.

Evaluation standard

?:? E * ab = 2.0 or less

Δ: ΔE * ab = more than 2.0 and less than 3.0

×: ΔE * ab exceeding 3.0.

<Development Unevenness>

By the above experimental method, DI was dropped on the developed substrate, and the contact angle was measured using a contact angle meter (Kruss: DSA-100).

○: Contact angle is 70 degrees or more

?: Contact angle of 60 degrees or more and less than 70 degrees

X: contact angle less than 60 degrees

<Taper angle evaluation>

The slope of the pattern on the cross section of the coated film was measured using the SEM.

○: Taper angle is less than 40 degrees

△: Taper angle is more than 40 degrees and less than 60 degrees

×: Taper angle is 60 degrees or more

< Residue  Test>

The periphery of the coating film of the pattern formed by the above-described method was observed using a 3D shape measuring microscope (VK-9500, Keyence) to confirm presence or absence of development residue on the substrate.

Evaluation standard

○: No residue on substrate

X: development residue on the substrate

&Lt; PCT TEST (Pressure Cooker Test) >

100 boards each having a size of 1 mm x 1 mm were stuck on the substrate having the coating film formed thereon under the following conditions under the following conditions and the peeled state after the peeling test with the adhesive tape was measured using an ultrasound 3D shape measuring microscope (VK- 9500, Keyence).

Evaluation condition

High temperature (120) / high humidity (100% humidity) / air pressure (2atm)

Evaluation standard

○: 100/100 (number of peeled blocks / total number of blocks) - Peeled off at all

?: 80/100 to 99/100

×: 0/100 to 79/100

Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Spectroscopy O O O O O X X O O O X responsibility
(Heat resistance) O O O O O O O O X X O Stain O O O O O X Δ X Δ Δ Δ Taper angle O O O O O O O O Δ X O The color coordinates (Gx, Gy) (0.262, 0.640)

Example 6 Example 7 Example 8 Example 9 Example 10 Example 11 Example 12 Example 13 Comparative Example 7 Comparative Example 8 Comparative Example 9 Comparative Example 10 Comparative Example 11 Comparative Example 12 Comparative Example 13 Spectroscopy O O O O O O O O O O O X X O O responsibility
(NMP) O O O O O O O O Δ Δ Δ O Δ O X Residual TEST O O O O O O O O O X X O O X O PCT TEST O O O O O O O O X Δ O Δ O O Δ The color coordinates (Gx, Gy) (0.262, 0.640)

It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit or scope of the invention. Do. 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 invention as defined by the appended claims.

Accordingly, the actual scope of the invention is defined by the appended claims and their equivalents.

Claims (11)

At least one selected from the group consisting of (A) a colorant, (B) an alkali-soluble resin, (C) a photopolymerizable compound, (D) a photopolymerization initiator, (E) a polyfunctional thiol compound and a silicone compound, and (F) ;
Wherein the colorant (A) comprises at least one selected from CI Pigment Green 59, 62, and 63, and at least one selected from pigments and dyes. The method according to claim 1,
Wherein the polyfunctional thiol compound (E) is at least one compound selected from the group consisting of 4-mercapto hydrocinnamic acid, 4-mercaptobenzoic acid, thiosalicylic acid, 3,4-dimeroxybenzenethiol, 3-ethoxybenzenethiol, , 3-methoxybenzenethiol, 2-hydroxybenzenethiol, 4-methoxybenzenethiol, 3-hydroxybenzenethiol, 2-methoxybenzenethiol, methylthiosalicylate, 2-mercaptobenzothiazole, 1,4-bis (3-mercaptobutyryloxy) butane,? -Mercaptopropionic acid, methyl 3-mercaptopropionate, 2 -Ethylhexyl 3-mercaptopropionate, n-octyl 3-mercaptopropionate, methoxybutyl 3-mercaptopropionate, stearyl 3-mercaptopropionate, trimethylolpropane tris (3- Mercaptopropionate), tris [3-mercaptopropionyloxy) -ethyl] -isocyanurate, pentaerythritol tetrakis (3-mercaptopropionate) (3-mercaptopropionate), and dipentaerythritol hexakis (3-mercapto propionate). In the present invention, it is preferable to use at least one selected from the group consisting of tetraethylene glycol bis By weight. The method of claim 2,
The polyfunctional thiol compound (E) is at least one selected from the group consisting of trimethylolpropane tris (3-mercaptopropionate) and pentaerythritol hexakis (3-mercaptopropionate) By weight based on the total weight of the colored photosensitive resin composition. The method according to claim 1,
The colored photosensitive resin composition according to (E), wherein the silicone compound comprises a compound represented by the following formula (4):
[Chemical Formula 4]

Wherein R1 and
In Formula 4,
R1 and R2 are each independently selected from the group consisting of a glycidyl group, a (meth) acryloyl group, an aminopropyl group, a mercaptopropyl group, a cyanopropyl group, a vinyl group, and an isocyanatopropyl group An aliphatic or aromatic hydrocarbon group having 1 to 20 carbon atoms and having either one organic functional group or any organic functional group selected from the group, R2 is a hydrogen atom, a methyl group, an ethyl group or a hydroxy group,
n is an integer of 1 to 13; The method according to claim 1,
At least one selected from the group consisting of CI Pigment Green 59, 62 and 63, and at least one selected from pigments and dyes is contained in a weight ratio of 1: 0.050 to 1: 18.0. The method according to claim 1,
The colored photosensitive resin composition preferably contains, relative to the total solid content of the composition,
(A) from 5 to 70% by weight of a colorant, (B) from 5 to 85% by weight of an alkali-soluble resin, (C) from 5 to 45% by weight of a photopolymerizable compound, from 0.1 to 40% by weight of a photopolymerization initiator, 0.1 to 8% by weight of at least one selected from a functional thiol compound and a silicone compound,
Based on the total weight of the colored photosensitive resin composition,
(F) 40 to 90% by weight of a solvent. The method according to claim 1,
Wherein the coloring photosensitive resin composition further comprises at least one additive selected from the group consisting of another polymer compound, a curing agent, a surfactant, an adhesion promoter, an aggregation inhibitor, and a pigment dispersant. The method according to claim 1,
Wherein the firing temperature of the colored photosensitive resin composition is 80 to 180 占 폚. A color filter comprising a coloring pattern made of the colored photosensitive resin composition according to any one of claims 1 to 8. An image display device comprising the color filter of claim 9. A process for producing a color filter, which comprises the step of forming a colored pattern by a low-temperature baking process at 80 to 180 캜 using the colored photosensitive resin composition of any one of claims 1 to 8.

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