KR102192236B1 - A color photosensitive resin composition, color filter and display device comprising the same - Google Patents

Abstract

The present invention relates to a colored photosensitive resin composition, a color filter and a display device including the same, and in more detail, a colorant, an alkali-soluble resin, a compound containing at least one carboxyl group and at least 5 photocurable vinyl groups in a molecule, and in a molecule It relates to a photopolymerizable compound including a compound containing 7 or more photocurable vinyl groups, a photopolymerization initiator and a colored photosensitive resin composition having excellent development speed, sensitivity and solvent resistance including a photopolymerization initiator and a solvent, and a color filter and a display device including the same.

Description

A color photosensitive resin composition, color filter and display device comprising the same}

The present invention relates to a colored photosensitive resin composition, a color filter and a display device including the same, and more specifically, a coloring agent, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator and a solvent containing excellent development speed, sensitivity and solvent resistance. It relates to a photosensitive resin composition, a color filter including the same, and a display device.

A color filter used in a liquid crystal display device is one in which fine pixels such as red, green, and blue are formed on a transparent substrate such as glass by a dyeing method, a printing method, an electrodeposition method, a pigment dispersion method, or the like.

Among these, in recent years, for the manufacture of a color filter for a liquid crystal display, a pigment dispersion method having high productivity and excellent microprocessability, that is, a manufacturing method using a colored photosensitive resin composition in which a pigment is dispersed, has been widely used. In this method, a colored photosensitive resin composition in which a pigment is dispersed is applied on a transparent substrate such as glass to form a coating film, and after exposure to the coating film by irradiation with radiation through a photomask, the unexposed part is removed by developing treatment. This is a method of forming a pattern. Hereinafter, a colored photosensitive resin composition in which a pigment used for manufacturing a color filter is dispersed as described above is referred to as a photosensitive resin composition for a color filter.

The photosensitive resin composition for a color filter usually contains a pigment, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator and a solvent, and a surfactant, an adhesion promoter, a compound for reducing residues, and the like are added thereto as necessary.

In recent years, as color filters have become increasingly higher in color and higher color reproduction, the concentration of pigments in the photosensitive resin composition for color filters is increasing.

However, when pixels are formed using a colored photosensitive resin composition with a high content of colored materials, a developing residue is generated on the substrate of the unexposed portion during the development process, or the unexposed portion is developed in a peeling type rather than a completely dissolved type. There arises a problem that impurities that remain undissolved during the process are clogged or adhered to the pixel and non-pixel part substrates. In addition, the sensitivity of the pixels formed in the exposed portion is also insufficient, resulting in a defect in the surface of the coating film or insufficient curing, resulting in a problem of insufficient solvent resistance.

Therefore, as a method of preparing a colored photosensitive resin composition to increase the sensitivity of a pixel, a technology for improving the sensitivity by using a photocurable monomer containing a polyfunctional group as a photopolymerizable compound has been developed, and Korean Patent Laid-Open No. 10-2011 In No. -0030084, the content of a colored photosensitive resin composition using a photocurable monomer containing a polyfunctional group was published.

However, in recent years, although the demand for shortening the process time is increasing, the photocurable monomer including the polyfunctional group does not show a development speed sufficient to shorten the process time. Therefore, in the case of manufacturing by shortening the process time, there is a problem that a lot of development residues in which the resin remains without being removed during development occurs.

Therefore, even if the process time is shortened, there is a need for a study on a photopolymerizable compound capable of reducing development residues and increasing sensitivity.

Republic of Korea Patent Publication No. 10-2011-0030084

The present invention uses a compound containing at least one carboxyl group and at least 5 photocurable vinyl groups in the molecule as a photopolymerizable compound, and a compound containing at least 7 photocurable vinyl groups in the molecule, so that the development rate is excellent and the developing residue is It does not occur, and it is an object of the present invention to provide a colored photosensitive resin composition having excellent sensitivity, reliability and solvent resistance.

Another object of the present invention is to provide a color filter having excellent high color reproducibility and a display device including the color filter by using the colored photosensitive resin composition for manufacturing a color filter.

To achieve the above object,

The present invention is a colored photosensitive resin composition containing a colorant, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator and a solvent,

The photopolymerizable compound provides a colored photosensitive resin composition comprising a compound containing at least one carboxyl group and at least 5 photocurable vinyl groups in a molecule, and a compound containing at least 7 photocurable vinyl groups in the molecule.

In addition, the present invention provides a color filter containing the colored photosensitive resin composition.

In addition, the present invention provides a display device including the color filter.

The colored photosensitive resin composition of the present invention uses a compound containing at least one carboxyl group and at least 5 photocurable vinyl groups in a molecule as a photopolymerizable compound, and a compound containing at least 7 photocurable vinyl groups in the molecule, so that the development speed is increased. It is excellent and does not generate developing residue, and has excellent effects in sensitivity, reliability and solvent resistance.

In addition, a color filter having excellent high color reproducibility and a display device including the same can be manufactured by using the colored photosensitive resin composition of the present invention.

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

The present invention is a colored photosensitive resin composition containing a colorant, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator and a solvent,

The photopolymerizable compound relates to a colored photosensitive resin composition comprising a compound including at least one carboxyl group and at least 5 photocurable vinyl groups in a molecule, and a compound including at least 7 photocurable vinyl groups in the molecule.

That is, the present invention uses a compound containing at least one carboxyl group and at least 5 photocurable vinyl groups in the molecule, and a compound containing at least 7 photocurable vinyl groups in the molecule as a photopolymerizable compound, and has excellent development speed. No residue is generated, and a colored photosensitive resin composition having excellent sensitivity, reliability, and solvent resistance can be provided.

If, as a photopolymerizable compound, only a compound containing at least one carboxyl group and at least five photocurable vinyl groups in the molecule is used, or if only a compound containing at least 7 photocurable vinyl groups in the molecule is used alone, it is reliable due to insufficient curing degree. This is insufficient, and the development speed is lowered, which may cause a problem in which residues are generated.

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

(A) colorant

In the present invention, the colorant includes at least one pigment, at least one dye, or a mixture thereof, and preferably at least one pigment.

( a1 ) Pigment

As the pigment, organic or inorganic pigments generally used in the art may be used. In addition, the pigment is a resin treatment, surface treatment using a pigment derivative into which an acidic group or a basic group is introduced, a grafting treatment on the pigment surface with a polymer compound, atomization treatment by sulfuric acid atomization, etc., to remove impurities. Washing treatment with an organic solvent, water, or the like, or removal treatment of ionic impurities by an ion exchange method or the like may be performed.

The organic pigment may be a variety of pigments used in printing ink, inkjet ink, etc., specifically water-soluble azo pigment, insoluble azo pigment, phthalocyanine pigment, quinacridone pigment, isoindolinone pigment, isoindoline pigment, Ferriene Pigment, Perinone Pigment, Dioxazine Pigment, Anthraquinone Pigment, Dianthraquinonyl Pigment, Anthrapyrimidine Pigment, Antantrone Pigment, Indanthrone Pigment, Pravantron Pigment, Pyrantrone Pigment, Diketopyrropyrrole Pigment And the like.

In addition, as the inorganic pigment, metal compounds such as metal oxides or metal complex salts may be used. Specifically, iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony, carbon black, organic And oxides of metals such as black pigments, titanium blacks, and pigments in which red, green, and blue are mixed to give a black color, or complex metal oxides.

In particular, the organic pigments and inorganic pigments include compounds classified as pigments in the color index (published by The Society of Dyers and Colorists), and more specifically, the color index (CI) number as follows. Although a pigment can be mentioned, it is not necessarily limited to these.

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;

Pigments such as CI pigment black 1 and 7 are mentioned.

The pigments may be used alone or in combination of two or more.

C.I. Among the pigment pigments, C.I. Pigment Yellow 138, C.I. Pigment Yellow 139, C.I. Pigment Yellow 150, C.I. Pigment Yellow 185, C.I. Pigment Orange 38, C.I. Pigment Red 122, C.I. Pigment Red 166, C.I. Pigment Red 177, C.I. Pigment Red 208, C.I. Pigment Red 242, C.I. Pigment Red 254, C.I. Pigment Red 255, C.I. Pigment Violet 23, C.I. Pigment Blue 15:3, Pigment Blue 15:6, C.I. Pigment Green 7, C.I. Pigment Green 36 and C.I. It is preferred to use at least one pigment selected from the group consisting of Pigment Green 58.

The colorant may be used alone, and when mixed with a dye, the pigment is contained in an amount of 50 to 99% by weight based on the total weight of solids in the colorant, and is preferably 30 to 99% by weight. When the content of the pigment is less than 50% by weight, it is difficult to ensure the reliability of the colored photosensitive resin composition, and when it exceeds 99% by weight, the transmittance characteristics of the colored photosensitive resin composition are deteriorated.

It is preferable to use a pigment dispersion in which the pigment particle diameter is uniformly dispersed. An example of a method for uniformly dispersing the particle diameter of the pigment may include a method of dispersing by containing a pigment dispersant (a2), and a pigment dispersion in a state in which the pigment is uniformly dispersed in a solution can be obtained. have.

( a2 ) Pigment Dispersant

The pigment dispersant is added for deagglomeration and stability of the pigment. Specific examples of the pigment dispersant include surfactants such as cationic, anionic, nonionic, amphoteric, polyester, and polyamine. And these may be used alone or in combination of two or more.

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

Specific examples of the anionic surfactant include higher alcohol sulfate ester salts such as sodium lauryl alcohol sulfate and sodium oleyl alcohol sulfate, alkyl sulfates such as sodium lauryl sulfate and ammonium lauryl sulfate, sodium dodecylbenzenesulfonate, and Alkyl aryl sulfonates, such as sodium dodecyl naphthalene sulfonate, etc. are mentioned.

Specific examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene aryl ether, polyoxyethylene alkyl aryl ether, other polyoxyethylene derivatives, oxyethylene/oxypropylene block copolymers, sorbitan fatty acid esters, Polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, glycerin fatty acid ester, polyoxyethylene fatty acid ester, and polyoxyethylene alkylamine.

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 are listed. have.

In addition, the pigment dispersant preferably includes an acrylate-based dispersant (hereinafter, an acrylate-based dispersant) including butyl methacrylate (BMA) or N,N-dimethylaminoethyl methacrylate (DMAEMA). Commercially available products of the acrylate-based dispersant include DISPER BYK-2000, DISPER BYK-2001, DISPER BYK-2070, or DISPER BYK-2150, and the acrylate-based dispersants are used alone or in combination of two or more. I can.

In addition to the acrylate-based dispersant, the pigment dispersant may use other resin type pigment dispersants. The other resin type pigment dispersants include known resin type pigment dispersants, especially polycarboxylic acid esters typified by polyurethanes and polyacrylates, unsaturated polyamides, polycarboxylic acids, and (partial) of polycarboxylic acids. Amine salts, ammonium salts of polycarboxylic acids, alkylamine salts of polycarboxylic acids, polysiloxanes, long chain polyaminoamide phosphate salts, esters of hydroxyl group-containing polycarboxylic acids and modified products thereof, or free ) An oily dispersant such as an amide formed by the reaction of a polyester having a carboxyl group with a poly(lower alkyleneimine) or a salt thereof; Water-soluble resins or water-soluble polymer compounds such as (meth)acrylic acid-styrene copolymer, (meth)acrylic acid-(meth)acrylate ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol or polyvinyl pyrrolidone; Polyester; Modified polyacrylate; Adducts of ethylene oxide/propylene oxide; And phosphate esters.

Commercially available products of the above other resin type pigment dispersants include cationic resin dispersants, for example, BYK (BIC) Chemie's brand names: 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; BASF's brand names: EFKA-44, EFKA-46, EFKA-47, EFKA-48, EFKA-4010, EFKA-4050, EFKA-4055, EFKA-4020, EFKA-4015, EFKA-4060, EFKA-4300, EFKA- 4330, EFKA-4400, EFKA-4406, EFKA-4510, EFKA-4800; Trade names of Lubirzol: SOLSPERS-24000, SOLSPERS-32550, NBZ-4204/10; Kawaken Fine Chemical's trade names: Hinoact T-6000, Hinoact T-7000, Hinoact T-8000; Ajinomoto's brand names: AJISPUR PB-821, Ajisper PB-822, Ajisper PB-823; Kyoeisha Chemical Co., Ltd. trade names: FLORENE DOPA-17HF, Florene DOPA-15BHF, Floren DOPA-33, Florene DOPA-44, and the like.

In addition to the above acrylate-based dispersants, other resin-type pigment dispersants may be used alone or in combination of two or more, or may be used in combination with an acrylate-based dispersant.

The pigment dispersant is contained in an amount of 5 to 60% by weight, preferably 15 to 50% by weight, based on the total weight of the solid content in the pigment. If the pigment dispersant is contained in an amount of less than 5% by weight, it is difficult to atomize the pigment, and problems such as gelation after dispersion may occur. If it is included in an amount exceeding 60% by weight, the viscosity may increase.

( a3 )dyes

The dye may be used without limitation as long as it has solubility in an organic solvent. Preferably, it is preferable to use a dye that has solubility in an organic solvent and can secure reliability such as solubility in an alkali developer, heat resistance, and solvent resistance.

As the dye, one selected from acidic dyes having an acidic group such as sulfonic acid or carboxylic acid, salts of acidic dyes and nitrogen-containing compounds, sulfonamides of acidic dyes, and derivatives thereof. In addition, azo-based, xanthene-based, phthalocyanine Acid dyes and derivatives thereof of the system may also be selected. Preferably, the dyes include compounds classified as dyes in the color index (published by The Society of Dyers and Colorists) or known dyes described in the dye notes (color dyes).

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

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, 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. And dyes such as Solvent Green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34 and 35.

Among the CI solvent dyes, CI solvent yellow 14, 16, 21, 56, 79, 93, 151 having excellent solubility in organic solvents; CI Solvent Red 8, 49, 89, 111, 122, 132, 146, 179; CI Solvent Orange 41, 45, 62; CI Solvent Blue 35, 36, 44, 45, 70; CI Solvent Violet 13 is preferred, and CI Solvent Yellow 21, 79; CI Solvent Red 8, 122, 132; CI solvent orange 45 and 62 are more preferable.

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, 195, 198, 206, 211, 215, 216 , 217, 227, 228, 249, 252, 257, 258, 260, 261, 266, 268, 270, 274, 277, 280, 281, 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, 92, 96, 103 , 112, 113, 120, 129, 138, 147, 150, 158, 171, 182, 192, 210, 242, 243, 256, 259, 267, 278, 280, 285, 290, 296, 315, 324:1 , 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, are mentioned.

CI Acid Yellow 42 among the CI acid dyes; CI Acid Red 92; CI Acid Blue 80, 90; CI acid violet 66; CI Acid Green 27 is preferred because of its excellent solubility in organic solvents.

In addition, 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;

CI Direct Green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, and dyestuffs, such as 82, are mentioned.

In addition, as a C.I. modanto dye,

C.I. modanto yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62 and 65;

CI Moderno Red 1, 2, 3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 30, 32, 33, 36, 37, 38, 39, 41, 43, 45, 46, 48, 53, 56, 63, 71, 74, 85, 86, 88, 90, 94 and 95;

C.I. Moderno 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 Moderno Blue 1, 2, 3, 7, 8, 9, 12, 13, 15, 16, 19, 20, 21, 22, 23, 24, 26, 30, 31, 32, 39, 40, 41, 43, 44, 48, 49, 53, 61, 74, 77, 83 and 84;

C.I. modanto 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. modanto green 1, 3, 4, 5, 10, 15, 19, 26, 29, 33, 34, 35, 41, 43, and 53, are mentioned.

Each of the above dyes may be used alone or in combination of two or more.

The dye can be used alone, and when used together with a pigment, the content of the dye is 1 to 50% by weight, preferably 1 to 40% by weight, and 5 to 30% by weight based on the total weight of the solids in the colorant. More preferable. If the content of the dye in the colorant is 1 to 50% by weight, it is possible to prevent the problem of reducing the reliability of the dye eluting by the organic solvent after pattern formation, and the sensitivity is increased.

The content of the colorant is included in an amount of 15 to 80% by weight, preferably 30 to 50% by weight, based on the total weight of the solid content in the colored photosensitive resin composition. When the colorant is contained in an amount of 15 to 80% by weight, a pattern having sufficient color concentration and sufficient mechanical strength may be formed when manufacturing a color filter.

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

(B) alkali-soluble resin

The alkali-soluble resin is prepared by copolymerization with an ethylenically unsaturated monomer containing a carboxyl group as an essential component in order to have solubility in an alkali developer used in the development treatment process when forming a pattern.

Specific examples of the ethylenically unsaturated monomer containing a carboxyl group include monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; Dicarboxylic acids such as fumaric acid, mesaconic acid and itaconic acid; Anhydrides of dicarboxylic acids; Mono (meth)acrylates of a polymer containing a carboxyl group and a hydroxyl group at both ends, such as ω-carboxypolycaprolactone mono(meth)acrylate; And the like, and acrylic acid and methacrylic acid are preferable.

In addition, a hydroxyl group may be provided to the alkali-soluble resin to secure additional developability.

As a method for imparting the hydroxyl group, (1) a method of copolymerizing an ethylenically unsaturated monomer containing a carboxyl group and an ethylenically unsaturated monomer containing a hydroxyl group, and (2) copolymerization of an ethylenically unsaturated monomer containing a carboxyl group A method of preparing by further reacting a compound containing a glycidyl group to the coalescence, and (3) a copolymer of an ethylenically unsaturated monomer containing a carboxyl group and an ethylenically unsaturated monomer containing a hydroxyl group, having an additional glycidyl group The method of manufacturing by reacting a compound, etc. are mentioned.

Specific examples of the ethylenically unsaturated monomer containing a hydroxyl group include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-hydroxy Hydroxy-3-phenoxypropyl (meth)acrylate and N-hydroxyethylacrylamide, among others, 2-hydroxyethyl (meth)acrylate is preferred, and the ethylenically unsaturated monomer containing a hydroxyl group is It can be used in combination of two or more.

Specific examples of the compound containing the glycidyl group include butyl glycidyl ether, glycidyl propyl ether, glycidyl phenyl ether, 2-ethylhexyl glycidyl ether, glycidyl butyrate, glycidyl methyl Ether, ethyl glycidyl ether, glycidyl isopropyl ether, t-butyl glycidyl ether, benzyl glycidyl ether, glycidyl 4-t-butyl benzoate, glycidyl stearate, aryl glycidyl Ether and methacrylic acid glycidyl ester, and the like, preferably butyl glycidyl ether, aryl glycidyl ether, and methacrylate glycidyl ester, and the compound containing a glycidyl group is at least two Can be used in combination.

In addition, unsaturated monomers copolymerizable with ethylenically unsaturated monomers containing a carboxyl group in the preparation of the alkali-soluble resin are aromatic vinyl compounds, N-substituted maleimide compounds, alicyclic (meth)acrylates, hydroxyethyl (meth) Acrylates, aryl (meth)acrylates, unsaturated oxetane compounds, and the like, but are not limited thereto.

The aromatic vinyl compound is specifically, for example, styrene, vinyltoluene, α-methylstyrene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinylbenzylmethyl ether , m-vinyl benzyl methyl ether, p-vinyl benzyl methyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, and p-vinyl benzyl glycidyl ether.

The N-substituted maleimide compound is specifically, for example, N-cyclohexylmaleimide, N-benzylmaleimide, N-phenylmaleimide, No-hydroxyphenylmaleimide, Nm-hydroxyphenylmaleimide, Np-hydroxyphenylmaleimide, No-methylphenylmaleimide, Nm-methylphenylmaleimide, Np-methylphenylmaleimide, No-methoxyphenylmaleimide, Nm-methoxyphenylmaleimide and Np-methoxyphenylmaleimide, etc. Can be mentioned.

The alicyclic (meth) acrylates are specifically, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n- Alkyl (meth)acrylates such as butyl (meth)acrylate, i-butyl (meth)acrylate, sec-butyl (meth)acrylate, and t-butyl (meth)acrylate; Cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, tricyclo[5.2.1.0 2,6]decane-8-yl (meth)acrylate, 2- Dicyclopentanyloxyethyl (meth)acrylate, isobornyl (meth)acrylate, and the like.

The hydroxyethyl (meth)acrylates are specifically, for example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate and N-hydroxyethyl acrylamide, and the like.

Specifically, the aryl (meth) acrylates include, for example, phenyl (meth) acrylate and benzyl (meth) acrylate.

The unsaturated oxetane compound is specifically, for example, 3-(methacryloyloxymethyl)oxetane, 3-(methacryloyloxymethyl)-3-ethyloxetane, 3-(methacryloyloxymethyl )-2-trifluoromethyloxetane, 3-(methacryloyloxymethyl)-2-phenyloxetane, 2-(methacryloyloxymethyl)oxetane and 2-(methacryloyloxymethyl) )-4-trifluoromethyloxetane, etc. are mentioned.

Each of the unsaturated monomers may be used alone or in combination of two or more.

In addition, it is preferable that the alkali-soluble resin has an acid value of 30 to 150 mgKOH/g in order to secure compatibility with dyes and storage stability of the colored photosensitive resin composition. When the acid value of the alkali-soluble resin is less than 30 mgKOH/g, the developing speed of the colored photosensitive resin composition is slow, and when it exceeds 150 mgKOH/g, the adhesion of the colored photosensitive resin composition to the substrate decreases, causing a short circuit in the pattern. It is easy, and a problem of compatibility with the dye occurs, causing a problem in that the dye in the colored photosensitive resin composition is precipitated or the storage stability is lowered and the viscosity is increased.

In addition, the alkali-soluble resin is contained in an amount of 1 to 80% by weight, preferably 10 to 50% by weight, based on the total weight of the solid content in the colored photosensitive resin composition.

When the content of the alkali-soluble resin is 1 to 80% by weight, a pattern can be formed, and resolution and residual film rate can be improved.

(C) Photopolymerization compound

The photopolymerizable compound is characterized by including a compound including at least one carboxyl group and at least 5 photocurable vinyl groups in a molecule, and a compound including at least 7 photocurable vinyl groups in the molecule.

Preferably, the compound comprising at least one carboxyl group and at least 5 photocurable vinyl groups in the molecule is a compound comprising the following Formula 1 or Formula 2, and the compound comprising at least 7 photocurable vinyl groups in the molecule is represented by the following formula It is a compound containing 3.

[Formula 1]

[Formula 2]

[Formula 3]

As a photopolymerizable compound, if only a compound containing one or more carboxyl groups and five or more photocurable vinyl groups in the molecule is used alone, or if only a compound containing seven or more photocurable vinyl groups in the molecule is used alone, it is reliable due to insufficient curing degree. This is insufficient, and the development speed is lowered, which may cause a problem in which residues are generated.

Therefore, by using a compound containing at least one carboxyl group and at least five photocurable vinyl groups in the molecule, and a compound containing at least seven photocurable vinyl groups in the molecule as a photopolymerizable compound, the development speed is excellent and the developing residue Does not occur, it is possible to provide a colored photosensitive resin composition excellent in sensitivity, reliability and solvent resistance.

The compound containing at least one carboxyl group and at least 5 photocurable vinyl groups in the molecule is contained in an amount of 10 to 90% by weight, based on the total weight of the photopolymerizable compound, and the compound containing at least 7 photocurable vinyl groups in the molecule is It is included in 10 to 90% by weight.

When the compound containing at least one carboxyl group and at least 5 photocurable vinyl groups in the molecule is contained in an amount of less than 10% by weight, developability is insufficient and a residue is generated during color filter production.If it is contained in an amount exceeding 90% by weight, the degree of curing When the color filter is manufactured, the pattern is peeled off.

In addition, when the compound containing 7 or more photocurable vinyl groups is contained in less than 10% by weight in the molecule, the degree of curing may be insufficient, resulting in a lack of reliability when manufacturing a color filter. If it is contained in excess of the weight %, a problem occurs in that the unexposed part is not removed during the development process.

In addition, the photopolymerizable compound is included in an amount of 0.5 to 60% by weight, preferably 5 to 40% by weight, based on the total weight of the solid content in the colored photosensitive resin composition. When the photopolymerizable compound is included in an amount of less than 0.5% by weight, sensitivity is insufficient, and when it is included in an amount exceeding 60% by weight, developability is insufficient.

(D) Light polymerization Initiator

The photopolymerization initiator may be used without particular limitation on its kind as long as it can polymerize the photopolymerizable compound (C).

In particular, the photopolymerization initiator is an acetophenone compound, a benzophenone compound, a triazine compound, a biimidazole compound, an oxime compound and a thioxanthone compound from the viewpoint of polymerization characteristics, initiation efficiency, absorption wavelength, availability and price. It is preferable to use at least one compound selected from the group consisting of compounds.

Specific examples of the acetophenone compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 2-hydroxy-1-[4-(2- Hydroxyethoxy)phenyl]-2-methylpropan-1-one, 1-hydroxycyclohexylphenylketone, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one , 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propane- 1-one and 2-(4-methylbenzyl)-2-(dimethylamino)-1-(4-morpholinophenyl)butan-1-one, and the like.

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

Specific examples of the triazine-based 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, 2,4- Bis(trichloromethyl)-6-(4-methoxystyryl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(5-methylfuran-2) -Yl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)ethenyl]-1,3,5-tri Azine, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)ethenyl]-1,3,5-triazine and 2,4-bis(trichloro Methyl)-6-[2-(3,4-dimethoxyphenyl)ethenyl]-1,3,5-triazine, and the like.

Specific examples of the biimidazole compound include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3- Dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(alkoxyphenyl)biimi Dazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(trialkoxyphenyl)biimidazole, 2,2-bis(2,6-dichlorophenyl)-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 with a carboalkoxy group, and the like. . Among these, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-dichlorophenyl)-4,4' ,5,5'-tetraphenylbiimidazole and 2,2-bis(2,6-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole are preferably Can be used.

Specific examples of the oxime compound include o-ethoxycarbonyl-α-oxyimino-1-phenylpropan-1-one, and commercially available products include BASF's OXE-01 and OXE-02.

Specific examples of the thioxanthone-based compound include 2-isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-dichloro thioxanthone, and 1-chloro-4-propoxy thioxanthone. Can be mentioned.

In addition, in addition to the photopolymerization initiators exemplified above, other photopolymerization initiators may be further used in combination within the range not impairing the effects of the present invention.

Other photopolymerization initiators include benzoin compounds, anthracene compounds, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenane Trenquinone, campoquinone, methyl phenylclioxylate, and titanocene compounds.

Specific examples of the benzoin-based compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether.

Specific examples of the anthracene-based compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene and 2-ethyl-9,10-diethoxy Anthracene and the like.

In addition, the photopolymerization initiator may further contain a photopolymerization initiation aid (D-1) in order to improve the sensitivity of the colored photosensitive resin composition of the present invention. The colored photosensitive resin composition according to the present invention contains a photopolymerization initiation aid (D-1), whereby the sensitivity is further increased and productivity can be improved.

As the photopolymerization initiation aid, 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 may be preferably used.

It is preferable to use an aromatic amine compound as the amine compound, and specifically, for example, aliphatic amine compounds such as triethanolamine, methyl diethanolamine, and triisopropanolamine, methyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoic acid Ethyl, 4-dimethylaminobenzoic acid isoamyl, 4-dimethylaminobenzoic acid 2-ethylhexyl, benzoic acid 2-dimethylaminoethyl, N, N-dimethylparatoluidine, 4,4'-bis(dimethylamino)benzophenone (common name : Michler's ketone) and 4,4'-bis (diethylamino) benzophenone, etc. are mentioned.

The carboxylic acid compound is preferably an aromatic heteroacetic acid, specifically, for example, phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, Dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, and naphthoxyacetic acid.

The organic sulfur compound having a thiol group is specifically, for example, 2-mercaptobenzothiazole, 1,4-bis(3-mercaptobutyryloxy)butane, 1,3,5-tris(3-mercaptobutyl) Oxyethyl)-1,3,5-triazine-2,4,6 (1H, 3H, 5H)-trione, trimethylolpropanetris (3-mercaptopropionate), pentaerythritol tetrakis (3 -Mercaptobutylate), pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptopropionate) and tetraethylene glycolbis (3-mercaptopropionate) ), etc.

The photopolymerization initiator may be included in an amount of 0.1 to 30% by weight, preferably 1 to 20% by weight, based on the total weight of solids in the colored photosensitive resin composition of the present invention.

When the photopolymerization initiator is included in the above range, the colored photosensitive resin composition is highly sensitive and thus the exposure time is shortened, so that productivity is improved and high resolution can be maintained. Further, the strength of the pixel portion formed by using the colored photosensitive resin composition and smoothness on the surface of the pixel portion can be improved.

In addition, when the photopolymerization initiation aid is additionally used, it is preferable to use the same content range as the photopolymerization initiator, and when used in the above content, the sensitivity of the colored photosensitive resin composition is further improved, and the colored photosensitive resin composition is used. Thus, the productivity of the formed color filter can be improved.

(E) solvent

As long as the solvent is effective in dissolving other components included in the colored photosensitive resin composition, the solvent used in the usual colored photosensitive resin composition may be used without particular limitation, and in particular, ethers, acetates, aromatic hydrocarbons, ketones, Alcohols, esters, and the like are preferable.

Examples of the ethers include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether;

Diethylene glycol dialkyl ethers, such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, and diethylene glycol dibutyl ether, etc. are mentioned.

Examples of the acetates include methyl cellosolve acetate, ethyl cellosolve acetate, ethyl acetate, butyl acetate, amyl acetate, methyl lactate, ethyl lactate, butyl lactate, 3-methoxybutyl acetate, 3 -Methyl-3-methoxy-1-butyl acetate, methoxypentyl acetate, ethylene glycol monoacetate, ethylene glycol diacetate, methyl 3-methocypropionate, propylene glycol methyl ether acetate, 3-methoxy-1- Butyl acetate, 1,2-propylene glycol diacetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, 1,3-butylene glycol diacetate, diethylene glycol monobutyl ether Acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoacetate, diethylene glycol diacetate, diethylene glycol monobutyl ether acetate, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol monomethyl Ether acetate, propylene glycol monoethyl ether acetate, ethylene carbonate, propylene carbonate, and the like.

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

Examples of the ketones include methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, and cyclohexanone.

Examples of the alcohols include ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, glycerin, and 4-hydroxy-4-methyl-2-pentanone.

Examples of the esters include ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, and γ-butyrolactone.

Each of the above solvents may be used alone or in combination of two or more.

The solvent is preferably an organic solvent having a boiling point of 100°C to 200°C in terms of applicability and drying properties, and, for example, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, ethyllac Tate, butyl lactate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, and the like.

The solvent is contained in an amount of 60 to 95% by weight, preferably 70 to 85% by weight, based on the total weight of the colored photosensitive resin composition. If the solvent is included in the range of 60 to 95% by weight, coating properties are good when applied with a coating device such as a roll coater, a spin coater, a slit and spin coater, a slit coater (sometimes referred to as a die coater) and inkjet. Can be set.

(F) additive

The additive may be selectively added as needed, and may include, for example, at least one selected from the group consisting of other polymer compounds, curing agents, surfactants, adhesion promoters, antioxidants, ultraviolet absorbers, and anti-aggregation agents. have.

In addition, among the additives, it is most preferable to include a surfactant.

Specific examples of the other polymer compounds include curable resins such as epoxy resins and maleimide resins, thermoplastic resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, polyester, and polyurethane. Can be lifted.

The curing agent is used to increase deep curing and mechanical strength, and 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, noblock type epoxy resin, other aromatic epoxy resins, alicyclic epoxy resins , Glycidyl ester resins, glycidylamine resins, or brominated derivatives of the above epoxy resins, aliphatic, alicyclic or aromatic epoxy compounds other than the epoxy resins and brominated derivatives thereof, butadiene (co)polymer epoxides, isoprene ( Co)polymer epoxidation products, glycidyl (meth)acrylate (co)polymer, triglycidyl isocyanurate, and the like.

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

The curing agent may be used in combination with a curing agent and 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.

Examples of the curing auxiliary compound include polyvalent carboxylic acids, polyvalent carboxylic anhydrides, and acid generators. The polyhydric carboxylic anhydrides may be commercially available as an epoxy resin curing agent. Examples of the commercially available products include Adeka Hadona EH-700 (manufactured by Adeka Industries Co., Ltd.), Rika Shiddo HH (manufactured by Shin Nippa Ewha Corporation), and MH-700 (manufactured by Shin Nihon Ewha Corporation). The curing agent exemplified above may be used alone or in combination of two or more.

The surfactant may be used to further improve the film formation of the colored photosensitive resin composition, and silicone-based, fluorine-based, ester-based, cationic, anionic, nonionic, amphoteric surfactants, etc. may be preferably used.

The silicone-based surfactants include, for example, DC3PA, DC7PA, SH11PA, SH21PA, and SH8400 of Dow Corning Toray Silicones as commercial products, and TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF of GE Toshiba Silicones. -4460 and TSF-4452.

Examples of the fluorine-based surfactant are commercially available products such as Megapieces F-470, F-471, F-475, F-482, and F-489 manufactured by Dai Nippon Ink Chemical Co., Ltd.

In addition, other commercially available products include KP (Shin-Etsu Chemical Co., Ltd.), POLYFLOW (Kyoeisha Chemical Co., Ltd.), EFTOP (Tochem Products), and MEGAFAC. (Dai Nippon Ink Kagaku High School Co., Ltd.), Flourad (Sumitomo 3M Co., Ltd.), Asahi guard, Surflon (above, Asahi Glass Co., Ltd.), SOLSPERSE (Lubrisol) , EFKA (EFKA Chemicals), PB 821 (Ajinomoto), Disperbyk-series (BYK-chemi), and the like.

The cationic surfactant may be, for example, an amine salt such as stearylamine hydrochloride and lauryl trimethylammonium chloride, or a quaternary ammonium salt.

The anionic surfactants are, for example, higher alcohol sulfate ester salts such as sodium lauryl alcohol sulfate and sodium oleyl alcohol sulfate, alkyl sulfates such as sodium lauryl sulfate and ammonium lauryl sulfate, sodium dodecylbenzenesulfonate And alkylarylsulfonic acid salts such as sodium dodecylnaphthalenesulfonate.

The nonionic surfactant is, for example, polyoxyethylene alkyl ether, polyoxyethylene aryl ether, polyoxyethylene alkyl aryl ether, other polyoxyethylene derivatives, oxyethylene/oxypropylene block copolymer, sorbitan fatty acid ester , Polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, glycerin fatty acid ester, polyoxyethylene fatty acid ester, and polyoxyethylene alkylamine.

Each of the above-exemplified surfactants may be used alone or in combination of two or more.

The type of adhesion promoter is not particularly limited, and specific examples of the adhesion promoter that can be used include vinyl trimethoxysilane, vinyl triethoxysilane, vinyl tris (2-methoxyethoxy) silane, N-(2-aminoethyl) )-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3 -Glycidoxypropylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxy And propyl trimethoxysilane, 3-mercaptopropyl trimethoxysilane, 3-isocyanate propyl trimethoxy silane, and 3-isocyanate propyl triethoxy silane.

The adhesion promoters exemplified above may be used alone or in combination of two or more. The adhesion promoter may be included in a range of usually 0.01 to 10% by weight, preferably 0.05 to 2% by weight, based on the total weight of the solid content in the red photosensitive resin composition.

The kind of the antioxidant is not particularly limited, but may include 2,2'-thiobis(4-methyl-6-t-butylphenol), 2,6-di-t-butyl-4-methylphenol, and the like. .

The type of the ultraviolet absorber is not particularly limited, but specific examples that can be used include 2-(3-tert-butyl-2-hydroxy-5-methylphenyl)-5-chlorobenzotyrazole, alkoxybenzophenone, and the like. .

The type of the anti-aggregation agent is not particularly limited, but specific examples that can be used include sodium polyacrylate.

The manufacturing method of the colored photosensitive resin composition of this invention is as follows.

First, the colorant (A) is mixed with the solvent (E) 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, some or all of the pigment dispersant (a2) and the alkali-soluble resin (B) may be mixed together with the solvent (E) to be dissolved or dispersed.

The present invention by further adding the rest of the alkali-soluble resin (B), a photopolymerizable compound (C), a photopolymerization initiator (D), and optionally an additive (F) and a solvent (E) to a predetermined concentration to the mixed dispersion. A colored photosensitive resin composition according to can be prepared.

In addition, the present invention provides a color filter made of a colored photosensitive resin composition and a display device including the same.

First, a colored photosensitive resin composition is applied onto a substrate (usually glass) or a layer made of a solid content of the previously formed colored photosensitive resin composition, followed by heating and drying to remove volatile components such as a solvent to obtain a smooth coating film.

As the coating method, for example, it can be performed by spin coating, casting coating, roll coating, slit and spin coating, or slit coating. After application, heat-drying (pre-baking) or drying under reduced pressure is performed, followed by heating to volatilize volatile components such as a solvent. Here, the heating temperature is usually 70 to 200°C, preferably 80 to 130°C. The thickness of the coating film after heat drying is usually about 1 to 8 µm. The thus obtained coating film is irradiated with ultraviolet rays through a mask for forming a target pattern. At this time, it is preferable to use a device such as a mask aligner or a stepper so that parallel light rays are uniformly irradiated to the entire exposed portion and accurate positioning of the mask and the substrate is performed. When ultraviolet rays are irradiated, curing of the ultraviolet rays is irradiated.

As the ultraviolet rays, g-line (wavelength: 436 nm), h-line, and i-line (wavelength: 365 nm) may be used. The irradiation amount of ultraviolet rays can be appropriately selected as needed, and the present invention is not limited thereto. When the cured coating film is brought into contact with a developer to dissolve and develop the non-exposed portion, a spacer having a target pattern shape can be obtained.

The developing method is not particularly limited to a liquid addition method, a dipping method, a spray method, or the like. Further, the substrate may be tilted at an arbitrary angle during development. The developer is usually an aqueous solution containing an alkaline compound and a surfactant.

The alkaline compound is not particularly limited to an inorganic or organic alkaline compound. Examples of the inorganic alkaline compound include sodium hydroxide, potassium hydroxide, disodium hydrogen phosphate, sodium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, sodium silicate, potassium silicate, sodium carbonate, Potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium borate, potassium borate, ammonia, and the like.

In addition, as an organic alkaline compound, for example, tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine , Monoisopropylamine, diisopropylamine, and ethanolamine.

The inorganic or organic alkaline compounds may be used alone or in combination of two or more. The concentration of the alkaline compound in the developer is 0.01 to 10% by weight, preferably 0.03 to 5% by weight, based on the total weight of the developer.

The surfactant in the developer may be at least one selected from the group consisting of the above-described nonionic surfactants, anionic surfactants, and cationic surfactants. The concentration of the surfactant in the developer is included in an amount of 0.01 to 10% by weight, preferably 0.05 to 8% by weight, and more preferably 0.1 to 5% by weight, based on the total weight of the developer. After image development, it can wash with water, and post-baking for 10 to 60 minutes can also be performed at 150-230 degreeC as needed.

Using the colored photosensitive resin composition of the present invention, a specific pattern can be formed on a substrate through each of the steps as described above.

Hereinafter, examples will be described in detail to illustrate the present invention in detail. However, the embodiments according to the present invention may be modified in various other forms, and the scope of the present invention should not be construed as being limited to the embodiments described below. Embodiments of the present invention are provided to more completely describe the present invention to those of ordinary skill in the art.

<Preparation of pigment dispersion composition>

Manufacturing example One.

13.5 parts by weight of CI Pigment Red 177 as a pigment, 5.0 parts by weight of DISPERBYK-2001 (manufactured by BYK) as a pigment dispersant, 61.5 parts by weight of propylene glycol monomethyl ether acetate as a solvent and 4-hydroxy-4-methyl-2-pentane A pigment dispersion composition M1 was prepared by mixing and dispersing 20 parts by weight of on a bead mill for 12 hours.

Manufacturing example 2.

13.5 parts by weight of CI Pigment Green 7 as a pigment, 5.0 parts by weight of DISPERBYK-2001 (manufactured by BYK) as a pigment dispersant, 61.5 parts by weight of propylene glycol monomethyl ether acetate as a solvent and 4-hydroxy-4-methyl-2-pentane A pigment dispersion composition M2 was prepared by mixing and dispersing 20 parts by weight on a bead mill for 12 hours.

<Preparation of colored photosensitive resin composition>

Example 1 to 5 and Comparative example 1 to 4.

The colored photosensitive resin compositions of Examples 1 to 5 and Comparative Examples 1 to 4 were prepared with the composition of Table 1 below.

(Unit: wt%) division Example Comparative example One 2 3 4 5 One 2 3 4 Pigment dispersion composition (A) M1 57.45 57.45 57.45 - - 57.45 57.45 57.45 M2 - - - 57.45 57.45 - - - 57.45 Alkali Soluble Resin (B) 1.58 Photopolymerizable compound (C) C1 2.13 1.42 0.71 2.13 0.71 - 2.84 - - C2 0.71 1.42 2.13 0.71 2.13 - - 2.84 - C3 2.84 - - 2.84 Light polymerization
Initiator (D) 0.71 Solvent (E) 37.25 Additive (F) 0.17

Pigment dispersion composition (A): Pigment dispersion composition M1 prepared in Preparation Example 1

Pigment dispersion composition M2 prepared in Preparation Example 2

Alkali-soluble resin (B): Copolymer of methacrylic acid and benzyl methacrylate (the molar ratio of the methacrylic acid unit and the benzyl methacrylate unit is 31:69, the acid value is 100 mgKOH/g, and the weight average molecular weight in terms of polystyrene is 20,000)

Photopolymerizable compound (C)

C1: CBZ-SA (Shin-Nakamura Chemical)

C2: T-PE-A(Koei)

C3: KAYARAD DPHA (Nippon Kayaku Co., Ltd.)

Wherein C1 is a compound comprising Formula 1 and Formula 2,

C2 is a compound comprising Formula 3,

C3 is a compound not including all of Chemical Formula 1, Chemical Formula 2, and Chemical Formula 3.

Photopolymerization initiator (D): Irgacure OXE02 (manufactured by BASF)

Solvent (E): Propylene glycol monomethyl ether acetate

Additive (F): SH-8400 (Dow Corning)

Experimental example One. Developability evaluation

Each of the colored photosensitive resin compositions prepared in Examples 1 to 5 and Comparative Examples 1 to 4 was applied to a 5×5 cm glass, dried, and then coated to a thickness of 2.5 μm. Thereafter, it was dried in an oven at 100° C. for 5 minutes and the solvent was removed to prepare a color filter before exposure to evaluate developability.

The color filter before exposure is immersed in KOH aqueous solution of pH 14 and pH 10 for 1 minute, then taken out, immersed in distilled water for 1 minute, and then dried in an oven at 100° C. for 1 minute to check the surface condition of the color filter before exposure I did.

Developability evaluation criteria are as follows, and the results are shown in Table 2 below.

<Development evaluation criteria>

○: Surface resin remaining is not recognized at all

△: Surface resin remaining is recognized, but slightly recognized

X: Surface resin remaining is visually recognized

Experimental example 2. Sensitivity evaluation

Each of the colored photosensitive resin compositions prepared in Examples 1 to 5 and Comparative Examples 1 to 4 was applied to a 5×5 cm glass, dried, and then bar-coated to a thickness of 2.5 μm. Then, after drying in an oven at 100° C. for 3 minutes to remove the solvent, a color filter was manufactured by exposing the fusion lamp so that the cumulative amount of light at a wavelength of 313 nm was 40 mJ with a distance of 300 μm to the photo mask.

The color filters were immersed in a KOH aqueous solution having a pH of 14 for 3 minutes and then taken out, and then immersed in distilled water for 1 minute to take out, and then cured in an oven at 230° C. for 20 minutes to measure the degree of development of the pattern line width and tearing of the color filter.

The pattern line width was measured by measuring the difference between the line width (X1) of the pattern and the line width (X2) of the photomask.

The evaluation criteria of the pattern tearing are as follows, and the pattern line width and the result of the pattern tearing are shown in Table 2 below.

<Pattern tearing evaluation criteria>

○: No tearing in the pattern,

△: 1 to 3 tears in the pattern,

×: 4 or more tears in the pattern

Experimental example 3. Solvent resistance evaluation

Each of the colored photosensitive resin compositions prepared in Examples 1 to 5 and Comparative Examples 1 to 4 was applied to a 5×5 cm glass, dried, and then bar-coated to a thickness of 2.5 μm. After drying in an oven at 100° C. for 3 minutes to remove the solvent, the fusion lamp was exposed to a total of 40 mJ at a wavelength of 313 nm with a distance of 300 μm to the photo mask, and cured in a 230° C. oven for 20 minutes to prepare a color filter.

The color filter was immersed in an NMP solution at room temperature for 30 minutes, washed with ultrapure water and dried on a hot plate heated to 120° C. for 2 minutes, and then the chromaticity before and after immersion was measured.

The equation used at this time is the following equation (1) representing the color change in a three-dimensional colorimeter defined by L*, a*, and b*, and the smaller the color change value, the more reliable color filters can be manufactured.

The results are shown in Table 2 below.

[Equation 1]

△Eab* =[(△L*)2+(△a*)2+(△b*)2] ^0.5

Developability Pattern line width Pattern tearing Solvent resistance Example 1 ○ +8 ○ 2.4 Example 2 ○ +13 ○ 1.8 Example 3 △ +16 ○ 1.2 Example 4 △ +15 ○ 1.4 Example 5 ○ +7 ○ 2.1 Comparative Example 1 △ +1 △ 4.6 Comparative Example 2 ○ -6 × 6.1 Comparative Example 3 × +18 ○ 1.4 Comparative Example 4 △ -One △ 4.3

In the results of Table 2, the colored photosensitive resin composition of the present invention comprising a compound containing at least one carboxyl group and at least 5 photocurable vinyl groups in the molecule, and a compound containing at least 7 photocurable vinyl groups in the molecule Examples 1 to 5 were observed to be excellent or good in all of developability, sensitivity and solvent resistance.

However, the colored photosensitive resin compositions of Comparative Examples 1 and 4 containing only a compound containing 7 or more photocurable vinyl groups in the molecule showed poor pattern line width and solvent resistance, and 7 or more photocurable vinyls in the molecule The colored photosensitive resin composition of Comparative Example 2, which does not contain a compound containing a group, has a poor pattern line width and a pattern tearing, resulting in poor sensitivity. In addition, the colored photosensitive resin composition of Comparative Example 3, which did not contain a compound containing at least one carboxyl group and at least 5 photocurable vinyl groups in the molecule, showed poor developability and solvent resistance.

Accordingly, the colored photosensitive resin composition of the present invention comprising a compound containing at least one carboxyl group and at least 5 photocurable vinyl groups in the molecule as a photopolymerizable compound, and a compound containing at least 7 photocurable vinyl groups in the molecule is It was found through experiments that no developing residue was generated and that the sensitivity and solvent resistance were excellent.

Therefore, when a color filter having a high color reproducibility is prepared by using the colored photosensitive resin composition of the present invention, problems of lowering sensitivity and developability that may occur during the production of the color filter can be solved.

Claims (9)

A colored photosensitive resin composition containing a colorant, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator and a solvent,
The photopolymerizable compound includes a compound containing at least one carboxyl group and at least 5 photocurable vinyl groups in a molecule, and a compound containing at least 7 photocurable vinyl groups in the molecule,
The alkali-soluble resin is a copolymer copolymerized including an ethylenically unsaturated monomer containing a carboxyl group,
Compounds containing at least one carboxyl group and at least 5 photocurable vinyl groups in the molecule include compounds of the following formula 1 or 2,
The compound containing 7 or more photocurable vinyl groups in the molecule comprises a compound of the following formula (3), colored photosensitive resin composition.
[Formula 1]

[Formula 2]

[Formula 3]

delete delete The method according to claim 1, wherein, based on the total weight of the photopolymerizable compound, 10 to 90% by weight of the compound containing at least one carboxyl group and at least 5 photocurable vinyl groups in the molecule and 7 or more photocurable vinyl groups in the molecule. A colored photosensitive resin composition comprising 10 to 90% by weight of the compound. The method of claim 1, wherein the colored photosensitive resin composition comprises 15 to 80% by weight of a colorant, 1 to 80% by weight of an alkali-soluble resin, 0.5 to 60% by weight of a photopolymerizable compound, and 0.1 To 30% by weight, and a colored photosensitive resin composition comprising 60 to 95% by weight of a solvent based on the total weight of the colored photosensitive resin composition. The colored photosensitive resin composition according to claim 1, wherein the colored photosensitive resin composition further contains an additive. The colored photosensitive resin composition according to claim 6, wherein the additive contains a surfactant. A color filter containing the colored photosensitive resin composition of claim 1. A display device comprising the color filter of claim 8.