TW201403232A - Colored photosensitive resin composition and color filter using the same - Google Patents

Abstract

Disclosed herein is a colored photosensitive resin composition, including: a colorant (A); an alkali-soluble resin (B); a photopolymerizable compound (C); a photopolymerization initiator (D); and a solvent (E), wherein the colorant includes at least one pigment and at least one dye, and the alkali-soluble resin includes a compound of Formula 1 above.

Description

Colored photosensitive resin composition and color filter using the same

The present invention relates to a photosensitive resin composition, and more particularly to a colored photosensitive resin composition for producing a color filter for display such as a color liquid crystal display, and a color filter manufactured using the composition.

Color filters are widely used in image pickup devices, liquid crystal displays, etc., and their application range is rapidly expanding. A color filter for a color liquid crystal display, an image pickup device, or the like is manufactured by a method including the steps of: coating a colored photosensitive resin composition including red, green, and blue colorants by spin coating to be provided with a substrate of a black matrix pattern; heating and drying (referred to as "primary calcination") a colored photosensitive resin composition that has been coated on a substrate to form a film; exposing and developing the film; and exposing and developing The film is heated and cured (referred to as "post-smoke") to form pixels corresponding to each color.

A pigment dispersion composition is generally used as a coloring agent for coloring a photosensitive resin composition. For this purpose, a pigment dispersion method is used. Due to the pigment dispersion method, there is a method of producing a color filter by photolithography using a coloring photosensitive composition obtained by dispersing a pigment into a photosensitive composition. This method has been widely used to manufacture color filters for large-area high-resolution color displays because it ensures sufficient light reliability or thermal reliability due to the use of pigments (refer to Korean Patent Registration No. 10- 0881860).

Such a color filter requires the following characteristics such as film coating property, solubility in an organic solvent, heat resistance at the time of curing the sealant, chemical resistance, physical resistance Longness, VHR is 95% or more, high brightness and darkness ratio.

In particular, the reliability of the colored photosensitive resin composition of the color filter can be evaluated only when the composition has a voltage holding ratio (VHR) of 95% or more. Conventional colored photosensitive resin compositions for color filters have problems because they deteriorate in subsequent processes due to their VHR characteristics, and they are caused by deterioration of their chemical resistance. Storage stability is deteriorated.

Therefore, there is a need to develop a colored photosensitive resin composition having improved chemical resistance and VHR characteristics.

[references] [Patent Literature]

Korean Patent Registration No. 10-0881860

Korean Unexamined Patent Application Publication No. 10-0843804

Accordingly, the present invention has been devised to solve the above problems, and an object of the present invention is to provide a colored photosensitive resin composition for a color filter which can be used for manufacturing color filter having high transmittance and high reliability. sheet.

Another object of the present invention is to provide a colored photosensitive resin composition which does not cause defects in a subsequent process because of its excellent VHR characteristics and chemical resistance, and which is excellent in storage stability Even when it is stored for a long time, its sensitivity will not deteriorate or the viscosity will not increase.

In order to achieve the above object, an aspect of the invention provides a colored photosensitive resin composition comprising: a colorant (A), an alkali-soluble resin (B), a photopolymerizable compound (C), and a photopolymerization initiator (D). And a solvent (E), wherein the colorant comprises at least one pigment and at least one dye, and the alkali-soluble resin comprises a compound of the following formula 1:

Wherein R1 is a linking group including a polymerizable unsaturated group, R2 is a hydrogen atom or a C1 to C12 alkyl group, R3 is a hydrogen atom, a C1 to C12 alkyl group, a C1 to C8 aliphatic group, and C1~ An aromatic group of C8, a cyclic group of C1 to C8 or a heterocyclic group of C1 to C8, and n is 1 or 2.

Another aspect of the present invention provides a color filter produced using the colored photosensitive resin composition.

Hereinafter, each component of the present invention will be described in detail.

Colorant (A)

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

The pigment (a1) may include organic pigments and inorganic pigments which are generally used in the related art. As the above organic pigment, various pigments for printing inks, inkjet inks and the like can be used. Specific examples of the organic pigment may include a water-soluble azo pigment, an insoluble azo pigment, a phthalocyanine pigment, a quinacridone pigment, an isoindolinone pigment, an isoindoline pigment, an anthraquinone pigment, a picone pigment, and two Azide pigment, anthraquinone pigment, diterpene-based pigment, alizarin pyrimidine pigment, indole-dione pigment, indanthrone pigment, flavanone pigment, picone pigment, pyrrolopyrroledione pigment, and the like. A metal compound such as a metal oxide, a metal complex salt or the like can be used as the above inorganic pigment. Specific examples of the inorganic pigment may include: metal oxides such as iron oxide, cobalt oxide, cadmium oxide, lead oxide, copper oxide, titanium oxide, magnesium oxide, chromium oxide, zinc oxide, cerium oxide, etc.; carbon black; and composite metal Oxide. In particular, organic pigments and inorganic pigments may include compounds that are classified as pigments in the color index (published by the Colorists and Colorists Association). More specifically, examples of the organic pigment and the inorganic pigment may include, but are not limited to, the following CI pigments: 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, CI Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61 , 64, 65 and 71, CI Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 215, 216, 224, 242, 254, 255 and 264, CI Pigment Violet 14, 19, 23, 29, 32, 33, 36, 37 and 38, CI Pigment Blue 15 (15:3, 15:4, 15:6, etc.), 21, 28, 60, 64 and 76, CI Pigment Green 7, 10, 15, 25, 36, 47 and 58, CI Pigment Brown 28, and CI Pigment Blacks 1 and 7.

The above pigment (a1) may be used singly or in combination thereof.

Among the CI pigments exemplified above, those selected from the group consisting of 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 can be preferably used. Pigment Red 255, CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 150, CI Pigment Yellow 185, CI Pigment Green 7, CI Pigment Green 36, CI Pigment Green 58, CI Pigment Violet 23, CI Pigment Blue 15:3 And pigments in Pigment Blue 15:6.

It is preferred to use the pigment (a1) in the form of a pigment dispersion composition in which pigment particles having a uniform diameter are dispersed in the pigment dispersion composition. As a method of uniformly dispersing the pigment particles, a method of dispersing the pigment particles using the pigment dispersant (a3) is employed. According to this method, a pigment dispersion composition in which pigment particles are uniformly dispersed can be obtained.

Specific examples of the pigment dispersant (a3) may include a cationic surfactant, an anionic surfactant, a nonionic surfactant, an amphoteric surfactant, and a polyester. Surfactants, polyamine surfactants, etc. These pigment dispersants can be used independently or in a combination thereof.

The amount of the pigment (a1) is 20 to 90% by weight, preferably 30 to 70% by weight, based on the total solid content of the pigment dispersion composition. When the amount of the pigment (a1) is 20 to 90% by weight, the coloring photosensitive resin composition has low viscosity, excellent storage stability, and high dispersion efficiency, thereby effectively increasing the ratio of brightness to darkness.

In addition to the above acrylic dispersant, a resin type pigment dispersant can be used as the above pigment dispersant (a3). Examples of the resin type pigment dispersant may include: conventionally known resin type pigment dispersants, particularly polyurethane, polycarboxylate represented by polyacrylate, unsaturated polyimine, polycarboxylic acid, polycarboxylate Acidic (partial) amine salts, ammonium salts of polycarboxylic acids, alkylamine salts of polycarboxylic acids, polyoxyalkylene oxides, long-chain polyamine phosphates, esters of hydroxyl-containing polycarboxylic acids and their modification a product; or a dispersant such as a guanamine obtained by reacting a polyester having a free carboxylic acid and a poly(lower alkyleneimine) or a salt thereof; a (meth)acrylic-styrene copolymer, a water-soluble resin or a water-soluble polymer such as a (meth)acrylic acid-(meth)acrylate copolymer, a styrene-maleic acid copolymer, a polyvinyl alcohol or a polyvinylpyrrolidone; a polyester; a modified polyacrylate; and a ring An adduct of oxyethylene/propylene oxide, phosphate, or the like. As a commercial product of a resin type dispersant, examples of the cationic resin dispersing agent may include: DISPER BYK-161, DISPER BYK-162, DISPER BYK-163, DISPER BYK-164, DISPER BYK-166, DISPER BYK-160, DISPER BYK-171, DISPER BYK-182, DISPER BYK-184 (both trade names of BYK Chemicals LLC); 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 (all products of BASF LLC) Name); SOLSPERS-24000, SOLSPERS-32550 and NBZ-4204/10 (both trade names of Lubrizol GmbH); HINOACT T-6000, HINOACT T-7000 and HINOACT T-8000 (all are Chuanyan Fine) Chemicals limited liability company's goods Name); AJISPUR PB-821, AJISPUR PB-822 and AJISPUR PB-823 (both trade names of Ajinomoto Co., Ltd.); FLORENE DOPA-17HF, FLORENE DOPA-15BHF, FLORENE DOPA-33, FLORENE DOPA-44 (All are the trade names of Xierong Chemical Co., Ltd.). These resin type pigment dispersants may be used singly or in combination, and may also be used in combination with an acrylic dispersant.

The amount of the pigment dispersant (a3) may be 5 to 60 parts by weight, preferably 15 to 50 parts by weight, based on 100 parts by weight of the solid content of the pigment (a1). When the amount of the pigment dispersant (a3) is more than 60 parts by weight, there is a problem that the viscosity of the colored photosensitive resin composition becomes high. Further, when the amount of the pigment dispersant (a3) is less than 5 parts by weight, there is a problem that the pigment cannot be easily broken and may be gelated after dispersion.

As long as the dye (a2) has solubility in an organic solvent, it can be used without limitation. It is preferable to use a dye having solubility in an organic solvent, solubility in an alkali developer, heat resistance, and solvent resistance as the above dye (a2).

The dye (a2) may be selected from the group consisting of an acid dye having an acidic group such as a sulfonic acid group, a carboxylic acid group or the like, a salt of an acid dye and a nitrogen-containing compound, a decylamine of an acid dye, and a derivative thereof. Further, the dye (a2) may be selected from the group consisting of an azo dye, a xanthene dye, a phthalocyanine dye, and a derivative thereof. Preferably, the dye (a2) may be selected from the group of compounds classified as dyes in the color index (published by the Colorists and Colorists Association) and the conventionally known ones disclosed in the dye notes (published by Shikisensha Co., Ltd.). dye.

As the CI solvent dye, specific examples of the dye (a2) may include: a red dye such as CI solvent red 8, 45, 49, 89, 111, 122, 125, 130, 132, 146, 179, etc.; a blue dye such as CI solvent blue 5, 35, 36, 37, 44, 59, 67, 70, etc.; purple dyes, such as CI solvent violet 8, 9, 13, 14, 36, 37, 47, 49, etc.; yellow dyes, such as CI solvent Yellow 4, 14, 15, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99, 162, etc.; orange dyes, such as CI solvent orange 2, 7, 11, 15, 26, 56, etc.; And green dyes such as CI Solvent Green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, 35, etc.

Among these CI solvent dyes, it is preferred to use CI Solvent Red 8, 49, 89, 111, 122, 132, 146 and 179 which have high solubility in an organic solvent, respectively, CI Solvent Blue 35, 36, 44, 45 And 70, and CI Solvent Violet 13, and more preferably CI Solvent Red 8, 122 and 132 are used.

As the CI acid dye, specific examples of the dye (a2) may include: a red dye such as CI acid red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 66, 73, 80, 87, 88, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 182, 183, 198, 206, 211, 215, 216, 217, 227, 228, 249, 252, 257, 258, 260, 261, 266, 268, 270, 274, 277, 280, 281, 195, 308, 312, 315, 316, 339, 341, 345, 346, 349, 382, 383, 394, 401, 412, 417, 418, 422, 426, etc.; yellow dyes, such as 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, 251, etc.; orange dyes such as CI Acid Orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 169, 173 et al; blue dyes such as 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, etc.; purple dyes, such as CI acid violet 6B, 7, 9, 17, 19, 66, etc.; green dyes, such as CI acid green 1, 3, 5, 9, 16 , 25, 27, 50, 58, 63, 65, 80, 104, 105, 106, 109, and the like.

Among these C.I. acid dyes, it is preferred to use C.I. Acid Red 92, C.I. Acid Blue 80 and 90 and C.I. Acid Violet 66 which have high solubility in an organic solvent, respectively.

As the CI direct dye, specific examples of the dye (a2) may include: a red dye such as CI Direct Red 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176, 177, 179, 181, 182, 184, 204, 207, 211, 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246, 250, etc.; yellow dye, such as 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, 141, etc.; orange dyes such as CI Direct Orange 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107, blue Dyes such as 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, 2 22, 228, 229, 237, 238, 242, 243, 244, 245, 247, 248, 250, 251, 252, 256, 257, 259, 260, 268, 274, 275, 293, etc.; purple dyes, such as CI Direct violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104, etc., and green dyes, such as CI Direct Green 25 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82, and the like.

As the CI mordant dye, specific examples of the dye (a2) may include: a yellow dye such as CI mordant yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65, etc.; red dyes, such as CI mordant 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, etc.; orange dye, such as CI mord orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48, etc.; blue dyes, such as CI mord 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, etc.; purple dyes, such as CI mordant purple 1, 2, 4, 5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44 , 45, 47, 48, 53, 58 etc.; and green dyes, such as CI mord green 1, 3, 4, 5, 10, 15, 19, 26, 29, 33, 34, 35, 41, 43, 53, etc. .

These dyes can be used independently or in a combination thereof.

The amount of the dye in the colorant (A) is from 0.5 to 80% by weight, preferably from 0.5 to 60% by weight, more preferably from 1 to 50% by weight, based on the solid content of the colorant (A). When the amount of the dye in the colorant (A) is in the above range, it can prevent the problem that the dye elutes from the colored photosensitive resin composition due to the organic solvent after patterning, and the colored photosensitive resin composition Excellent sensitivity.

The content of the colorant (A) may be 5 to 60% by weight, preferably 10 to 45% by weight, based on the total solid content of the colored photosensitive resin composition. When the content of the colorant (A) is from 5 to 60% by weight, even when a film is formed using the colored photosensitive resin composition, the chroma of the pixel is sufficient, and residual dross is not easily formed because of the absence of the non-pixel region. (omission) did not decrease.

In the present invention, the term "total solid content of the colored photosensitive resin composition" means the total amount of components other than the solvent in the colored photosensitive resin composition.

Alkali soluble resin (B)

The alkali-soluble resin (B) includes the compound of the following formula 1 as an essential component:

Wherein R ₁ is a linking group including a polymerizable unsaturated group, R ₂ is a hydrogen atom or a C ₁ -C ₁₂ alkyl group, R ₃ is a hydrogen atom, a C ₁ -C ₁₂ alkyl group, C ₁ -C An aliphatic group of ₈ , a C ₁ -C ₈ aromatic group, a C ₁ -C ₈ cyclic group or a C ₁ -C ₈ heterocyclic group, and n is 1 or 2.

In order to make the alkali-soluble resin (B) have solubility in an alkaline developing solution used in a developing process at the time of pattern formation, the alkali-soluble resin (B) can be obtained by using an ethylenically unsaturated monomer (b1) having a carboxyl group as The essential components are prepared by copolymerization with other monomers. Further, in order to improve the compatibility of the alkali-soluble resin (B) with the dye (a2) and the storage stability of the colored photosensitive resin composition, the alkali-soluble resin (B) may have an acid value of 30 to 150 mg KOH/g. When the acid value of the alkali-soluble resin (B) is less than 30 mg KOH/g, it is difficult to make the colored photosensitive resin composition have a sufficient development speed. In addition, when the acid value exceeds 150 mg KOH/g, the adhesion of the colored photosensitive resin composition to the substrate becomes low, the pattern which is easily generated is insufficient, and the compatibility of the alkali-soluble resin (B) with the dye becomes There is a problem that the dye is precipitated from the colored photosensitive resin composition or the storage stability of the colored photosensitive resin composition is deteriorated, thereby increasing the viscosity of the colored photosensitive resin composition.

Specific examples of the ethylenically unsaturated monomer (b1) having a carboxyl group may include: a monocarboxylic acid such as acrylic acid, methacrylic acid, crotonic acid, etc.; a dicarboxylic acid such as fumaric acid, mesaconic acid, itaconic acid, or the like An acid anhydride of a dicarboxylic acid; and a mono(meth)acrylate of a polymer having a carboxyl group and a hydroxide group at both ends of the ω-carboxypolycaprolactone mono(meth)acrylate. Among these unsaturated ethylenic monomers, acrylic acid and methacrylic acid are preferably used.

In order to provide a hydroxyl group to the alkali-soluble resin (B), the alkali-soluble resin (B) can be produced by copolymerizing an ethylenically unsaturated monomer (b1) having a carboxyl group with an ethylenically unsaturated monomer (b2) having a hydroxyl group, or It can be produced by reacting a copolymer of a ethylenically unsaturated monomer (b1) having a carboxyl group with a compound (b3) having a glycidyl group. Further, the alkali-soluble resin (B) can be reacted with a copolymer having an ethylenically unsaturated monomer (b1) having a carboxyl group and an ethylenically unsaturated monomer (b2) having a hydroxyl group, and a compound (b3) having a glycidyl group. To prepare.

Specific examples of the compound (b3) having a glycidyl group may 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, tert-butyl glycidyl ether, benzyl glycidyl ether, glycidyl 4-tert-butylbenzoate, glycidyl stearate Ester, allyl glycidyl ether, glycidyl methacrylate, and the like. Among these compounds, it is preferred to use butyl glycidyl ether, allyl glycidyl ether or glycidyl methacrylate. They can be used independently or in combination.

In the process of preparing the alkali-soluble resin (B), the copolymerizable unsaturated monomer (b4) is exemplified as follows, but is not limited thereto.

Specific examples of the copolymerizable unsaturated monomer (b4) may include: an aromatic vinyl compound such as styrene, vinyl toluene, α-methylstyrene, p-chlorostyrene, o-methoxystyrene, M-methoxystyrene, p-methoxystyrene, o-vinylbenzyl methyl ether, m-vinylbenzyl methyl ether, p-vinylbenzyl methyl ether, o-vinyl benzyl Glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, etc.; N-substituted maleimide compound, such as N-cyclohexylmaleimide, N- Benzylmaleimide, N-phenylmaleimide, N-o-hydroxyphenylmaleimide, N-m-hydroxyphenylmaleimide, N-p-hydroxyphenyl Malay Yttrium, N-o-methylphenylmaleimide, N-m-methylphenylmaleimide, N-p-methylphenylmaleimide, N-o-methoxybenzene Kimalyimide, N-m-methoxyphenylmaleimide, N-p-methoxyphenylmaleimide, etc.; alkyl (methyl) Acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, (methyl) ) isobutyl acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, etc.; alicyclic (meth) acrylates such as cyclopentyl (meth) acrylate, cyclohexyl (A) Acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0.2.6] decane-8-yl (meth) acrylate, 2-dicyclopentyloxyethyl ( Methyl) acrylate, isobornyl (meth) acrylate, etc.; hydroxyethyl (meth) acrylate such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate Ester, 4-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, N-hydroxyethyl acrylamide, etc.; aryl (meth) acrylate, Such as phenyl (meth) acrylate, benzyl (meth) acrylate, etc.; unsaturated oxetane compounds, such as 3-(methacryloxymethyl) oxetane, 3-( Methyl propylene methoxymethyl)-3-ethyl oxetane, 3-(methyl Enoxamethoxymethyl)-2-trifluoromethyloxetane, 3-(methacryloxymethyl)-2-phenyloxetane, 2-(methacryl oxime) Oxymethyl)oxetane, 2-(methacryloxymethyl)-4-trifluoromethyloxetane, and the like.

These copolymerizable unsaturated monomers (b4) may be used independently of each other or in a combination thereof.

The content of the alkali-soluble resin (B) may be 10 to 80% by weight, preferably 10 to 70% by weight, based on the solid content of the colored photosensitive resin composition. When the content of the alkali-soluble resin (B) is from 10 to 80% by weight, the solubility of the composition in the developer is sufficient to easily form a pattern, and the film in the pixel region of the film which has been exposed during development is prevented. Reduction, so that the loss of its non-pixel area decreases.

Further, the content of the compound of the above formula 1 is from 1 to 50% by weight based on the total amount of the alkali-soluble resin (B).

Photopolymerizable compound (C)

The photopolymerizable compound (C) is a compound which can be polymerized by the action of the following photopolymerization initiator (D). A monofunctional monomer, a difunctional monomer or a polyfunctional monomer, preferably a polyfunctional monomer, may be used as the photopolymerizable compound. (C).

Specific examples of the monofunctional monomer may include, but are not limited to, nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2 - hydroxyethyl acrylate, N-vinyl pyrrolidone, and the like.

Specific examples of the difunctional monomer may include, but are not limited to, 1,6-hexanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylic acid. Ester, triethylene glycol di(meth)acrylate, bis(acryloxyethyl)ether of bisphenol A, 3-methylpentanediol di(meth)acrylate, and the like.

Specific examples of the polyfunctional monomer may include, but are not limited to, trimethylolpropane tri(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, propoxylated Trimethylolpropane tri(meth) acrylate, pentaerythritol tri(meth) acrylate, pentaerythritol tetra(meth) acrylate, dipentaerythritol penta (meth) acrylate, ethoxylated dipentaerythritol hexa Methyl) acrylate, propoxylated dipentaerythritol hexa (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like.

The content of the photopolymerizable compound (C) may be 5 to 45 wt%, preferably 7 to 45 wt%, based on the solid content of the colored photosensitive resin composition. When the content of the photopolymerizable compound (C) is 5 to 45 wt%, the strength and smoothness of the pixel region are good.

Photopolymerization initiator (D)

As long as the photopolymerization initiator (D) can polymerize the photopolymerizable compound (C), it can be used without limitation. In particular, the photopolymerization initiator (D) may be selected from the group consisting of an acetophenone compound, a benzophenone compound, a triazine compound, a biimidazole compound, in terms of polymerization characteristics, initiation efficiency, absorption wavelength, availability, and price. At least one of the group consisting of a ruthenium compound and a thioxanthone compound.

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

Specific examples of the benzophenone compound may include benzophenone, o-benzoyl acid methyl, 4-phenylbenzophenone, 4-benzylidene-4'- Methyl diphenyl sulfide, 3,3', 4,4'-tetrakis(tert-butylperoxycarbonyl)benzophenone, 2,4,6-trimethylbenzophenone, and the like.

Specific examples of the triazine compound may include 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4-bis(trichloromethane) 6-(4-methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-piperidin-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)ethylene 1,1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)vinyl]-1- 1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)vinyl]-1,3,5-triazine Wait.

Specific examples of the biimidazole compound may include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-di Chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(alkoxy) Phenyl)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, wherein the phenyl group at the 4,4',5,5'-position is substituted by an alkoxycarbonyl group Imidazole compounds and the like. Among these biimidazole compounds, it is preferred to use 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis ( 2,3-Dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2-bis(2,6-dichlorophenyl)-4,4',5,5 '-Tetraphenyl-1,2'-biimidazole.

Specific examples of the hydrazine compound may include o-ethoxycarbonyl- α -oxyimino-1-phenylpropan-1-one and the like. Commercially available products may include OXE01, OXE02 manufactured by BASF Corporation.

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

Further, the photopolymerization initiator (D) may be included in the photopolymerization initiation assistant (d1) in order to improve the sensitivity of the coloring photosensitive resin composition of the present invention. Since the colored photosensitive resin composition of the present invention further includes a photopolymerization initiating auxiliary (d1), the sensitivity thereof is increased, so that the productivity can be improved.

The photopolymerization initiation aid (d1) may be at least one selected from the group consisting of an amine compound, a carboxyl compound, and an organic sulfur compound having a mercapto group.

Preferably, an aromatic amine compound is used as the above amine compound. Specific examples of the amine compound may include: an aliphatic amine compound such as triethanolamine, methyldiethanolamine, triisopropanolamine or the like; methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate , isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, N,N-dimethyl pair Toluidine, 4,4'-bis(dimethylamino)benzophenone (commonly known as Michler's ketone), 4,4'-bis(diethylamino)benzophenone, and the like.

Specific examples of the carboxy compound may include aromatic heteroacetic acid such as phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, 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 mercapto group may include 2-mercaptobenzothiazole, 1,4-bis(3-mercaptobutoxy)butane, 1,3,5-tris(3-decylbutoxy B 1,3,5-triazine-2,4,6(1H,3H,5H)-trione, trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptobutyl) Acid ester), pentaerythritol tetrakis(3-mercaptopropionate), dipentaerythritol hexa(3-mercaptopropionate), tetraethylene glycol bis(3-mercaptopropionate), and the like.

The content of the photopolymerization initiator (D) based on the total amount of the alkali-soluble resin (B) and the photopolymerizable compound (C) may be 0.1 to 40% by weight based on the total solid content of the colored photosensitive resin composition of the present invention, and It is preferably 1 to 30% by weight. When the content of the photopolymerization initiator (D) is from 0.1 to 40% by weight, the sensitivity of the colored photosensitive resin composition becomes High, so its exposure time is shortened, which improves its productivity and maintains high resolution. In addition, the intensity of the pixel formed by the composition using the above-described regulation and the smoothness of the pixel surface can be improved.

Further, the photopolymerization initiation aid (d1) may be contained in an amount of 10 to 80% by weight, preferably 20 to 70% by weight based on the total amount of the photopolymerization initiator (D). When the amount of the photopolymerization initiation aid (d1) in the photopolymerization initiator (D) is less than 10% by weight, the deterioration of the sensitivity of the colored photosensitive resin composition caused by the dye cannot be overcome, and the pattern may be during the development process. It is easy to be missing.

Solvent (E)

As long as the solvent (E) can effectively dissolve other components included in the colored photosensitive resin composition, it can be used without limitation. Specifically, it is preferred to use an ether, an aromatic hydrocarbon, a ketone, an alcohol, an ester or a decylamine as the solvent (E).

Specific examples of the solvent (E) may include: ethylene glycol monoalkyl ether such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, and the like. Diethylene glycol dialkyl ether, such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, etc.; ethylene glycol alkyl ether Acid esters, such as methyl cellosolve acetate, ethyl cellosolve acetate, etc.; alkylene glycol alkyl ether acetate, such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, Propylene glycol monopropyl ether acetate, methoxybutyl acetate, methoxypentyl acetate, etc.; aromatic hydrocarbons such as benzene, toluene, xylene, 1,3,5-trimethylbenzene, etc.; ketone , such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, cyclohexanone, etc.; alcohols, such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, Glycerin or the like; an ester such as ethyl 3-ethoxypropionate, methyl 3-methoxypropionate or the like; and a cyclic ester such as γ-butyrolactone or the like.

In terms of coatability and drying characteristics, an organic solvent having a boiling point of from 100 ° C to 200 ° C can be preferably used as the above solvent (E). More preferably, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, ethyl lactate, butyl lactate, ethyl 3-ethoxypropionate, 3-methyl can also be used. Methyl oxypropionate or the like is used as the above solvent (E).

The solvents exemplified above may be used independently or in the form of a mixture thereof. The content of the solvent (E) may be 60 to 90% by weight, preferably 70 to 85% by weight, based on the total amount of the colored photosensitive resin composition of the present invention. When the amount of the solvent (E) is 60 to 90% by weight, when the composition is used by using, for example, a roll coater, a spin coater, a slit type and a rotary coater, a slit coater (referred to as a mold) When coating by a coater such as a coater or an inkjet machine, the coatability of the colored photosensitive resin composition is good.

Additive (F)

The additive (F) can be selectively added as needed. For example, a polymer compound, a curing agent, a surfactant, an adhesion promoter, an antioxidant, a UV absorber, an aggregation inhibitor, and the like.

Specific examples of the polymer compound may include: a thermosetting resin such as an epoxy resin, a maleimide resin, or the like; a thermoplastic resin such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylic acid Ester, polyester, polyurethane, etc.

The curing agent is used to improve the curability at the deep portion and the mechanical strength of the colored photosensitive resin composition. Specific examples of the curing agent may include an epoxy compound, a polyfunctional isocyanate compound, a melamine compound, an oxetane compound, and the like.

In the curing agent, specific examples of the epoxy compound may include: bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol F type epoxy resin, novolac Epoxy resin, other aromatic epoxy resin, cycloaliphatic epoxy resin, glycidyl ester resin, glycidylamine resin, bromate derivative of epoxy resin, aliphatic and lipid other than epoxy resin a cyclo- or aromatic epoxy compound and a bromate derivative thereof, an epoxidized butadiene (copolymer) polymer, an epoxidized isoprene (copolymer) polymer, and a glycidyl (meth)acrylate ( Copolymer) polymer, triglycidyl isocyanurate, and the like.

In the curing agent, specific examples of the oxetane compound may include carbonate dioxetane, xylene dioxetane, adipate dioxetane, p-xylene An acid ester dioxetane, a cyclohexane dicarboxylate dioxetane or the like.

The curing agent may be used in combination with a curing auxiliary compound which undergoes ring-opening polymerization of an epoxy group of an epoxy compound and an oxetane frame of an oxetane compound. Examples of the curing auxiliary compound may include a polycarboxylic acid, a polycarboxylic acid anhydride, an acid generator, and the like. A commercially available epoxy resin curing agent can be used as the polycarboxylic acid anhydride. Specific examples of the commercially available epoxy resin curing agent may include ADEKAHADONA EH-700 (manufactured by ADEKA Industries, Ltd.), RIKACID HH (manufactured by Nippon Chemical Co., Ltd.), RIKACID MH-700 (by Nippon Chemical Product limited liability company manufacturing) and so on. The curing agents exemplified above may be used independently or in a mixture thereof.

The surfactant is used to improve the film forming property of the colored photosensitive resin composition. Preferably, a fluorine-based surfactant, an organic terpene surfactant or the like can be used as the above surfactant.

As a commercially available product, examples of the organic terpene surfactant may include: DC3PA, DC7PA, SH11PA, SH21PA, SH8400, etc. manufactured by Dow Corning Toray Organic Co., Ltd., TSF manufactured by GE Toshiba Organic Co., Ltd. 4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460, TSF-4452, and the like. As a commercial item, examples of the fluorine-based surfactant may include MEGAPIECE F-470, F-471, F-475, F-482, F-489, and the like manufactured by Dainippon Ink and Chemicals Co., Ltd. The surfactants exemplified above may be used independently or in a combination thereof.

Specific examples of the adhesion promoter may include vinyl trimethoxy decane, vinyl triethoxy decane, vinyl tris(2-methoxyethoxy) decane, and N-(2-aminoethyl)-3. -aminopropylmethyldimethoxydecane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 3-glycidyloxypropane Trimethoxy decane, 3-glycidyloxypropylmethyldimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 3-chloropropylmethyldi Methoxydecane, 3-chloropropyltrimethoxydecane, 3-methylpropenyloxypropyltrimethoxydecane, 3-mercaptopropyltrimethoxydecane, 3-isocyanatepropyltrimethoxydecane, 3-isocyanate-propyl Triethoxy decane and the like. The adhesion promoters exemplified above may be used singly or in combination. The content of the adhesion promoter may be from 0.01 to 10% by weight, preferably from 0.05 to 2% by weight, based on the total solid content of the colored photosensitive resin composition.

Specific examples of the antioxidant may include: 2,2'-thiobis(4-methyl-6-tert-butylphenol), 2,6-di-tert-butyl-4-methylphenol, and the like.

Specific examples of the ultraviolet absorber may include 2-(3-tert-butyl-2-hydroxy-5-methylphenyl)-5-chlorobenzobenzotriazole, alkoxybenzophenone and the like.

Specific examples of the aggregation inhibitor may include sodium polyacrylate and the like.

A method of preparing the colored photosensitive resin composition according to the present invention will be described below.

First, the pigment (a1) in the colorant (A) was mixed with the solvent (E), and then dispersed in the solvent (E) using a bead mill until the average particle diameter in the pigment (a1) was 0.2 μm. In this case, if necessary, the pigment (a1) may be mixed with the solvent (E) and the pigment dispersant (a3), all or part of the alkali-soluble resin (B) or the dye (a2). A1) Dissolved or dispersed in the solvent (E) to prepare a mixed dispersion.

Subsequently, the dye (a2), the remaining alkali-soluble resin (B), the photopolymerizable compound (C), the photopolymerization initiator (D), and, if necessary, the additive (F) are added to the above-mentioned mixed dispersion to a predetermined concentration. Thus, the colored photosensitive resin composition of the present invention is prepared.

Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the examples are set forth to illustrate the invention, and the scope of the invention is not limited thereto. The "%" and "parts" indicating the content of the ingredients in the following examples and comparative examples are based on the weight, unless otherwise specified.

Preparation of pigment dispersion composition (M)

12.0 parts by weight of CI Pigment Blue 15 as a pigment by a bead mill, 4.0 parts by weight of DISPERBYK-2001 (manufactured by BYK Corporation) as a pigment dispersant, and 44 parts by weight of propylene glycol methyl ether acetate as a solvent Ester and 40 parts by weight The propylene glycol methyl ether as a solvent was mixed and dispersed for 12 hours to prepare a pigment dispersion composition (M).

Monomer synthesis

<Synthesis of M1>

4.0 parts by weight of sodium 4-ethylbenzenesulfonate and 40.0 parts by weight of chloroform were introduced into a four-necked round bottom flask equipped with a cooling tube and a stirrer, and then stirred at 15 ° C to 25 ° C under a nitrogen atmosphere. 15 minutes. Subsequently, 2.0 parts by weight of dimethylformamide was dropped thereto at 15 ° C to 25 ° C, followed by stirring for 30 minutes. Subsequently, 2.0 parts by weight of sulfinium chloride was slowly added dropwise at 15 ° C to 18 ° C. Subsequently, 2.0 parts by weight of amino-2-methylpropionate was slowly added dropwise, followed by stirring for about 60 minutes, and then 6.0 parts by weight of triethanolamine was added thereto to complete the reaction. First, 20.0 parts by weight of methanol was added to the reaction product, and second, 24.0 parts by weight of methanol was added to the reaction product, and then the organic solvent was removed from the reaction product by a rotary evaporator. After the reaction, a small amount of piecemeal product was dissolved in water, and a water-soluble material and a water-insoluble material were observed. Further, after the reaction, a small amount of the fragmented product was dissolved in an aqueous acetic acid solution (5%), and a material soluble in acetic acid and a material insoluble in acetic acid were observed. The reaction product was thoroughly washed with water and an aqueous acetic acid solution, and then dried.

<Synthesis of M2>

4.0 parts by weight of sodium 4-n-octylbenzenesulfonate and 40.0 parts by weight of chloroform were introduced into a four-necked round bottom flask equipped with a cooling tube and a stirrer, and then under a nitrogen atmosphere at 15 ° C to 25 ° C. Stir for 15 minutes. Subsequently, 2.0 parts by weight of dimethylformamide was dropped thereto at 15 ° C to 25 ° C, followed by stirring for 30 minutes. Subsequently, 2.0 parts by weight of sulfinium chloride was slowly added dropwise at 15 ° C to 18 ° C. Subsequently, 2.0 parts by weight of 4-aminostyrene was slowly added dropwise, followed by stirring for about 60 minutes, and then 6.0 parts by weight of triethanolamine was added thereto to complete the reaction. First, 20.0 parts by weight of methanol was added to the reaction product, and second, 24.0 parts by weight of methanol was added to the reaction product, and then the organic solvent was removed from the reaction product by a rotary evaporator. After the reaction, a small amount of fragmented product was dissolved in water, and water soluble materials were observed and not A material that is soluble in water. Further, after the reaction, a small amount of the fragmented product was dissolved in an aqueous acetic acid solution (5%), and a material soluble in acetic acid and a material insoluble in acetic acid were observed. The reaction product was thoroughly washed with water and an aqueous acetic acid solution, and then dried.

<Synthesis of M3>

4.0 parts by weight of sodium 4-ethylbenzenesulfonate and 40.0 parts by weight of chloroform were introduced into a four-necked round bottom flask equipped with a cooling tube and a stirrer, and then stirred at 15 ° C to 25 ° C under a nitrogen atmosphere. 15 minutes. Subsequently, 2.0 parts by weight of dimethylformamide was dropped thereto at 15 ° C to 25 ° C, followed by stirring for 30 minutes. Subsequently, 2.0 parts by weight of sulfinium chloride was slowly added dropwise at 15 ° C to 18 ° C. Subsequently, 2.0 parts by weight of 4-aminostyrene was slowly added dropwise, followed by stirring for about 60 minutes, and then 6.0 parts by weight of triethanolamine was added thereto to complete the reaction. First, 20.0 parts by weight of methanol was added to the reaction product, and second, 24.0 parts by weight of methanol was added to the reaction product, and then the organic solvent was removed from the reaction product by a rotary evaporator. After the reaction, a small amount of the fragmented product was dissolved in water, and a water-soluble material and a water-insoluble material were observed. Further, after the reaction, a small amount of the fragmented product was dissolved in an aqueous acetic acid solution (5%), and a material soluble in acetic acid and a material insoluble in acetic acid were observed. The reaction product was thoroughly washed with water and an aqueous acetic acid solution, and then dried.

<Synthesis of M4>

4.0 parts by weight of sodium 4-n-octylbenzenesulfonate and 40.0 parts by weight of chloroform were introduced into a four-necked round bottom flask equipped with a cooling tube and a stirrer, and then under a nitrogen atmosphere at 15 ° C to 25 ° C. Stir for 15 minutes. Subsequently, 2.0 parts by weight of dimethylformamide was dropped thereto at 15 ° C to 25 ° C, followed by stirring for 30 minutes. Subsequently, 2.0 parts by weight of sulfinium chloride was slowly added dropwise at 15 ° C to 18 ° C. Subsequently, 2.0 parts by weight of amino-2-methylpropionate was slowly added dropwise, followed by stirring for about 60 minutes, and then 6.0 parts by weight of triethanolamine was added thereto to complete the reaction. First, 20.0 parts by weight of methanol was added to the reaction product, and second, 24.0 parts by weight of methanol was added to the reaction product, and then the organic solvent was removed from the reaction product by a rotary evaporator. After the reaction, a small amount of the fragmented product was dissolved in water, and water-soluble materials and Insoluble in water. Further, after the reaction, a small amount of the fragmented product was dissolved in an aqueous acetic acid solution (5%), and a material soluble in acetic acid and a material insoluble in acetic acid were observed. The reaction product was thoroughly washed with water and an aqueous acetic acid solution, and then dried.

Synthesis of alkali soluble resin

<Synthesis Example 1>

120 parts of propylene glycol monomethyl ether acetate, 80 parts of propylene glycol monomethyl ether, 2 parts of AIBN, 22.0 parts of M1, 58.0 parts of 4-methylstyrene, 10 parts of benzyl methacrylate, 10 parts of methyl methacrylate and 3 parts of n-dodecylmercapto were introduced into a flask provided with a stirrer, a thermometer, a reflux cooling tube, a dripping lot and a nitrogen supply tube. And then replaced with nitrogen. Thereafter, the reaction mixture was stirred, heated to 80 ° C, and then reacted for 8 hours to synthesize an alkali-soluble resin. The solid content of the synthesized alkali-soluble resin had an acid value of 79.2 mg KOH/g, and its weight average molecular weight (Mw) as determined by GPC was about 14,950.

<Synthesis Example 2>

120 parts of propylene glycol monomethyl ether acetate, 80 parts of propylene glycol monomethyl ether, 2 parts of AIBN, 22.0 parts of M2, 58.0 parts of 4-methylstyrene, 10 parts of benzyl methacrylate, Ten parts of methyl methacrylate and 3 parts of n-dodecyldecyl group were introduced into a flask equipped with a stirrer, a thermometer, a reflux cooling tube, a dropping funnel, and a nitrogen supply tube, and then replaced with nitrogen. Thereafter, the reaction mixture was stirred, heated to 80 ° C, and then reacted for 8 hours to synthesize an alkali-soluble resin. The alkali-soluble resin synthesized had a solid content of 84.5 mg KOH/g, and its weight average molecular weight (Mw) as determined by GPC was about 17720.

<Synthesis Example 3>

120 parts of propylene glycol monomethyl ether acetate, 80 parts of propylene glycol monomethyl ether, 2 parts of AIBN, 22.0 parts of M3, 58.0 parts of 4-methylstyrene, 10 parts of benzyl methacrylate, Ten parts of methyl methacrylate and 3 parts of n-dodecyldecyl group were introduced into a flask equipped with a stirrer, a thermometer, a reflux cooling tube, a dropping funnel, and a nitrogen supply tube, and then replaced with nitrogen. Thereafter, the reaction mixture is stirred and heated The mixture was further reacted for 8 hours at 80 ° C to synthesize an alkali-soluble resin. The alkali-soluble resin thus synthesized had a solid content acid value of 82.9 mg KOH/g, and its weight average molecular weight (Mw) as determined by GPC was about 15,370.

<Synthesis Example 4>

120 parts of propylene glycol monomethyl ether acetate, 80 parts of propylene glycol monomethyl ether, 2 parts of AIBN, 22.0 parts of M4, 58.0 parts of 4-methylstyrene, 10 parts of benzyl methacrylate, Ten parts of methyl methacrylate and 3 parts of n-dodecyldecyl group were introduced into a flask equipped with a stirrer, a thermometer, a reflux cooling tube, a dropping funnel, and a nitrogen supply tube, and then replaced with nitrogen. Thereafter, the reaction mixture was stirred, heated to 80 ° C, and then reacted for 8 hours to synthesize an alkali-soluble resin. The solid content of the synthesized alkali-soluble resin had an acid value of 91.7 mg KOH/g, and its weight average molecular weight (Mw) as determined by GPC was about 18,920.

<Synthesis Example 5>

120 parts of propylene glycol monomethyl ether acetate, 80 parts of propylene glycol monomethyl ether, 2 parts of AIBN, 22.0 parts of N-cyclohexylmaleimide, 58.0 parts of 4-methylstyrene, 10 a portion of benzyl methacrylate, 10 parts of methyl methacrylate and 3 parts of n-dodecyldecyl group are introduced into a flask provided with a stirrer, a thermometer, a reflux cooling tube, a dropping funnel and a nitrogen supply tube. It was then replaced with nitrogen. Thereafter, the reaction mixture was stirred, heated to 80 ° C, and then reacted for 8 hours to synthesize an alkali-soluble resin. The alkali-soluble resin synthesized had a solid content of 80.5 mg KOH/g, and its weight average molecular weight (Mw) as determined by GPC was about 15250.

<Synthesis Example 6>

120 parts of propylene glycol monomethyl ether acetate, 80 parts of propylene glycol monomethyl ether, 2 parts of AIBN, 22.0 parts of N-benzyl maleimide, 58.0 parts of 4-methylstyrene, 10 a portion of benzyl methacrylate, 10 parts of methyl methacrylate and 3 parts of n-dodecyldecyl group are introduced into a flask provided with a stirrer, a thermometer, a reflux cooling tube, a dropping funnel and a nitrogen supply tube. It was then replaced with nitrogen. Thereafter, the reaction mixture was stirred, heated to 80 ° C, and then reacted for 8 hours to synthesize an alkali-soluble resin. The solid content of the synthesized alkali-soluble resin had an acid value of 87.9 mg KOH/g, and its weight average molecular weight (Mw) as determined by GPC was about 17910.

Preparation of coloring photosensitive resin composition

<Example 1>

22.5 parts of the pigment dispersion composition (M), 16.5 parts of the alkali-soluble resin of Synthesis Example 1, 5.0 parts of KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.), and 0.3 parts of Irgacure 907 (by BASF Co., Ltd.) 0.7 parts of OXE-01 (manufactured by BASF Co., Ltd.), 20.5 parts of propylene glycol monomethyl ether acetate, and 34.0 parts of propylene glycol monomethyl ether were mixed to prepare a colored photosensitive resin composition.

<Example 2>

22.5 parts of the pigment dispersion composition (M), 16.5 parts of the alkali-soluble resin of Synthesis Example 2, 5.0 parts of KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.), and 0.3 parts of Irgacure 907 (by BASF Co., Ltd.) 0.7 parts of OXE-01 (manufactured by BASF Co., Ltd.), 20.5 parts of propylene glycol monomethyl ether acetate, and 34.0 parts of propylene glycol monomethyl ether were mixed to prepare a colored photosensitive resin composition.

<Example 3>

22.5 parts of the pigment dispersion composition (M), 16.5 parts of the alkali-soluble resin of Synthesis Example 3, 5.0 parts of KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.), and 0.3 parts of Irgacure 907 (by BASF Co., Ltd.) 0.7 parts of OXE-01 (manufactured by BASF Co., Ltd.), 20.5 parts of propylene glycol monomethyl ether acetate, and 34.0 parts of propylene glycol monomethyl ether were mixed to prepare a colored photosensitive resin composition.

<Example 4>

22.5 parts of the pigment dispersion composition (M), 16.5 parts of the alkali-soluble resin of Synthesis Example 4, 5.0 parts of KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.), and 0.3 parts of Irgacure 907 (by BASF Co., Ltd.) System), 0.7 parts OXE-01 (manufactured by BASF Co., Ltd.), 20.5 parts of propylene glycol monomethyl ether acetate, and 34.0 parts of propylene glycol monomethyl ether were mixed to prepare a colored photosensitive resin composition.

<Comparative Example 1>

22.5 parts of the pigment dispersion composition (M), 16.5 parts of the alkali-soluble resin of Synthesis Example 5, 5.0 parts of KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.), and 0.3 parts of Irgacure 907 (by BASF Co., Ltd.) 0.7 parts of OXE-01 (manufactured by BASF Co., Ltd.), 20.5 parts of propylene glycol monomethyl ether acetate, and 34.0 parts of propylene glycol monomethyl ether were mixed to prepare a colored photosensitive resin composition.

<Comparative Example 2>

22.5 parts of the pigment dispersion composition (M), 16.5 parts of the alkali-soluble resin of Synthesis Example 6, 5.0 parts of KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.), and 0.3 parts of Irgacure 907 (by BASF Co., Ltd.) 0.7 parts of OXE-01 (manufactured by BASF Co., Ltd.), 20.5 parts of propylene glycol monomethyl ether acetate, and 34.0 parts of propylene glycol monomethyl ether were mixed to prepare a colored photosensitive resin composition.

<Test example>

Manufacture of color filters

A color filter was produced using the colored photosensitive resin compositions of Examples 1 to 4 and Comparative Examples 1 and 2, respectively.

Specifically, each of the colored photosensitive resin compositions was applied by spin coating to a 2-inch glass substrate ("EAGLE XG", manufactured by Corning), heated to 100 ° C, and then kept at 100 ° C for 3 minutes. A film is formed. Subsequently, a test photomask is placed on the film, the test photomask has a pattern of transmittance gradually changing in the range of 1 to 100% and has a line/space pattern of 1 μm to 50 μm, and then masks the test light. The film was irradiated with ultraviolet rays while the distance between the mold and the film was set to 100 μm. In this case, ultraviolet rays were applied to the film at a luminance of 60 mJ/cm ² by emitting all of the g, h, and i-ray KW high-pressure mercury lamps without using a special optical filter. The ultraviolet-irradiated film was immersed in a developing solution (aqueous solution of KOH having a pH of 10.5) for development. The film-coated glass substrate was washed with distilled water, dried by blowing nitrogen gas, and then heated in an oven at 220 ° C for 25 minutes to manufacture a color filter. The manufactured color filter had a film thickness of 2.0 μm.

<Chemical resistance to NMP>

Each of the colored photosensitive resin compositions of Examples 1 to 4 and Comparative Examples 1 and 2 was applied onto a 2-inch glass substrate by spin coating, and then prebaked at 100 ° C for 3 minutes to form a film. Subsequently, a test photomask was placed on the film, and then the film was irradiated with ultraviolet rays and developed while the distance between the test photomask and the film was set to 100 μm to form a pattern on the film. Subsequently, the patterned film was heated in an oven at 220 ° C for 25 minutes to produce a color filter. The produced color filter was immersed in a NMP (N-methyl-2-pyrrolidone) solution for 30 minutes, and then the color difference between before and after immersion was observed. The results are shown in Table 1 below.

○: The value of ΔE * ab is less than 3

×: The value of ΔE * ab is 3 or more

<VHR measurement>

When no voltage is applied, the liquid crystal layer of the pixel charged by the applied voltage is discharged by the resistance in the liquid crystal layer. In this case, the degree to which the liquid crystal layer electrode maintains the charging voltage is referred to as "VHR (voltage holding ratio)".

The VHR of the color filter fabricated in each test example was measured. The conditions for assembling the VHR unit and the conditions for measuring the VHR are as follows.

The color resist substrate was scraped to obtain a powdery resist. The powder resist was mixed with LC at a ratio of resist: LC = 3:97, and then the mixture of the resist and the LC was aged at 80 ° C for 20 hours. IPA was introduced into the unit for measuring VHR and then ultrasonically washed at 35 ° C for 30 minutes. After aging, the mixture of resist and LC was filtered using a 0.2 μm syringe. The LC obtained after filtration was introduced into the unit. After welding, the VHR was measured by using a VHR measuring instrument (manufactured by Toyo Corporation), and the result was obtained. Shown in Table 1 below.

From the results in the above Table 1, it can be concluded that the color filters produced by using the colored photosensitive resin compositions of Examples 1 to 4 have excellent chemical resistance and VHR characteristics.

As described above, since the colored photosensitive resin composition of the present invention is excellent in VHR characteristics and chemical resistance, it does not cause defects in the subsequent process, thereby improving the productivity of the color filter. In addition, since the color filter manufactured using this composition has excellent storage stability, it deteriorates sensitivity or increases viscosity even if it is stored for a long period of time.

While the preferred embodiment of the present invention has been disclosed for illustrative purposes, it will be understood by those skilled in the art that various modifications, additions and substitutions are The scope and spirit of the invention.

Claims (11)

A colored photosensitive resin composition comprising: a colorant (A), an alkali-soluble resin (B), a photopolymerizable compound (C), a photopolymerization initiator (D), and a solvent (E), wherein the colorant (A) comprising at least one pigment and at least one dye, and the alkali-soluble resin (B) comprises a compound of the following formula 1: Wherein R1 is a linking group including a polymerizable unsaturated group, R2 is a hydrogen atom or a C1 to C12 alkyl group, R3 is a hydrogen atom, a C1 to C12 alkyl group, a C1 to C8 aliphatic group, C1~ An aromatic group of C8, a cyclic group of C1 to C8 or a heterocyclic group of C1 to C8, and n is 1 or 2. The colored photosensitive resin composition according to the above aspect of the invention, wherein the content of the colorant (A) is 5 to 60% by weight based on the total solid content of the composition, based on the composition a total solid content, the content of the alkali-soluble resin (B) is 10 to 80% by weight, based on the total solid content of the composition, the content of the photopolymerizable compound (C) is 5 to 45 wt%, based on the The total amount of the alkali-soluble resin (B) and the photopolymerizable compound (C), the photopolymerization initiator (D) is contained in an amount of 0.1 to 40% by weight, and the solvent is based on the total amount of the composition. The content of (E) is 60 to 90% by weight. The colored photosensitive resin composition according to the first aspect of the invention, wherein the alkali-soluble resin (B) has an acid value of 30 to 150 mg KOH/g. The colored photosensitive resin composition according to claim 1, wherein the amount of the dye in the colorant (A) is 0.5 to 80% by weight based on the total solid content of the colorant (A). The colored photosensitive resin composition according to claim 1, wherein the pigment is a pigment dispersion composition including a pigment dispersant, and the amount of the pigment is based on the total solid content of the pigment dispersion composition. 20~90wt%. The colored photosensitive resin composition according to claim 1, wherein the amount of the pigment dispersant is 5 to 60 parts by weight based on 100 parts by weight of the solid content of the pigment. The colored photosensitive resin composition according to the first aspect of the invention, wherein the content of the compound of the above formula 1 is from 1 to 50% by weight based on the total amount of the alkali-soluble resin (B). The coloring photosensitive resin composition according to the first aspect of the invention, wherein the photopolymerization initiator (D) is selected from the group consisting of an acetophenone compound, a benzophenone compound, a triazine compound, a biimidazole compound, At least one of the group consisting of a ruthenium compound and a thioxanthone compound. The coloring photosensitive resin composition according to claim 8, wherein the photopolymerization initiator (D) comprises at least one selected from the group consisting of an amine compound, a carboxyl compound, and an organic sulfur compound having a mercapto group. Photopolymerization initiation aid (d1). The colored photosensitive resin composition according to claim 9, wherein the photopolymerization initiating aid (d1) is based on the total solid content of the composition with respect to the alkali-soluble resin (B) and The content of the photopolymerizable compound (C) is from 0.1 to 40% by weight. A color filter produced by using the colored photosensitive resin composition according to any one of claims 1 to 10.