KR101938427B1 - A photosensitive resin composition, color filter and liquid crystal display device using the same - Google Patents

Abstract

상기 화학식 1에서 R₁, R₂, R₃, R₄는 서로 독립적으로, 수소원자, 할로겐 원자 또는 탄소수 1∼20의 유기잔기(유기잔기는 산소원자를 함유할 수도 있다)를 나타낸다.
<화학식 2>

상기 화학식 2에서 R₅, R₆, R₇, R₈은 서로 독립적으로, 수소원자, 할로겐 원자 또는 탄소수 1∼20의 유기잔기(유기잔기는 산소원자를 함유할 수도 있다)를 나타낸다.According to the present invention,
Wherein the binder resin (B) is a photosensitive resin composition comprising a colorant (A), a binder resin (B), a photopolymerizable monomer (C), a photopolymerization initiator (D), an antioxidant (E) and a solvent (F) Wherein the antioxidant (E) comprises a monomer selected from the group consisting of a first antioxidant selected from phenolic compounds; And a second antioxidant selected from the group consisting of a phosphorus compound, a sulfur-based compound and a mixture thereof, or a compound having at least one of phenolic functional groups and phosphorus-containing functional groups and sulfur-containing functional groups simultaneously in one molecule A photosensitive resin composition is provided.
&Lt; Formula 1 >

In Formula 1, R ₁ , R ₂ , R ₃ , and R ₄ independently represent a hydrogen atom, a halogen atom, or an organic residue having 1 to 20 carbon atoms (the organic residue may contain an oxygen atom).
(2)

In the general formula (2), R ₅ , R ₆ , R ₇ and R ₈ independently represent a hydrogen atom, a halogen atom or an organic residue having 1 to 20 carbon atoms (the organic residue may contain an oxygen atom).

Description

TECHNICAL FIELD [0001] The present invention relates to a photosensitive resin composition, a color filter using the same, and a liquid crystal display device using the same. BACKGROUND ART &lt; RTI ID = 0.0 &gt;

The present invention relates to a photosensitive resin composition, a color filter manufactured using the same, and a liquid crystal display device.

The photosensitive resin composition is used in the form of a dry film photoresist or a liquid photoresist used in a printed circuit board (hereinafter referred to as a PCB) or a lead frame. Such a photosensitive resin composition is applied on a substrate to a predetermined thickness, and then subjected to a developing process for selectively irradiating light to form a desired circuit and then forming a desired circuit by a solvent. After the developing process, the substrate is etched according to the process Or a process of plating the substrate portion using a metal is performed. In the photosensitive resin composition, the chemical resistance plays an important role in both the development, etching and plating processes. In the development process, the resist solution resistance is increased, so that a high-resolution circuit can be formed, etching defect in the etching process is reduced, It is important to minimize plating defects.

Korean Patent Laid-Open Publication No. 2007-0133687 discloses an antioxidant capable of preventing the oxidation of the photosensitive resin composition during the production of the photosensitive resin composition to improve the thermal stability, and further comprises an acrylic binder resin, The present invention provides a photosensitive resin composition for a color filter capable of improving the thermal characteristics of a color filter by increasing crosslinking formation by photoinitiation using a resin.

However, in this case, although the heat resistance is partially improved, there is a disadvantage that it is still insufficient and the luminance is low.

Korea Patent Publication No. 2007-0133687

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems of the prior art, and it is an object of the present invention to provide a resin composition containing a furan or furan structure as a binder resin and comprising a mixture of a first antioxidant and a second antioxidant as antioxidants, And an object of the present invention is to provide a photosensitive resin composition which can increase the sensitivity of development.

In order to solve the above object,

According to the present invention,

Wherein the binder resin (B) is a photosensitive resin composition comprising a colorant (A), a binder resin (B), a photopolymerizable monomer (C), a photopolymerization initiator (D), an antioxidant (E) and a solvent (F) Wherein the antioxidant (E) comprises a monomer selected from the group consisting of a first antioxidant selected from phenolic compounds; And a second antioxidant selected from the group consisting of a phosphorus compound, a sulfur-based compound and a mixture thereof, or a compound having at least one of phenolic functional groups and phosphorus-containing functional groups and sulfur-containing functional groups simultaneously in one molecule A photosensitive resin composition is provided.

&Lt; Formula 1 >

In Formula 1, R ₁ , R ₂ , R ₃ , and R ₄ independently represent a hydrogen atom, a halogen atom, or an organic residue having 1 to 20 carbon atoms (the organic residue may contain an oxygen atom).

(2)

In the general formula (2), R ₅ , R ₆ , R ₇ and R ₈ independently represent a hydrogen atom, a halogen atom or an organic residue having 1 to 20 carbon atoms (the organic residue may contain an oxygen atom).

The present invention also provides a color filter made of the photosensitive resin composition of the present invention.

The present invention also provides a liquid crystal display device including a color filter made of the photosensitive resin composition of the present invention.

The photosensitive resin composition of the present invention improves the adhesion and permeability by including a furan or furan structure as a binder resin and can exhibit excellent heat resistance by including a mixture of the first antioxidant and the second antioxidant as the antioxidant. Further, the color filter manufactured using the photosensitive resin composition of the present invention can exhibit excellent developing sensitivity even at a low exposure dose.

According to the present invention,

Wherein the binder resin (B) is a photosensitive resin composition comprising a colorant (A), a binder resin (B), a photopolymerizable monomer (C), a photopolymerization initiator (D), an antioxidant (E) and a solvent (F) Wherein the antioxidant (E) comprises a monomer selected from the group consisting of a first antioxidant selected from phenolic compounds; And a second antioxidant selected from the group consisting of a phosphorus compound, a sulfur-based compound and a mixture thereof, or a compound having at least one of phenolic functional groups and phosphorus-containing functional groups and sulfur-containing functional groups simultaneously in one molecule A photosensitive resin composition is provided.

&Lt; Formula 1 >

In Formula 1, R ₁ , R ₂ , R ₃ , and R ₄ independently represent a hydrogen atom, a halogen atom, or an organic residue having 1 to 20 carbon atoms (the organic residue may contain an oxygen atom).

(2)

In the general formula (2), R ₅ , R ₆ , R ₇ and R ₈ independently represent a hydrogen atom, a halogen atom or an organic residue having 1 to 20 carbon atoms (the organic residue may contain an oxygen atom).

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

(A) Colorant

The colorant (A) contains at least one pigment (a1) and at least one dye (a2) as essential components.

The pigment (a1)

The pigment may be an organic pigment or an inorganic pigment generally used in the art. The above-mentioned pigments can be used in various kinds of pigments used in printing ink, ink jet ink and the like. Specific examples thereof include water-soluble azo pigments, insoluble azo pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, And an anthanthrone pigment, an anthanthrone pigment, a pravanthrone pigment, a pyranthrone pigment, an anthanthrone pigment, an anthanthrone pigment, an anthanthrone pigment, an anthanthrone pigment, an anthanthrone pigment, a pyranthrone pigment, pyranthrone pigments, diketopyrrolopyrrole pigments, and the like.

Examples of the inorganic pigments include metallic compounds such as metal oxides and metal complex salts. Specific examples of the inorganic pigments include oxides of metals such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony and carbon black Or composite metal oxides. Particularly, the above organic pigments and inorganic pigments are specifically classified into pigments in the Color Index (published by Thesociety of Dyers and Colourists), and more specifically, pigments of the following color index (CI) number However, the present invention is not limited thereto.

C.I. Pigment Yellow 13,20,24,31,53,83,86,93,94,109,110,115,127,138,139,147,148,151,153,154,166,173,181 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, 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

C.I Pigment Black 1 and 7, etc.

The above-mentioned pigments (a1) may be used alone or in combination of two or more.

Of the exemplified CI pigment pigments, CI Pigment Orange 38, CI Pigment Red 122, CI Pigment Red 166, CI Pigment Red 177, CI Pigment Red 208, CI Pigment Red 242, CI Pigment Red 254, CI Pigment Red 255, CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 150, CI Pigment Yellow 185, CI Pigment Green 7, CI Pigment Green 36, CI Pigment Green 58, Pigment Blue 23, CI Pigment Blue 15: 3, Pigment Blue 15: 6 can be preferably used.

It is preferable to use a pigment dispersion in which the particle diameter of the pigment is uniformly dispersed. An example of a method for uniformly dispersing the particle diameter of the pigment includes a method of dispersing the pigment dispersion (a3) by containing the pigment dispersant (a3). According to this method, a pigment dispersion in which the pigment is uniformly dispersed in a solution can be obtained have.

Specific examples of the pigment dispersant include cationic surfactants, anionic surfactants, nonionic surfactants, amphoteric surfactants, polyester surfactants, and polyamine surfactants. These surfactants may be used singly or in combination of two or more thereof .

The content of the pigment (a1) is in the range of 20 to 90% by weight, preferably 30 to 70% by weight with respect to the total solid content in the pigment dispersion composition. When the content of the pigment is in the range of 20 to 90% by weight, the viscosity is low, the storage stability is excellent, and the dispersion efficiency is high, which is effective for increasing the contrast ratio.

As the dispersant (a3), other resin type pigment dispersants other than the acrylic dispersant may be used. The other resin type pigment dispersing agent may be a known resin type pigment dispersing agent, especially a polycarboxylic acid ester such as polyurethane, polyacrylate, unsaturated polyamide, polycarboxylic acid, polycarboxylic acid (partial) Amine salts of polycarboxylic acids, alkylamine salts of polycarboxylic acids, polysiloxanes, long chain polyaminoamide phosphate salts, esters of hydroxyl group-containing polycarboxylic acids and their modified products, or free ) Oil-based dispersants such as amides formed by reaction of a polyester having a carboxyl group with poly (lower alkyleneimine) or salts 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. As a commercially available product of the above-mentioned resinous dispersant, as the cationic resin dispersant,

DISPER BYK-160, DISPER BYK-161, DISPER BYK-162, DISPER BYK-163, DISPER BYK-164, 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; trade names: 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.,

In addition to the acrylic dispersant, other resin type pigment dispersants may be used alone or in combination of two or more, and may be used in combination with acrylic dispersion.

The amount of the dispersant (a3) to be used is in the range of 5 to 60 parts by weight, more preferably 15 to 50 parts by weight, based on 100 parts by weight of the solid content of the pigment (a1). If the content of the dispersant (a3) exceeds 60 parts by weight, the viscosity may be increased. If the content of the dispersant (a3) is less than 5 parts by weight, it may be difficult to atomize the pigment or cause gelation after dispersion.

The dye (a2)

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 derivatives thereof. Preferably, the dye is a compound classified as a dye in a 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. As solvent dyes,

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

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

C.I. Violet dyes such as solvent violet 8, 9, 13, 14, 36, 37, 47, 49;

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

C.I. Orange dyes such as solvent orange 2, 7, 11, 15, 26, 56;

C.I. Green dyes such as solvent green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, 35;

C.I. Solvent dye having excellent solubility in an organic solvent. Solvent Red 8, 49, 89, 111, 122, 132, 146, 179; C.I. Solvent Blue 35, 36, 44, 45, 70;

CI Solvent Violet 13 is preferred, and CI Solvent Red 8, 122, 132 is more preferred.

Also, C.I. As the 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, Red dyes such as 412, 417, 418, 422, 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 , Yellow dyes such as 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243,

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

Violet dyes such as C.I. Acid Violet 6B, 7, 9, 17, 19, 66 and the like;

Green dyes such as CI Acid Green 1, 3, 5, 9, 16, 25, 27, 50, 58, 63, 65, 80, 104, 105, 106,

CI Acid Red 92 with high solubility in organic solvents in acid dyes; CI Acid Blue 80, 90; CI Acid Violet 66 is preferred.

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, 250 and the like;

C.I. Direct Yellow 2, 33, 34, 35, 38, 39, 43, 47, 50, 54, 58,

Yellow dyes such as 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129, 136, 138 and 141;

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

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

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

Yellow dyes such as C.I. Modantho Yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65;

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

CI Modanth Orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, dyes;

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, 84;

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

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

As the dye in the present invention, Solvent Red 124 (trade name: Savinyl Fire Red 3GLS) may be used.

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

The content of the dye in the colorant (A) is preferably 0.5 to 80% by weight, more preferably 0.5 to 60% by weight, and particularly preferably 1 to 50% by weight based on the solid content in the colorant (A) .

When the content of the dye in the colorant (A) is in the above range, it is possible to prevent the problem of lowering the reliability of elution of the dye by the organic solvent after formation of the pattern.

The content of the colorant (A) is preferably 5 to 80% by weight, more preferably 10 to 45% by weight based on the solid content in the photosensitive resin composition. When the colorant (A) is contained in an amount of 5 to 80% by weight on the basis of the above criteria, the color density of the pixel is sufficient even when a thin film is formed, and the residue of the non- Do.

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

(B) binder resin

The binder resin of the present invention may be a copolymer containing a monomer represented by the following general formula (1) or (2). Preferably a copolymer of a monomer containing a carboxyl group and another monomer copolymerizable with the monomer, and the like.

&Lt; Formula 1 >

In Formula 1, R ₁ , R ₂ , R ₃ , and R ₄ independently represent a hydrogen atom, a halogen atom, or an organic residue having 1 to 20 carbon atoms (the organic residue may contain an oxygen atom).

(2)

In the general formula (2), R ₅ , R ₆ , R ₇ and R ₈ independently represent a hydrogen atom, a halogen atom or an organic residue having 1 to 20 carbon atoms (the organic residue may contain an oxygen atom).

The monomer of the above formula (1) is obtained by reacting methyl-2- (bromomethyl) -acrylate (product of Aldrich), triethylamine (product of Aldrich), methyl 2- (hydroxymethyl) &Lt; / RTI &gt; As the solvent used in the polymerization, propylene glycol methyl ether (manufactured by TCI) and 2,2'-azobisisobutyronitrile (manufactured by Wako Co., Ltd.) can be used.

The copolymer containing the monomer of Formula 2 may be substituted or unsubstituted dihydrofuran, or may be polymerized in the same manner as in Formula 1.

The content of the monomer of the formula (1) or (2) in the binding resin is 5 to 50% by weight, preferably 10 to 40% by weight, more preferably 25 to 40% by weight based on the total amount. Within this range, there are advantages of adhesion and transparency.

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

Examples of the unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, crotonic acid,? -Chloroacrylic acid, cinnamic acid, and the like

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, citraconic anhydride and the like. The unsaturated polycarboxylic acid may also be a mono (2-methacryloyloxyalkyl) ester thereof, for example, mono (2-acryloyloxyethyl) succinate, mono (2-methacryloyloxy Ethyl), phthalic acid mono (2-acryloyloxyethyl), phthalic acid mono (2-methacryloyloxyethyl), and the like. The unsaturated polycarboxylic acid may be mono (meth) acrylate of the dicarboxylic polymer of both ends thereof, and examples thereof include ω-carboxypolycaprolactone monoacrylate, ω-carboxypolycaprolactone monomethacrylate, and the like .

The carboxyl group-containing monomers may be used alone or in combination of two or more.

Examples of the other monomer 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, dicyclopentane Dienyl acrylate, dicyclopentadiethyl methacrylate, 2-hydroxy-3-phenoxy Acrylate, 2-hydroxy-3-phenoxypropyl methacrylate, unsaturated carboxylic acid esters such as glycerol monoacrylate, 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; Maleimide, N-phenylmaleimide. Unsaturated imides such as N-cyclohexylmaleimide; Aliphatic conjugated dienes such as 1,3-butadiene, isoprene and chloroprene; And 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 the like. These monomers may be used alone or in combination of two or more.

In the case where the binder resin is a copolymer of a carboxyl group-containing monomer and another monomer copolymerizable with the monomer, the content ratio of the constituent unit derived from the carboxyl group-containing monomer is preferably in a ratio by weight relative to the total content of the constituent units constituting the copolymer 10 to 50% by weight, preferably 15 to 40% by weight, and more preferably 25 to 40% by weight. 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, the solubility in a developer is good and a pattern is accurately formed at the time of development.

The content of other monomers copolymerizable with the carboxyl group-containing monomer is 10 to 50% by weight, preferably 15 to 40% by weight, more preferably 25 to 40% by weight based on the total amount of the constituent units constituting the copolymer 40% by weight.

The binder resin (B) is used in an amount 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 of the present invention. When the binder resin (B) is in the range of 1 to 60% by weight, the solubility is good and the pattern formation is excellent.

(C) Photopolymerization  Monomer

In the present invention, the photopolymerizable monomer is a monomer that can be polymerized by an active radical, acid, or the like generated from a photopolymerization initiator by light irradiation.

Specific examples of the photopolymerizable monomer include ethylene glycol diacrylate, triethylene glycol diacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, pentaerythritol Acrylate, pentaerythritol triacrylate, dipentaerythritol triacrylate, dipentaerythritol triacrylate, dipentaerythritol pentaacrylate, pentaerythritol hexaacrylate, bisphenol A di Acrylate, trimethylolpropane triacrylate, novolac epoxy acrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,4- Butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, KAYARAD DPHA (Nihon Yakku there may be mentioned, Ltd.) and the like.

The photopolymerizable monomer is preferably contained in an amount of 5 to 45% by weight based on the solid content in the photosensitive resin composition, more preferably 10 to 35% by weight. When the content of the photopolymerizable monomer is within the range of 5 to 45% by weight based on the above-mentioned criteria, the strength and flatness of the pixel portion are preferably improved.

(D) Light curing Initiator

The photopolymerization initiator (D) can be used without particular limitation as long as it can polymerize the binder resin (B) and the photopolymerizable monomer (C). In particular, it is preferable to use at least one compound selected from the group consisting of a triazine-based compound, an acetophenone-based compound, a nonimidazole-based compound and an oxime compound from the viewpoints of polymerization characteristics, initiation efficiency, absorption wavelength, availability, desirable.

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-bis (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 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 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) Imidazole compounds in which 4'5,5'-tetraphenyl-1,2'-biimidazole or phenyl groups at 4,4 ', 5,5' positions are substituted by carboalkoxy groups.

Among them, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3- , 2,2-bis (2,6-dichlorophenyl) -4,4'5,5'-tetraphenyl-1,2'-biimidazole is preferably used do.

Specific examples of the oxime compounds include o-ethoxycarbonyl- alpha -oximimino-1-phenylpropan-1-one and the compounds represented by the following formulas (3) to (5).

(3)

&Lt; Formula 4 >

&Lt; Formula 5 >

Further, as long as the effect of the present invention is not impaired, other photopolymerization initiators generally used in this field may be further used in combination. Examples of other photopolymerization initiators include benzoin-based compounds, benzophenone-based compounds, thioxanthone-based compounds, and anthracene-based compounds, and these may be used alone or in combination of two or more.

Examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether.

Examples of the benzophenone compound include benzophenone, methyl 0-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3 ', 4,4'-tetra tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, and the like.

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

Examples of the anthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene and 2-ethyl-9,10-diethoxyanthracene. have.

Other examples include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, phenylclyoxylic acid Methyl, titanocene compounds, OXE-01 (manufactured by BASF), and other photopolymerization initiators.

The photopolymerization initiator (D) may be used in combination with the photopolymerization initiator (D-1). When the photopolymerization initiator (D) is used in combination with the photopolymerization initiator auxiliary (D-1), the photosensitive resin composition containing the photopolymerization initiator (D-1) is preferable because the sensitivity becomes higher and the productivity is improved.

As the photopolymerization initiation auxiliary (D-1), for example, at least one compound selected from the group consisting of an amine compound, a carboxylic acid compound and an organic sulfur compound having a thiol group can be preferably used.

Specific examples of the amine compound include aliphatic amine compounds such as triethanolamine, methyldiethanolamine and triisopropanolamine, 4-dimethylaminobenzoic acid

N, N-dimethyl paratoluidine, 4,4'-bis (4-dimethylaminobenzoic acid), 4-dimethylaminobenzoic acid isoamyl, 2-ethylhexyl 4-dimethylaminobenzoate, Dimethylamino) benzophenone (commonly known as Michler's ketone), and 4,4'-bis (diethylamino) benzophenone. As the amine compound, an aromatic amine compound is preferably used.

Specific examples of the carboxylic acid compound include phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, dichloro And aromatic heteroacetic acids such as phenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, and naphthoxyacetic acid.

Specific examples of the organic sulfur compound having a thiol group include 2-mercaptobenzothiazole, 1,4-bis (3-mercaptobutyryloxy) butane, 1,3,5-tris (3-mercaptobutyloxyethyl) 1,3,5-triazine-2,4,6 (1H, 3H, 5H) -thione, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexacis (3-mercaptopropionate), and tetraethylene glycol bis (3-mercaptopropionate) .

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 solid content in the photosensitive resin composition.

When the photopolymerization initiator (D) is in the range of 0.1 to 40% by weight based on the above-mentioned criteria, the photosensitive resin composition is highly sensitized and the exposure time is shortened, thereby improving productivity and maintaining high resolution. It is preferable that the strength of one pixel portion and the smoothness on the surface of the pixel portion become good.

When the photopolymerization initiation assistant (D-1) is used, it is preferably contained in an amount of 0.1 to 50% by weight, more preferably 1 to 40% by weight based on the solid content in the photosensitive resin composition.

When the amount of the photopolymerization initiator auxiliary (D-1) is in the range of 0.1 to 50% by weight based on the above-mentioned criteria, the sensitivity of the photosensitive resin composition becomes higher and the productivity of the color filter formed using the composition is improved, Do.

(E) Antioxidant

The antioxidant serves to prevent oxidation of the colored resin composition during the production of the colored resin composition to improve thermal stability. The antioxidant may include a first antioxidant selected from phenolic compounds; And a second antioxidant selected from the group consisting of a phosphorus compound, a sulfur-based compound and a mixture thereof, or a compound having at least one of phenolic functional groups and phosphorus-containing functional groups and sulfur functional groups at the same time.

When a mixture of the first antioxidant and the second antioxidant is used, heat resistance, adhesion, transmittance and brightness are high, and the developing sensitivity is good even at a low exposure amount.

As the phenol-based antioxidant, known compounds can be used. Specifically, it is preferable to use 3,9-bis [2- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethoxy] , A 10-tetraoxaspiro [5.5] undecane, and pentaerythrityl tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] Phenolic compounds; (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 Butyl), 1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) Butene, 1,3,5-tris (4-hydroxybenzyl) benzene and tetrakis [methylene-3- (3,5'-di-t-butyl-4'-hydroxyphenylpropionate)] methane, 3,9-bis [2- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethoxy] -2,4,8,10-tetra 1,3,5-trimethyl-2,4,6-tris (3'5'-di-t-butyl-4-hydroxybenzyl) benzene, pentaerythrityl Bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate], triethyleneglycol-bis [3- Hydroxyphenyl) propionate], 4,4'-thiobis (6-t-butyl-3-methylphenol), tris- (3,5- (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) -isocyanurate, 1,6-hexanediol-bis [3- Di-t-butyl-4-hydroxyphenyl) (3,5-di-t-butyl-4-hydroxyphenyl) propionate], N, N'-hexamethylenebis (3, Di-t-butyl-4-hydroxy-hydrocinnamamide), 1,3,5-trimethyl-2,4,6-tris (3,5- Benzene, 2,4-bis [(octylthio) methyl] -O-cresol and AO-60 (manufactured by Adeka).

As the phosphorus antioxidant, known compounds can be used. Specifically, there can be mentioned 3,9-bis (2,6-di-tert-butyl-4-methylphenoxy) -2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane , Diisodecyl pentaerythritol diphosphite, bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite, and the like; phosphite compounds having a spirocyclic skeleton such as 2,2'-methylenebis Butyl-1-phenyloxy) (2-ethylhexyloxy) phosphorus, 6- [3- (3- 4,8,10-tetra-t-butyldibenz [d, f] [1,3,2] dioxaphosphperine, triphenylphosphite, diphenyl isodecylphosphite, phenyldiisodecylphosphite, 4 , 4'-butylidene-bis (3-methyl-6-t-butylphenyl dontridecyl) phosphite, octadecyl phosphite, tris (nonylphenyl) phosphite, 9,10-dihydro- 10-phosphaphenanthrene-10-oxide, 10- (3,5-di-t-butyl-4-hydroxybenzyl) -9,10-dihydro- 10-oxide, 10-decylox -9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, tris (2,4-di-t-butylphenyl) phosphite, cyclic neopentanetetraylbis Di-t-butylphenyl) phosphite, cyclic neopentanetetraylbis (2,6-di-t-butylphenyl) phosphite, 2,2-methylenebis (4,6- (2,4-di-t-butylphenyl) [1,1-biphenyl] -4,4 ' -dihydroxyphenyl) phosphite, tetrakis Bis (1,1-dimethylethyl) -6-methylphenyl] ethyl ester, phosphonic acid, 2,2'-methylenebis (4,6-di- (2,6-di-tert-butyl-4-methylphenoxy) -2,4,8,10-tetraoxa-3 (2-ethylhexyloxy) , 9-diphosphaspiro [5.5] undecane, 6- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propoxy] -2,4,8,10-tetra- Dibenz [d, f] [1,3,2] dioxaphosphperin, HP-10 (manufactured by Adeka), and the like.

As the sulfur-based antioxidant, known compounds can be used. Specific examples thereof include: 2,2-bis ({[3- (dodecylthio) propionyl] oxy} methyl) -1,3-propanediyl-bis [3- (dodecylthio) propionate] Mercapto benzimidazole, dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, distearyl-3,3'-thiodipropionate, Compounds having a thioether structure such as pentaerythrityl-tetrakis (3-laurylthiopropionate); Bis [3- (dodecylthio) propionyl] oxy} methyl) -1,3-propanediyl-bis [3- (dodecylthio) Propionate], 2-mercaptobenzimidazole, and the like.

In addition, sumilizer GP (manufactured by Sumitomo Co., Ltd.), which is an antioxidant containing a phenol system and phosphorus at the same time, may be used in one molecule.

The mixing ratio of the first antioxidant to the second antioxidant is preferably 2: 1 by weight.

The antioxidant (E) is included in an amount of 5 to 75 parts by weight based on 100 parts by weight of the initiator (D).

The antioxidant (E) is contained in an amount of 0.1 to 20% by weight based on the solid content in the photosensitive resin composition of the present invention. Within the above range, there is an advantage that the heat resistance is high.

(F) Solvent

The solvent (F) may be any solvent which is effective for dispersing or dissolving the other components contained in the photosensitive resin composition without any particular limitation, and examples thereof include ethers, aromatic hydrocarbons, ketones, alcohols, esters, amides .

Examples of the solvent (F) include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether and ethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol di Diethylene glycol dialkyl ethers such as ethyl ether, diethylene glycol dipropyl ether and diethylene glycol dibutyl ether, ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate, propylene glycol monomethyl Alkylene glycol alkyl ether acetates such as ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate and methoxypentyl acetate, benzene, toluene, xylene, Such as Alcohols such as methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol and glycerin, alcohols such as methanol, ethanol and the like; aliphatic hydrocarbons, such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone and cyclohexanone; Esters such as ethyl ethoxypropionate and methyl 3-methoxypropionate, and cyclic esters such as? -Butyrolactone.

Among the solvents exemplified above, an organic solvent having a boiling point of 100 ° C to 200 ° C is preferably used in consideration of the coating property and the drying surface, more preferably an alkylene glycol alkyl ether acetates, a ketone, a 3-ethoxy Propylene glycol monomethyl ether acetate, cyclohexanone, ethyl 3-ethoxypropionate, 3-ethoxypropionate, and 3-methoxypropionate are more preferable. Examples of the solvent include propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, Methyl methoxypropionate, and the like. These (F) solvents may be used alone or in combination of two or more.

The content of the (F) solvent in the photosensitive resin composition of the present invention is 10 to 90% by weight, preferably 70 to 85% by weight based on the total amount of the photosensitive resin composition of the present invention. (F) When the content of the solvent is in the range of 10 to 90% by weight on the basis of the above criteria, it may be applied by means of a roll coater, a spin coater, a slit and spin coater, a slit coater (sometimes referred to as a die coater) It is preferable since the coating property tends to be good.

(G) Additive

In the photosensitive resin composition of the present invention, other additives such as a polymer compound, a curing agent, a surfactant, an adhesion promoter, and an anti-aggregation agent may be used in parallel 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 curing agent is used for deep curing and for increasing mechanical strength. Specific examples of the curing agent 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, and triglycidyl isocyanurate.

Specific examples of the oxetane compound in the curing agent include carbonates bisoxetane, xylene bisoxetane, adipate bisoxetane, terephthalate bisoxetane, cyclohexanedicarboxylic acid bisoxetane, and the like. The curing agent may be used together with a curing agent 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.

Specific examples of the adhesion promoter include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- Aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- ( 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3- 3-isocyanatopropyltrimethoxysilane, 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 solid content of the photosensitive resin composition.

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

The present invention also provides a color filter made of the photosensitive resin composition of the present invention and a liquid crystal display device including the same.

A liquid crystal display device of the present invention comprises a color filter of the present invention comprising a substrate and a color layer. The liquid crystal display device includes a configuration known to those skilled in the art, except that the liquid crystal display device is provided with the color filter.

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 present invention. Such variations and modifications are intended to be within the scope of the appended claims.

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, the pigment dispersant (a3), a part or all of the binder resin (B), or a solvent may be mixed and dissolved or dispersed.

The binder resin (B), the photopolymerizable monomer (C), the photopolymerization initiator (D), the antioxidant (E) and the solvent (F) were further added to the mixed dispersion to a predetermined concentration to obtain the photosensitive resin composition Can be prepared.

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, &quot;%" and " part " representing the content are on a mass basis unless otherwise specified.

Example

Preparation of pigment dispersion composition

<Pigment dispersion composition M1>

, 12.0 parts by weight of CI Pigment Blue 15: 6 as a pigment, 4.0 parts by weight of DISPERBYK-2001 (manufactured by BYK) as a pigment dispersant, 44 parts by weight of propylene glycol methyl ether acetate as a solvent and 40 parts by weight of propylene glycol methyl ether And mixed / dispersed for 12 hours to prepare a pigment dispersion M1.

Synthesis of binder resin

Synthesis Example 1: Binder resin B1 containing the monomer represented by the formula (1)

23.3 g of methyl-2- (bromomethyl) -acrylate (manufactured by Aldrich), 15.8 g of triethylamine (manufactured by Aldrich), 15 g of propylene glycol methyl Ether (manufactured by TCI) was added and the inside of the four-necked flask was replaced with nitrogen. Next, the flask was heated to 90 占 폚 and then 15.1 g of methyl-2- (hydroxymethyl) -acrylate (manufactured by Aldrich), 3.2 g of 2,2'-azobisisobutyronitrile (manufactured by Wako) And 110.0 g of glycol methyl ether (manufactured by TCI) was added dropwise over 1 hour and the polymerization reaction was carried out for 0.5 hour to produce a pyran-containing polymer. Next, a mixed solution of 37.5 g of methacrylic acid, 19.0 g of methyl methacrylate, 225.0 g of propylene glycol methyl ether and 3.2 g of 2,2'-azobisisobutyronitrile (manufactured by Wako Co.) was slowly added dropwise over 1 hour And polymerization was carried out for 8 hours, followed by cooling to room temperature. After replacing the inside of the four-necked flask with nitrogen, 61.5 parts by weight of glycidyl methacrylate (manufactured by Mitsubishi Rayon Co., Ltd.), 3.6 g of tetra-n-butylammonium bromide (manufactured by TCI) And the reaction was carried out at 80 DEG C for 12 hours to add GMA to the carboxyl group of the copolymer to obtain a binder resin B1. The weight average molecular weight of the binder resin B1 measured by GPC was 23,000.

Synthesis Example 2: Binder resin B2 containing the monomer represented by the formula (2)

37.5 g of methacrylic acid (manufactured by Kyoeisha Chemical Co., Ltd.), 19.0 g of methyl methacrylate (manufactured by Kyoeisha Chemical Co., Ltd.), 2.5 g of 2,5-dihydrofuran (manufactured by TCI Corporation) Product) and 225.0 g of propylene glycol methyl ether (manufactured by TCI), and the inside of the four-necked flask was replaced with nitrogen. Next, the flask was heated to 70 캜, and then 37.5 g of methacrylic acid, 19.0 g of methyl methacrylate, 9.1 g of 2,5-dihydrofuran, 225.0 g of propylene glycol methyl ether and 2,2'-azobisisobutylo Nitrile (manufactured by Wako Co., Ltd.) was gradually added dropwise over 1 hour. After polymerization for 8 hours, the resultant was allowed to cool to room temperature, and then the inside of the four-necked flask was replaced with nitrogen. Then, 61.5 parts by weight of glycidyl methacrylate (manufactured by Mitsubishi Rayon Co., Ltd.), and tetra-n-butylammonium bromide ) And 0.15 g of methoquinone (manufactured by Kasei Kogyo Co., Ltd.) were added, and the reaction was carried out at 80 DEG C for 12 hours to add GMA to the carboxyl group of the copolymer to obtain binder resin B2. The weight average molecular weight of the binder resin B2 measured by GPC was 17,000.

Preparation of Photosensitive Resin Composition

&Lt; Example 1 >

(Pigment dispersion composition M1), (a2) 0.5 part of dye Solvent Red 124, 10.1 parts of resin of Synthesis Example 1, 4.0 parts of KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.), 1.0 part of OXE-01 0.2 part of AO-60 (manufactured by Adeka), 0.1 part of AO-412S (manufactured by Adeka), 12.0 parts of propylene glycol monomethyl ether acetate and 34.0 parts of propylene glycol monomethyl ether were mixed to prepare a photosensitive resin composition.

&Lt; Example 2 >

A photosensitive resin composition was prepared in the same manner as in Example 1, except that the resin of Synthesis Example 2 was used in Example 1.

&Lt; Example 3 >

A photosensitive resin composition was prepared in the same manner as in Example 2, except that the antioxidant was changed in Example 2.

<Example 4>

A photosensitive resin composition was prepared in the same manner as in Example 1, except that the mixed antioxidant was used in Example 1.

&Lt; Comparative Example 1 &

A photosensitive resin composition was prepared in the same manner as in Example 1, except that the binder resin B3 (copolymer of methacrylic acid and benzyl methacrylate, weight average molecular weight in terms of polystyrene: 20,000) was used in Example 1.

&Lt; Comparative Example 2 &

A photosensitive resin composition was prepared in the same manner as in Example 1, except that the binder resin B4 (copolymer of methacrylic acid and benzyl methacrylate (weight average molecular weight in terms of polystyrene: 26,000) was used in Example 1).

&Lt; Comparative Example 3 &

A photosensitive resin composition was prepared in the same manner as in Example 1, except that the antioxidant was omitted.

&Lt; Comparative Example 4 &

A photosensitive resin composition was prepared in the same manner as in Example 2, except that the antioxidant was omitted.

 (Unit: parts by weight) Example Comparative Example One 2 3 4 One 2 3 4 The colorant (A) The pigment dispersion composition (M1) 38.1 38.1 38.1 38.1 38.1 38.1 38.1 38.1 The dye (a2) 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 The binder resin (B) Synthesis Example 1 (B1) 10.1 0 0 10.1 0 0 10.25 0 Synthesis Example 2 (B2) 0 10.1 10.1 0 0 0 0 10.25 B3 0 0 0 0 10.1 0 0 0 B4 0 0 0 0 0 10.1 0 0 The photopolymerizable monomer (C) 4 4 4 4 4 4 4.15 4.15 Photopolymerization initiator (D) One One One One One One One One Antioxidant (E) (E1) 0.2 0.2 0.1 0 0.2 0.1 0 0 (E2) 0.1 0.1 0 0 0.1 0.2 0 0 (E3) 0 0 0.2 0.3 0 0 0 0 Solvent (F) (F1) 34 34 34 34 34 34 34 34 (F2) 12 12 12 12 12 12 12 12

Pigment Dispersion Composition (M1): Refer to M1 synthesis example

Dye (a2): Solvent Red 124 (trade name: Savinyl Fire Red 3GLS)

Binder resin (B): Refer to Synthesis Examples 1 and 2 and Comparative Examples 1 and 2

Photopolymerizable monomer (C): KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.)

Photopolymerization initiator (D): OXE-01 (BASF)

Antioxidant (E1): Phenolic antioxidant AO-60 (manufactured by Adeka)

Antioxidant (E2): Phosphorus antioxidant HP-10 (manufactured by Adeka)

Antioxidant (E3): Mixed antioxidant sumilizer GP (Sumitomo)

Solvent (F1): Propylene glycol monomethyl ether

Solvent (F2): Propylene glycol monomethyl ether acetate

<Experimental Example>

Heat resistance, adhesion, transmittance and developing sensitivity were measured using the photosensitive resin compositions prepared in the above Examples and Comparative Examples, and the results are shown in Table 2 below.

Example Comparative Example One 2 3 4 One 2 3 4 Heat resistance (ΔE * ab) O O O O Δ X X X Adhesiveness O O O O O X X X Transmittance (Y) 13.7 13.7 13.7 13.7 13.5 13.5 13.5 13.5 Developing sensitivity Exposure dose of 100 mJ O O O O O O O O (Pattern peeling) Exposure dose of 60 mJ O O O O Δ Δ Δ Δ Exposure dose 40 mJ O O O O X X X X

1) Heat resistance measurement

A color filter was prepared using the photosensitive resin compositions prepared in Examples 1 to 4 and Comparative Examples 1 to 4.

Specifically, each of the photosensitive resin compositions was coated on a 2-inch-square glass substrate ("EAGLE XG", manufactured by Corning Inc.) by spin coating, then placed on a heating plate and held at a temperature of 100 ° C. 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, and then blown with nitrogen gas, dried, and heated in a heating oven at 200 ° C for 25 minutes to prepare a color filter. The film thickness of the color filter prepared above was 2.0 mu m.

<Heat resistance>

The color filter thus prepared is heated in an oven at 230 DEG C for 2 hours to measure the value of DELTA E * ab.

?:? E * ab value: 0 to 1 or less

Δ: ΔE * ab value: more than 1 and not more than 3

X: ΔE * ab value: exceeding 3

2) Measurement of adhesion

The adhesion was measured using a color filter manufactured in the same manner as in the heat resistance test.

&Lt; Adhesion >

The resultant pattern was evaluated by an optical microscope, and the degree of peeling was evaluated on the following pattern. The results are shown in Table 2 below.

○: No pattern peeling

△: 1 to 3 pattern peeling

X: Pattern peeling 4 or more

3) Measurement of transmittance

The transmittance was measured using the same color filter except that the test photomask was not used in the heat resistance test.

<Transmittance>

The transmittance was measured using a colorimeter (OSP-200 manufactured by Olympus Corporation).

4) Developing sensitivity

The development sensitivity was measured using a color filter manufactured in the same manner as in the heat resistance test.

<Development Sensitivity>

○: Pattern existence

△: Pattern peeling occurred

X: Pattern does not exist.

As shown in Table 2, the color filters produced by using the photosensitive resin compositions of Examples 1 to 4 of the present invention did not cause pattern peeling even under developing conditions in which the exposure amount was as low as 40 mJ / cm 2. On the other hand, in the color filters manufactured using the photosensitive resin compositions of Comparative Examples 1 to 4, pattern peeling did not occur under a developing condition with a high exposure amount, but pattern peeling occurred as the amount of exposure decreased.

Therefore, by applying the photosensitive resin composition of the present invention, it is possible to improve the process productivity and yield by pattern peeling that can occur after development, and to form a high-quality color filter pattern.

Claims (6)

Wherein the binder resin (B) is a photosensitive resin composition comprising a colorant (A), a binder resin (B), a photopolymerizable monomer (C), a photopolymerization initiator (D), an antioxidant (E) and a solvent (F) Wherein the antioxidant (E) comprises a compound having a phenolic functional group and a phosphorus-containing functional group at the same time in one molecule, wherein the antioxidant (E) comprises a monomer containing a carboxyl group in addition to the monomer of the general formula (1) or (2).
&Lt; Formula 1 >

In Formula 1, R ₁ , R ₂ , R ₃ , and R ₄ independently represent a hydrogen atom, a halogen atom, or an organic residue having 1 to 20 carbon atoms (the organic residue may contain an oxygen atom).
(2)

In the general formula (2), R ₅ , R ₆ , R ₇ and R ₈ independently represent a hydrogen atom, a halogen atom or an organic residue having 1 to 20 carbon atoms (the organic residue may contain an oxygen atom). delete The photosensitive resin composition according to claim 1, wherein 5 to 80% by weight of the colorant (A), 1 to 60% by weight of the binder resin (B), 5 to 45% by weight of the photopolymerizable monomer (C) 0.1 to 40% by weight of initiator (D) and 0.1 to 20% by weight of antioxidant (E); Wherein the photosensitive resin composition comprises 10 to 90% by weight of a solvent (F) based on the total weight of the photosensitive resin composition. delete A color filter made of the photosensitive resin composition of claim 1. A liquid crystal display device comprising the color filter of claim 5.