KR20200114021A - A colored photo sensitive resin composition, a color filter comprising the same, and an image display devide comprising the color filter - Google Patents

Abstract

The present invention relates to a colored photosensitive resin composition comprising: a colorant; an alkali-soluble resin; a photopolymerizable compound; a photopolymerization initiator; a thermal acid generator; and a solvent, wherein the thermal acid generator includes at least one selected from the group consisting of compounds represented by chemical formulas 1 to 4, to a color filter produced using the same, and to an image display device comprising the color filter. In addition, the colored photosensitive resin composition has excellent reliability such as solvent resistance.

Description

A colored photosensitive resin composition, a color filter manufactured using the same, and an image display device including the color filter TECHNICAL FIELD [A COLOR FILTER COMPRISING THE SAME, AND AN IMAGE DISPLAY DEVIDE COMPRISING THE COLOR FILTER}

The present invention relates to a colored photosensitive resin composition, a color filter manufactured using the same, and an image display device including the color filter.

Color filters are widely used in imaging devices, liquid crystal displays, and the like, and their application range is rapidly expanding. A color filter used in a color liquid crystal display device or an image pickup device is usually applied by spin coating a photosensitive resin composition containing a colorant corresponding to each color of red, green, and blue on a substrate on which a black matrix is patterned. , Heat-drying (hereinafter, sometimes referred to as pre-baking) to expose and develop the formed coating film, and, if necessary, further heat-curing (hereinafter, also referred to as post-baking) operations for each color to repeat each color pixel. It is manufactured by forming.

One of the methods of implementing a color filter, the pigment dispersion method, is to coat and form a photosensitive resin composition including a colorant, alkali-soluble resin, photopolymerization monomer, photoinitiator, epoxy resin, solvent and other additives on a transparent substrate provided with a black matrix. This is a method of forming a colored thin film by repeating a series of processes of thermally curing by removing the unexposed part with a solvent after exposing the pattern of the desired shape to light. However, outgas generated by decomposition of the colored photosensitive resin composition during the thermal curing process has a problem in that an afterimage is generated in the pixel portion.

Meanwhile, as the display field gradually shifts to flexible displays, a flexible substrate is required, and the conventional glass substrate is being replaced with a polymer resin film such as polyimide and polyethylene terephthalate film. In the case of forming, it is not a problem, but in the case of a polymer resin film, a problem such as shrinkage or deterioration occurs due to high temperature heat. Accordingly, there is a need for a resin composition capable of curing even at a low temperature such that a polymer resin film used for a flexible substrate or the like is not deteriorated.

Republic of Korea Patent Publication No. 10-2016-0018424 relates to a photosensitive resin composition, an alkali-soluble polymer (A), a compound having at least one group selected from the group consisting of an acryloyl group and a methacryloyl group (B), It is characterized by comprising a polymerization initiator (C) and a thermal acid generator (D) having a decomposition initiation temperature of 60°C or more and less than 140°C.

However, the composition according to the prior literature does not solve the problem of thermal curing and outgas reduction in a process of less than 120°C.

Republic of Korea Patent Publication No. 10-2016-0018424

The present invention is to improve the above-described conventional technical problem, excellent curing properties even in a low-temperature sintering process of less than 120 ℃, it is possible to reduce the damage to the lower substrate generated during lamination evaluation, and outgas generated in the thermal curing process It is an object of the present invention to provide a colored photosensitive resin composition that can reduce (outgas) and has excellent reliability such as solvent resistance.

Another object of the present invention is to provide a color filter manufactured by using the colored photosensitive resin composition and an image display device including the color filter.

In order to achieve the above object, the present invention is a colored photosensitive resin composition comprising a colorant, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, a thermal acid generator and a solvent,

The thermal acid generator provides a colored photosensitive resin composition comprising at least one selected from the group consisting of compounds represented by the following Chemical Formulas 1 to 4.

[Formula 1]

[Formula 2]

[Formula 3]

[Formula 4]

In addition, the present invention provides a color filter including a colored pattern made of the colored photosensitive resin composition.

Further, the present invention provides an image display device including the color filter.

Since the colored photosensitive resin composition of the present invention contains a specific thermal acid generator, excellent curing properties can be obtained even when a color filter is manufactured through a low temperature process of less than 120°C, and outgas is generated in the thermal curing process. This is reduced, and an effect excellent in reliability such as solvent resistance is provided.

In addition, since the color filter manufactured using the colored photosensitive resin composition of the present invention has excellent curing properties, damage to the color filter at the bottom can be minimized even when other substrates are laminated on the color filter in a subsequent process. Since afterimages due to outgas do not occur, high-quality color filters and image display devices can be manufactured.

The present invention is a colored photosensitive resin composition comprising a colorant, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, a thermal acid generator, and a solvent, wherein the thermal acid generator is one selected from the group consisting of compounds represented by Formulas 1 to 4 It relates to a colored photosensitive resin composition comprising the above, a color filter prepared using the same, and an image display device including the color filter, wherein the colored photosensitive resin composition according to the present invention comprises the specific thermal acid generator , Even when manufacturing a color filter through a low-temperature process of less than 120℃, excellent curing properties can be obtained, outgas generation in the thermal curing process is reduced, and reliability such as solvent resistance is excellent, and subsequent processes Even if other substrates are stacked on the top of the color filter, damage to the lower color filter can be minimized, and afterimages due to outgas do not occur, it has been experimentally confirmed that high-quality color filters and image display devices can be manufactured. The invention was completed.

Hereinafter, each component constituting the colored photosensitive resin composition of the present invention will be described in detail. However, the present invention is not limited by these components.

<Colored photosensitive resin composition>

coloring agent

The colorant comprises at least one pigment (a1) or at least one dye (a3).

(a1) pigment

As the pigment, organic or inorganic pigments generally used in the art may be used.

The pigment may be a variety of pigments used in printing ink, inkjet ink, etc., specifically, water-soluble azo pigment, insoluble azo pigment, phthalocyanine pigment, quinacridone pigment, isoindolinone pigment, isoindolin Pigments, ferriene pigments, perinone pigments, dioxazine pigments, anthraquinone pigments, dianthraquinonyl pigments, anthrapyrimidine pigments, anthanthrone pigments, indanthrone pigments, flavantron pigments, pyrantrone (pyranthrone) pigment, diketopyrropyrrole pigment, etc. are mentioned.

Examples of the inorganic pigments include metal compounds such as metal oxides and metal complex salts. Specifically, oxides of metals such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony, and carbon black Or a composite metal oxide, etc. are mentioned.

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

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

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

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

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

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

C.I. Pigment Green 7, 10, 15, 25, 36, 47, 58, 59, 62 and 63

C.I Pigment Brown 28

C.I Pigment Black 1 and 7 etc.

Each of the pigments (a1) may be used alone or in combination of two or more.

C.I. Among the pigment pigments, C.I. Pigment Yellow 138, C.I. Pigment Yellow 139, C.I. Pigment Yellow 150, C.I. Pigment Yellow 185, C.I. Pigment Orange 38, C.I. Pigment Red 122, C.I. Pigment Red 166, C.I. Pigment Red 177, C.I. Pigment Red 208, C.I. Pigment Red 242, C.I. Pigment Red 254, C.I. Pigment Red 255, C.I. Pigment Violet 23, C.I. Pigment Blue 15:3, Pigment Blue 15:6, C.I. Pigment Green 7, C.I. Pigment Green 36 and C.I. Pigments selected from Pigment Green 58 can be preferably used.

The content of the pigment (a1) is in the range of 0 to 100% by weight, preferably 5 to 95% by weight, based on the total weight of the solid content of the colorant. When the content of the pigment (a1) satisfies the above range, it is preferable because processability and reliability are excellent in manufacturing a color filter.

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

(a2) pigment dispersant

The pigment dispersant is added for deagglomeration and stability of the pigment, and specific examples of the pigment dispersant include surfactants such as cationic, anionic, nonionic, amphoteric, polyester, and polyamine. And these may be used alone or in combination of two or more. In addition, it is preferable to include an acrylate-based dispersant (hereinafter referred to as an acrylate-based dispersant) containing butyl methacrylate (BMA) or N,N-dimethylaminoethyl methacrylate (DMAEMA).

Commercially available products of the acrylate-based dispersant include DISPER BYK-2000, DISPER BYK-2001, DISPER BYK-2070, or DISPER BYK-2150, and the acrylate-based dispersants can be used alone or in combination of two or more. I can.

As the pigment dispersant (a2), other resin type pigment dispersants may be used in addition to the acrylate-based dispersant. The other resin type pigment dispersants include known resin type pigment dispersants, especially polyurethanes, polycarboxylic acid esters typified by polyacrylates, unsaturated polyamides, polycarboxylic acids, (partially) of polycarboxylic acids. Amine salts, ammonium salts of polycarboxylic acids, alkylamine salts of polycarboxylic acids, polysiloxanes, long chain polyaminoamide phosphate salts, esters of hydroxyl group-containing polycarboxylic acids and modified products thereof, or free ) An oily dispersant such as an amide formed by the reaction of a polyester having a carboxyl group with a poly (lower alkyleneimine) or a salt thereof; Water-soluble resins or water-soluble polymer compounds such as (meth)acrylic acid-styrene copolymer, (meth)acrylic acid-(meth)acrylate ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol or polyvinyl pyrrolidone; Polyester; Modified polyacrylate; And phosphate esters and adducts of ethylene oxide/propylene oxide.

Commercially available products of the above resin-type dispersants include cationic resin dispersants, for example, BYK (Big) Chemie's brand names: DISPER BYK-160, DISPER BYK-161, DISPER BYK-162, DISPER BYK-163, DISPER BYK- 164, DISPER BYK-166, DISPER BYK-171, DISPER BYK-182, DISPER BYK-184; BASF's brand names: EFKA-44, EFKA-46, EFKA-47, EFKA-48, EFKA-4010, EFKA-4050, EFKA-4055, EFKA-4020, EFKA-4015, EFKA-4060, EFKA-4300, EFKA- 4330, EFKA-4400, EFKA-4406, EFKA-4510, EFKA-4800; Trade names of Lubirzol: SOLSPERS-24000, SOLSPERS-32550, NBZ-4204/10; Kawaken Fine Chemical's trade names: Hinoact T-6000, Hinoact T-7000, Hinoact T-8000; Ajinomoto's brand names: AJISPUR PB-821, Ajisper PB-822, Ajisper PB-823; Kyoeisha Chemical Co., Ltd. brand names: FLORENE DOPA-17HF, Florene DOPA-15BHF, Floren DOPA-33, Florene DOPA-44, and the like. In addition to the above acrylic dispersants, other resin type pigment dispersants may be used alone or in combination of two or more, or may be used in combination with an acrylic dispersant.

The content of the pigment dispersant (a2) is 5 to 60 parts by weight, preferably 10 to 50 parts by weight, based on 100 parts by weight of the solid content of the pigment (a1). If the content of the pigment dispersant (a2) exceeds 60 parts by weight, the viscosity may increase, and if it is less than 5 parts by weight, it may be difficult to atomize the pigment or cause problems such as gelation after dispersion.

(a3) dye

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

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

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

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

C.I. Solvent Blue 5, 35, 36, 37, 44, 45, 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.

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

Also, C.I. As an acid dye

CI Acid Red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 66, 73, 80, 87, 88 , 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 182, 183, 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 and 426;

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

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

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

C.I. acid violet 6B, 7, 9, 17, 19 and 66;

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

C.I. acid yellow 42 having excellent solubility in organic solvents in C.I. acid dyes; C.I. Acid Red 92; C.I. Acid Blue 80, 90; C.I. acid violet 66; C.I. Acid Green 27 is preferred.

Also, C.I. As a direct dye,

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

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

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

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

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

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

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;

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

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

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

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

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

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

When the dye (a3) is further included in the colorant, the content of the dye is in the range of 0.1 to 99% by weight, preferably 5 to 95% by weight, based on the total weight of the solid content of the colorant. If the content of the dye is in the above range, it is preferable because the luminance characteristic after pattern formation is excellent.

The content of the colorant may be included in 10 to 70% by weight, preferably 15 to 50% by weight, based on the total weight of the solid content of the colored photosensitive resin composition. When the colorant is included within the above range, it is preferable because a pattern having sufficient color density and sufficient mechanical strength can be formed when formed as a color filter.

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

Alkali-soluble resin

The alkali-soluble resin is a component that imparts solubility to an alkali developer used in the development treatment process when forming a pattern, and the alkali-soluble resin can be polymerized by including an ethylenically unsaturated monomer having a carboxyl group.

The ethylenically unsaturated monomer having a carboxy group is not particularly limited, and examples thereof include monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; Dicarboxylic acids such as fumaric acid, mesaconic acid, and itaconic acid, and anhydrides thereof; ω-carboxy polycaprolactone mono (meth) acrylate, and the like, mono (meth) acrylates of a polymer having a carboxyl group and a hydroxyl group at both ends, preferably acrylic acid and methacrylic acid. These can be used alone or in combination of two or more.

The alkali-soluble resin according to the present invention may be polymerized by further including at least one other monomer copolymerizable with the monomer. For example, styrene, vinyltoluene, methylstyrene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinylbenzylmethylether, m-vinylbenzylmethylether, p- Aromatic vinyl compounds such as vinyl benzyl methyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, and p-vinyl benzyl glycidyl ether; N-cyclohexylmaleimide, N-benzylmaleimide, N-phenylmaleimide, No-hydroxyphenylmaleimide, Nm-hydroxyphenylmaleimide, Np-hydroxyphenylmaleimide, No-methylphenylmaleimide, Nm -N-substituted maleimide compounds such as methylphenylmaleimide, Np-methylphenylmaleimide, No-methoxyphenylmaleimide, Nm-methoxyphenylmaleimide, and Np-methoxyphenylmaleimide; Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, alkyl (meth)acrylates such as sec-butyl (meth)acrylate and t-butyl (meth)acrylate; Cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, 2-dicyclopentanyloxyethyl (meth)acrylate, isobornyl (meth)acrylate, etc. Alicyclic (meth)acrylates; Aryl (meth)acrylates such as phenyl (meth)acrylate and benzyl (meth)acrylate; 3-(methacryloyloxymethyl)oxetane, 3-(methacryloyloxymethyl)-3-ethyloxetane, 3-(methacryloyloxymethyl)-2-trifluoromethyloxetane, 3-(methacryloyloxymethyl)-2-phenyloxetane, 2-(methacryloyloxymethyl)oxetane, 2-(methacryloyloxymethyl)-4-trifluoromethyloxetane, etc. And unsaturated oxetane compounds. These can be used alone or in combination of two or more.

In the present specification, (meth)acrylate means acrylate or methacrylate.

In addition, in order to secure the developability of the colored photosensitive resin composition, the acid value of the alkali-soluble resin is preferably 20 to 200 mgKOH/g, preferably 30 to 150 mgKOH/g. When the acid value of the alkali-soluble resin satisfies the above range, it is preferable that the colored photosensitive resin composition can secure a sufficient developing speed and improve adhesion to the substrate to prevent the occurrence of a short circuit in the pattern.

The weight average molecular weight (Mw) of the alkali-soluble resin of the present invention may be 3,000 to 30,000, preferably 5,000 to 25,000. In addition, the molecular weight distribution of the alkali-soluble resin of the present invention, that is, the weight average molecular weight (weight average molecular weight (Mw) / number average molecular weight (Mn)) relative to the number average molecular weight may be 1.5 to 6.0, preferably 1.8 to 4.0, and If the alkali-soluble resin satisfies the range of the weight average molecular weight and molecular weight distribution, there is an advantage of excellent developability.

The content of the alkali-soluble resin may be 5 to 75% by weight, preferably 10 to 70% by weight, based on the total weight of the solid content of the colored photosensitive resin composition. When the alkali-soluble resin is contained within the above range, it is preferable because it has sufficient solubility in a developer to facilitate pattern formation, prevents film reduction in the pixel portion of the exposed portion during development, and improves omission of non-pixel portions. Do.

Photopolymerizable compound

In one embodiment of the present invention, the photopolymerizable compound (C) is a compound that can be polymerized by the action of light and a photopolymerization initiator described later, and includes monofunctional monomers, difunctional monomers, and other polyfunctional monomers. .

Specific examples of the monofunctional monomer include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethylacrylate, and N-vinylpi And rolidone.

Specific examples of the bifunctional monomer include 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.

Specific examples of other polyfunctional monomers include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, di And pentaerythritol hexa(meth)acrylate. Among these, a bifunctional or higher polyfunctional monomer is preferably used.

The content of the photopolymerizable compound may be included in 5 to 50% by weight, preferably 7 to 45% by weight, based on the total weight of the solid content of the colored photosensitive resin composition. When the photopolymerizable compound is contained within the above range, it is preferable because the strength and smoothness of the pixel portion become good.

Photopolymerization initiator

The photopolymerization initiator contained in the colored photosensitive resin composition of the present invention is not limited, but is preferably at least one compound selected from the group consisting of a triazine compound, an acetophenone compound, a biimidazole compound, and an oxime compound. The photosensitive resin composition containing the photopolymerization initiator has a high sensitivity, and a pixel pixel formed using this composition has good strength and pattern properties of the pixel portion.

Further, when a photopolymerization initiator is used in combination with the photopolymerization initiator, the photosensitive resin composition containing them becomes more sensitive, and the productivity when forming a color filter using this composition is improved, so it is preferable.

As a triazine-based compound, for example, 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-triazine , 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl )-6-[2-(3,4-dimethoxyphenyl)ethenyl]-1,3,5-triazine, and the like.

Examples of the acetophenone-based compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, and 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 oligomers, etc. are mentioned.

Examples of the biimidazole compound include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3- Dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(alkoxyphenyl)biimi Dazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(trialkoxyphenyl)biimidazole, phenyl group carbohydrate at the 4,4',5,5' position And imidazole compounds substituted with an alkoxy group. Among these, 2,2'bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-dichlorophenyl)-4,4', 5,5'-tetraphenylbiimidazole is preferably used.

The oxime compound is, for example, 2-(O-benzoyloxime)-1-[4-(phenylthio)phenyl]-1,2-octanedione, 1-(4-methylsulfanyl-phenyl)-butane-1 ,2-butane-2-oxime-O-acetate, 1-(4-methylsulfanyl-phenyl)-butan-1-oneoxime-O-acetate, hydroxyimino-(4-methylsulfanyl-phenyl)- Ethyl acetate ester-O-acetate, hydroxyimino-(4-methylsulfanyl-phenyl)-ethyl acetate ester-O-benzoate, and the like.

Further, other photopolymerization initiators commonly used in this field may be further included as long as the effect of the present invention is not impaired. As other photoinitiators, a benzoin type compound, a benzophenone type compound, a thioxanthone type compound, an anthracene type compound, etc. are mentioned, for example. These may be used alone or in combination of two or more.

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

Examples of the benzophenone compound include benzophenone, methyl 0-benzoylbenzoate, 4-phenyl benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3',4,4'-tetra (tert-butylperoxycarbonyl)benzophenone, 2,4,6-trimethylbenzophenone, 4,4'-di(N,N'-dimethylamino)-benzophenone, etc. are mentioned.

As a thioxanthone compound, for example, 2-isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-dichloro thioxanthone, 1-chloro-4-propoxy thioxanthone And the like.

As an anthracene-based compound, for example, 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, etc. Can be mentioned.

Other 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, campoquinone, phenylclioxylic acid Methyl, titanocene compounds, etc. are mentioned as other photoinitiators.

In addition, as the photopolymerization initiator auxiliary agent that can be used in combination with the photopolymerization initiator in the present invention, at least one compound selected from the group consisting of amine compounds, carboxylic acid compounds, and the like may be preferably used.

Specific examples of the amine compound among the photopolymerization initiation aids include aliphatic amine compounds such as triethanolamine, methyldiethanolamine, and triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoic acid 2-ethylhexyl, benzoic acid 2-dimethylaminoethyl, N,N-dimethylparatoluidine, 4,4'-bis(dimethylamino)benzophenone (common name: Michler's ketone), 4,4'- And aromatic amine compounds such as bis(diethylamino)benzophenone. As the amine compound, an aromatic amine compound is preferably used.

Carboxylic acid compounds are, for example, phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, Aromatic heteroacetic acids such as dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, and naphthoxyacetic acid.

When the photopolymerization initiation aid is further included, the content of the photopolymerization initiation aid may be included in an amount of 0.1 to 20% by weight, preferably 3 to 15% by weight, based on the total weight of the solid content of the colored photosensitive resin composition. When the photopolymerization initiation aid is included within the above range, the sensitivity efficiency of the colored photosensitive resin composition is further increased, and the productivity of a color filter formed using the colored photosensitive resin composition may be improved.

The photopolymerization initiator may be included in an amount of 0.1 to 20% by weight, preferably 1 to 12% by weight, based on the total weight of the solid content of the colored photosensitive resin composition. When the photopolymerization initiator is contained within the above range, the colored photosensitive resin composition is highly sensitive, and the strength of the pixel portion and smoothness on the surface of the pixel portion are excellent.

Thermal acid generator

The colored photosensitive resin composition of the present invention contains a thermal acid generator. The thermal acid generator refers to a compound that generates an acid by the action of heat.

The thermal acid generator may be characterized in that at least one selected from the group consisting of compounds represented by the following Chemical Formulas 1 to 4.

[Formula 1]

[Formula 2]

[Formula 3]

[Formula 4]

The thermal acid generator may have a decomposition initiation temperature of 80 to 150°C. In the case of using the nonionic thermal acid generator according to the present invention, sufficient curing is possible even in a low-temperature firing process of less than 120°C, and the color filter formed by using it can be stacked on top of the color filter in a subsequent process In addition, the damage can be minimized, outgas generation in the heat curing process is reduced, and reliability such as solvent resistance can be excellent.

The thermal acid generator may be included in an amount of 0.1 to 20% by weight, preferably 0.5 to 10% by weight, based on the total weight of the solid content of the colored photosensitive resin composition. When the thermal acid generator is included within the above range, it is preferable because it is easy to sufficiently cure even at low temperatures.

solvent

In one embodiment of the present invention, the solvent is not particularly limited as long as the colored photosensitive resin composition has an appropriate viscosity and can easily dissolve the remaining components, and various organic solvents used in the field of the colored photosensitive resin composition can be used. have.

Specific examples of the solvent include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and styrene glycol monobutyl ether; Diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, and ethylene glycol dibutyl ether; Ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate; Propylene glycol dialkyl ethers such as propylene glycol monomethyl ether; Alkylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate and methoxypentyl acetate; Aromatic hydrocarbons such as benzene, toluene, xylene, and mesitylene; Ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, and cyclohexanone; alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, and glycerin; Esters such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate; Cyclic esters, such as γ-butyrolactone, etc. are mentioned.

Among the above solvents, organic solvents having a boiling point of 100° C. to 200° C. are preferably used from the viewpoint of coating properties and drying properties, more preferably alkylene glycol alkyl ether acetates, ketones, ethyl 3-ethoxypropionate, or , Esters such as methyl 3-methoxypropionate, and more preferably propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, 3-ethoxy ethylpropionate And methyl 3-methoxypropionate.

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

The solvent may be included in an amount of 50 to 90% by weight, preferably 55 to 90% by weight, based on the total weight of the colored photosensitive resin composition. When the solvent is contained within the above content range, the effect of improving the coating properties when applied with a coating device such as a roll coater, a spin coater, a slit and spin coater, a slit coater (sometimes referred to as a die coater), or inkjet. It is desirable because it provides.

additive

In addition to the above components, the colored photosensitive resin composition of the present invention may further include a nonionic, anionic or cationic dispersant to improve dispersibility of the colorant within a range that does not impair the object of the present invention.

Examples of the dispersant include polyalkylene glycol and esters thereof, polyoxyalkylene, polyhydric alcohol ester alkylene oxide adduct, alcohol alkylene oxide adduct, sulfonic acid ester, sulfonic acid salt, carboxylic acid ester, carboxylate, alkyl An amide alkylene oxide adduct, an alkylamine, or the like may be added alone or in combination of two or more.

The dispersant may be included in an amount of 10 to 20 parts by weight based on the total weight of the colored photosensitive resin composition.

In addition, the colored photosensitive resin composition may further include a coating improving agent such as a silicone-based or fluorine-based coating agent or an adhesion improving agent to improve adhesion to the substrate, if necessary to improve coating properties and defoaming properties.

The coating improving agent and the adhesion improving agent may be included in an amount of 0.01 to 1% by weight based on the total weight of the colored photosensitive resin composition.

In addition, in order to prevent spots or spots during application and to prevent the generation of residues due to leveling properties or undeveloped, the colored photosensitive resin composition may include an epoxy compound; Malonic acid; 3-amino-1,2-propanediol; A silane-based coupling agent having a vinyl group or a (meth)acryloxy group; Leveling agents; Fluorine-based surfactant; Other additives such as a radical polymerization initiator may be further included. The amount of these additives can be easily adjusted according to the desired physical properties.

Examples of the epoxy compound include phenol novolac epoxy resin, tetramethyl bi-phenyl epoxy resin, bisphenol A type epoxy resin, alicyclic epoxy resin, ortho-cresol novolac resin.

The epoxy compound may be included in an amount of 0.01 to 10% by weight, based on the total weight of the colored photosensitive resin composition, and when the content of the epoxy compound is within the above range, storage properties and process margin are excellent.

Specific examples of the silane-based coupling agent are vinyl trimethoxysilane, vinyl tris (2-methoxyethoxysilane), 3-glycidoxypropyl trimethoxysilane, 2-(3,4-epoxy cyclohexyl) Ethyl trimethoxysilane, 3-chloropropyl methyldimethoxysilane, 3-chloropropyl trimethoxysilane, 3-methacryloxypropyl trimethoxysilane, 3-mercaptopropyl trimethoxysilane, and the like.

The silane-based coupling agent may be included in an amount of 0.01 to 2% by weight based on the total weight of the colored photosensitive resin composition, and when the content of the silane-based coupling agent is within the above range, adhesion, storage stability and coating properties are excellent.

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 (a1) of the colorant is mixed with a solvent and dispersed using a bead mill or the like until the average particle diameter of the pigment becomes about 0.2 μm or less. At this time, if necessary, a pigment dispersant (a2), part or all of the alkali-soluble resin, or a dye (a3) may be mixed with a solvent to be dissolved or dispersed. To the mixed dispersion, the rest of the alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, a thermal acid generator, and additives, and a solvent may be further added to a predetermined concentration as necessary to prepare a colored photosensitive resin composition according to the present invention. .

<Color filter>

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

Hereinafter, a method for forming a pattern using the colored photosensitive resin composition of the present invention will be described in detail.

The method for forming a pattern using the colored photosensitive resin composition of the present invention may be a method known in the art, but is usually a coating step; Exposure step; And a removing step. By coating the colored photosensitive resin composition of the present invention on a substrate, photocuring and developing to form a pattern, it can be used as a colored pixel (colored image).

Specifically, the colored photosensitive resin composition was applied on a glass substrate to which nothing was applied and a glass substrate on which SiNx (protective film) was applied to a thickness of 500 to 1,500 Å by using a suitable method such as spin coating or slit coating, from 2.0 to Apply to a thickness of 3.4 μm. After application, light is irradiated to form a pattern necessary for the color filter. After light is irradiated, the coating layer is treated with an alkali developer to dissolve the unirradiated portion of the coating layer and a pattern necessary for the color filter is formed. By repeating this process according to the number of required R, G, and B colors, a color filter having a desired pattern can be obtained. In addition, in the above process, crack resistance, solvent resistance, etc. can be further improved by heating the image pattern obtained by development again or curing it by irradiation with actinic rays.

<Image display device>

An embodiment of the present invention relates to an image display device including the color filter described above.

The color filter of the present invention displays various images such as an electroluminescent display device (EL), a plasma display device (PDP), a field emission display device (FED), an organic light emitting device (OLED), as well as a conventional liquid crystal display device (LCD). Applicable to the device.

The image display device of the present invention includes a configuration known in the art, except for the color filter described above.

An image display device according to an embodiment of the present invention includes a red pattern layer containing red quantum dot particles, a green pattern layer containing green quantum dot particles, and a blue pattern layer containing blue quantum dot particles in addition to the color filters described above. A color filter may be additionally provided. In such a case, the emission light of the light source applied to the image display device is not particularly limited, but a light source that emits blue light may preferably be used in terms of more excellent color reproducibility.

In addition to the above-described color filter, the image display device according to an exemplary embodiment of the present invention may further include a color filter including only pattern layers of two colors among a red pattern layer, a green pattern layer, and a blue pattern layer. In such a case, the color filter further includes a transparent pattern layer containing no quantum dot particles. When only the pattern layer of two colors is provided, a light source that emits light having a wavelength representing the remaining colors not included may be used. For example, when only a red pattern layer and a green pattern layer are included, a light source emitting blue light may be used. In such a case, red quantum dot particles emit red light, green quantum dot particles emit green light, and blue light is transmitted through the transparent pattern layer to show blue.

Hereinafter, the present invention will be described in more detail based on examples, but the embodiments of the present invention disclosed below are illustrative only, and the scope of the present invention is not limited to these embodiments. The scope of the present invention is indicated in the claims, and furthermore, it contains the meanings equivalent to the claims recorded and all modifications within the scope. In addition, in the following Examples and Comparative Examples, "%" and "parts" indicating content are based on mass unless otherwise noted.

<Example>

Synthesis Example: Synthesis of alkali-soluble resin

In a 1 L flask equipped with a reflux condenser, a dropping funnel, and a stirrer, nitrogen was flowed at 0.02 L/min to obtain a nitrogen atmosphere, and 150 g of diethylene glycol methyl ethyl ether was added and heated to 70° C. while stirring. Subsequently, a solution is prepared by dissolving in 150 g of diethyl glycol methyl ethyl ether according to each ratio so that the total of EDCPA and AA is 1 mol. After dropping the prepared solution into a flask using a dropping funnel, 27.9 g (0.11 mol) of a polymerization initiator 2,2'-azobis (2,4-dimethylvaleronitrile) was added to 200 g of diethylene glycol methylethyl ether. The solution dissolved in was added dropwise into the flask over 4 hours using a separate dropping funnel. After the dropping of the polymerization initiator solution was completed, the solution was maintained at 70° C. for 4 hours, and then cooled to room temperature to obtain a binder resin having a solid acid value of 75 mgKOH/g. The weight average molecular weight measured by GPC was 13,000, and the molecular weight distribution (Mw/Mn) was 2.1.

The measurement of the weight average molecular weight (Mw) and number average molecular weight (Mn) of the above resin was performed under the following conditions using the GPC method.

Device: HLC-8120GPC (manufactured by Tosoh Corporation)

Column: TSK-GELG4000HXL + TSK-GELG2000HXL (serial connection)

Column temperature: 40 °C

Mobile phase solvent: tetrahydrofuran

Flow rate: 1.0 ml/min

Injection volume: 50 µl

Detector: RI

Measurement sample concentration: 0.6% by mass (solvent = tetrahydrofuran)

Standard material for calibration: TSK STANDARD POLYSTYRENE F-40, F-4, F-1, A-2500, A-500 (manufactured by Tosoh Corporation)

The ratio of the weight average molecular weight and number average molecular weight obtained above was taken as molecular weight distribution (Mw/Mn).

Preparation Example: Preparation of a colorant dispersion

C.I. Pigment Green 58 10.12 parts by weight, C.I. Pigment Yellow 138 3.88 parts by weight, acrylic dispersant (DisperBYK-2000, manufactured by Vicchemy) 4.84 parts by weight, resin of Synthesis Example 3.88 parts by weight, propylene glycol monomethyl ether acetate 68.04 parts by weight and propylene glycol monomethyl ether 9.24 parts by weight , 360 parts by weight of zirconia beads having a diameter of 0.2 mm were added to a mayonnaise bottle having a capacity of 140 ml, and kneaded at 60° C. for 10 hours with a paint conditioner to perform dispersion treatment. Thereafter, the zirconia beads were removed to obtain a dispersion. The dispersion was filtered through a membrane filter having a pore size of 1.0 µm to obtain a colorant dispersion.

Examples 1 to 4 and Comparative Examples 1 to 2: Preparation of green photosensitive resin composition

Green photosensitive resin compositions of Examples 1 to 4 and Comparative Examples 1 to 2 were prepared according to the composition of Table 1 below.

division Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Colorant dispersion 40 40 40 40 40 40 Alkali-soluble resin 2.5 2.5 2.5 2.5 2.5 2.5 Photopolymerizable compound 3.5 3.5 3.5 3.5 3.5 3.5 Photopolymerization initiator 0.8 0.8 0.8 0.8 1.4 0.8 Thermal acid generator 1 0.6 - - - - - Thermal acid generator 2 - 0.6 - - - - Thermal acid generator 3 - - 0.6 - - - Thermal acid generator 4 - - - 0.6 - - Thermal acid generator 5 - - - - - 0.6 additive 0.1 0.1 0.1 0.1 0.1 0.1 solvent 52.5 52.5 52.5 52.5 52.5 52.5

Colorant Dispersion: Colorant Dispersion of Preparation Example

Alkali-soluble resin: Alkali-soluble resin of Synthesis Example

Photopolymerizable compound: dipentaerythritol hexaacrylate (KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.)

Photopolymerization initiator: OXE-02 (manufactured by BASF)

Thermal acid generator 1: compound represented by formula 1

Thermal acid generator 2: compound represented by formula (2)

Thermal acid generator 3: compound represented by formula (3)

Thermal acid generator 4: compound represented by formula 4

Thermal acid generator 5: compound represented by the following formula (5)

[Formula 5]

Additive: SH-8400 (manufactured by Dow Corning)

Solvent: Propylene glycol monomethyl ether acetate (PGMEA)

Manufacturing Example: Manufacturing of color filters

Each photosensitive resin composition prepared in Examples 1 to 4 and Comparative Examples 1 to 2 was applied using a spin coater, and on a glass substrate of 50 mm to 50 mm, the number of rotations was adjusted so that the film thickness after drying was 2.5 μm. Then, it was dried in an oven at 100° C. for 3 minutes. The dried substrate was exposed so that the total amount of light at a wavelength of 313 nm of the fusion lamp was 40 mJ with a photomask spacing of 300 μm. Then, after developing with a KOH aqueous solution of pH 10.5 for 1 minute using a spray developing apparatus, it washed with water, and it wind-dried. Then, it was cured in an oven at 100° C. for 30 minutes to prepare a color filter.

<Experimental Example>

Experimental Example 1: Evaluation of solvent resistance

The color filter prepared above was immersed in an NMP solution at room temperature for 30 minutes, washed with ultrapure water, dried on a hot plate heated to 120° C. for 2 minutes, and then the chromaticity before and after immersion was measured. The equation used at this time is calculated by the following equation (1) representing the color change in a three-dimensional colorimeter defined by L*, a*, b*, and the smaller the color change value, the better the solvent resistance. The results are shown in Table 2 below.

[Equation 1]

△Eab* =[(△L*)2+(△a*)2+(△b*)2]^0.5

<Based on evaluation of solvent resistance>

○: △Eab* 3 or less,

X: greater than △Eab* 3

Experimental Example 2: Evaluation of the degree of damage when stacking other substrates

On the color filter prepared above, the composition of Comparative Example 1 was again coated and dried in an oven at 100° C. for 3 minutes. The dried substrate was rotated to be 90° of the already formed pattern, and the distance from the photomask was set to 300 μm, and the fusion lamp was exposed so that the accumulated light amount of 313 nm wavelength was 40 mJ, thereby manufacturing an upper color filter. Thereafter, development was performed with a KOH aqueous solution having a pH of 10.5 for 1 minute using a spray developing apparatus, followed by washing with water and air drying. At this time, after checking the already formed lower color filter with an optical microscope, the degree of peeling of the pattern was measured. The results are shown in Table 2 below.

<Standards for evaluating the degree of damage when laminating other substrates>

○: No peeling off of the lower color filter pattern,

Δ: 1 to 3 peeling of lower color filter patterns,

X: 4 or more peeling of lower color filter patterns

Experimental Example 3: Outgas Characteristics Evaluation

The gas component including the sublimable material generated by heating the color filter prepared above at 150° C. for 30 minutes using GC/MS was analyzed. The total amount of the compound component detected from the gas component generated in the coating film made of the composition of Comparative Example 1 that does not contain a thermal acid generator is set as a standard as 100%, and compared to the sublimation component of the coating film formed using the remaining composition (Outgas) was analyzed. The smaller the total, the better the material. The results are shown in Table 2 below.

Solvent resistance Degree of damage to the lower color filter Outgas Example 1 ○ ○ 80% Example 2 ○ ○ 76% Example 3 ○ ○ 81% Example 4 ○ ○ 78% Comparative Example 1 X X 100% Comparative Example 2 X △ 92%

Referring to the results of Table 2, in the case of Examples 1 to 4 including the thermal acid generator represented by Chemical Formulas 1 to 4, it was found that excellent effects were all in terms of solvent resistance, damage to the lower color filter, and outgas characteristics. I can confirm.

On the other hand, in the case of Comparative Example 1 not including the thermal acid generator, it can be seen that both the solvent resistance, the damage degree of the lower color filter, and the outgas characteristics are significantly reduced. In addition, in the case of Comparative Example 2 including the thermal acid generator represented by Formula 5, not the thermal acid generator according to the present invention, the solvent resistance is significantly lowered, the damage degree characteristics of the lower color filter are not excellent, and in particular, the amount of outgassing It can be seen that 92% represents a large difference of 11 to 16% compared to the present example.

From the above results, the colored photosensitive resin composition of the present invention includes a specific thermal acid generator, thereby reducing outgas generation in the thermal curing process, excellent reliability in solvent resistance, etc., and at a low temperature process of less than 120°C. It can be seen that even when the color filter is manufactured through the method, excellent curing properties can be obtained, so that damage to the lower color filter can be minimized even when other substrates are laminated on the top of the color filter in a later process.

Claims (9)

As a colored photosensitive resin composition comprising a colorant, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, a thermal acid generator, and a solvent,
The thermal acid generator is a colored photosensitive resin composition comprising at least one selected from the group consisting of compounds represented by the following Chemical Formulas 1 to 4.
[Formula 1]

[Formula 2]

[Formula 3]

[Formula 4]

The method according to claim 1,
The colored photosensitive resin composition, characterized in that the colorant contains a green pigment. The method according to claim 1,
The photopolymerizable compound is nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate, N-vinylpyrrolidone, 1 ,6-hexanedioldi(meth)acrylate, ethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, bis(acryloyloxy) of bisphenol A Ethyl) ether, 3-methylpentanediol di(meth)acrylate, 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(meth)acrylate, Colored photosensitive resin composition, characterized in that at least one selected from the group consisting of propoxylated dipentaerythritol hexa (meth) acrylate and dipentaerythritol hexa (meth) acrylate. The method according to claim 1,
The photopolymerization initiator is a colored photosensitive resin composition comprising an oxime compound. The method according to claim 1,
The colored photosensitive resin composition further comprises one or more additives selected from the group consisting of a dispersant, a coating improver, an adhesion improver, an epoxy compound, a silane coupling agent, a leveling agent, a fluorine surfactant, and a radical polymerization initiator. Colored photosensitive resin composition. The method according to claim 1,
Based on the total weight of the solid content of the colored photosensitive resin composition,
10 to 70% by weight of colorant,
5 to 75% by weight of an alkali-soluble resin,
5 to 50% by weight of a photopolymerizable compound,
0.1 to 20% by weight of a photopolymerization initiator, and
Including 0.1 to 20% by weight of a thermal acid generator,
A colored photosensitive resin composition comprising 50 to 90% by weight of a solvent based on the total weight of the colored photosensitive resin composition. The method according to claim 1,
The colored photosensitive resin composition is a colored photosensitive resin composition, characterized in that for reducing outgas generated during the manufacture of the color filter. A color filter comprising a colored pattern made of the colored photosensitive resin composition of any one of claims 1 to 7. An image display device comprising the color filter of claim 8.