TW201712075A - Colored photosensitive resin composition and color filter made using the same capable of exhibiting excellent sensitivity due to a sufficient curing in the low-temperature heating process - Google Patents

Abstract

The present invention relates to a colored photosensitive resin composition and a color filter made using the same, and more particularly, to a colored photosensitive resin composition for manufacturing a color filter which is used in manufacturing a colored liquid crystal display, and a color filter made using the resin composition. The colored photosensitive resin composition of the present invention exhibits excellent sensitivity due to sufficient curing in the low-temperature heating process, thereby providing a highly reliable color filter.

Description

Coloring photosensitive resin composition and color filter using the same Field of invention

The present invention relates to a colored photosensitive resin composition and a color filter using the same, and more particularly to a coloring photosensitive resin composition for color filters used in the production of a color filter used in a color liquid crystal display device or the like, and a use thereof Manufactured color filter.

Background of the invention

The color filter is manufactured by a dyeing method, a printing method, an electrodeposition method, a pigment dispersion method, a film transfer method, or the like, not only in a liquid crystal display device (LCD) but also in a charge coupled device (charge). It is widely used in coupled devices, CCDs, and liquid crystal switches. In particular, color filters are one of the most important components for reproducing hue in LCDs whose use is expanded.

In the LCD manufacturing process, in order to improve the productivity, in the production of the color filter pattern, a high-reliability color filter is produced in the low-temperature firing step as compared with the high-temperature firing step. However, when the conventional colored photosensitive resin composition is cured at 200 ° C or lower, the resin composition is not sufficiently cured and the adhesion to the lower substrate is insufficient. The film is peeled off, or the film is peeled off, or the amount of exposure is increased, the sensitivity is lowered, or the like in order to form a film. Therefore, the demand for the low-temperature curing type coloring photosensitive resin composition which can provide sufficient coloring and high reliability in the baking process of 200 degreeC or less is high, and the research on it is active. Conducted. In the case of a low-temperature firing step of 200 ° C or lower, it is possible to perform sufficient curing on a substrate and to have excellent coloring sensitivity to adhesion to a substrate after low-temperature firing. A resin composition comprising a colorant, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, a solvent, an azo compound, a mercapto compound, and an epoxy compound. However, since the above-mentioned prior art contains an azo compound, the transparency of the color filter is lowered, and the azo compound is thermally decomposed to cause a problem of smoke, and the substrate is required to be cooled at a low temperature baking step of 200 ° C or lower. A colored photosensitive resin composition which can be sufficiently cured and has improved reliability.

Prior art literature Patent literature

Patent Document 1: Korean Patent Publication No. 10-2012-0088026

Summary of invention

An object of the present invention is to provide a colored photosensitive resin composition which can perform sufficient curing on a substrate and exhibit excellent sensitivity in a low-temperature firing step.

Further, it is an object of the present invention to provide a colored photosensitive resin as described above. A color filter made of a composition with high reliability.

The present invention provides a colored photosensitive resin composition comprising a colorant (A), an alkali-soluble resin (B), a polyfunctional monomer (C), a photopolymerization initiator (D), a solvent (E), And the fluorenyl compound (F), the polyfunctional monomer (C) contains a trifunctional or higher (meth)acrylic polyfunctional monomer (C-1), and a polyfunctional monomer represented by the following Chemical Formula 1 (C-2).

In the above Chemical Formula 1, X is an aliphatic hydrocarbon having 1 to 10 carbon atoms which contains a hetero atom or does not contain a hetero atom, and R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ are each independently an epoxy compound. Or a compound represented by the following Chemical Formula 2, wherein at least one or more of R ₁ to R ₆ are a compound represented by Chemical Formula 2 and an epoxy compound.

n is an integer from 0 to 5.

In one embodiment, the polyfunctional monomer (C-2) represented by Chemical Formula 1 may be a compound represented by the following Chemical Formula 3.

[Chemical Formula 3]

In another embodiment, the trifunctional or higher (meth)acrylic polyfunctional monomer (C-1) may be selected from trimethylolpropane tri(meth)acrylate and ethoxylated trimethylol. Propane tri(meth)acrylate, propoxylated trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(methyl) One or more of acrylate, ethoxylated dipentaerythritol hexa(meth) acrylate, propoxylated dipentaerythritol hexa(meth) acrylate, and dipentaerythritol hexa (meth) acrylate.

Further, in other embodiments, the mercapto compound (F) may be selected from the group consisting of 4-Mercaptohydrocinnamic Acid, 4-Mercaptobenzoic Acid, and Thiosalicylic Acid. , 3,4-Dimethoxybenzenethiol, 3-Ethoxybenzenethiol, 4-Hydroxybenzenethiol, 3-A 3-Methoxybenzenethiol, 2-Hydroxybenzenethiol, 4-Methoxybenzenethiol, 3-Hydroxybenzenethiol, 2 2-Methoxybenzenethiol, methyl thiosalicylate, 2,3,5,6-tetrafluoro-4-mercaptobenzoic acid (2,3,5,6-Tetrafluoro-4-mercaptobenzoic Acid), 2-mercaptobenzothiazole, 1,4-bis(3-mercaptobutyloxy)butane, β-mercaptopropionic acid (β-Mercaptopropionic acid) , Methyl 3-Mercaptopropionate, 2-Ethylhexyl 3-Mercaptopropionate, n-Octyl 3-(3-ctylpropionate) Mercaptopropionate), Methoxybuthyl 3-Mercaptopropionate, Stearyl 3-Mercaptopropionate, Trimethylolpropane Tris(3-mercaptopropionate) Trimethylolpropanetris (3-mercaptopropionate), Tris[(3-Mercaptopropionyloxy)-ethyl]-isocyanurate, pentaerythritol tetrakis(3-mercapto) (Pentaerythritol tetrakis (3-mercaptopropionate), Tetraethyleneglycol bis (3-mercaptopropionate), and dipentaerythritol (Dipentaerythritol) One or more of hexakis (3-mercaptopropionate).

Further, other embodiments may include 5 to 60% by weight of a coloring agent (A), 10 to 80% by weight of an alkali-soluble resin (B), and 5 to 80% by weight of a polyfunctional monomer (C). ), containing 0.1 to 5% by weight of a mercapto compound (F), and containing 0.1 to 40% by weight of a photopolymerization initiator based on the total content of the alkali-soluble resin (B) and the polyfunctional monomer (C) The solvent (E) is contained in an amount of 60 to 90% by weight based on the total weight of the colored photosensitive resin composition.

Further, the present invention provides a color filter produced by using the above colored photosensitive resin composition.

Since the colored photosensitive resin composition of the present invention can be sufficiently cured in a low-temperature baking step and exhibits excellent sensitivity, it is possible to provide a highly reliable color filter.

detailed description

The present invention relates to a colored photosensitive resin composition and a color filter produced using the same.

The colored photosensitive resin composition of the present invention is characterized in that it contains a polyfunctional monomer (C-2) represented by Chemical Formula 1 and a mercapto compound (F), and can be sufficiently cured in a low-temperature baking step. The reliability of the color filter is improved.

The invention is explained in detail below.

Colorant (A)

The coloring agent (A) contains one or more kinds of pigments (a1) or one or more types of dyes (a2) as essential components.

Pigment (a1)

As the above pigment, an organic pigment or an inorganic pigment which is generally used in the art can be used. As the pigment, various pigments used in printing inks, inkjet inks, and the like can be used, and specific examples thereof include water-soluble azo pigments and insoluble materials. Azo pigments, phthalocyanine pigments, quinacridone pigments, isoindanone pigments, isoindan pigments, anthraquinone pigments, anthrone pigments, dioxazine pigments, anthraquinone pigments, hydrazine pigments, hydrazine Pyrimidine pigments, anthanthrone pigments, indanthrone pigments, xanthone pigments, pyranthrone pigments, diketopyrrolopyrrole pigments, and the like. Examples of the inorganic pigment include metal compounds such as metal oxides and metal complex salts, and specific examples thereof include iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, cerium, carbon black, and the like. A metal oxide or a composite metal oxide or the like. In particular, examples of the organic pigment and the inorganic pigment include a compound classified as a pigment in the excellent index (published by The Society of Dyers and Colourists), and more specifically, the following color index (CI) number is exemplified. The pigments are not necessarily limited to these, and these may be used alone or in combination of two or more.

CI 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 Oranges 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

C.I. Pigment Black 1 and 7, etc.

As the above-mentioned pigment, an organic pigment or an inorganic pigment which is generally used in the art can be used, and these may be used alone or in combination of two or more.

Among the CI pigments exemplified above, it is preferably selected from the group consisting of CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 150, CI Pigment Yellow 185, 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 Violet 23, CI Pigment Blue 15:3, Pigment Blue 15:6, CI Pigment Green 7, CI Pigment Green 36, CI Pigment in Pigment Green 58.

The above pigment is preferably a pigment dispersion liquid in which the particle diameter is uniformly dispersed. An example of a method for uniformly dispersing the particle diameter of the pigment is a method of dispersing the pigment dispersant (a3), and a pigment in a state in which the pigment is uniformly dispersed in a solution can be obtained. Dispersions.

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

Pigment dispersant (a3)

The above pigment dispersant (a3) is added in order to maintain deagglomeration and stability of the pigment, and a pigment dispersant generally used in the art can be used without limitation. Preferably, it contains BMA (butyl methacrylate) or A pigment dispersant of DMAEMA (N,N-dimethylaminoethyl methacrylate) acrylate dispersant (hereinafter referred to as an acrylic dispersant) is preferred. In this case, it is preferable to use an acrylic dispersant produced by the activity control method proposed in the Korean Patent Publication No. 2004-0014311 as a commercially available product of the acrylate-based dispersant produced by the above-described activity control method. Examples include DISPER BYK-2000, DISPER BYK-2001, DISPER BYK-2070, DISPER BYK-2150, and the like.

The acrylic dispersing agents exemplified above may be used singly or in combination of two or more kinds.

In addition to the above-described acrylic dispersant, the above dispersant (a3) may be a pigment dispersant of another resin type. Examples of the other resin type pigment dispersant include a known resin type pigment dispersant, in particular, a polyurethane, a polycarboxylate represented by a polyacrylate, an unsaturated polyamine, a polycarboxylic acid, and a polycarboxylate. An acid (partial) amine salt, an ammonium salt of a polycarboxylic acid, an alkylamine salt of a polycarboxylic acid, a polyoxyalkylene oxide, a long-chain polyaminoguanamine phosphate, an ester of a hydroxyl group-containing polycarboxylic acid, and the like a modified product, or an oily dispersant such as a guanamine or a salt thereof formed by the reaction of a polyester having a free carboxyl group and a poly(lower alkyleneimine); (meth)acrylic acid- a water-soluble resin or a water-soluble polymer compound such as a styrene copolymer, a (meth)acrylic acid-(meth)acrylate copolymer, a styrene-maleic acid copolymer, a polyvinyl alcohol, or a polyvinylpyrrolidone; Polyester; modified polyacrylate; addition product of ethylene oxide/propylene oxide and phosphate ester. As a commercial product of the above-mentioned resin-type dispersing agent, as a cationic-type resin dispersing agent, BYK ( Chemical company's trade name: 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 trade 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; Lubirzol's trade name: SOLSPERS-24000, SOLSPERS-32550, NBZ-4204/10; trade name of Chuanyan Fine Chemical Co., Ltd. : (HINOACT) T-6000, T-7000, T-8000; Ajinomoto's trade name: (AJISPUR) PB-821, PB-822, PB-823; Trade name of Gongrongshe Chemical Society: (FLORENE) DOPA-17HF, DOPA-15BHF, DOPA-33, DOPA-44 and so on. In addition to the above-mentioned acrylic dispersant, the other resin type pigment dispersing agents may be used singly or in combination of two or more kinds, and may be used in combination with an acrylic dispersing agent.

The amount of the dispersing agent (a3) to be used is 5 to 60 parts by weight, and more preferably 15 to 50 parts by weight, based on 100 parts by weight of the solid content of the pigment (a1) to be used. When the content of the dispersant (a3) exceeds 60 parts by weight based on the above-mentioned criteria, the viscosity is increased. When the content is less than 5 parts by weight, the microparticulation of the pigment is difficult, or problems such as gelation after dispersion may occur.

Dye (a2)

The above dye (a2) is only required to have solubility in an organic solvent. Can be used without restrictions. Preferably, it is preferable to use a dye having solubility in an organic solvent and ensuring reliability with respect to solubility and solvent resistance to an alkali developing solution, stability over time, and the like.

As the dye, an acid dye selected from the group consisting of an acid dye having an acidic group such as a sulfonic acid or a carboxylic acid, a salt of an acid dye and a nitrogen-containing compound, a sulfonamide of an acid dye, and the like, and a dye thereof may be used. Azo dyes, xanthene systems, phthalocyanine acid dyes and derivatives thereof can also be selected.

Preferably, the above-mentioned dyes include a compound classified as a dye in a color index (published by The Society of Dyers and Colourists), and a known dye described in a dyeing note (color dyeing company).

Specific examples of the dye include CI solvent yellow 4, 14, 15, 16, 21, 23, 24, 38, 56, 62, 63, 68, 79, 82, 93, 94. Yellow dyes such as 98, 99, 151, 162, 163; red solvents such as CI solvent red 8, 45, 49, 89, 111, 122, 125, 130, 132, 146, 179; CI solvent orange 2, 7, 11 Orange dyes such as 15, 26, 41, 45, 56, 62; blue solvents such as CI solvent blue 5, 35, 36, 37, 44, 59, 67, 70; CI solvent violet 8, 9, 13, 14, 36 , 37, 47, 49 and other purple dyes; CI solvent green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, 35 and other green dyes.

C.I. Solvent dyes are preferably excellent in solubility in organic solvents. CI Solvent Yellow 14, 16, 21, 56, 151, 79, 93; 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, wherein, more preferably CI solvent yellow 21, 79; CI solvent red 8, 122, 132; CI.

Further, as the CI acid dye, CI acid yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76 can be cited. , 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, 251 and other yellow dyes; 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 Red dyes such as 339, 341, 345, 346, 349, 382, 383, 394, 401, 412, 417, 418, 422, 426; CI Acid Orange 6, 7, 8, Orange dyes such as 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, 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, 340 and other blue dyes; CI acid violet 6B, 7, 9, 17, 19, 66 and other purple dyes; CI acid green 1, 3, 5, 9, 16, 25, 27, 50, 58, 63, 65, 80, 104, 105, 106, 109 and other green dyes.

Among the acid dyes, C.I. Acid Yellow 42 which is excellent in solubility in an organic solvent; C.I. Acid Red 92; C.I. Acid Blue 80, 90; C.I. Acid Violet 66; C.I. Acid Green 27.

Further, as the CI direct dye, CI direct yellow 2, 33, 34, 35, 38, 39, 43, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95 , yellow dyes such as 98, 102, 108, 109, 129, 136, 138, 141; CI direct red 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172 Red dyes such as 173, 176, 177, 179, 181, 182, 184, 204, 207, 211, 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246, 250; Orange dyes such as oranges 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, 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, 293 and other blue dyes; CI direct violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104 Such as purple dye; CI direct green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82 and other green dyes.

Further, examples of the CI mord dye include yellow dyes such as CI mordant yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, and 65; 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, 95 and other red dyes; CI mordant orange 3, 4, 5, 8, 12, 13, 14, 20 , 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48 and other orange dyes; CI mordant 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, 84 Such as blue dye; CI mordant purple 1, 2, 4, 5, 7, 14, 22, 24, 30, 31, 32, Purple dyes such as 37, 40, 41, 44, 45, 47, 48, 53, 58; CI mordant green 1, 3, 4, 5, 10, 15, 19, 26, 29, 33, 34, 35, 41, 43, 53 and other green dyes.

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

The content of the coloring agent (A) is preferably 5 to 60% by weight, preferably 10 to 45% by weight based on the solid content of the colored photosensitive resin composition. When the coloring agent (A) is contained in an amount of 5 to 60% by weight, the color density of the pixel is sufficient even when the film is formed, and the non-pixel portion peeling property during development is not lowered, and residue is less likely to occur, which is preferable.

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

Alkali soluble resin (B)

It is produced by copolymerizing an ethylenically unsaturated monomer (b1) having a carboxyl group as an essential component in order to be soluble in the alkali developer used in the development treatment step at the time of pattern formation.

Moreover, in order to ensure compatibility with the dye (a2) and the temporal stability of the colored photosensitive resin composition, the acid value of the alkali-soluble resin (B) is preferably from 30 to 150 mgKOH/g. When the acid value of the alkali-soluble resin (B) is less than 30 mgKOH/g, the coloring photosensitive resin composition is less likely to ensure a sufficient development speed, and when it exceeds 150 mgKOH/g, the adhesion to the substrate is reduced, which is liable to occur. Short circuit of the pattern, produced in compatibility with the dye The problem is that the dye in the colored photosensitive resin composition is precipitated, and the temporal stability of the colored photosensitive resin composition is lowered, and the viscosity is likely to increase.

In order to ensure additional developability of the above alkali-soluble resin (B), a hydroxyl group can be provided. The hydroxyl group is provided with an effect of improving the development speed, and the total of the hydroxyl value of the alkali-soluble resin (B) and the polyfunctional monomer (C) is limited to 50 mgKOH/g or more and 250 mgKOH/g or less. When the total of the hydroxyl value is less than 50 mgKOH/g, a sufficient development speed cannot be ensured, and when it exceeds 250 mgKOH/g, the dimensional stability of the formed pattern is lowered, and the straightness of the pattern tends to be poor, and the dye is easily formed. The compatibility is lowered, and the problem of stability over time is easily generated.

The ethylenically unsaturated monomer (b1) having a carboxyl group, and specific examples thereof include monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; and dicarboxylic acids such as fumaric acid, mesaconic acid, and itaconic acid; And an acid anhydride of these dicarboxylic acids; a mono(meth)acrylate of a polymer having a carboxyl group and a hydroxyl group at both terminals, such as ω-carboxypolycaprolactone mono(meth)acrylate, preferably acrylic acid, methacrylic acid .

In order to impart a hydroxyl group to the alkali-soluble resin (B), an ethylenically unsaturated monomer (b1) having a carboxyl group may be copolymerized with an ethylenically unsaturated monomer (b2) having a hydroxyl group to produce a compound having a glycidyl group. (b3) It is produced by additionally reacting with a copolymer of an ethylenically unsaturated monomer (b1) having a carboxyl group. Further, it can be produced by additionally reacting a compound having a glycidyl group (b3) with a copolymer of an ethylenically unsaturated monomer (b1) having a carboxyl group and an ethylenically unsaturated monomer (b2) having a hydroxyl group.

As a specific example of the above ethylenically unsaturated monomer (b2) having a hydroxyl group, There are 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate N-hydroxyethyl acrylamide or the like is preferably 2-hydroxyethyl (meth) acrylate, and two or more kinds thereof may be used in combination.

Specific examples of the above glycidyl group-containing compound (b3) include butyl glycidyl ether, glycidyl propyl ether, glycidyl phenyl ether, 2-ethylhexyl glycidyl ether, and butyric acid shrinkage Glyceryl ester, glycidyl methyl ether, ethyl glycidyl ether, glycidyl isopropyl ether, tert-butyl glycidyl ether, benzyl glycidyl ether, 4-tert-butylbenzoic acid glycidol Ester, glycidyl stearate, aryl glycidyl ether, glycidyl methacrylate, etc., preferably butyl glycidyl ether, aryl glycidyl ether, glycidyl methacrylate, two kinds of The above combination is used.

The monomers exemplified as the glycidyl group-containing compound (b3) may be used singly or in combination of two or more kinds.

Specific examples of the polymerizable monomer (b4) having a copolymerizable unsaturated bond include styrene, vinyl toluene, α-methylstyrene, p-chlorostyrene, o-methoxystyrene, and the like. M-methoxystyrene, p-methoxystyrene, o-vinylbenzyl methyl ether, m-vinylbenzyl methyl ether, p-vinylbenzyl methyl ether, o-vinyl An aromatic vinyl compound such as benzyl glycidyl ether, m-vinylbenzyl glycidyl ether or p-vinylbenzyl glycidyl ether; N-cyclohexylmaleimide, N-benzyl horse醯imine, N-phenylmaleimide, N-o-hydroxyphenylmaleimide, N-m-hydroxyphenyl horse Indole, N-p-hydroxyphenylmaleimide, N-o-methylphenylmaleimide, N-m-methylphenylmaleimide, N-pair Methylphenylmaleimide, N-o-methoxyphenylmaleimide, N-m-methoxyphenylmaleimide, N-p-methoxyphenyl An N-substituted maleimide compound such as ruthenium imine; methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, (meth)acrylic acid alkyl esters such as n-butyl (meth)acrylate, isobutyl (meth)acrylate, sec-butyl (meth)acrylate, and t-butyl (meth)acrylate; (methyl) Cyclopentyl acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.02,6] decane-8-yl (meth) acrylate, ( An alicyclic (meth) acrylate such as 2-dicyclopentyloxyethyl (meth)acrylate or isobornyl (meth)acrylate; phenyl (meth) acrylate or benzyl (meth) acrylate ( Aryl methacrylates; 3-(methacryloxymethyl)oxetane, 3-(methacryloxymethyl)-3- Oxycyclobutane, 3-(methacryloxymethyl)-2-trifluoromethyloxetane, 3-(methacryloxymethyl)-2-phenyloxy Unsaturated, such as heterocyclobutane, 2-(methacryloxymethyl)oxetane, 2-(methacryloxymethyl)-4-trifluoromethyloxetane An oxetane compound or the like.

The content of the alkali-soluble resin (B) is required to satisfy the condition that the total of the hydroxyl groups of the alkali-soluble resin (B) and the polyfunctional monomer (C) is 50 mgKOH/g or more and 250 mgKOH/g or less, and the colored photosensitive resin composition is colored. in The solid content standard is in the range of 10 to 80% by weight, preferably 10 to 70% by weight. When the content of the alkali-soluble resin (B) is from 10 to 80% by weight based on the above criteria, the solubility in the developer is sufficient, pattern formation is easy, and the film of the pixel portion of the exposed portion is prevented from being reduced during development, and the non-pixel portion is Since the peeling property is good, it is preferable.

Polyfunctional monomer (C)

The polyfunctional monomer (C) must contain a trifunctional or higher (meth)acrylic polyfunctional monomer (C-1) and a polyfunctional monomer (C-2) represented by the following Chemical Formula 1.

In the above Chemical Formula 1, X is an aliphatic hydrocarbon containing a heteroatom or contains no heteroatoms having 1 to 10 carbon _{atoms, R 1, R 2, R} 3, R 4, R 5 and R ₆ are each independently an epoxy compound Or a compound represented by the following Chemical Formula 2, wherein at least one or more of R ₁ to R ₆ are a compound represented by Chemical Formula 2 and an epoxy compound.

n is an integer from 0 to 5.

More specifically, the polyfunctional monomer (C-2) represented by the above Chemical Formula 1 may be a compound represented by the following Chemical Formula 3.

[Chemical Formula 3]

When the coloring photosensitive resin composition of the present invention contains the above-mentioned polyfunctional monomer (C), it is possible to sufficiently cure the substrate in the low-temperature firing step, and the sensitivity is excellent, thereby providing highly reliable color filter. Device. Further, since the high light polymerization density is excellent, the adhesion to the glass substrate and the coloring power are excellent.

The polyfunctional monomer (C) can be used in combination with a monofunctional monomer or a bifunctional monomer. Preferably, a bifunctional or higher polyfunctional monomer can be used.

Specific examples of the monofunctional monomer include mercaptophenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, and acrylic acid 2- Examples of the commercially available products include hydroxyethyl ester and N-vinylpyrrolidone, and ARONIX M-101 (East Asia Synthetic), KAYARAD TC-110S (Nippon Chemical Co., Ltd.), and VISCOAT 158 (Osaka Organic Chemical Industry).

Specific examples of the bifunctional monomer include 1,6-hexanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, and neopentyl glycol di(meth)acrylate. , triethylene glycol di(meth)acrylate, bis(acryloxyethyl)ether of bisphenol A, 3-methylpentanediol di(meth)acrylate, etc., as a commercial item, ARONIX M-210, M-1100, 1200 (East Asian Synthetic), KAYARAD HDDA (Nippon Chemical), VISCOAT 260 (Osaka Organic Chemical Industry), AH-600, AT-600, UA-306H (Kyoeisha Chemical Co., Ltd.) .

Specific examples of the above-mentioned trifunctional or higher (meth)acrylic polyfunctional monomer (C-1) include trimethylolpropane tri(meth)acrylate and ethoxylated trimethylolpropane tris(A). Acrylate, propoxylated trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, Ethoxydipentaerythritol hexa(meth) acrylate, propoxylated dipentaerythritol hexa(meth) acrylate, dipentaerythritol hexa (meth) acrylate, etc., as a commercial product, ARONIX M-309, TO-1382 (East Asia Synthetic), KAYARAD TMPTA, KAYARAD DPHA, KAYARAD DPHA-40H (Nippon Chemical), etc., (meth) acrylates and urethane (meth) acrylates are excellent in polymerizability and can be improved The aspect of strength is particularly preferred.

When it is used in combination with a trifunctional or higher (meth)acrylic polyfunctional monomer (C-1) and a polyfunctional monomer (C-2) represented by the above Chemical Formula 1, it is preferred based on all monomers. The total content of the trifunctional or higher (meth)acrylic polyfunctional monomer (C-1) and the polyfunctional monomer (C-2) represented by the above Chemical Formula 1 is 80% by weight or less. When it is used in an amount of more than 80% by weight, it is difficult to achieve the performance of the above polyfunctional monomer.

The polyfunctional monomer (C) is preferably contained in an amount of 5 to 80% by weight, particularly preferably 20 to 70% by weight, based on the solid content of the colored photosensitive resin composition. When 20 to 45% by weight of the photopolymerizable compound (C) is contained in accordance with the above criteria, the strength and smoothness of the pixel portion are good, which is preferable.

The polyfunctional monomer (C-2) represented by the above Chemical Formula 1 is in the entirety The body preferably contains 0.01 to 60% by weight, particularly preferably more preferably 1 to 40% by weight.

Photopolymerization initiator (D)

The photopolymerization initiator (D) can be used without particular limitation as long as it can polymerize the polyfunctional monomer (C). In particular, the photopolymerization initiator (D) is preferably selected from the group consisting of an acetophenone-based compound, a benzophenone-based compound, and a triazine-based compound from the viewpoints of polymerization characteristics, initiation efficiency, absorption wavelength, availability, and price. One or more compounds selected from the group consisting of a biimidazole compound, an anthraquinone compound, and a thioxanthone compound.

Specific examples of the acetophenone-based compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, and benzoin dimethyl ketal. 2-hydroxy-1-[4-(2-hydroxyethoxy)phenyl]-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 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]propan-1-one, 2-(4-methylbenzyl)-2-(dimethylamino)-1 -(4-morpholinophenyl)butan-1-one and the like.

Examples of the benzophenone-based compound include benzophenone, methyl O-benzoylbenzoate, 4-phenylbenzophenone, and 4-benzylidene-4'-methyldiphenyl. A thioether, 3,3',4,4'-tetrakis(tert-butylperoxycarbonyl)benzophenone, 2,4,6-trimethylbenzophenone or the like.

Specific examples of the triazine-based compound include 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine and 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)vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl) )-6-[2-(furan-2-yl)vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(4-diethyl) Amino-2-methylphenyl)vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl) ) vinyl]-1,3,5-triazine, and the like.

Specific examples of the biimidazole compound include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, and 2,2'-bis (2). ,3-dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-four (alkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(trialkoxyphenyl)biimidazole, 2,2- Bis(2,6-dichlorophenyl)-4,4'5,5'-tetraphenyl-1,2'-biimidazole, or 4,4',5,5' phenyl group by alkoxy A carbonyl-substituted imidazole compound or the like. Among these, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-dichlorophenyl) is preferably used. -4,4',5,5'-tetraphenylbiimidazole, 2,2-bis(2,6-dichlorophenyl)-4,4'5,5'-tetraphenyl-1,2 '-Biimidazole.

Specific examples of the above-mentioned hydrazine compound include o-ethoxycarbonyl-α-oxyimino-1-phenylpropan-1 ketone, and the like, and as a commercial product, OXE01 and OXE02 of BASF Corporation are representative.

As the above thioxanthone-based compound, for example, 2-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythiophene Tons of ketone and so on.

Further, the photopolymerization initiator (D) may further include photopolymerization initiation in order to improve the sensitivity of the colored photosensitive resin composition of the present invention. Adjuvant (d2). When the coloring photosensitive resin composition of the present invention contains a photopolymerization initiation aid (d2), the sensitivity is further improved, and productivity can be improved.

As the photopolymerization initiation aid (d2), for example, one or more compounds selected from the group consisting of an amine compound, a carboxylic acid compound, and an organic sulfur compound having a thiol group are preferably used.

As the amine compound, an aromatic amine compound is preferably used. Specifically, an aliphatic amine compound such as triethanolamine, methyldiethanolamine or triisopropanolamine, methyl 4-dimethylaminobenzoate or 4-di can be used. Ethyl methylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, N,N- Dimethyl-p-toluidine, 4,4'-bis(dimethylamino)benzophenone (commonly known as: Michler's ketone), 4,4'-bis(diethylamino)benzophenone, and the like.

The carboxylic acid compound is preferably an aromatic heteroacetic acid, and specific examples thereof include phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, and methylethylphenylthioacetic acid. Dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, benzene Oxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthyloxyacetic acid, and the like.

Specific examples of the organic sulfur compound having a thiol group include 2-mercaptobenzothiazole, 1,4-bis(3-mercaptobutyloxy)butane, and 1,3,5-tris(3). - mercaptobutoxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, trimethylolpropane tris(3-mercaptopropionate), pentaerythritol Tetrakis(3-mercaptobutyrate), pentaerythritol tetrakis(3-mercaptopropionate), dipentaerythritol Hexa(3-mercaptopropionate), tetraethylene glycol bis(3-mercaptopropionate), and the like.

The photopolymerization initiator (D) is contained in the total content of the alkali-soluble resin (B) and the polyfunctional monomer (C) based on the total weight of the solid content of the colored photosensitive resin composition of the present invention. 0.1 to 40% by weight, preferably 1 to 30% by weight. When the photopolymerization initiator (D) is in the range of 0.1 to 40% by weight, the coloring photosensitive resin composition is highly sensitive, and the exposure time is shortened. Therefore, productivity is improved and high resolution can be maintained, which is preferable. Moreover, the intensity of the pixel portion formed using the composition of the above-described conditions and the smoothness in the surface of the above-described pixel portion become good.

In the case where the photopolymerization initiation aid (d2) is further used, the photopolymerization initiation aid (d2) is based on the total weight of the solid component of the colored photosensitive resin composition of the present invention. The total content of the alkali-soluble resin and the (B) polyfunctional monomer (C) is 0.1 to 40% by weight, preferably 1 to 30% by weight. When the amount of use of the photopolymerization initiation aid (d2) is in the range of 0.1 to 40% by weight as described above, the sensitivity of providing the colored photosensitive resin composition is further improved, and the productivity of the color filter formed using the composition is improved. effect.

Solvent (E)

The solvent is preferably used in order to dissolve other components contained in the colored photosensitive resin composition, and a solvent used in a usual colored photosensitive resin composition can be used without particular limitation, and ethers, aromatic hydrocarbons, and ketones are particularly preferable. Classes, alcohols, esters, or guanamines.

The solvent (E), specifically, ethylene glycol monomethyl ether, Ethylene glycol monoethyl ether such as ethylene glycol monoethyl ether, ethylene glycol monopropyl ether or ethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, two Glycol alkyl ether acetate such as diethylene glycol dialkyl ether such as diethylene glycol diethylene ether or diethylene glycol dibutyl ether, methyl cellosolve acetate, ethyl cellosolve acetate Alkylene groups such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate, methoxypentyl acetate Alkylene glycol acetates, aromatic hydrocarbons such as benzene, toluene, xylene, and mesitylene, methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, cyclohexanone, etc. Alcohols such as ketones, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, glycerol, esters such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate, a cyclic ester such as γ-butyrolactone.

The solvent (E) is preferably an organic solvent having a boiling point of from 100 ° C to 200 ° C in terms of coatability and drying property, and more preferably propylene glycol monomethyl ether acetate or propylene glycol monoethyl ether acetate. Cyclohexanone, ethyl lactate, butyl lactate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, and the like.

The solvent (E) exemplified above may be used singly or in combination of two or more kinds, and is contained in an amount of 60 to 90% by weight, preferably 70 to 85% by weight based on the total weight of the colored photosensitive resin composition of the present invention. . If the solvent (E) is in the range of 60 to 90% by weight as described above, a roll coater, a spin coater, a slit and a spin coater, a slit coater (sometimes referred to as a press coater), and an ink jet are used. When the coating device is applied, the coating property is improved. Effect.

Mercapto compound (F)

The polyfunctional monomer (C-2) represented by the above Chemical Formula 1 can achieve a high degree of crosslinking even at a low temperature firing, but in the case where a polyfunctional monomer (C-2) is used alone. Since the efficiency of the polyfunctional monomer at the time of exposure is lowered, a short circuit of the pattern can occur, so that if it is used in combination with a polyfunctional thiol compound, the efficiency of the polyfunctional monomer can be prevented from being lowered by the polyfunctional thiol compound.

The above polyfunctional thiol compound is a mercapto compound (F).

The above mercapto compound (F) may be selected from the group consisting of 4-Mercaptohydrocinnamic Acid, 4-Mercaptobenzoic Acid, Thiosalicylic Acid, 3,4-di 3,4-Dimethoxybenzenethiol, 3-Ethoxybenzenethiol, 4-Hydroxybenzenethiol, 3-methoxythiophenol (3) -Methoxybenzenethiol), 2-Hydroxybenzenethiol, 4-Methoxybenzenethiol, 3-Hydroxybenzenethiol, 2-methoxythiophenol (2-Methoxybenzenethiol), MethylThiosalicylate, 2,3,5,6-Tetrafluoro-4-mercaptobenzoic acid, 2-mercaptobenzothiazole, 1,4-bis(3-mercaptobutoxy)butane, β-mercaptopropionic acid, methyl 3-mercaptopropionate (Methyl) 3-Mercaptopropionate), 2-Ethylhexyl 3-Mercaptopropionate, n-Octyl 3-Mercaptopropionate, 3-mercaptopropionate methoxy Methoxybuthyl 3-Mercaptopropionate, Stearyl 3-Mercaptopropionate, Trimethylolpropanetris (3-mercaptopropionate), Tri[( 3-mercaptopropoxyl-ethyl-isocyanurate, pentaerythritol tetrakis (3-mercaptopropionate) )), one of Tetraethyleneglycol bis (3-mercaptopropionate), and Dipentaerythritol hexakis (3-mercaptopropionate) the above.

The mercapto compound (F) is contained in the colored photosensitive resin composition in an amount of 0.1 to 5% by weight based on the total solid content. When the above-mentioned mercapto compound (F) is contained in the above range, even if it is baked at a low temperature, the degree of crosslinking can be prevented from being lowered by the polyfunctional monomer, the sensitivity of the colored photosensitive resin composition can be further improved, or the filter formed by using the composition can be used. The productivity of the color filter can be improved.

The colored photosensitive resin composition of the present invention may further contain an additive as needed, and as a specific example, at least one selected from the group consisting of a dispersing agent, a wetting agent, a decane coupling agent, and an anti-agglomeration agent may be used.

The following is an example of the production of the colored photosensitive resin composition of the present invention. The law is explained.

First, the pigment (a1) in the coloring agent (A) is mixed with the solvent (E), and dispersed by using a bead mill or the like until the average particle diameter of the pigment is 0.2 μm or less. At this time, if necessary, a part or all of the pigment dispersant (a3), the alkali-soluble resin (B), or the dye (a2) may be mixed with the solvent (E) to be dissolved or dispersed.

Further, a dye (a2), a residue (B) of an alkali-soluble resin, a polyfunctional monomer (C), and a photopolymerization initiator (D), an additive and a solvent added as needed may be further added to the above-mentioned mixed dispersion. The colored photosensitive resin composition according to the present invention is produced at a predetermined concentration.

Hereinafter, the present invention will be described in detail using synthesis examples, examples, comparative examples and experimental examples. However, the following synthesis examples, examples, comparative examples, and experimental examples are intended to illustrate the present invention, and the present invention is not limited by the following synthesis examples, examples, comparative examples, and experimental examples, and various modifications and changes can be made. .

Synthesis Example 1. Synthesis of A-1

In a 250 ml three-necked flask, a reaction mixture in which pentaerythritol (10 mmol), NaOH (20 mmol), and epichlorohydrin (80 ml) were dissolved in 200 ml of ethanol was heated to 90 ° C, and stirred for 12 hours. After 12 hours, make NaOH (2.89 g, 72.20 mmol) was dissolved in 20 ml of distilled water, and the mixture was slowly added dropwise at 60 ° C for 1 hour, and then reacted at 80 ° C for 2 hours. After completion of the reaction, 50 ml of purified water and 50 ml of THF were added, and the mixture was stirred for 30 minutes to separate the organic layer. The organic layer was dried over anhydrous magnesium sulfate and filtered, and the filtrate was concentrated under reduced pressure, and methanol and distilled water were added to the residue to remove the impurities to obtain a white solid A-1 5.3 g (yield 84%). .

Synthesis Example 2. Synthesis of T-1

In the reactor, the above A-1 30 mmol and pent-4-enyl chloride (40 ml), 0.1% by weight of sodium, 0.02% by weight of calcium, and 15 mmol of p-toluenesulfonic acid monohydrate were dissolved in 200 ml of toluene. The mixture was heated to 120 ° C under a nitrogen stream and stirred. After completion of the reaction, after cooling to room temperature, 400 ml of toluene was added. After the organic layer was taken out, 200 ml of purified water was added and washed, and anhydrous magnesium sulfate was added to the organic layer, followed by stirring for 30 minutes. The organic layer was filtered, and then concentrated under reduced pressure. EtOAc m.

Synthesis Example 3. Synthesis of alkali-soluble resin (B)

120 parts of propylene glycol monomethyl ether acetate, 80 parts of propylene glycol monomethyl ether, 2 parts of AIBN, and 19.0 parts of acrylic acid were placed in a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel, and a nitrogen introduction tube. 10 parts of benzyl methacrylate, 51.0 parts of styrene, 3 parts of n-dodecyl mercaptan, and nitrogen substitution. Then, the mixture was stirred, and the temperature was raised to 110 ° C to cause a reaction for 6 hours. Next, the temperature of the reaction liquid was lowered to normal temperature, and the air in the flask was again replaced with normal air, and then 0.3 parts of triethylamine and 20 parts of glycidyl methacrylate were added, and the mixture was reacted at 110 ° C for 5 hours. The alkali-soluble resin thus synthesized had a solid content acid value of 80 mgKOH/g, and a weight average molecular weight Mw measured by GPC was about 22,000.

Example 1. Production of Colored Photosensitive Resin Composition

12 parts by weight of CI Pigment Blue 15:6 (pigment), 1.8 1.8 parts by weight of CI Acid Red, 4.0 parts by weight of BYK-2001 as a pigment dispersant, and 82.2 parts by weight of propylene glycol monomethyl ether acetate, using bead mill The pigment was sufficiently dispersed (A-1), and then 18.2 parts by weight of the alkali-soluble resin (B) of Synthesis Example 3 and 4.9 parts by weight of the polyfunctional monomer (C-1) (product name: DPHA, manufactured) Company: Nippon Chemical Co., Ltd., 1.2 parts by weight of the polyfunctional monomer (C-2) of T-1 of the above Synthesis Example 2, and PBG-305 (D, manufacturing company: TRONLY) as an oxime ester-based initiator 1 weight 4 parts by weight of propylene glycol monomethyl ether acetate (E) and 0.2 parts by weight of trimethylolpropane tris(F-2) as a mercapto compound (product name: TMMP, manufacturing company: 堺Chemistry) were mixed. The colored photosensitive resin composition (refer to Table 1).

Example 2. Production of Colored Photosensitive Resin Composition

12 parts by weight of CI Pigment Blue 15:6 (pigment), 1.8 1.8 parts by weight of CI Acid Red, 4.0 parts by weight of BYK-2001 as a pigment dispersant, and 82.2 parts by weight of propylene glycol monomethyl ether acetate, using bead mill The pigment was sufficiently dispersed (A-1), and then 18.2 parts by weight of the alkali-soluble resin (B) of Synthesis Example 3 and 4.9 parts by weight of the polyfunctional monomer (C-1) (product name: DPHA, a manufacturing company: a Japanese chemical), 1.2 parts by weight of the polyfunctional monomer (C-2) of T-1 of the above Synthesis Example 2, and PBG-305 as an oxime ester-based initiator (D, manufacturing company: TRONLY 1 part by weight, 48.4 parts by weight of propylene glycol monomethyl ether acetate (E), and 0.2 parts by weight of dipentaerythritol hexa(F-2) as a mercapto compound (product name: DPMP, manufacturing company: 堺Chemistry) were mixed. The colored photosensitive resin composition (refer to Table 1).

Example 3. Production of Colored Photosensitive Resin Composition

12 parts by weight of CI Pigment Blue 15:6 (pigment), 1.8 1.8 parts by weight of CI Acid Red, 4.0 parts by weight of BYK-2001 as a pigment dispersant, and 82.2 parts by weight of propylene glycol monomethyl ether acetate, using bead mill The pigment was sufficiently dispersed (A-1), and then 18.2 parts by weight of the alkali-soluble resin (B) of Synthesis Example 3 and 3.1 parts by weight of the polyfunctional monomer (C-1) (product name: DPHA, manufactured) Company: Nippon Chemical Co., Ltd., 3.1 parts by weight of T-1 polyfunctional monomer (C-2) of Synthesis Example 2, and 1 part by weight of PBG-305 (D, manufacturing company: TRONLY) as an oxime ester-based initiator 48.4 parts by weight of propylene glycol monomethyl ether acetate (E), 0.2 parts by weight of trimethylolpropane tri(F-1) as a mercapto compound (product name: TMMP, manufacturing company: 堺Chemistry), and obtained The photosensitive resin composition was colored (refer to Table 1).

Example 4. Production of Colored Photosensitive Resin Composition

12 parts by weight of CI Pigment Blue 15:6 (pigment), 1.8 1.8 parts by weight of CI Acid Red, 4.0 parts by weight of BYK-2001 as a pigment dispersant, and 82.2 parts by weight of propylene glycol monomethyl ether acetate, using bead mill The pigment was sufficiently dispersed (A-1), and then 18.2 parts by weight of the alkali-soluble resin (B) of Synthesis Example 3 and 3.1 parts by weight of the polyfunctional monomer (C-1) (product name: DPHA, manufacturing company: Nippon Chemical Co., Ltd., 3.1 parts by weight of T-1 polyfunctional monomer (C-2) of Synthesis Example 2, and PBG-305 (D, manufacturing company: TRONLY) as an oxime ester-based initiator 1 part by weight, 48.4 parts by weight of propylene glycol monomethyl ether acetate (E), and 0.2 parts by weight of dipentaerythritol hexa(F-2) as a mercapto compound (product name: DPMP, manufacturing company: 堺Chemistry) were mixed. The photosensitive resin composition was colored (refer to Table 1).

Example 5. Production of Colored Photosensitive Resin Composition

12 parts by weight of CI Pigment Blue 15:6 (pigment), 1.8 1.8 parts by weight of CI Acid Red, 4.0 parts by weight of BYK-2001 as a pigment dispersant, and 82.2 parts by weight of propylene glycol monomethyl ether acetate mixed pigment dispersion (A-1) and CI Acid Violet 66 (A-2) were sufficiently dispersed using a bead mill, and then, 18.4 parts by weight of the alkali-soluble resin (B) of Synthesis Example 3, a polyfunctional monomer (C-1) 4.9 parts by weight (product name: DPHA, manufacturing company: Nippon Chemical Co., Ltd.), 1.2 parts by weight of the T-1 polyfunctional monomer (C-2) of Synthesis Example 2, and PBG-305 as an oxime ester-based initiator (D, manufacturing company: TRONLY) 1 part by weight, propylene glycol monomethyl ether acetate (E) 50.4 parts by weight, trimethylolpropane tri(F-1) as a mercapto compound 0.2 parts by weight (product name: TMMP) The manufacturing company: 堺Chemical) was mixed to obtain a colored photosensitive resin composition (see Table 1).

Example 6. Production of Colored Photosensitive Resin Composition

12 parts by weight of CI Pigment Blue 15:6 (pigment), 1.8 1.8 parts by weight of CI Acid Red, 4.0 parts by weight of BYK-2001 as a pigment dispersant, and 82.2 parts by weight of propylene glycol monomethyl ether acetate mixed pigment dispersion (A-1), CI Acid Violet 66 (A-2) is sufficiently dispersed using a bead mill, and then, it will be synthesized. 18.4 parts by weight of the alkali-soluble resin (B) of Example 3, 4.9 parts by weight of the polyfunctional monomer (C-1) (product name: DPHA, manufacturing company: Nippon Chemical Co., Ltd.), and T-1 of the synthesis example 2 1.2 parts by weight of the monomer (C-2), 1 part by weight of PBG-305 (D, manufacturing company: TRONLY) as an oxime ester initiator, and 50.4 parts by weight of propylene glycol monomethyl ether acetate (E) 0.2 parts by weight of dipentaerythritol hexahydrate (F-2) of the mercapto compound (product name: DPMP, manufacturing company: 堺Chemistry) was mixed to obtain a colored photosensitive resin composition (see Table 1).

Comparative Example 1. Production of colored photosensitive resin composition

12 parts by weight of CI Pigment Blue 15:6 (pigment), 1.8 1.8 parts by weight of CI Acid Red, 4.0 parts by weight of BYK-2001 as a pigment dispersant, and 82.2 parts by weight of propylene glycol monomethyl ether acetate, using bead mill The pigment was sufficiently dispersed (A-1), and then 18.2 parts by weight of the alkali-soluble resin (B) of Synthesis Example 3 and 4.9 parts by weight of the polyfunctional monomer (C-1) (product name: DPHA, manufactured) Company: Nippon Chemical Co., Ltd., 1.2 parts by weight of T-1 polyfunctional monomer (C-2) of Synthesis Example 2, and 1.2 parts by weight of PBG-305 (D, manufacturing company: TRONLY) as an oxime ester-based initiator Further, 48.4 parts by weight of propylene glycol monomethyl ether acetate (E) was mixed to obtain a colored photosensitive resin composition (see Table 1).

Comparative Example 2. Production of colored photosensitive resin composition

12 parts by weight of CI Pigment Blue 15:6 (pigment), 1.8 1.8 parts by weight of CI Acid Red, 4.0 parts by weight of BYK-2001 as a pigment dispersant, and 82.2 parts by weight of propylene glycol monomethyl ether acetate, using bead mill The pigment is sufficiently dispersed (A-1), and then the alkali-soluble resin of Synthesis Example 3 (B) 18.2 parts by weight, 4.9 parts by weight of polyfunctional monomer (C-1) (product name: DPHA, manufacturing company: Nippon Chemical Co., Ltd.), polyfunctional monomer (C-2) of T-1 of Synthesis Example 2 1.2 parts by weight of PBG-305 (D, manufacturing company: TRONLY) as an oxime ester-based initiator, and 48.4 parts by weight of propylene glycol monomethyl ether acetate (E) were mixed to obtain a colored photosensitive resin composition ( Refer to Table 1).

Comparative Example 3. Production of colored photosensitive resin composition

12 parts by weight of CI Pigment Blue 15:6 (pigment), 1.8 1.8 parts by weight of CI Acid Red, 4.0 parts by weight of BYK-2001 as a pigment dispersant, and 82.2 parts by weight of propylene glycol monomethyl ether acetate mixed pigment dispersion (A-1), CI Acid Violet 66 (A-2) was sufficiently dispersed using a bead mill, and then, 18.4 parts by weight of the alkali-soluble resin (B) of Synthesis Example 3, a polyfunctional monomer (C-1) 6.1 parts by weight (product name: DPHA, manufacturing company: Nippon Chemical Co., Ltd.), PBG-305 (D, manufacturing company: TRONLY) as an oxime ester-based initiator, 1 part by weight, propylene glycol monomethyl ether acetate (E) 50.4 parts by weight and 0.2 parts by weight of trimethylolpropane tris(F-1) (product name: TMMP, manufactured by Nippon Chemical Co., Ltd.) were mixed to obtain a colored photosensitive resin composition (see Table 1).

Comparative Example 4. Production of colored photosensitive resin composition

12 parts by weight of CI Pigment Blue 15:6 (pigment), 1.8 1.8 parts by weight of CI Acid Red, 4.0 parts by weight of BYK-2001 as a pigment dispersant, and 82.2 parts by weight of propylene glycol monomethyl ether acetate mixed pigment dispersion (A-1), CI Acid Violet 66 (A-2) was sufficiently dispersed using a bead mill, and then, 18.4 parts by weight of the alkali-soluble resin (B) of Synthesis Example 3, a polyfunctional monomer (C-1) ) 4.9 parts by weight (product name: DPHA, manufacturing company: Nippon Kayaku), synthesis 1.2 parts by weight of the polyfunctional monomer (C-2) of T-1 of Example 2, 1.2 parts by weight of PBG-305 (D, manufacturing company: TRONLY) as an oxime ester-based initiator, propylene glycol monomethyl ether acetate 50.4 parts by weight of the ester (E) was mixed to obtain a colored photosensitive resin composition (see Table 1).

Experimental Example 1. Sensitivity measurement, adhesion evaluation and solvent resistance evaluation

A color filter was produced using the colored photosensitive resin compositions produced in the above Examples 1 to 6 and Comparative Examples 1 to 4.

Specifically, each of the above colored photosensitive resin compositions was applied onto a 2 inch square glass substrate ("EAGLE XG" manufactured by Corning Co., Ltd.) by spin coating, placed on a hot plate, and maintained at a temperature of 100 ° C. After 3 minutes, a film was formed. Next, a test photomask having a pattern in which the transmittance is changed stepwise in a range of 1 to 100% and a line/space pattern of 1 μm to 50 μm is placed on the film so that the interval from the test photomask is 100 μm. Irradiation of ultraviolet light. At this time, the ultraviolet light source was irradiated with an illuminance of 100 mJ/cm ² using a 1 KW high-pressure mercury lamp including all the g, h, and i lines, and no special optical filter was used. The above-mentioned ultraviolet-irradiated film was immersed in a KOH aqueous solution developing solution of pH 10.5 for 2 minutes, and developed. The glass plate coated with the above film was washed with distilled water, and then nitrogen gas was sprayed, dried, and heated in a heating oven at 150 ° C for 20 minutes to produce a color filter.

The color filter manufactured above had a film thickness of 2.0 μm. The coloring photosensitive resin compositions produced in the above Examples 1 to 6 and Comparative Examples 1 to 4 were evaluated for reliability by the following methods, and the results are shown in Table 2 below.

<sensitivity>

After development, the minimum amount of exposure necessary to form a film without pattern defects was measured.

<adhesion>

When the generated pattern was evaluated by an optical microscope, it was evaluated according to the degree of the defect phenomenon in the following pattern.

○: no defect on the pattern

△: 1 to 3 defects on the pattern

X: 4 or more defects on the pattern

<Solvent resistance>

The color filter prepared above was immersed in an N-methylpyrrolidone solvent for 30 minutes, and the color change before and after the evaluation was comparatively evaluated. For the equation used at this time, the following mathematical formula 1 representing the color change in the 3-dimensional colorimeter defined by L*, a*, b* is used, and the smaller the color change value, the higher the reliability can be manufactured. Color filter.

When the value of ΔE*ab is 3.0 or less, the standard of chromatic aberration is not perceived.

[Math 1] △ Eab* = [(ΔL*) ² + (Δa*) ² + (Δb*) ² ] (1/2)

As shown in Table 2, in the case of the colored photosensitive resin compositions of Examples 1 to 6, it was confirmed that the heat resistance and the solvent resistance were excellent, and the degree of curing was excellent.

Specifically, since the colored photosensitive resin compositions of Examples 1 to 6 are sufficiently cured in the low-temperature baking step, the adhesion to the substrate is excellent, and the solvent resistance is improved. From this, it was confirmed that even if the colored photosensitive resin composition of the present invention is used in a low-temperature baking step, it is possible to provide a highly reliable color filter.

On the other hand, Comparative Example 2 and Comparative Example 4 relate to a colored photosensitive resin composition in which no mercapto compound was added, and it was confirmed that the solvent resistance was good, but the adhesion of the pattern was lowered. In addition, in the colored photosensitive resin compositions of Comparative Example 1 and Comparative Example 3 in which the polyfunctional monomer (C-2) represented by Chemical Formula 1 was not added, it was confirmed that the solvent resistance after low-temperature curing was poor.

Claims (6)

A colored photosensitive resin composition comprising a colorant, an alkali-soluble resin, a polyfunctional monomer, a photopolymerization initiator, a solvent, and a mercapto compound, wherein the polyfunctional monomer contains a trifunctional or higher functional group ( a methyl)acrylic polyfunctional monomer and a polyfunctional monomer represented by the following Chemical Formula 1: In the above Chemical Formula 1, X is an aliphatic hydrocarbon having 1 to 10 carbon atoms which contains a hetero atom or does not contain a hetero atom, and R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ are each independently an epoxy compound. Or a compound represented by the following Chemical Formula 2, wherein at least one or more of R ₁ to R ₆ are a compound represented by Chemical Formula 2 and an epoxy compound. n is an integer from 0 to 5. The colored photosensitive resin composition according to claim 1, wherein the polyfunctional monomer represented by the chemical formula 1 is a compound represented by the following Chemical Formula 3, [Chemical Formula 3] The colored photosensitive resin composition according to claim 1, wherein the trifunctional or higher (meth)acrylic polyfunctional monomer is selected from trimethylolpropane tri(meth)acrylate. Ethoxylated trimethylolpropane tri(meth)acrylate, propoxylated trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylic acid Ester, dipentaerythritol penta (meth) acrylate, ethoxylated dipentaerythritol hexa (meth) acrylate, propoxylated dipentaerythritol hexa (meth) acrylate, and dipentaerythritol hexa (meth) acrylate One or more of them. The colored photosensitive resin composition according to claim 1, wherein the mercapto compound is selected from the group consisting of 4-mercaptohydrocinnamic acid, 4-mercaptobenzoic acid, thiosalicylic acid, and 3,4-dimethyl Oxythiobenzene, 3-ethoxythiophenol, 4-hydroxythiophenol, 3-methoxythiophenol, 2-hydroxythiophenol, 4-methoxythiophenol, 3-hydroxyl Thiophenol, 2-methoxythiophenol, methyl thiosalicylate, 2,3,5,6-tetrafluoro-4-mercaptobenzoic acid, 2-mercaptobenzothiazole, 1,4-double (3-mercaptobutyloxy)butane, β-mercaptopropionic acid, methyl 3-mercaptopropionate, 2-ethylhexyl 3-mercaptopropionate, n-octyl 3-mercaptopropionate, 3-mercapto Methoxybutyl propionate, stearyl 3-mercaptopropionate, trimethylolpropane tris(3-mercaptopropionate), tris[(3-mercaptopropyloxy)-ethyl]-isocyanate Urea, pentaerythritol tetrakis(3-mercaptopropionate), tetraethylene glycol bis(3-mercaptopropionate), and dipentaerythritol hexa(3-mercaptopropionic acid) One or more of the esters. The colored photosensitive resin composition according to claim 1, wherein the colored photosensitive resin composition contains 5 to 60% by weight of the coloring agent based on the total weight of the solid component, and contains 10 ~80% by weight of the alkali-soluble resin, containing 5 to 80% by weight of the polyfunctional monomer, containing 0.1 to 5% by weight of the mercapto compound, and the total of the alkali-soluble resin and the polyfunctional monomer The photopolymerization initiator is contained in an amount of 0.1 to 40% by weight based on the total amount of the photosensitive resin composition, and 60 to 90% by weight of the solvent is contained based on the total weight of the colored photosensitive resin composition. A color filter produced by the colored photosensitive resin composition according to any one of claims 1 to 5.