KR20150088507A - The a colored photosensitive resin composition for forming the frontal light shielding layer of a display device - Google Patents

Abstract

The present invention relates to a photosensitive resin composition for forming the light-shielding layer of the front display device, and more particularly, the density of the photosensitive resin composition has a value of 0.5T ^1/3 to 2T ^1/2, made of the photosensitive resin composition And the optical density of the front light-shielding layer of the display device is 0.7 to 6.0. The present invention also relates to a photosensitive resin composition for forming a front light-shielding layer of a display device.
And T is the thickness of the front shading layer of the display device.

Description

[0001] The present invention relates to a photosensitive resin composition for forming a front light-shielding layer of a display device,

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composition for forming a front light shielding layer of a display device, and more particularly, to a composition for forming a front light shielding layer of a display device capable of minimizing warping of a substrate due to a difference in thermal expansion coefficient during a manufacturing process.

Generally, in order to improve the visibility of the display, the reflectance is decreased in the front edge of a display device such as an LCD (Liquid Crystal Display), a PDP (Plasma Display Panel), an OLED (Organic Light Emitting Diode) and an AMOLED (Active Matrix Organic Light Emitting Diode) And a bezel which is a front shading layer of a display device that performs a function of shielding light such that the inside of the display is not visible is formed. As a material of such a bezel part, a black coating composition is widely used in terms of function, but in recent years, a coating composition having various colors has been used in consideration of various taste of consumers and display.

Meanwhile, in recent years, the demand and supply of a display device driven by a touch method has been greatly expanded. Among the touch panels, there are a resistance method, an electrostatic method, a SAW method, and an infrared method depending on a driving method. Among them, an electrostatic method which is a method of sensing and driving static electricity generated in a human body is mainly used. In the past, in addition to the tempered glass corresponding to the front surface of the product, one or two separate inner glass plates or transparent films for vacuum-depositing the ITO pattern inside the tempered glass were inserted into the inner glass plate or the transparent film And then assembled to complete the touch panel. However, since the thickness of the touch panel becomes thick, a method of manufacturing a touch panel including a process of vacuum-depositing the ITO pattern directly on tempered glass has been widely adopted. In this method, a bezel portion as a light shielding layer is formed on the tempered glass, and an ITO pattern is directly formed. Accordingly, the bezel portion formed in the tempered glass is exposed to chemical agents in a process such as lithography for forming a pattern of the ITO electrode, and is exposed to a high temperature during the heat treatment of the ITO electrode.

In the heat treatment process, contraction due to high temperature occurs, and the touch panel is bent. As a result, defects such as breakage may be caused in the manufacturing process of the product, and defects such as excessive size and adherence may occur due to deterioration of adhesion. Therefore, it is necessary to study a photosensitive resin composition for forming a front light-shielding layer of a display device which can prevent such a bending of the touch panel.

Korean Patent Publication No. 10-2008-0005412 Korean Patent Publication No. 10-2013-0115410

The present invention relates to a photosensitive resin composition for forming a front light shielding layer of a display device capable of minimizing warping of a substrate due to shrinkage of a light shielding layer in a curing step when a light shielding layer is formed by coating a photosensitive resin composition on a front surface of a display device The purpose is to provide.

Another object of the present invention is to provide a display device including a front shading layer formed by coating a photosensitive resin composition for forming a front shading layer of the display device on a substrate.

In order to achieve the above object,

The invention as a front light-shielding layer formed in the photosensitive resin composition for a display device, the density of the photosensitive resin composition is 0.5T ^1/3 to 2T ^1/2 has a value of, the front light-shielding of the display device manufactured with the photosensitive resin composition And the optical density of the layer is 0.7 to 6.0. The present invention also provides a photosensitive resin composition for forming a front light-shielding layer of a display device.

And T is the thickness of the front shading layer of the display device.

The present invention also provides a display device including a front shading layer formed by coating a photosensitive resin composition for forming a front shading layer of the display device on a substrate.

When the front light-shielding layer is formed of the photosensitive resin composition for forming the front light-shielding layer of the display device of the present invention, the deflection of the substrate generated during the curing process in the manufacturing process can be minimized and the defective rate can be reduced, have.

Hereinafter, the present invention will be described in more detail.

The present invention provides a display device made of a light-shielding layer having the front forming the photosensitive resin composition, more particularly the value of the density of the photosensitive resin composition is 0.5T ^1/3 to 2T ^1/2 of the display device, wherein the photosensitive resin composition And the optical density of the front shading layer of the display device is 0.7 to 6.0. Value of the front light-shielding layer density of the photosensitive resin composition for the formation of the display device 0.5T ^1/3 to 2T ^1/2 is more preferably having a value of from 0.9 to 3.0.

And T is the thickness of the front shading layer of the display device.

The front light-shielding layer of the photosensitive resin composition for forming a display device of the present invention is a shrinkage of the light-shielding layer from the front light-shielding layer during manufacture, the curing step of the display device because it has a value of the density of 0.5T ^1/3 to 2T ^1/2 It is possible to prevent defects such as dimensional change of the substrate manufactured after curing, deterioration of adhesion and pattern peeling. When the substrate is placed on a uniform platen, it is preferable to measure the maximum height of the four corners from the bottom to judge the degree of curl, and to measure the value to 400 m or less.

The optical density of the light-shielding layer made of the photosensitive resin composition for forming the front light-shielding layer of the display device of the present invention has a close correlation with the thickness of the light-shielding layer. Optical density is a measure of the degree to which light passes through or reflects from the inside of a material. It refers to the amount of light that has a constant intensity after the light passes through the light-shielding layer and has a constant intensity.

[Equation 1]

_{D = log 10 (I0 / I} ) = log 10 (1 / T) = εcd

Wherein? Is a molar extinction coefficient,

C is the molar concentration of the solution,

D is the thickness of the liquid layer.

The above equation (1) is a Lambert-Beer law. When the above rule holds, log ₁₀ (I0 / I) = epsilon cd is established. Therefore, at the same concentration, the optical density increases as the thickness of the light-shielding layer becomes thicker.

If the optical density of the front light-shielding layer of the display device made of the photosensitive resin composition for forming the front light-shielding layer of the display device of the present invention is less than 0.7, light is transmitted through the rear surface of the light-shielding layer, Exceeds 6.0, the pigment concentration is excessively used and the process characteristic becomes difficult.

The light-sensitive resin composition for forming the front light-shielding layer of the display device of the present invention includes a colorant, an alkali-soluble binder resin, a photopolymerizable compound, a polymerization initiator and a solvent.

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

(A) Colorant

The colorant may include all pigments or dyes capable of realizing color, and those generally used in the art may be used. The colorant may be, but is not necessarily limited to, compounds classified as pigments or dyes in the color index (The Society of Dyers and Colourists). These may be used alone or in combination of two or more.

( a1 ) Pigment

The pigment may be an organic pigment or an inorganic pigment generally used in the art. The pigment may be subjected to a surface treatment using a pigment treatment, a pigment derivative into which an acidic group or a basic group is introduced, a graft treatment of the surface of the pigment with a polymer compound, an atomization treatment using a sulfuric acid atomization method or the like, A cleaning treatment with an organic solvent or water, or a treatment for removing ionic impurities by ion exchange or the like.

The organic pigments may be various pigments used in printing ink, ink jet ink, etc. Specific examples thereof include water-soluble azo pigments, insoluble azo pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, isoindoline pigments, A pyranthrone pigment, a diketopyrrolopyrrole pigment, an anthraquinone pigment, an anthraquinone pigment, an anthrone pigment, an anthrone pigment, an indanthrone pigment, a pravanthrone pigment, a pyranthrone pigment, a diketopyrrolopyrrole pigment And the like.

As the inorganic pigment, metal compounds such as metal oxides and metal complex salts can be used. Specific examples of the inorganic pigments include iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony, A black pigment, a titanium black, and an oxide of a metal such as a pigment that mixes red, green, and blue to give a black color, or a composite metal oxide.

Particularly, the organic pigments and inorganic pigments may be specifically classified into pigments in the Society of Dyers and Colourists, and more specifically, those having a color index (CI) number Pigments, but are not limited thereto.

C.I. Pigment White 4, 5, 6, 6: 1, 7, 18, 18: 1, 19, 20, 22, 25, 26, 27, 28 and 32;

C.I. Pigment Yellow 13, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 180 And 185;

C.I. Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, and 71;

C.I. Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 208, 215, 216, 224, 242, 254, 255 and 264;

C.I. Pigment Violet 14, 19, 23, 29, 32, 33, 36, 37 and 38;

C.I. Pigment Blue 15 (15: 3, 15: 4, 15: 6, etc.), 21, 28, 60, 64 and 76;

C.I. Pigment Green 7, 10, 15, 25, 36, 47 and 58;

C.I. Pigment Brown 28;

And C.I. Pigment Black 1 and 7 pigments.

The pigment is preferably a pigment dispersion in which the particle diameter of the pigment is uniformly dispersed. Examples of a method for uniformly dispersing the particle diameter of the pigment include a method of dispersing the pigment dispersion (a2) by containing the pigment dispersant (a2), and a pigment dispersion in which the pigment is uniformly dispersed in the solution can be obtained have.

( a2 ) Pigment Dispersant

The pigment dispersant is added for the purpose of deaggregation of the pigment and maintenance of stability. Specific examples of the pigment dispersant include surfactants such as silicone, fluorine, cationic, anionic, nonionic, amphoteric, polyester, and polyamine These may be used alone or in combination of two or more.

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 Megaface F-470, F-471, F-475, F-482 and F-489 commercially available from Dainippon Ink and Chemicals, Incorporated. Other commercially available products include KP (Shinetsugaku Kagaku Kogyo Co., Ltd.), POLYFLOW (Kyoeisha Chemical Co., Ltd.), EFTOP (manufactured by TOKEM PRODUCTS CO., LTD.), MEGAFAC Asoui guard, Surflon (available from Asahi Glass Co., Ltd.), SOLSPERSE (Lubrisol) (available from Dainippon Ink and Chemicals Inc.), Flourad (Sumitomo 3M Co., Ltd.) , EFKA (EFKA Chemical), PB 821 (Ajinomoto), and Disperbyk-series (BYK-chemi).

Specific examples of the cationic surfactant include amine salts such as stearylamine hydrochloride and lauryltrimethylammonium chloride, and quaternary ammonium salts.

Specific examples of the anionic surfactant include higher alcohol sulfuric acid ester salts such as sodium lauryl alcohol sulfate ester and sodium oleyl alcohol sulfate ester, alkylsulfates such as sodium laurylsulfate and ammonium laurylsulfate, sodium dodecylbenzenesulfonate, And alkylarylsulfonic acid salts such as sodium dodecylnaphthalenesulfonate.

Specific examples of the nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene aryl ethers, polyoxyethylene alkyl aryl ethers, other polyoxyethylene derivatives, oxyethylene / oxypropylene block copolymers, sorbitan fatty acid esters, Polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid esters, glycerin fatty acid esters, polyoxyethylene fatty acid esters, and polyoxyethylene alkylamines.

In addition, polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid modified polyesters, tertiary amine-modified polyurethanes, and polyethyleneimines .

The pigment dispersant is used in an amount of 1 part by weight or less, preferably 0.05 to 0.5 part by weight, based on 1 part by weight of the solid content of the pigment. When the above pigment dispersant is used in the same amount as above, a pigment dispersed with a uniform particle diameter can be obtained.

( a3 )dyes

The dye can be used without limitation as long as it has solubility 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.

Examples of the dye include acid dyes having an acidic group such as a sulfonic acid and a carboxylic acid, salts of an acidic dye and a nitrogen-containing compound, sulfonamides of an acidic dye and derivatives thereof, and azo, xanthate, phthalocyanine Based acid dyes and their derivatives can also be selected. Preferably, the dye is 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 (color dyeing).

Specific examples of the dye include C.I. As solvent dyes,

C.I. Solvent Red 8, 45, 49, 89, 111, 122, 125, 130, 132, 146 and 179;

C.I. Solvent Blue 5, 35, 36, 37, 44, 45, 59, 67 and 70;

C.I. Solvent Violet 8, 9, 13, 14, 36, 37, 47 and 49;

C.I. Solvent Yellow 4, 14, 15, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99 and 162;

C.I. Solvent Orange 2, 7, 11, 15, 26 and 56;

C.I. Solvent Green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34 and 35.

Also, C.I. As an acid dye

CI Acid Red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 66, 73, 80, 87, 88 , 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 182, 183, 198, 206, 211, 215, 216, 217 , 227, 228, 249, 252, 257, 258, 260, 261, 266, 268, 270, 274, 277, 280, 281, 195, 308, 312, 315, 316, 339, 341, 345, 346, 349 , 382, 383, 394, 401, 412, 417, 418, 422 and 426;

CI Acid Yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112 , 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184 , 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243 and 251;

C.I. Acid Orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 169 and 173;

CI Acid Blue 1, 7, 9, 15, 18, 23, 25, 27, 29, 40, 42, 45, 51, 62, 70, 74, 80, 83, 86, 87, 90, , 112, 113, 120, 129, 138, 147, 150, 158, 171, 182, 192, 210, 242, 243, 256, 259, 267, 278, 280, 285, 290, 296, 315, , 335 and 340;

C.I. Acid Violet 6B, 7, 9, 17, 19 and 66;

Dyes such as C.I. Acid Green 1, 3, 5, 9, 16, 25, 27, 50, 58, 63, 65, 80, 104, 105, 106 and 109.

Further, as a C.I. direct dye,

CI Direct Red 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176, 177, 179, 181, 182, 184, 204, 207, 211 , 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246 and 250;

CI Direct Yellow 2, 33, 34, 35, 38, 39, 43, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129 , 136, 138 and 141;

C.I. Direct Orange 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106 and 107;

CI Direct Blue 38, 44, 57, 70, 77, 80, 81, 84, 85, 86, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113 , 114, 115, 117, 119, 137, 149, 150, 153, 155, 156, 158, 159, 160, 161, 162, 163, 164, 166, 167, 170, 171, 172, 173, 188, 189 , 190, 192, 193, 194, 196, 198, 199, 200, 207, 209, 210, 212, 213, 214, 222, 228, 229, 237, 238, 242, 243, 244, 245, 247, 248 , 250, 251, 252, 256, 257, 259, 260, 268, 274, 275 and 293;

C. I. Direct Violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103 and 104;

Dyes such as C.I. Direct Green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79 and 82

Also, as C.I. modantoic dyes,

CI. Modetto Yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62 and 65;

CI Modal Red 1, 2, 3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 30, 32, 33, 36, 37, 41, 43, 45, 46, 48, 53, 56, 63, 71, 74, 85, 86, 88, 90, 94 and 95;

C. I. Modanto orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47 and 48;

CI Modanito Blue 1, 2, 3, 7, 8, 9, 12, 13, 15, 16, 19, 20, 21, 22, 23, 24, 26, 30, 31, 32, 39, 43, 44, 48, 49, 53, 61, 74, 77, 83 and 84;

C. I. Modanth violet 1, 2, 4, 5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53 and 58;

Dyes such as C.I. Modatto Green 1, 3, 4, 5, 10, 15, 19, 26, 29, 33, 34, 35, 41, 43 and 53.

These dyes may be used alone or in combination of two or more.

The colorant is contained in an amount of 10 to 90% by weight, and more preferably 20 to 80% by weight based on the total weight of the solid content of the photosensitive resin composition for forming the front light shielding layer of the display device. When the front light-shielding layer of the display device is manufactured using the photosensitive resin composition for forming the front light-shielding layer of the display device of the present invention within the above-mentioned range, the warpage of the substrate can be improved during the process, have.

In the present invention, the solid content refers to a component excluding a solvent.

(B) an alkali-soluble binder resin

The alkali-soluble binder resin can be used in the present invention without any particular limitation as long as it is soluble in the solvent of the present invention, functions as a binder resin for the colorant, and is soluble in an alkaline developer. The alkali-soluble binder resin includes, for example, a copolymer of a carboxyl group-containing monomer and another monomer copolymerizable with the carboxyl group-containing monomer.

Examples of the carboxyl group-containing monomer include unsaturated carboxylic acids such as unsaturated polycarboxylic acids having at least one carboxyl group in the molecule such as unsaturated monocarboxylic acid, unsaturated dicarboxylic acid and unsaturated tricarboxylic acid. .

Examples of the unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, crotonic acid,? -Chloroacrylic acid and cinnamic acid. Examples of the unsaturated dicarboxylic acid include maleic acid, fumaric acid, itaconic acid, citraconic acid and mesaconic acid. The unsaturated polycarboxylic acid may be an acid anhydride, and specific examples thereof include maleic anhydride, itaconic anhydride and citraconic anhydride. The unsaturated polycarboxylic acid may also be mono (2-methacryloyloxyalkyl) ester, and examples thereof include mono (2-acryloyloxyethyl) succinate, mono (2-methacryloyloxyethyl) ), Phthalic acid mono (2-acryloyloxyethyl), and phthalic acid mono (2-methacryloyloxyethyl). The unsaturated polycarboxylic acid may be a mono (meth) acrylate of a dicarboxylic polymer at both ends, and examples thereof include ω-carboxypolycaprolactone monoacrylate and ω-carboxypolycaprolactone monomethacrylate. . The carboxyl group-containing monomers may be used alone or in combination of two or more.

Examples of other monomers copolymerizable with the carboxyl group-containing monomer include styrene,? -Methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-chlorostyrene, o- P-methoxy styrene, o-vinyl benzyl methyl ether, m-vinyl benzyl methyl ether, p-vinyl benzyl methyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, Aromatic vinyl compounds such as vinylbenzyl glycidyl ether and indene;

Methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, i-propyl acrylate, i-propyl methacrylate, butyl methacrylate, i-butyl acrylate, i-butyl methacrylate, sec-butyl acrylate, sec-butyl methacrylate, t-butyl acrylate, t-butyl methacrylate, Ethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, 3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, Acrylate, benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, phenyl acrylate, phenyl methacrylate, 2-methoxyethyl acrylate, 2-methoxyethyl Methacrylate, 2-phenoxyethyl acrylate, 2-phenoxyethyl methacrylate, methoxy diethylene glycol acrylate, methoxy diethylene glycol methacrylate, methoxy triethylene glycol acrylate, methoxy triethylene glycol methacrylate Acrylate, methoxypropylene glycol methacrylate, methoxypropylene glycol acrylate, methoxydipropylene glycol methacrylate, isobornyl acrylate, isobornyl methacrylate, dicyclopentadiene Acrylate, dicyclopentadiethyl methacrylate, 2-hydroxy-3-phenoxy Acrylate, 2-hydroxy-3-phenoxypropyl methacrylate, unsaturated carboxylic acid esters such as glycerol monoacrylate and glycerol monomethacrylate;

Aminoethyl methacrylate, 2-aminoethyl methacrylate, 2-dimethylaminoethyl acrylate, 2-dimethylaminoethyl methacrylate, 2-aminopropyl acrylate, 2-aminopropyl methacrylate, 2- Unsaturated carboxylates such as methyl acrylate, ethyl acrylate, propyl methacrylate, isopropyl acrylate, isopropyl acrylate, isopropyl acrylate, isopropyl acrylate, isopropyl acrylate, Acid amino alkyl esters;

Unsaturated carboxylic acid glycidyl esters such as glycidyl acrylate and glycidyl methacrylate;

Carboxylic acid vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate and vinyl benzoate;

Unsaturated ethers such as vinyl methyl ether, vinyl ethyl ether and allyl glycidyl ether;

Vinyl cyanide compounds such as acrylonitrile, methacrylonitrile,? -Chloroacrylonitrile and vinylidene cyanide;

Unsaturated amides such as acrylamide, methacrylamide,? -Chloroacrylamide, N-2-hydroxyethyl acrylamide and N-2-hydroxyethyl methacrylamide;

Unsaturated imides such as maleimide, N-phenylmaleimide and N-cyclohexylmaleimide;

Aliphatic conjugated dienes such as 1,3-butadiene, isoprene and chloroprene; And

Having a monoacryloyl group or monomethacryloyl group at the end of the polymer molecular chain of polystyrene, polymethyl acrylate, polymethyl methacrylate, poly-n-butyl acrylate, poly-n-butyl methacrylate and polysiloxane Macromers and the like. These monomers may be used alone or in combination of two or more.

Thus, the copolymer of the carboxyl group-containing monomer and other monomer copolymerizable with the alkali-soluble binder resin includes, for example, (meth) acrylic acid / methyl (meth) acrylate copolymer, (meth) acrylic acid / benzyl (Meth) acrylic acid / methyl (meth) acrylate / polystyrene macromonomer copolymer, (meth) acrylic acid / benzyl (meth) acrylate copolymer, Acrylic acid / benzyl (meth) acrylate / polystyrene macromonomer copolymer, (meth) acrylic acid / benzyl (meth) acrylate / polymethyl (meth) acrylate macromonomer copolymer, Polymethyl (meth) acrylate macromonomer copolymer, (meth) acrylic acid / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / polystyrene macromolecule (Meth) acrylate / benzyl (meth) acrylate / polymethyl (meth) acrylate macromonomer copolymer, (meth) acrylic acid / styrene / Acrylate / N-phenylmaleimide copolymer, (meth) acrylic acid / succinic acid mono (2-acryloyloxy) Acrylic acid / benzyl (meth) acrylate / N-phenylmaleimide / styrene / glycerol mono (meth) acrylate / mono (2-acryloyloxyethyl) / styrene / (Meth) acrylate copolymer, and the like.

Of these, (meth) acrylic acid / benzyl (meth) acrylate copolymer, (meth) acrylic acid / benzyl (meth) acrylate / styrene copolymer, (meth) acrylic acid / methyl / Methyl (meth) acrylate / styrene copolymer can be preferably used.

In the case where the alkali-soluble binder resin is a copolymer of a carboxyl group-containing monomer and another monomer capable of copolymerizing with the carboxyl group-containing monomer, the content ratio of the constituent unit derived from the carboxyl group- By weight, preferably 25 to 40% by weight, based on the total weight of the composition. When the content ratio of the constituent unit derived from the carboxyl group-containing monomer is 10 to 50% by weight based on the above-mentioned criteria, solubility in a developing solution is good and a pattern is accurately formed at the time of development.

The alkali-soluble binder resin is not particularly limited, but preferably has a weight average molecular weight in terms of polystyrene of 3,000 to 100,000, more preferably 3,000 to 50,000, and still more preferably 5,000 to 50,000. When the weight average molecular weight of the alkali-soluble binder resin is in the range of 3,000 to 100,000, the colorant is easily dispersed, the viscosity is low, and the storage stability is excellent.

The content of the alkali-soluble binder resin is 3 to 80% by weight, preferably 5 to 70% by weight, based on the solid content in the photosensitive resin composition for forming the front light-shielding layer of the display device. When the content of the alkali-soluble binder resin is in the range of 3 to 80% by weight, the colorant is easily dispersed and the storage stability is excellent.

(C) Photopolymerization  compound

The photopolymerizable compound contained in the photosensitive resin composition for forming the front light-shielding layer of the display device of the present invention is a compound capable of polymerizing under the action of light and a polymerization initiator (D) described later, and includes monofunctional monomers, bifunctional monomers, Polyfunctional monomers and the like.

The photopolymerizable compound to be used in the present invention is a compound having two or more functional groups which are different in the structure or functional group of the functional group to improve the developability, sensitivity, adhesion and surface problems of the photosensitive resin composition for forming the front light- Can be used in combination, and the range is not limited

The monofunctional monomer may be, for example, nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate and N- Ralidon, and the like. Commercially available products include Aronix M-101 (Toagosei), KAYARAD TC-110S (Nippon Kayaku) and Biscoat 158 (Osaka Yuki Kagaku Kogyo).

The bifunctional monomer may be, for example, 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (Acryloyloxyethyl) ether of bisphenol A and 3-methylpentanediol di (meth) acrylate. Commercially available products include Aronix M-210, M-1100 and 1200 (Doagosei) KAYARAD HDDA (Nippon Kayaku), Viscoat 260 (Osaka Yuki Kagaku Kogyo), AH-600, AT-600 and UA-306H (Kyoeisha Chemical Co., Ltd.).

The other polyfunctional monomer may be, for example, 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 penta (meth) acrylate, ethoxylated dipentaerythritol hexa (Meth) acrylate, dipentaerythritol hexa (meth) acrylate and dipentaerythritol hexa (meth) acrylate. Commercially available products include Aronix M-309, TO-1382 (Toagosei), KAYARAD TMPTA, KAYARAD DPHA and KAYARAD DPHA-40H (Nippon Kayaku).

In the present invention, the photopolymerizable compound is preferably a polyfunctional monomer having two or more functional groups.

The photopolymerizable compound is used in a range of 1 to 60% by weight, preferably 5 to 50% by weight based on the total weight of the solid content in the photosensitive resin composition for forming the front light shielding layer of the display device. When the photopolymerizable compound is in the range of 1 to 60% by weight, the strength and smoothness of the pixel portion of the substrate are favorable.

(D) polymerization Initiator

The polymerization initiator can be used without particular limitation as long as it is used in the art, and specific examples thereof include a triazine-based compound, an acetophenone-based compound, a phosphine oxide-based compound, a thioxanthone-based compound, , An organic peroxide, and an azo compound may be used.

Examples of the triazine-based compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4- (Trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4-bis (trichloromethyl) Bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) -Yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan- Azine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine and 2,4- Methyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine.

The acetophenone-based compounds include, for example, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 2- (4-methylthioxy) phenyl] -2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2- 2-methyl-1- [4- (1-methylvinyl) phenyl] propane-1-one, 1-one and 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one.

Examples of the phosphine oxide compound include 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide.

The non-imidazole compounds include, for example, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbimidazole, 2,2'-bis -Dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4' Imidazole, 2,2'-bis (2,6-dichlorophenyl) - 4,4 ', 5,5'-tetra (trialkoxyphenyl) 4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole and imidazole compounds in which the phenyl group at the 4,4', 5,5 'position is substituted by a carboalkoxy group have. Among the imidazole compounds, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3- 4,4 ', 5,5'-tetraphenylbiimidazole and 2,2-bis (2,6-dichlorophenyl) -4,4'5,5'-tetraphenyl-1,2'-biimidazole Is preferably used.

The thioxanthone compound may be, for example, 2-isopropylthioxanecone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone and 1-chloro-4- .

Examples of the oxime compounds include o-ethoxycarbonyl-α-oximino-1-phenylpropan-1-one and OXE01 and OXE02 of BASF Corporation.

The organic peroxide may be, for example, o-chloro benzoyl peroxide, o-methoxy benzoyl peroxide, lauroyl peroxide, peroctanoyl peroxide, methyl ethyl ketone peroxide, diisopropyl peroxydicarbonate, Non-hydroxide, t-butyl hydroperoxide and diisopropylbenzene hydroperoxide.

These organic peroxides may be used alone or in combination of two or more. Among the above organic peroxides, it is preferable to use an organic peroxide having an aliphatic alkyl structure (organic peroxide having an alicyclic alkyl structure) without having a benzene ring structure. When the organic peroxide having a benzene ring structure is used, the decomposition product of the organic peroxide may adversely affect the heat resistance yellowing of the (meth) acrylic crosslinked microparticles. In particular, the degradation product of the benzoyl peroxide affects the heat resistance yellowing of the crosslinked microparticles give.

Azo-based compounds include, for example, 2,2'-azobis (2-methyl-N-phenylpropionamidine) dihydrochloride, 2,2'-azobis [N- 2-methylpropionamidine] dihydrochloride, 2,2'-azobis [2-methyl-thiophene] dihydrochloride, 2,2'-azobis [N- (4- Azobis [2-methyl-N- (2-propenyl) propionamidine] dihydrochloride, 2,2'-azobis 2-methylpropionamidine) dihydrochloride and 2,2'-azobis [N- (2-hydroxyethyl) -2-methylpropionamidine] dihydrochloride.

More specifically, the azo-based compound includes an azo-based cyclic amidine compound, an azo-based amide compound, an azo-based alkyl compound, and an azo-based ester compound.

Examples of the azo type cyclic amidine compound include 2,2'-azobis [2- (5-methyl-2-imidazolin-2-yl) propane] dihydrochloride, 2,2'-azo Bis [2- (2-imidazolin-2-yl) propane] dihydrochloride, 2,2'-azobis [2- (4,5,6,7-tetrahydro-1H- 2-yl) propane] dihydrochloride, 2,2'-azobis [2- (3,4,5,6-tetrahydropyrimidin- -Azobis {2- [1- (2, 3, 4, 5, 6-tetrahydropyrimidin-2- yl) propane] dihydrochloride, 2-yl] propane} dihydrochloride and 2,2'-azobis [2- (2-imidazolin-2-yl) propane] .

Examples of the azo type amide compound include 2,2'-azobis {2-methyl-N- [1,1-bis (hydroxymethyl) -2-hydroxyethyl] propionamide} Azobis [2-methyl-N- (1,1-bis (hydroxymethyl) ethyl] propionamide}, 2,2'- Amide] and 2,2'-azobis (2-methylpropionamide) dihydrate.

Examples of the azo-based alkyl compound include 2,2'-azobis (2,4,4-trimethylpentane) and 2,2'-azobis (2-methylpropane) Examples of the ternary ester compound include dimethyl-2,2'-azobis (2-methylpropionate) and the like.

Therefore, the azo-based polymerization initiator in the present invention does not include an azo-based nitrile compound such as 2,2'-azobisisobutyronitrile (AIBN), and the azo- Or more can be mixed and used.

Further, other polymerization initiators commonly used in the art may be further used insofar as the effect of the present invention is not impaired. The polymerization initiator may be used in combination with polymerization initiators generally used in the art.

The polymerization initiator may be an amine compound or a carboxylic acid compound.

The amine compounds include, for example, aliphatic amine compounds such as triethanolamine, methyldiethanolamine and triisopropanolamine; 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, N, N-dimethylparatoluidine, 4,4- Aromatic amine compounds such as bis (dimethylamino) benzophenone (commonly known as Michler's ketone) and 4,4'-bis (diethylamino) benzophenone, and aromatic amine compounds are used as the amine compounds .

The carboxylic acid compound is, for example, selected from the group consisting of phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthioacetic acid, , And aromatic heteroacetic acids such as dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine and naphthoxyacetic acid.

When the polymerization initiator is used together, high sensitivity can be exhibited even in a small amount.

In the present invention, the polymerization initiator is preferably contained in the photosensitive resin composition for forming the front light-shielding layer of the display device in an amount of 0.5 to 40% by weight, preferably 3 to 20% by weight based on the total weight of the solid content. When the polymerization initiator is contained in the above content range, the sensitivity can be increased, the exposure time can be shortened, and productivity can be improved.

(E) Solvent

In the present invention, the solvent is not particularly limited, but ethers, aromatic hydrocarbons, ketones, alcohols, esters or amides are preferably used.

Examples of the ethers include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol di Propyl ether and diethylene glycol dibutyl ether.

Examples of the aromatic hydrocarbons include benzene, toluene, xylene, and mesitylene.

The ketones include, for example, methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, and cyclohexanone.

Examples of the alcohols include ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, and glycerin.

Examples of the esters include ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, methylcellosolve acetate, ethylcellosolve acetate, ethyl acetate, butyl acetate, amyl acetate, methyl lactate, ethyl lactate Methoxybutyl acetate, methoxypentyl acetate, ethylene glycol monoacetate, ethylene glycol diacetate, methyl 3-methoxypropionate, methyl 3-methoxypropionate Propylene glycol, propylene glycol methyl ether acetate, 2-amino-2-methyl-1,3-propanediol, 2-amino- Propylene glycol monobutyl ether, 3-methoxy-1-butyl acetate, ethylene glycol monobutyl ether, diethylene glycol methyl ethyl ether, 1, 2-propylene glycolide Propylene glycol monomethyl ether, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether, gamma butyrolactone, diethylene glycol monoethyl ether acetate, dipropylene glycol Methyl ether acetate, diethylene glycol monobutyl ether, 1,3-butylene glycol diacetate, diethylene glycol monobutyl ether acetate ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol mono Propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene carbonate, propylene carbonate, and? -Butyrolactone, and the like. Examples of the organic solvent include at least one selected from the group consisting of acetone, diethylene glycol diacetate, diethylene glycol monobutyl ether acetate, propylene glycol monoacetate, Rock And the like.

In view of the coatability and dry surface of the solvents exemplified above, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, ethyl lactate, butylacetate, ethyl 3-ethoxypropionate, Methyl 3-methoxypropionate, diethylene glycol monoethyl ether acetate, 1,3-butylene glycol diacetate, and diethylene glycol monobutyl ether acetate.

The solvents exemplified above may be used alone or in combination of two or more. The solvent is contained in an amount of 20 to 90% by weight, preferably 30 to 85% by weight based on the total weight of the photosensitive resin composition for forming the front light-shielding layer of the display device of the present invention. When the solvent is contained in the range of 20 to 90% by weight, it is preferable to use a roll coater, a spin coater, a slit and spin coater, a slit coater (sometimes referred to as a die coater), a spray coater, And when applied with a coating device such as an inkjet, the coating property is improved.

(F) Additive

The photosensitive resin composition for forming the front light-shielding layer of the display device of the present invention may further contain additives such as fillers, other polymer compounds, curing agents, pigment dispersants, adhesion promoters, antioxidants, ultraviolet absorbers and anti- .

As the filler, glass, silica and alumina can be used.

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

The above-mentioned curing agent is used for enhancing deep curing and mechanical strength, and examples of the curing agent that can be used include an epoxy compound, a polyfunctional isocyanate compound, a melamine compound and an oxetane compound.

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, Epoxy resin, glycidyl ester resin, glycidylamine resin, aliphatic, alicyclic or aromatic epoxy compounds other than the brominated derivatives, epoxy resins and brominated derivatives of such epoxy resins, butadiene (co) polymeric epoxides, Isoprene (co) polymer epoxide, glycidyl (meth) acrylate (co) polymer and triglycidyl isocyanurate.

Examples of the oxetane compound in the curing agent include carbonate bisoxetane, xylene bisoxetane, adipate bisoxetane, terephthalate bisoxetane, and cyclohexanedicarboxylic acid bisoxetane. .

Further, the curing agent may include a curing auxiliary compound capable of ring-opening polymerization of an epoxy group of an epoxy compound and an oxetane skeleton of an oxetane compound together with a curing agent. Examples of the curing assistant compound include polyvalent carboxylic acids, polyvalent carboxylic anhydrides and acid generators.

As the epoxy resin curing agent, there can be used, for example, Adekahadona EH-700 (manufactured by Adeka Kogyo Co., Ltd.), Rikashido HH Ltd.) and MH-700 (manufactured by Shin-Nihon Ehwa Co., Ltd.). These curing agents may be used alone or in combination of two or more.

Examples of the adhesion promoter include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, Aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2 (aminoethyl) - (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3- Trimethoxysilane, 3-isocyanatopropyltrimethoxysilane, and 3-isocyanatepropyltriethoxysilane. The above adhesion promoting agents may be used alone or in combination of two or more. The amount of the adhesion promoting agent may be 0.01 to 10% by weight, preferably 0.05 to 2% by weight, based on the total weight of the solid content of the photosensitive resin composition for forming the front light- %.

The antioxidant serves to prevent oxidation and improve thermal stability in the production of a photosensitive resin composition for forming a front light-shielding layer of a display device. The antioxidant is a primary antioxidant that is directly involved in oxidation to prevent oxidation, consumes excessive primary antioxidant Secondary antioxidants and mixtures thereof may be used.

The primary antioxidant includes a phenol-based antioxidant, and the secondary antioxidant includes a phosphorus-based or sulfur-based antioxidant. In the present invention, the phenolic antioxidant, which is the primary antioxidant, may be used alone, or a secondary antioxidant may be mixed with one selected from phosphorus-based and sulfur-based antioxidants.

The phenolic antioxidant may be, for example, 3,9-bis [2- 3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethoxy] -2,4,8,10-tetraoxaspiro [5.5] undecane and pentaerythrityl tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] Of a phenolic compound having a spirocyclic skeleton; (3'-di-t-butyl-4-hydroxybenzyl) benzene, triethylene glycol-bis [3- Butyl-5-methyl-4-hydroxyphenyl) propionate], 4,4'-thiobis (6-t- (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) -isocyanurate, 1,6-hexanediol (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,2-thio-diethylenebis [3- Hydroxyphenyl) propionate], N, N'-hexamethylenebis (3,5-di-t-butyl-4-hydroxy-hydrocinnamamide), 1,3,5- Bis [(octylthio) methyl] -O-cresol, 1,6-hexanediol-bis- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], octadecyl- [3- (3,5- 2,2'-methylenebis (4-methyl-6-t-butyl Phenol), 4,4'-butylidene-bis (3-methyl-6-t-butylphenol), 1,1,3- Butene, 1,3,5-tris (4-hydroxybenzyl) benzene and tetrakis [methylene-3- (3,5'-di-t-butyl-4'-hydroxyphenylpropionate)] methane .

In the phenolic antioxidant, 3,9-bis [2-3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1- 2, 4, 8, 10-tetraoxasaspiro [5.5] undecane, 1,3,5-trimethyl-2,4,6-tris (3'5'- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], triethylene glycol-bis [3- butylphenyl) propionate], 4,4'-thiobis (6-t-butyl-3-methylphenol), tris- (3,5-di-t-butyl-5-methyl- (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) -isocyanurate, 1,6-tris (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,2-thio-diethylenebis [3- -Butyl-4-hydroxyphenyl) propionate], N, N'-hexamethylenebis (3,5-di- (3,5-di-t-butyl-4-hydroxybenzyl) benzene, 2,4-bis [(octylthio) methyl] -O-cresol, and the like.

The phenolic antioxidants may be used alone or in combination of two or more. When the phenol-based antioxidant is mixed with at least one selected from the group consisting of phosphorus-based and sulfur-based antioxidants, the content of the phenol-based antioxidant is preferably 50 to 100% by weight based on the total weight of the antioxidant .

As the phosphorus antioxidant, known compounds may be used. For example, there can be mentioned 3,9-bis (2,6-di-t-butyl-4-methylphenoxy) -2,4,8,10-tetraoxa- , A phosphite compound having a spirocyclic skeleton such as diisodecyl pentaerythritol diphosphite and bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite; (2-ethylhexyloxy) phosphorus, 6- [3- (3-t-butyl-4-hydroxy -5-methylphenyl) propoxy] -2,4,8,10-tetra-t-butyldibenz [d, f] [1,3,2] dioxaphosphper, triphenylphosphite, diphenyl isodecyl (3-methyl-6-t-butylphenyl dontridecyl) phosphite, octadecyl phosphite, tris (nonylphenyl) phosphite , 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (3,5- Oxa-10-phosphaphenanthrene-10-oxide, 10-decyloxy-9,10-dihydro-9-oxa- (2,4-di-t-butylphenyl) phosphite, cyclic neopentanetetraylbis (2,6-di-t-butylphenyl) phosphite, cyclic neopentanetetraylbis Phosphite, 2,2-methylene bis (4,6-di-t-butyl (2,4-di-t-butylphenyl) [1,1-biphenyl] -4,4 ' -dihydroxyphenyl) phosphite, tetrakis Bis [2,4-bis (1,1-dimethylethyl) -6-methylphenyl] ethyl ester, and phosphonic acid.

The phosphorus-based antioxidant is preferably selected from the group consisting of 2,2'-methylenebis (4,6-di-t-butyl-1-phenyloxy) (2-ethylhexyloxy) Bis (2,6-di-tert-butyl-4-methylphenoxy) -2,4,8,10-tetraoxa-3,9-diphospaspiro [5.5] undecane and 6- [3- propyl] -2,4,8,10-tetra-t-butyl dibenz [d, f] [1,3,2] dioxaphosphper Is preferably used.

Examples of the sulfur-based antioxidant include known compounds such as 2,2-bis ({[3- (dodecylthio) propionyl] oxy} methyl) -1,3-propanediyl-bis [3- (Dodecylthio) propionate], 2-mercaptobenzimidazole, dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, distearyl -3,3'-thiodipropionate, pentaerythrityl-tetrakis (3-laurylthiopropionate), and other compounds having a thioether structure; And 2-mercaptobenzimidazole.

The sulfur-based antioxidant is preferably selected from the group consisting of 2,2-bis ({3- (dodecylthio) propionyl] oxy} methyl) -1,3-propanediyl- ) Propionate] and 2-mercaptobenzimidazole are preferably used.

The antioxidant may be contained in an amount of 0.1 to 10% by weight, preferably 0.2 to 5% by weight based on the total weight of the solid content of the photosensitive resin composition for forming the front light-shielding layer of the display device. When the content is less than 0.1 wt%, heat discoloration occurs. When the content is more than 10 wt%, insolubles or post-development residue may occur.

Examples of the ultraviolet absorber include 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzothiazole and alkoxybenzophenone.

The anti-aggregation agent includes, for example, sodium polyacrylate.

The present invention also provides a display device including a front shading layer formed by coating a photosensitive resin composition for forming a front shading layer of the display device on a substrate.

A display device including a front shading layer can be manufactured by applying a photosensitive resin composition for forming a front shading layer of a display device of the substrate onto a substrate and curing and developing the pattern to form a pattern.

As a method of forming the pattern, a photosensitive resin composition for forming a front light-shielding layer of a display device of the substrate of the present invention may be formed on a substrate or a separate resin layer (for example, a separate colored resin composition layer previously formed on a substrate) A method of forming a coloring layer by removing volatile components such as a solvent and exposing and developing the colored layer through a photomask, and a method of performing inkjet, gravure printing, reverse printing, pad printing, and screen And a method of using a printing apparatus.

The photosensitive resin composition for forming the front light-shielding layer of the display device of the present invention comprises a colorant-dispersed composition as a coloring material. The colorant-dispersed composition can be obtained by adding (A) a colorant, (a2) a pigment dispersant and (E) a solvent, and optionally (B) an alkali-soluble binder resin to further knead and disperse. The dispersion is mainly carried out by using a sand grinder, a pin mill, a slit mill, an ultrasonic disperser or the like in a vertical or horizontal type and using beads formed of glass or zirconia having a particle diameter of 0.01 to 1 mm . In addition, before the bead dispersion is performed, a two-roll mill, a three-roll mill, a ball mill, a trommill, a disperser, a kneader, a coneerator, a homogenizer, a blender, Or a twin-screw extruder may be used to perform the kneading dispersion treatment while imparting a strong shearing force.

The front light-shielding layer of the display device including the photosensitive resin composition for forming the front light-shielding layer of the display device of the present invention has an optical density of 0.7 to 6.0, and a temperature of 230 ° C for 30 minutes is applied. The warpage is ± 400 μm or less so that warping of the substrate can be minimized. The warpage refers to a value obtained by measuring the highest height of the four corners of the floor when the substrate is placed on a uniform platen.

Accordingly, the photosensitive resin composition for forming the front light-shielding layer of the display device of the present invention can minimize the warping of the substrate due to the difference in thermal expansion coefficient during the curing step in the manufacturing process.

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail with reference to examples. However, the embodiments according to the present invention can be modified into various other forms, and the scope of the present invention should not be construed as being limited to the embodiments described below. The embodiments of the present invention are provided to enable those skilled in the art to more fully understand the present invention.

≪ Preparation of colorant dispersion composition &

Manufacturing example  One.

35.0 g of a white pigment of CI Pigment White 6 having an average particle size of 250 nm (density of the white pigment TiO ₂ of 4.2 g / cm ³ ), an alkali-soluble binder resin (a copolymer of methacrylic acid and benzyl methacrylate as the methacrylic acid unit (Benzyl methacrylate unit: 31:69, weight average molecular weight in terms of polystyrene: 20,000), 4.32 g of BYK-180 (manufactured by BYK) as a pigment dispersant, and 55.74 g of propylene glycol monomethyl ether acetate as a solvent And mixed and dispersed by a mill for 2 hours to prepare a white dispersion composition of a photosensitive resin composition for forming a front light shielding layer of a display device.

Manufacturing example  2.

12.0 g of carbon black (density 1.8 g / cm ³ ) as a black pigment, 4.0 g of DISPERBYK-2001 (BYK) as a pigment dispersant, 44 g of propylene glycol monomethyl ether acetate as a solvent and 40 g of propylene glycol monomethyl ether And mixed and dispersed for 12 hours to prepare a black dispersion composition of a photosensitive resin composition for forming a front light-shielding layer of a display device.

Manufacturing example  3.

(Density: 1.58 g / cm ³ ) of CI Pigment Brown 25 having an average particle size of 150 nm, an alkali-soluble binder resin (BYK-180, manufactured by BYK) as a dispersant and 77.24 g of propylene glycol monomethyl ether acetate as a solvent were mixed with a bead mill for 2 hours And the mixture was dispersed to prepare a brown dispersion composition of a photosensitive resin composition for forming a front light shielding layer of a display device.

<Front of Display Device Shading layer  &Lt; RTI ID = 0.0 &gt; &lt; / RTI &gt;

Example  One.

A mixture of 41.09 g of the white dispersion composition prepared in Preparation Example 1, an alkali-soluble resin (a copolymer of methacrylic acid and benzyl methacrylate in a molar ratio of methacrylic acid unit to benzyl methacrylate unit of 31:69, weight average in terms of polystyrene , 5.52 g of dipentaerythritol hexaacrylate (KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.) as a photopolymerizable compound, 20.0 g of bis (2,4,6-trimethylbenzoyl) 0.42 g of phenylphosphine oxide (Irgacure 819, manufactured by BASF), 0.52 g of 2,4-diethylthioxanthone (Speedcure DETX, manufactured by LAMBSON) as a polymerization initiation aid, 3 g of pentaerythrityl tetrakis [ (ADK STAB AO-60, manufactured by Adeka Co., Ltd.), 3-isocyanate propyltriethoxysilane (KBM- 9007; manufactured by Shin-Etsu), 0.32 g of a surfactant (SH-8400, Crude) 0.08g, as a solvent was prepared with propylene glycol monomethyl ether, the front light-shielding layer formed white photosensitive resin composition for a display device of a 65% pigment concentration by mixing 32.51g acetate, and the density was 1.86g / cm ^3.

The white photosensitive resin composition for forming the front light shielding layer of the display device was coated on a glass substrate by spin coating, and the substrate was placed on a heating plate and heated at 100 ° C for 3 minutes to form a film. Thereafter, a photomask was placed on the film, and ultraviolet rays were irradiated at a light intensity of 100 mJ / cm 2 using a high-pressure mercury lamp of 1 kW containing all g, h and i lines. The ultraviolet-irradiated glass substrate was immersed in a KOH aqueous solution developing solution having a pH of 10.5 for 100 seconds to be developed. The glass substrate coated with the coating film was washed with distilled water, dried using nitrogen gas, and heated in a heating oven at 230 ° C for 30 minutes to produce a front light-shielding layer of a patterned display device. The thickness of the front white light-shielding layer of the display device was 25.0 [mu] m, and the optical density (OD) was 0.87.

Example  2.

31.61 g of the white dispersion composition prepared in Preparation Example 1, 31.61 g of the alkali-soluble resin (the copolymer of methacrylic acid and benzyl methacrylate as a copolymer, the molar ratio of methacrylic acid unit to benzyl methacrylate unit was 31:69, 28.87 g of dipentaerythritol hexaacrylate (KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.) as a photopolymerizable compound, 8.28 g of bis (2,4,6-trimethylbenzoyl) 0.62 g of phenylphosphine oxide (Irgacure 819, manufactured by BASF), 0.78 g of 2,4-diethylthioxanthone (Speedcure DETX, manufactured by LAMBSON) as a polymerization initiator, 0.30 g of pentaerythrityl tetrakis [ (ADK STAB AO-60, manufactured by Adeka) and 3-isocyanate propyltriethoxysilane (KBM- 9007; manufactured by Shin-Etsu), 0.32 g of a surfactant (SH-8400, Crude) 0.08g, as a solvent was prepared with propylene glycol monomethyl ether, the front light-shielding layer formed in the photosensitive resin composition for white of the display device of the acetate by mixing 28.97g of 50% pigment concentration, density was 1.68 g / cm ^3.

A white light-sensitive resin composition for forming a front light-shielding layer of a display device manufactured as described above was prepared as a front light-shielding layer of a display device having a pattern formed thereon in the same manner as in Example 1. The thickness of the front white light-shielding layer of the display device manufactured above was 25.0 占 퐉 and the optical density (OD) was 0.81.

Example  3.

A white photosensitive resin composition for forming a front light shielding layer of a display device was prepared in the same manner as in Example 1, and the thickness of the front white light shielding layer of the patterned display device was set to 17.0 μm. The optical density (OD) of the front white light-shielding layer of the display device manufactured above was 0.73.

Example  4.

46.75 g of the black dispersion composition prepared in Preparation Example 2, an alkali-soluble resin (a copolymer of methacrylic acid and benzyl methacrylate in a molar ratio of methacrylic acid unit to benzyl methacrylate unit of 31:69, weight average in terms of polystyrene (Manufactured by Ciba Specialty Chemicals), 2.64 g of dipentaerythritol hexaacrylate (KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd.) as a photopolymerizable compound, 0.42 g of Irgacure OXE02 (manufactured by Ciba Specialty Chemicals) 0.53 g of 2,4-diethylthioxanthone (manufactured by LAMBSON) as an auxiliary agent, 0.23 g of 3-isocyanate propyltriethoxysilane (KBM-9007; Shin-Etsu) 8400, manufactured by Toray Silicone) and 43.34 g of propylene glycol monomethyl ether acetate as a solvent were mixed to prepare a black photosensitive resin composition for forming a front shading layer of a display device having a pigment concentration of 55% , And the density was 1.07 g / cm &lt; ^{3 &} gt ;.

The black light-sensitive resin composition for forming the front light-shielding layer of the display device manufactured above was prepared as a front light-shielding layer of a display device in which a pattern was formed in the same manner as in Example 1. [ The thickness of the front black light-shielding layer of the display device manufactured above was 1.2 탆 and the optical density (OD) was 4.8.

Example  5.

84.75 g of the brownish brown dispersion composition prepared in Preparation Example 3, an alkali-soluble resin (a copolymer of methacrylic acid and benzyl methacrylate as a copolymer, the molar ratio of methacrylic acid unit to benzyl methacrylate unit being 31:69, weight average in terms of polystyrene , 4.18 g of dipentaerythritol hexaacrylate (KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.), 0.34 g of Irgacure OXE02 (manufactured by Ciba Specialty Chemicals) as a photopolymerizable compound, , 0.27 g of 3-isocyanate propyltriethoxysilane (KBM-9007; Shin-Etsu), 0.03 g of a surfactant (SH-8400, manufactured by Toray Silicone Co., Ltd.) and 2.87 g of propylene glycol monomethyl ether acetate as a solvent A brown photosensitive resin composition for forming a front shading layer of a display device having a pigment concentration of 50% was prepared and the density was 1.09 g / cm ³ .

A front light-shielding layer of a display device having a pattern formed thereon was prepared in the same manner as in Example 1, except that a brown light-sensitive resin composition for forming a front light-shielding layer of the display device manufactured above was prepared. The thickness of the front brown light shielding layer of the display device was 10 μm and the optical density (OD) was 0.87.

Comparative Example  One.

18.96 g of the white dispersed composition prepared in Preparation Example 1, 18.96 g of the alkali-soluble resin (the copolymer of methacrylic acid and benzyl methacrylate as a copolymer, the molar ratio of methacrylic acid unit to benzyl methacrylate unit was 31:69, , 11.96 g of dipentaerythritol hexaacrylate (KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.) as a photopolymerizable compound, 0.5 g of bis (2,4,6-trimethylbenzoyl) , 0.9 g of phenylphosphine oxide (Irgacure 819, manufactured by BASF), 1.13 g of 2,4-diethylthioxanthone (Speedcure DETX, manufactured by LAMBSON) as a polymerization initiator, 0.30 g of pentaerythrityl tetrakis [ (ADK STAB AO-60, manufactured by Adeka) and 3-isocyanate propyltriethoxysilane (KBM- (3,5-di-tert- 9007; manufactured by Shin-Etsu), 0.32 g of a surfactant (SH-8400, Crude) 0.08g, as a solvent was prepared with propylene glycol monomethyl ether, the front light-shielding layer formed in the photosensitive resin composition for white of the display device of the acetate by mixing 24.25g of 25% pigment concentration, density was 1.43 g / cm ^3.

A white light-sensitive resin composition for forming a front light-shielding layer of a display device manufactured as described above was prepared as a front light-shielding layer of a display device having a pattern formed thereon in the same manner as in Example 1. The thickness of the front white light shielding layer of the display device was 25 탆 and the optical density (OD) thereof was 0.63.

Comparative Example  2.

12.64 g of the white dispersion composition prepared in Preparation Example 1, 12.64 g of the alkali-soluble resin (the copolymer of methacrylic acid and benzyl methacrylate in a molar ratio of methacrylic acid unit to benzyl methacrylate unit of 31:69, weight average in terms of polystyrene , 13.8 g of dipentaerythritol hexaacrylate (KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.) as a photopolymerizable compound, 12.8 g of bis (2,4,6-trimethylbenzoyl) , 1.0 g of phenylphosphine oxide (Irgacure 819, manufactured by BASF), 1.3 g of 2,4-diethylthioxanthone (Speedcure DETX, manufactured by LAMBSON) as a polymerization initiator and 1 g of pentaerythrityl tetrakis [ (ADK STAB AO-60, manufactured by Adeka Co., Ltd.) and 3-isocyanate propyltriethoxysilane (KBM- 9007; manufactured by Shin-Etsu), 0.32 g of a surfactant (SH-8400, Crude) 0.08g, as a solvent was prepared with propylene glycol monomethyl ether, the front light-shielding layer formed in the photosensitive resin composition for white of the display device of the acetate by mixing 21.89g of 25% pigment concentration, density was 1.31 g / cm ^3.

A white light-sensitive resin composition for forming a front light-shielding layer of a display device manufactured as described above was prepared as a front light-shielding layer of a display device having a pattern formed thereon in the same manner as in Example 1. The thickness of the front white light-shielding layer of the display device manufactured above was 25 탆 and the optical density (OD) was 0.56.

Comparative Example  3.

33.9 g of the brown-colored dispersion composition prepared in Preparation Example 3, an alkali-soluble resin (a copolymer of methacrylic acid and benzyl methacrylate in a molar ratio of methacrylic acid unit to benzyl methacrylate unit of 31:69, weight average in terms of polystyrene (Manufactured by Ciba Specialty Chemicals), 9.36 g of dipentaerythritol hexaacrylate (KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.) as a photopolymerizable compound, 0.78 g of Irgacure OXE02 (manufactured by Ciba Specialty Chemicals) 0.27 g of 3-isocyanate propyltriethoxysilane (KBM-9007; manufactured by Shin-Etsu), 0.03 g of a surfactant (SH-8400, manufactured by Toray Silicone Co., Ltd.) and 32.5 g of propylene glycol monomethyl ether acetate as a solvent A brown photosensitive resin composition for forming a front shading layer of a display device having a pigment concentration of 10% was prepared and the density was 1.06 g / cm ³ .

A front light-shielding layer of a display device having a pattern formed thereon was prepared in the same manner as in Example 1, except that a brown light-sensitive resin composition for forming a front light-shielding layer of the display device manufactured above was prepared. The thickness of the front brownish light shielding layer of the display device was 10 μm and the optical density (OD) was 0.68.

Experimental Example  1. Front of display device The light-  Warp warpage ) evaluation

The display devices manufactured in Examples 1 to 5 and Comparative Examples 1 to 3 were further heated in an oven at 230 DEG C for 30 minutes and the process was repeated five times to evaluate the warpage of the front shading layer of the display device The results are shown in Table 1 below.

Item Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2 Comparative Example 3 Pigment
density(%) 65 50 65 55 50 30 20 30 Density (g / cm ³⁾ 1.86 1.68 1.86 1.07 1.09 1.43 1.31 1.06 Film Thickness (㎛) 25 25 17 1.2 10 25 25 10 Formula value
(0.5T ^1/3 <density <2T ^1/2) 1.46 < 1.86 < 10.0 1.46 < 1.68 < 10.0 1.29 < 1.86 < 8.25 0.85 < 1.07 < 4.47 1.08 < 1.09 < 6.32 1.46 < 1.43 < 10.0 1.46 < 1.31 < 10.0 1.08 < 1.06 < 6.32 Optical density (OD) 0.89 0.82 0.73 4.8 0.87 0.63 0.56 0.68 Warpage (탆) 305 355 285 216 248 524 709 439

The density of the Example 1 to the photosensitive resin composition for a front light-shielding layer formed of a display device manufactured in 5 was confirmed to have a value in the formula, the value 0.5T ^1/3 to 2T ^1/2 range. (Wherein T is the thickness of the front light-shielding layer of the display device.) On the other hand, Comparative Example 1, the density of the photosensitive resin composition for a front light-shielding layer formed of a display device manufactured by 0.5T to 3 is the minimum of the value of ^1/3 of the formula And a result that does not belong to the range of the expression was shown, and the substrate was warped.

In the optical density (OD) measurement, the optical density of the front light-shielding layer of the display device manufactured in Examples 1 to 5 was all in the range of 0.7 to 6.0, but the optical density of the front light-shielding layer of the display device manufactured in Comparative Examples 1 to 3 The optical density of the layer showed a value of less than 0.7.

The warpage of the substrate is measured by measuring the maximum height of the four corners of the substrate when the substrate is placed on a uniform platen. The warpage of the substrate is minimized only if the value of ± 400 μm is satisfied.

The substrates produced in Examples 1 to 5 were found to have a warpage of less than ± 400 μm in all of the warpage measurements, but the substrates prepared in Comparative Examples 1 to 3 all exceeded ± 400 μm, It can be confirmed that the bending of the wedge has occurred.

Thus, a photosensitive resin composition for a front light-shielding layer formed on the display device satisfying the ^1/3 0.5T to 2T ^1/2 and the optical density value of the density range of 0.7 to 6.0 on the front light-shielding layer of the display device manufactured with the photosensitive resin composition of the It is possible to minimize warping of the substrate.

Claims (7)

The front light-shielding layer formed in the photosensitive resin composition for a display device, the density of the photosensitive resin composition is 0.5T ^1/3 to 2T ^1/2 has a value of optical shielding on the front layer of the display device manufactured with the photosensitive resin composition And a density of 0.7 to 6.0. The light-sensitive resin composition for forming a front light-shielding layer of a display device according to claim 1,
And T is the thickness of the front shading layer of the display device. The method according to claim 1, wherein the 0.5T ^1/3 to 2T ^1/2 value of 0.9 to the photosensitive resin composition for forming a light-shielding layer of the front display device, characterized in that 3.0. The display device according to claim 1, wherein the photosensitive resin composition for forming a front light-shielding layer of the display device comprises a colorant, an alkali-soluble binder resin, a photopolymerizable compound, a polymerization initiator and a solvent. Composition. The photosensitive resin composition according to claim 3, wherein the photosensitive resin composition for forming a front light-shielding layer of the display device comprises 10 to 90% by weight of a colorant, 3 to 80% by weight of an alkali-soluble binder resin, 1 to 60% by weight of a photopolymerizable compound, A photosensitive resin composition for forming a front shading layer of a display device, wherein the photosensitive resin composition comprises 1 to 40 wt% of an initiator and 20 to 90 wt% of a solvent based on a total weight of the photosensitive resin composition for forming a front shading layer of the display device . The photosensitive resin composition according to claim 3, wherein the alkali-soluble binder resin has a polystyrene-reduced weight average molecular weight of 3,000 to 100,000. The photosensitive resin composition according to claim 3, wherein the photosensitive resin composition for forming the front light-shielding layer of the display device is one or more selected from the group consisting of a filler, a polymer compound, a curing agent, a pigment dispersant, a contact promoter, an antioxidant, Wherein the photosensitive resin composition for forming the front light shielding layer of the display device comprises the photosensitive resin composition for forming the front light shielding layer. A display device comprising a front shading layer formed by coating a photosensitive resin composition for forming a front shading layer of the display device of claim 1 on a substrate.