KR102384001B1 - Colored Photosensitive Resin Composition and Color Filter Comprising the Same - Google Patents

Abstract

The present invention comprises a thermal acid generator (A), a colorant (B), an alkali-soluble resin (C), a photoinitiator (D), a photopolymerizable compound (E) and a solvent (F), wherein the thermal acid generator (A) Provided is a colored photosensitive resin composition that is a nonionic thermal acid generator having a decomposition initiation temperature of less than 200° C., a color filter and a liquid crystal display manufactured using the same. The colored photosensitive resin composition according to the present invention can be sufficiently cured even by a low-temperature sintering process, and a color filter formed using the same can exhibit excellent adhesion and chemical resistance.

Description

Colored photosensitive resin composition and color filter comprising same

The present invention relates to a colored photosensitive resin composition and a color filter comprising the same, and more particularly, to a colored photosensitive resin composition that can be sufficiently cured even by a low-temperature firing process of less than 200 ° C. It relates to a color filter formed by using the color filter and a liquid crystal display device having the color filter.

Color filters are widely used in imaging devices, liquid crystal displays (LCDs), and the like, and their application range is expanding. A color filter is usually formed by uniformly coating a colored photosensitive resin composition containing a pigment corresponding to each color of red, green, and blue on a substrate having a pattern formed thereon with a black matrix, and then heating and drying (pre-baking) to expose the formed film. It is manufactured by repeating operation of developing, further heat-hardening (post-baking, baking) as needed for each color to form the pixel of each color.

In this case, a post-baking process is usually performed at a high temperature in order to sufficiently advance the curing to improve the durability of the color filter, which has problems in terms of workability and production cost. Therefore, even when post-baking is processed at a lower temperature, hardening progresses sufficiently, and development of the coloring photosensitive resin composition which shows the outstanding adhesiveness has been calculated|required.

Japanese Patent No. 2937208 discloses a colored photosensitive resin composition capable of post-baking at a low temperature by including a thermal crosslinking agent such as a melamine resin or an epoxy resin. However, even if such a colored photosensitive resin composition is used, when the post-baking is still performed at less than 200° C., there is a problem that the degree of curing is still insufficient.

Japanese Patent Registration No. 2937208

One object of the present invention is to provide a colored photosensitive resin composition capable of sufficiently curing even by a low-temperature sintering process of less than 200° C. and exhibiting excellent adhesion and chemical resistance to a color layer formed using the same.

Another object of the present invention is to provide a color filter formed using the colored photosensitive resin composition.

Another object of the present invention is to provide a liquid crystal display including the color filter.

On the other hand, the present invention includes a thermal acid generator (A), a colorant (B), an alkali-soluble resin (C), a photoinitiator (D), a photopolymerizable compound (E) and a solvent (F), and the thermal acid generator (A) provides a colored photosensitive resin composition comprising a compound represented by the following formula (1).

[Formula 1]

In Formula 1,

R ₁ is a C ₁ -C ₃₀ alkyl group, C ₂ -C ₃₀ alkenyl group, C ₃ -C ₂₀ cycloalkyl group, C ₂ -C ₂₀ heterocycloalkyl group, C ₆ -C ₂₀ aryl group, or C ₅ -C ₂₀ heteroaryl group;

R ₂ is a C ₁ -C ₃₀ alkyl group, C ₂ -C ₃₀ alkenyl group, C ₃ -C ₂₀ cycloalkyl group, C ₂ -C ₂₀ heterocycloalkyl group, C ₆ -C ₂₀ aryl group, or C ₅ -C ₂₀ heteroaryl group;

R ₁ and R ₂ are each independently substituted with a halogen atom, a cyano group, a nitro group, a carbonyl group, a sulfonic acid group, -SO ₃ M, -CO ₂ M, a hydroxyl group, a formyl group, an amino group, or a C ₁ -C ₂₀ alkyl group can be;

M represents a metal ion.

In one embodiment of the present invention, the decomposition initiation temperature of the thermal acid generator (A) may be 140 °C or more and less than 200 °C.

On the other hand, the present invention provides a color filter formed using the colored photosensitive resin composition.

On the other hand, the present invention provides a liquid crystal display device characterized in that the color filter is provided.

Since the colored photosensitive resin composition according to the present invention contains a nonionic thermal acid generator, sufficient curing is possible even by a low-temperature sintering process of less than 200 ° C., and a color filter formed using the same can exhibit excellent adhesion and chemical resistance. .

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

One embodiment of the present invention includes a thermal acid generator (A), a colorant (B), an alkali-soluble resin (C), a photoinitiator (D), a photopolymerizable compound (E) and a solvent (F), wherein the thermal acid generation The agent (A) relates to a colored photosensitive resin composition comprising a compound represented by the following formula (1).

Thermal acid generator (A)

The colored photosensitive resin composition of the present invention includes a nonionic thermal acid generator represented by the following formula (1), so that sufficient curing is possible even by a low-temperature sintering process of less than 200 ° C., and the color layer formed using the same has excellent adhesion and resistance May indicate drug properties. A thermal acid generator (A) is a compound which generate|occur|produces an acid by the action of heat.

[Formula 1]

In Formula 1,

R ₁ is a C ₁ -C ₃₀ alkyl group, C ₂ -C ₃₀ alkenyl group, C ₃ -C ₂₀ cycloalkyl group, C ₂ -C ₂₀ heterocycloalkyl group, C ₆ -C ₂₀ aryl group, or C ₅ -C ₂₀ heteroaryl group;

R ₂ is a C ₁ -C ₃₀ alkyl group, C ₂ -C ₃₀ alkenyl group, C ₃ -C ₂₀ cycloalkyl group, C ₂ -C ₂₀ heterocycloalkyl group, C ₆ -C ₂₀ aryl group, or C ₅ -C ₂₀ heteroaryl group;

R ₁ and R ₂ are each independently substituted with a halogen atom, a cyano group, a nitro group, a carbonyl group, a sulfonic acid group, -SO ₃ M, -CO ₂ M, a hydroxyl group, a formyl group, an amino group, or a C ₁ -C ₂₀ alkyl group can be;

M represents a metal ion, particularly an alkali metal or alkaline earth metal ion.

In one embodiment of the present invention, R ₁ may be a C ₅ -C ₇ cycloalkyl group or a bridged C ₇ -C ₈ cycloalkyl group that is unsubstituted or substituted with a hydroxyl group.

In addition, R ₂ may be a C ₁ -C ₆ alkyl group or a group represented by Formula 2 below.

[Formula 2]

In Formula 2,

R ₃ to R ₇ each independently represents a hydrogen atom or a C ₁ -C ₆ alkyl group,

* indicates a bonding part.

In one embodiment of the present invention, the thermal acid generator (A) may include a compound represented by any one of the following Chemical Formulas 3 to 5 alone or in combination.

[Formula 3]

[Formula 4]

[Formula 5]

In one embodiment of the present invention, the thermal acid generator (A) may have a decomposition initiation temperature of 140 °C or more and less than 200 °C. Accordingly, when the thermal acid generator of the present invention is used, curing is sufficiently performed even at a relatively low temperature of less than 200° C., so that a color filter having excellent adhesion and chemical resistance can be formed.

The content of the thermal acid generator (A) may be usually 80 to 90% by weight based on the total amount of the alkali-soluble resin (B) and the photopolymerizable compound (C) based on the solid content. When it is in the above range, the uniformity of the solution with respect to the solvent is ensured, the solubility is improved, the color photosensitive resin composition is increased in sensitivity, and the strength of the pixel part formed using the composition and the smoothness on the surface of the pixel part are improved. It is preferable because it tends to

Colorant (B)

In one embodiment of the present invention, the colorant (B) may comprise at least one pigment (b1), at least one dye (b3) or a mixture thereof, in particular at least one pigment (b1).

Pigment (b1)

As the pigment (b1), organic or inorganic pigments generally used in the art may be used. In addition, the pigment may be subjected to resin treatment, surface treatment using a pigment derivative into which an acidic group or a basic group is introduced, graft treatment of the pigment surface with a polymer compound, etc., atomization treatment by sulfuric acid atomization method, etc., as necessary to remove impurities A cleaning treatment with an organic solvent, water, or the like, or a treatment for removing ionic impurities by an ion exchange method or the like may be performed.

The organic pigment includes various pigments used in printing inks, inkjet inks, etc., and specifically, water-soluble azo pigments, insoluble azo pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, isoindoline pigments, ferri Ren pigment, perinone pigment, dioxazine pigment, anthraquinone pigment, dianthraquinonyl pigment, anthrapyrimidine pigment, ananthrone pigment, indanthrone pigment, pravanthrone pigment, pyranthrone pigment, diketopyrroropyrrole pigment, etc. can be heard

In addition, as the inorganic pigment, a metal compound such as a metal oxide or a metal complex salt may be used, and specifically, a metal such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony, or titanium oxides or composite metal oxides, carbon black, and the like.

In particular, the organic and inorganic pigments include compounds classified as pigments in the color index (published by The Society of Dyers and Colorists), and more specifically, the color index (C.I.) number of pigments, but are not necessarily limited thereto.

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

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

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

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

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

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

C.I Pigment Brown 28;

C.I Pigment Black 1 and 7 etc.

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

Among the CI pigment pigments illustrated above, 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, CI Pigment Blue 15: It is preferable to use 1 or more types of pigments chosen from the group which consists of 6, CI pigment green 7, CI pigment green 36, and CI pigment green 58.

The pigment is preferably used as a pigment dispersion in which the particle size is uniformly dispersed. Examples of a method for uniformly dispersing the particle diameter of the pigment include a method of dispersing the pigment dispersant (b2) and containing the pigment dispersant (b2). there is.

Pigment dispersant (b2)

The pigment dispersant (b2) is added to deagglomerate and maintain stability of the pigment, and specific examples of the pigment dispersant include cationic, anionic, nonionic, amphoteric, polyester, polyamine surfactants, etc. These can be mentioned, respectively, and these can be used individually or in combination of 2 or more types.

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

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

Specific examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene aryl ether, polyoxyethylene alkyl aryl ether, other polyoxyethylene derivatives, oxyethylene/oxypropylene block copolymer, sorbitan fatty acid ester, Polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, glycerol fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene alkylamine, etc. are mentioned.

The content of the pigment dispersant (b2) may be 5 to 60 wt%, preferably 15 to 50 wt%, based on the total weight of the solid content of the pigment (b1). When the content of the pigment dispersant is less than 5% by weight, it may be difficult to atomize the pigment or problems such as gelation after dispersion may occur, and if the content of the pigment dispersant is more than 60% by weight, the viscosity may increase.

dye (b3)

The dye (b3) may be used without limitation as long as it has solubility in organic solvents. Preferably, it is possible to use a dye having solubility in an organic solvent and ensuring reliability such as solubility in an alkali developer, heat resistance, and solvent resistance.

As the dye, an acid dye having an acid group such as sulfonic acid or carboxylic acid, a salt of an acid dye and a nitrogen-containing compound, a sulfonamide compound of an acid dye, and derivatives thereof may be used. In addition, azo-based, xanthene-based, Phthalocyanine-based acid dyes and derivatives thereof can also be used.

Preferably, as the dye, a compound classified as a dye in the Color Index (published by The Society of Dyers and Colorists) or a dye described in a dyeing note (color dye) may be used.

As a specific example of the dye, C.I. As a solvent dye,

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

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

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

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

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

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

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

Also, C.I. As an acid dye,

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

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

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

C.I. Acid Blue 1, 7, 9, 15, 18, 23, 25, 27, 29, 40, 42, 45, 51, 62, 70, 74, 80, 83, 86, 87, 90, 92, 96, 103, 112, 113, 120, 129, 138, 147, 150, 158, 171, 182, 192, 210, 242, 243, 256, 259, 267, 278, 280, 285, 290, 296, 315, 324:1, 335 and 340;

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

C.I. and dyes such as acid green 1, 3, 5, 9, 16, 25, 27, 50, 58, 63, 65, 80, 104, 105, 106 and 109.

Among the CI acid dyes exemplified above, CI Acid Yellow 42; CI Acid Red 92; CI Acid Blue 80, 90; CI Acid Violet 66; CI acid green 27 is preferable because of its excellent solubility in organic solvents.

Also C.I. As a direct dye,

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

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

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

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

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

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

Also, C.I. As a modanto dye,

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

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

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

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

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

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

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

The content of the colorant (B) may be included in an amount of 10 to 70% by weight based on the total weight of the solid content in the colored photosensitive resin composition of the present invention. When the colorant is included in the above range, it is possible to form a pattern having sufficient color density and sufficient mechanical strength when made into a color filter.

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

Alkali-soluble resin (C)

In one embodiment of the present invention, the alkali-soluble resin (C) usually has reactivity and alkali solubility under the action of light or heat, and serves as a dispersion medium for a colorant.

The alkali-soluble resin (C) acts as a binder resin for the colorant, and if it is soluble in the alkaline developer used in the developing step for manufacturing the color filter, the type is not particularly limited, and all of them may be used.

As for the said alkali-soluble resin (C), the copolymer etc. of a carboxyl group containing monomer and the other monomer copolymerizable with the said monomer are mentioned, for example.

As said carboxyl group-containing monomer, the unsaturated carboxylic acid etc. which have one or more carboxyl groups in molecules, such as an unsaturated monocarboxylic acid, an unsaturated dicarboxylic acid, and an unsaturated tricarboxylic acid, are mentioned, for example.

Examples of the unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, and cinnamic acid. As said unsaturated dicarboxylic acid, maleic acid, a fumaric acid, itaconic acid, a citraconic acid, mesaconic acid etc. are mentioned, for example. The unsaturated polyhydric carboxylic acid may be an acid anhydride, and specific examples thereof include maleic anhydride, itaconic anhydride, and citraconic anhydride. In addition, the said unsaturated polyhydric carboxylic acid may be its mono(2-methacryloyloxyalkyl) ester, For example, succinic acid mono(2-acryloyloxyethyl), succinic acid mono(2-methacryloyloxy) ethyl), monophthalic acid mono(2-acryloyloxyethyl), phthalic acid mono(2-methacryloyloxyethyl), etc. are mentioned. In addition, the unsaturated polyvalent carboxylic acid may be a mono (meth) acrylate of the dicarboxy polymer at both terminals, for example, ω-carboxypolycaprolactone monoacrylate, ω-carboxypolycaprolactone monomethacrylate, etc. can be heard These carboxyl group-containing monomers can be used individually or in mixture of 2 or more types, respectively.

Examples of the other monomer copolymerizable with the carboxyl group-containing monomer include styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-chlorostyrene, o-methoxystyrene, m-methyl Toxystyrene, p-methoxystyrene, o-vinylbenzylmethyl ether, m-vinylbenzylmethylether, p-vinylbenzylmethylether, o-vinylbenzylglycidylether, m-vinylbenzylglycidylether, p- aromatic vinyl compounds such as vinyl benzyl glycidyl ether and indene; Methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, i-propyl acrylate, i-propyl methacrylate, n-butyl acrylate, n-butyl methacrylate, i-butyl acrylate, i-butyl methacrylate, sec-butyl acrylate, sec-butyl methacrylate, t-butyl acrylate, t-butyl methacrylate, 2-hydroxy Ethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2-hydroxy Oxybutyl acrylate, 2-hydroxybutyl methacrylate, 3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, allyl acryl Rate, allyl methacrylate, benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, phenyl acrylate, phenyl methacrylate, 2-methoxyethyl acrylate, 2-methoxyethyl methacrylate acrylate, 2-phenoxyethyl acrylate, 2-phenoxyethyl methacrylate, methoxydiethylene glycol acrylate, methoxydiethylene glycol methacrylate, methoxytriethylene glycol acrylate, methoxytriethylene glycol methacrylic Rate, methoxypropylene glycol acrylate, methoxy propylene glycol methacrylate, methoxy dipropylene glycol acrylate, methoxy dipropylene glycol methacrylate, isobornyl acrylate, isobornyl methacrylate, dicyclopentadiethyl Acrylate, dicyclopentadiethyl methacrylate, adamantyl (meth) acrylate, norbornyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3- unsaturated carboxylic acid esters such as phenoxypropyl methacrylate, glycerol monoacrylate, and glycerol monomethacrylate; 2-aminoethyl acrylate, 2-aminoethyl methacrylate, 2-dimethylaminoethyl acrylate, 2-dimethylaminoethyl methacrylate, 2-aminopropyl acrylate, 2-aminopropyl methacrylate, 2-dimethyl Unsaturated carboxyl groups such as aminopropyl acrylate, 2-dimethylaminopropyl methacrylate, 3-aminopropyl acrylate, 3-aminopropyl methacrylate, 3-dimethylaminopropyl acrylate, and 3-dimethylaminopropyl methacrylate acid aminoalkyl esters; unsaturated carboxylic acid glycidyl esters such as glycidyl acrylate and glycidyl methacrylate; Carboxylic acid vinyl esters, such as vinyl acetate, a vinyl propionate, a vinyl butyrate, and a vinyl benzoate; unsaturated ethers such as vinyl methyl ether, vinyl ethyl ether, and allyl glycidyl ether; vinyl cyanide compounds such as acrylonitrile, methacrylonitrile, α-chloroacrylonitrile and vinylidene cyanide; unsaturated amides such as acrylamide, methacrylamide, α-chloroacrylamide, N-2-hydroxyethylacrylamide, and N-2-hydroxyethylmethacrylamide; unsaturated imides such as maleimide, benzylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide; aliphatic conjugated dienes such as 1,3-butadiene, isoprene and chloroprene; and a monoacryloyl group or monomethacryloyl group at the end of the polymer molecular chain of polystyrene, polymethyl acrylate, polymethyl methacrylate, poly-n-butyl acrylate, poly-n-butyl methacrylate, and polysiloxane. macromonomers and the like. These monomers can be used individually or in mixture of 2 or more types, respectively.

The alkali-soluble resin preferably has an acid value (KOH mg/g) of 20 to 200. When the acid value is within the above range, solubility in the developer is improved, so that the unexposed portion is easily dissolved and the sensitivity is increased, and as a result, the pattern of the exposed portion remains at the time of development to improve the film remaining ratio, which is preferable.

The acid value is a value measured as the amount (mg) of potassium hydroxide (KOH) required to neutralize 1 g of the polymer, and can be usually obtained by titration using an aqueous potassium hydroxide solution.

In addition, the polystyrene equivalent weight average molecular weight measured by gel permeation chromatography (GPC, using tetrahydrofuran as an elution solvent) of the alkali-soluble resin is preferably 3,000 to 200,000, and more preferably 5,000 to 100,000.

When the molecular weight is within the above range, the hardness of the coating film is improved and the residual film rate is high, the solubility of the unexposed part in the developer is excellent, and the resolution tends to be improved.

Moreover, it is preferable that it is 1.5-6.0, and, as for the molecular weight distribution [weight average molecular weight (Mw)/number average molecular weight (Mn)] of the said alkali-soluble resin, it is more preferable that it is 1.8-4.0. When molecular weight distribution exists in the said range, there exists a tendency for developability to become excellent.

The content of the alkali-soluble resin (C) may be included in an amount of 5 to 85% by weight based on the total weight of the solid content in the colored photosensitive resin composition of the present invention. When the content of the alkali-soluble resin is within the above range, the solubility in the developer is sufficient, so that it is difficult to generate a developing residue on the substrate of the non-pixel portion, and it is difficult to reduce the film of the pixel portion of the exposed portion during development, so that the non-pixel portion omission property is improved.

Photoinitiator (D)

In one embodiment of the present invention, the photopolymerization initiator (D) can be used without particularly limiting the type as long as it can polymerize the photopolymerizable compound (E).

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

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

Specific examples of the benzophenone-based compound include benzophenone, 0-benzoylbenzoate methyl, 4-phenylbenzophenone, 4-benzoyl-4′-methyldiphenylsulfide, 3,3′,4,4′-tetra( tert-butylperoxycarbonyl)benzophenone, 2,4,6-trimethylbenzophenone, etc. are mentioned.

Specific examples of the triazine-based compound include 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)- 6-(4-methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-piperonyl-1,3,5-triazine, 2,4- Bis(trichloromethyl)-6-(4-methoxystyryl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(5-methylfuran-2) -yl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)ethenyl]-1,3,5-tri azine, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)ethenyl]-1,3,5-triazine and 2,4-bis(trichloro methyl)-6-[2-(3,4-dimethoxyphenyl)ethenyl]-1,3,5-triazine;

Specific examples of the biimidazole-based compound include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3- Dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(alkoxyphenyl)biimi Dazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(trialkoxyphenyl)biimidazole, 2,2-bis(2,6-dichlorophenyl)-4 ,4',5,5'-tetraphenyl-1,2'-biimidazole and imidazole compounds in which the phenyl group at the 4,4',5,5' position is substituted with a carboalkoxy group; . Among them, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-dichlorophenyl)-4,4' ,5,5'-tetraphenylbiimidazole and 2,2-bis(2,6-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole are preferably can be used

Specific examples of the oxime compound include o-ethoxycarbonyl-α-oxyimino-1-phenylpropan-1-one, and commercial products such as OXE-01 and OXE-02 from BASF are representative.

Specific examples of the thioxanthone-based compound include 2-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone and 1-chloro-4-propoxythioxanthone. can be heard

Moreover, within the range which does not impair the effect of this invention, other photoinitiators other than the photoinitiators exemplified above may be used in combination.

Other photopolymerization initiators include a benzoin-based compound, an anthracene-based compound, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenane Trenquinone, camphorquinone, methyl phenylclioxylate, titanocene compound, etc. are mentioned.

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

Examples of the anthracene-based compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, and 2-ethyl-9,10-diethoxyanthracene. can be heard

In addition, the photopolymerization initiator may further include a photopolymerization initiation adjuvant (D-1) in order to improve the sensitivity of the colored photosensitive resin composition of the present invention. When the colored photosensitive resin composition according to the present invention contains the photopolymerization initiation adjuvant (D-1), the sensitivity further increases and productivity can be improved.

As the photopolymerization initiation adjuvant, for example, at least one compound selected from the group consisting of an amine compound, a carboxylic acid compound, and an organic sulfur compound having a thiol group may be preferably used.

It is preferable to use an aromatic amine compound as the amine compound, for example, an aliphatic amine compound such as triethanolamine, methyldiethanolamine, and triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoic acid isoamyl, 4-dimethylaminobenzoic acid 2-ethylhexyl, benzoic acid 2-dimethylaminoethyl, N,N-dimethylparatoluidine, 4,4'-bis(dimethylamino)benzophenone (common name: US healer ketone) and 4,4'-bis(diethylamino)benzophenone.

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

The organic sulfur compound having a thiol group is, for example, 2-mercaptobenzothiazole, 1,4-bis(3-mercaptobutyryloxy)butane, 1,3,5-tris(3-mercaptobutyloxyethyl). )-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, trimethylolpropanetris(3-mercaptopropionate), pentaerythritoltetrakis(3-mer captobutylate), pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptopropionate) and tetraethylene glycol bis (3-mercaptopropionate), etc. can be heard

The photopolymerization initiator (D) may be included in an amount of 0.1 to 30% by weight based on the total weight of the solid content in the colored photosensitive resin composition of the present invention. When the photopolymerization initiator is included in the content within the above range, the colored photosensitive resin composition is highly sensitive and exposure time is shortened, so that productivity is improved and high resolution can be maintained. In addition, the strength of the pixel portion formed by using the colored photosensitive resin composition and the smoothness on the surface of the pixel portion may be improved.

In addition, when the photopolymerization initiator auxiliary (D-1) is additionally used, it may be used in an amount of 10 moles or less, preferably 0.01 to 5 moles per 1 mole of the photopolymerization initiator. When the photopolymerization initiation adjuvant is used in the above range, the sensitivity of the colored photosensitive resin composition may be improved, and productivity of a color filter including the same may be improved.

Photopolymerizable compound (E)

In one embodiment of the present invention, the photopolymerizable compound (E) is a compound capable of polymerization by the action of the photoinitiator (D), and includes a monofunctional photopolymerizable compound, a bifunctional photopolymerizable compound, or a trifunctional photopolymerizable compound. can be mentioned, but is not limited thereto.

The monofunctional photopolymerizable compound is, for example, nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl acrylate, N- Vinylpyrrolidone etc. are mentioned, As a commercial item, Aronix M-101 (Toagosei), KAYARAD TC-110S (Nippon Kayaku), or Viscot 158 (Osaka Yuki Chemical High School), etc. are mentioned.

The bifunctional photopolymerizable compound is, for example, 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, bis(acryloyloxyethyl) ether of bisphenol A, 3-methylpentanediol di(meth)acrylate, and the like. Commercially available products include Aronix M-210, M-1100, 1200 (Toagosei). ), KAYARAD HDDA (Nippon Kayaku), Biscott 260 (Osaka Yuki Chemical High School), AH-600, AT-600, or UA-306H (Kyoeisha Chemical).

The trifunctional or more multifunctional photopolymerizable compound is, for example, trimethylol propane tri (meth) acrylate, ethoxylated trimethylol propane tri (meth) acrylate, propoxylated trimethylol propane tri (meth) acrylic Rate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, ethoxylated dipentaerythritol hexa (meth) acrylate, propoxyl There are rated dipentaerythritol hexa(meth)acrylate, dipentaerythritol hexa(meth)acrylate, etc., and commercially available products include Aronix M-309, TO-1382 (Toagosei), KAYARAD TMPTA, KAYARAD DPHA or KAYARAD DPHA-40H (Nippon Kayaku) and others.

Among the photopolymerizable compounds exemplified above, trifunctional or higher (meth)acrylic acid esters are preferable because they have excellent polymerizability and can improve strength.

The photopolymerizable compound (E) may be included in an amount of 5 to 50% by weight based on the total weight of the solid content in the colored photosensitive resin composition of the present invention. The photopolymerizable compound may improve the strength or smoothness of the pixel portion within the above range.

Solvent (F)

In one embodiment of the present invention, if the solvent (F) is effective in dissolving other components included in the colored photosensitive resin composition of the present invention, the solvent used in the conventional colored photosensitive resin composition may be used without particular limitation, and , particularly preferably ethers, acetates, aromatic hydrocarbons, ketones, alcohols or esters.

Examples of the ethers include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether and ethylene glycol monobutyl ether; Diethylene glycol dialkyl ethers, such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, and diethylene glycol dibutyl ether, etc. are mentioned.

The acetates include, for example, methyl cellosolve acetate, ethyl cellosolve acetate, ethyl acetate, butyl acetate, amyl acetate, methyl lactate, ethyl lactate, butyl lactate, 3-methoxybutyl acetate, 3 -Methyl-3-methoxy-1-butyl acetate, methoxypentyl acetate, ethylene glycol monoacetate, ethylene glycol diacetate, methyl 3-methoxypropionate, propylene glycol methyl ether acetate, 3-methoxy-1- Butyl acetate, 1,2-propylene glycol diacetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, 1,3-butylene glycol diacetate, diethylene glycol monobutyl ether Acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoacetate, diethylene glycol diacetate, diethylene glycol monobutyl ether acetate, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol monomethyl Ether acetate, propylene glycol monoethyl ether acetate, ethylene carbonate, propylene carbonate, etc. are mentioned.

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

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

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

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

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

It is preferable to use an organic solvent having a boiling point of 100° C. to 200° C. in terms of coating properties and drying properties, for example, alkylene glycol alkyl ether acetates, ketones, 3-ethyl ethoxypropionate, 3-methyl and esters such as methyl oxypropionate, more preferably propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, ethyl lactate, butyl lactate, 3-ethoxypropionate ethyl and 3 -Methyl methoxypropionate, etc. are mentioned.

The solvent (F) may be included in an amount of 60 to 90% by weight based on the total weight of the colored photosensitive resin composition. When the solvent is included in the above range, the coating property may be improved when applied with an application device such as a roll coater, a spin coater, a slit and spin coater, a slit coater (sometimes referred to as a die coater), and an inkjet.

The coloring photosensitive resin composition of this invention can use together additives (G), such as a filler, another high molecular compound, an adhesion promoter, antioxidant, a ultraviolet absorber, and aggregation inhibitor, as needed.

Specific examples of the filler include glass, silica, alumina, and the like.

Specific examples of the other high molecular compound include curable resins such as epoxy resins and maleimide resins; and thermoplastic resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, polyester, and polyurethane.

As the adhesion promoter, for example, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2 -(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyl Trimethoxysilane etc. are mentioned.

Specific examples of the antioxidant include 2,2'-thiobis(4-methyl-6-t-butylphenol) and 2,6-di-t-butyl-4-methylphenol.

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

Specific examples of the aggregation inhibitor include sodium polyacrylate.

The colored photosensitive resin composition according to an embodiment of the present invention can be produced, for example, by the following method.

First, the pigment (b1) of the colorant (B) is mixed with the solvent (F) and dispersed using a bead mill or the like until the average particle diameter of the pigment is about 0.2 μm or less. At this time, if necessary, the pigment dispersant, part or all of the alkali-soluble resin (C), or the dye (b3) may be mixed with the solvent (F) to be dissolved or dispersed. The dye (b3), the remainder of the alkali-soluble resin (C), the photopolymerization initiator (D), the photopolymerizable compound (E) and additives and, if necessary, the solvent (F) are further added to the mixed dispersion to a predetermined concentration. The colored photosensitive resin composition according to the present invention can be prepared.

One embodiment of the present invention relates to a color filter formed using the above-described colored photosensitive resin composition. A color filter according to an embodiment of the present invention is characterized in that it includes a colored layer formed by coating the above-described colored photosensitive resin composition on a substrate and exposing and developing in a predetermined pattern.

Hereinafter, the pattern formation method using the coloring photosensitive resin composition of this invention is demonstrated in detail.

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

As a coating method, it can be implemented by the spin coating method, the casting|flow_spread coating method, the roll coating method, the slit-and-spin coating method, or the slit coating method, for example. Heat-drying after application|coating (pre-baking), or heating after drying under reduced pressure to volatilize volatile components, such as a solvent. Here, the heating temperature is usually 70 to 200°C, preferably 80 to 130°C. The coating film thickness after heat drying is about 1-8 micrometers normally.

In this way, an ultraviolet-ray is irradiated through the mask for forming the target pattern on the obtained coating film. At this time, it is preferable to use a device such as a mask aligner or a stepper so that parallel rays are uniformly irradiated to the entire exposed portion and the mask and the substrate are precisely aligned. When irradiated with ultraviolet rays, the portion irradiated with ultraviolet rays is cured. As the ultraviolet rays, g-line (wavelength: 436 nm), h-line, i-line (wavelength: 365 nm), etc. may be used. The irradiation amount of ultraviolet rays may be appropriately selected according to necessity, and the present invention is not limited thereto.

When the cured coating film is brought into contact with a developer to dissolve the unexposed portion and developed, a desired pattern can be obtained. The developing method is not particularly limited to a liquid addition method, a dipping method, a spray method, or the like. In addition, you may incline a board|substrate at an arbitrary angle at the time of development. The developer is usually an aqueous solution containing an alkaline compound and a surfactant.

The alkaline compound may be an inorganic or organic alkaline compound. Examples of the inorganic alkaline compound include sodium hydroxide, potassium hydroxide, disodium hydrogen phosphate, sodium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, sodium silicate, potassium silicate, sodium carbonate, carbonate Potassium, sodium hydrogencarbonate, potassium hydrogencarbonate, sodium borate, potassium borate, ammonia, etc. are mentioned.

In addition, as the organic alkaline compound, for example, tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethyl amine, monoisopropylamine, diisopropylamine, ethanolamine, and the like.

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

The surfactant in the developer may be at least one selected from the group consisting of the aforementioned nonionic surfactants, anionic surfactants and cationic surfactants. The concentration of the surfactant in the developer may be 0.01 to 10% by weight, preferably 0.05 to 8% by weight, more preferably 0.1 to 5% by weight based on the total weight of the developer.

After development, it may be washed with water and, if necessary, may be post-baked at 140 to 200°C for 10 to 60 minutes.

As described above, a pixel or a black matrix corresponding to the color of the coloring material in the photosensitive resin composition is obtained through the operations of application, drying, patterning exposure, and development of the colored photosensitive resin composition, and these operations are required for the color filter. A color filter can be obtained by repeating as many colors as . The configuration and manufacturing method of the color filter is based on a method known in the art, and detailed description will be omitted.

One embodiment of the present invention relates to a liquid crystal display device provided with the above-described color filter.

The liquid crystal display of the present invention includes a configuration known in the art, except for having the above-described color filter. That is, all liquid crystal display devices to which the color filter of the present invention can be applied are included in the present invention. As an example, a transmissive liquid crystal display device in which a counter electrode substrate having a thin film transistor (TFT element), a pixel electrode, and an alignment layer faces each other at a predetermined interval, and a liquid crystal material is injected into the gap to form a liquid crystal layer. can There is also a reflective type liquid crystal display device in which a reflective layer is provided between the color filter substrate and the colored layer. As another example, a thin film transistor (TFT) substrate combined on a transparent electrode of a color filter and a liquid crystal display including a backlight fixed at a position where the TFT substrate overlaps the color filter may be used.

Hereinafter, the present invention will be described in more detail by way of Examples, Comparative Examples and Experimental Examples. These Examples, Comparative Examples, and Experimental Examples are only for illustrating the present invention, and it is apparent to those skilled in the art that the scope of the present invention is not limited thereto.

Preparation Example 1: Preparation of alkali-soluble resin

200 parts by weight of propylene glycol monomethyl ether acetate, 45 parts by weight of propylene glycol monomethyl ether, 2 parts by weight of azobisisobutyronitrile (AIBN) to a flask equipped with a stirrer, thermometer, reflux cooling tube, dropping funnel and nitrogen inlet tube , 15 parts by weight of acrylic acid, 70 parts by weight of benzyl methacrylate, 15 parts by weight of styrene, and 3 parts by weight of n-dodecyl mercapto were added and nitrogen substituted. Thereafter, the temperature of the reaction solution was raised to 110° C. with stirring and reacted for 8 hours. The alkali-soluble resin thus prepared had a weight average molecular weight measured by GPC of about 16,000 and a solid content acid value of 100.4 mgKOH/g.

Examples 1 to 6 and Comparative Example 1: Preparation of colored photosensitive resin composition

Each component was mixed with the composition shown in Table 1 below to prepare a colored photosensitive resin composition (unit: parts by weight).

Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 thermal acid generator A-1 ¹⁾ 0.8 0.8 0.8 A-2 ²⁾ 0.8 0.8 0.8 A-3 ³⁾ 0.8 0.8 0.8 coloring agent CI Pigment Blue 15:6 ⁴⁾ 0.49 0.49 0.49 0.49 0.49 0.49 0.49 0.49 0.49 0.49 Alkali-soluble resin Preparation Example 1 ⁵⁾ 0.52 0.52 0.52 0.52 0.52 0.52 0.52 0.52 0.52 0.52 photopolymerizable compound Kayarad DPHA ^{6 )} 0.41 0.41 0.41 0.41 0.41 0.41 0.41 0.41 0.41 0.41 photopolymerization initiator Irgacure 369 ⁷⁾ 0.8 0.8 0.8 0.5 0.5 0.5 0.8 solvent PGMEA ⁸⁾ 6.98 6.98 6.98 7.28 7.28 7.28 7.78 7.78 7.78 7.78

1) LTN-207 (Rom Hitech Co., Ltd.)

2) LTN-201 (Rom Hitech Co., Ltd.)

3) LTN-107 (Rom Hitech Co., Ltd.)

4) C.I Pigment Blue 15:6

5) the resin prepared in Preparation Example 1

6) Dipentaerythritol hexaacrylate (Nippon Kayaku Co., Ltd.)

7) 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one (Ciba Specialty Chemicals)

8) Propylene glycol monomethyl ether acetate

Experimental Example 1: Evaluation of solvent resistance and adhesion

A color filter was prepared as follows by using the colored photosensitive resin composition prepared in Examples and Comparative Examples.

First, each of the colored photosensitive resin compositions was applied on a glass substrate by spin coating, placed on a heating plate, and maintained at a temperature of 100° C. for 3 minutes to form a thin film. Then, a test photomask having a pattern for changing the transmittance in a range of 1 to 100% stepwise and a line/space pattern of 1 μm to 50 μm is placed on the thin film, and the interval from the test photomask is 100 μm. was investigated. At this time, the ultraviolet light source was irradiated with an illuminance of 100mJ/cm2 using a 1KW high-pressure mercury lamp containing all of the g, h, and i lines, and no special optical filter was used. The thin film irradiated with ultraviolet light was developed by immersing it in a developing solution of an aqueous KOH solution having a pH of 10.5 for 2 minutes. The glass plate coated with this thin film was washed with distilled water, dried by blowing nitrogen gas, and heated in a heating oven at 150° C. for 20 minutes to prepare a color filter. The film thickness of the color filter prepared above was 2.0 μm.

The solvent resistance and adhesion of each manufactured color filter were measured and evaluated as follows, and the results are shown in Table 2 below.

(1) Solvent resistance

The prepared color filter was immersed in N-methylpyrrolidone solvent for 30 minutes, and color change before and after immersion was comparatively evaluated. The equation used at this time is calculated by the following Equation 1 representing the color change in a three-dimensional colorimeter defined by L*, a*, and b*, and as the color change value is small, a highly reliable color filter can be manufactured.

[Equation 1]

ΔEab ^* = [(ΔL ^* ) ² +(Δa ^* ) ² +(Δb ^* ) ² ] ^(1/2)

(2) Adhesion

When the generated pattern was evaluated through an optical microscope, adhesion was evaluated to the degree of tearing on the pattern as follows.

○: No tearing in pattern

△ : 1-3 pieces of tear in the pattern

×: 4 or more torn in the pattern

Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 solvent resistance 1.6 1.0 1.3 2.6 2.0 2.3 4.0 4.3 5.0 4.0 adhesion ○ ○ ○ ○ ○ ○ x x x x

Through the results of Table 2, the color filters prepared using the colored photosensitive resin compositions of Examples 1 to 6 according to the present invention containing a thermal acid generator do not contain a photopolymerization initiator or a thermal acid generator, Comparative Examples 1 to It was found that the color filter prepared by using the colored photosensitive resin composition of No. 4 was more excellent in solvent resistance and adhesiveness.

Claims (8)

A thermal acid generator (A), a colorant (B), an alkali-soluble resin (C), a photoinitiator (D), a photopolymerizable compound (E) and a solvent (F) are included, wherein the thermal acid generator (A) has the following formula Includes a compound represented by 1,
The content of the thermal acid generator (A) is 80 to 90% by weight of the total amount of the alkali-soluble resin (B) and the photopolymerizable compound (C) based on the solid content colored photosensitive resin composition:
[Formula 1]

In Formula 1,
R ₁ is a C ₁ -C ₃₀ alkyl group, C ₂ -C ₃₀ alkenyl group, C ₃ -C ₂₀ cycloalkyl group, C ₂ -C ₂₀ heterocycloalkyl group, C ₆ -C ₂₀ aryl group, or C ₅ -C ₂₀ heteroaryl group;
R ₂ is a C ₁ -C ₃₀ alkyl group, C ₂ -C ₃₀ alkenyl group, C ₃ -C ₂₀ cycloalkyl group, C ₂ -C ₂₀ heterocycloalkyl group, C ₆ -C ₂₀ aryl group, or C ₅ -C ₂₀ heteroaryl group;
R ₁ and R ₂ are each independently substituted with a halogen atom, a cyano group, a nitro group, a carbonyl group, a sulfonic acid group, -SO ₃ M, -CO ₂ M, a hydroxyl group, a formyl group, an amino group, or a C ₁ -C ₂₀ alkyl group can be;
M represents a metal ion. The colored photosensitive resin composition according to claim 1, wherein R ₁ is a C ₅ -C ₇ cycloalkyl group or a bridged C ₇ -C ₈ cycloalkyl group substituted or unsubstituted with a hydroxyl group. The colored photosensitive resin composition of claim 1, wherein R ₂ is a C ₁ -C ₆ alkyl group or a group represented by the following formula (2):
[Formula 2]

In Formula 2,
R ₃ to R ₇ each independently represents a hydrogen atom or a C ₁ -C ₆ alkyl group,
* indicates a bonding part. The colored photosensitive resin composition according to claim 1, wherein the thermal acid generator (A) comprises a compound represented by any one of the following Chemical Formulas 3 to 5, alone or in combination:
[Formula 3]

[Formula 4]

[Formula 5]

. The colored photosensitive resin composition of Claim 1 whose decomposition initiation temperature of the said thermal acid generator (A) is 140 degreeC or more and less than 200 degreeC. delete A color filter formed using the colored photosensitive resin composition according to any one of claims 1 to 5. A liquid crystal display device comprising the color filter according to claim 7 .