KR102241498B1 - Colored photosensitive resin composition for red or green pixel - Google Patents

Abstract

The present invention comprises a colorant (A), an alkali-soluble resin (B), a photopolymerizable compound (C), a photoinitiator (D), and a solvent (E),
The colorant (A) contains a compound of formula 1, and the alkali-soluble resin (B) contains a repeating unit of formula (2). It relates to a filter and a liquid crystal display device including the color filter.

Description

Colored photosensitive resin composition for red and green pixels {COLORED PHOTOSENSITIVE RESIN COMPOSITION FOR RED OR GREEN PIXEL}

The present invention relates to a colored photosensitive resin composition for red or green pixels, a colored pattern formed from the composition, a color filter including the colored pattern, and a liquid crystal display having the same.

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 a colored photosensitive resin containing a colorant corresponding to each color of red, green, and blue on a patterned substrate with a black matrix. After the composition is uniformly applied by spin coating, the coating film formed by heat drying (hereinafter, sometimes referred to as pre-baking) is exposed and developed, and further heat-cured if necessary (hereinafter, may be referred to as post-baking). ) Is repeated for each color to form pixels of each color.

Recently, a color filter for a liquid crystal display (LCD) is required to reproduce a high color, and a color coordinate change is required even by a change of a backlight, and a wide color reproduction range is required. In a color liquid crystal display, the color reproduction range is a range indicated by a triangle connecting the chromaticity coordinates of red, green, and blue in the XYZ color system, and is expressed as an area ratio to the NTSC (National Television System Committee) standard.

In a liquid crystal display device, when using an existing color material to form color pixels of a color filter with wide color reproducibility, there are methods of increasing the concentration of the pigment or thickening the coating film thickness of the pattern. There is a problem of lack of fairness, such as a decrease in straightness and generation of voids in a pattern due to undercut. In addition, there is a problem in that productivity is deteriorated due to problems such as defects in process and driving failures due to occurrence of outgas.

To this end, there is a need for a colored photosensitive resin composition having excellent color reproducibility, short development time, excellent etching characteristics, and less fear of outgassing while forming a thin coating film thickness of a pattern.

The present invention, as conceived to solve the problem of the prior art,

An object of the present invention is to provide a colored photosensitive resin composition for red or green pixels that has a thin film thickness, excellent luminance and coloring power, a high development speed, and capable of reducing out gas.

The present invention,

A colorant (A), an alkali-soluble resin (B), a photopolymerizable compound (C), a photoinitiator (D), and a solvent (E),

The colorant (A) contains a compound represented by the following formula (1),

The alkali-soluble resin (B) provides a colored photosensitive resin composition for red or green pixels, characterized in that it contains a repeating unit of the following formula (2).

[Formula 1]

In Formula 1, R1 to R13 are each independently hydrogen, halogen, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, an aryl group which may have a substituent, a phthalimidomethyl group which may have a substituent, and a substituent group. A sulfamoyl group which may have, -SO ₃ H, -COOH, -SO ₃ M, or -COOM;

M is a 1 to trivalent metal or alkyl ammonium;

Adjacent groups of R1 to R4 may be integrated to form an aromatic ring which may have a substituent, and R10 to R13 may be integrated with adjacent groups to form an aromatic ring which may have a substituent.

[Formula 2]

In addition, the present invention

It provides a color filter including a pattern formed of the colored photosensitive resin composition for red or green pixels.

In addition, the present invention

It provides a liquid crystal display device including the color filter.

The colored photosensitive resin composition for red or green pixels of the present invention has excellent luminance and coloring power even at a small amount of pigment, has a high development speed, and can reduce outgas, thereby providing an effect that does not cause defects in the process. I can.

The present invention,

A colorant (A), an alkali-soluble resin (B), a photopolymerizable compound (C), a photoinitiator (D), and a solvent (E),

The colorant (A) contains a compound represented by the following formula (1),

The alkali-soluble resin (B) provides a colored photosensitive resin composition for red or green pixels, characterized in that it contains a repeating unit of the following formula (2).

[Formula 1]

In Formula 1, R1 to R13 are each independently hydrogen, halogen, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, an aryl group which may have a substituent, a phthalimidomethyl group which may have a substituent, and a substituent group. A sulfamoyl group which may have, -SO ₃ H, -COOH, -SO ₃ M, or -COOM;

M is a 1 to trivalent metal or alkyl ammonium;

Adjacent groups of R1 to R4 may be integrated to form an aromatic ring which may have a substituent, and R10 to R13 may be integrated with adjacent groups to form an aromatic ring which may have a substituent.

[Formula 2]

Hereinafter, each component constituting the colored photosensitive resin composition for red or green pixels of the present invention will be described. However, the present invention is not limited to these components.

(A) colorant

Pigment( a1 )

The colorant (A) contained in the colored photosensitive resin composition for red or green pixels of the present invention is characterized in that it contains a compound represented by the following formula (1) as a pigment (a1). When the coloring agent (A) of the present invention contains a compound represented by the following formula (1) It is preferable because it has the advantage of being advantageous in coloring.

[Formula 1]

In Formula 1, R1 to R13 are each independently hydrogen, halogen, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, an aryl group which may have a substituent, a phthalimidomethyl group which may have a substituent, and a substituent group. A sulfamoyl group which may have, -SO ₃ H, -COOH, -SO ₃ M, or -COOM;

M is a 1 to trivalent metal or alkyl ammonium;

Adjacent groups of R1 to R4 may be integrated to form an aromatic ring which may have a substituent, and R10 to R13 may be integrated with adjacent groups to form an aromatic ring which may have a substituent.

The aromatic ring used herein includes a hydrocarbon aromatic ring and a heteroaromatic ring. As the hydrocarbon aromatic ring, a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, etc., and as a heteroaromatic ring, a pyridine ring, a pyra Jin ring, pyrrole ring, quinoline ring, quinoxaline ring, furan ring, benzofuran ring, thiophene ring, benzothiophene ring, oxazole ring, thiazole ring, imidazole ring, pyrazole ring, indole ring, carbazole ring, etc. I can.

Specifically, the compound of Formula 1 is also referred to as a quinophthalone pigment. For R1 to R13 in the above formula (1), examples of the halogen atom include fluorine, chlorine, bromine, and iodine.

In addition, examples of the alkyl group which may have a substituent include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, neopentyl group, n-hexyl group, n-octyl group, stearyl group In addition to linear or branched alkyl groups such as 2-ethylhexyl group, trichloromethyl group, trifluoromethyl group, 2,2,2-trifluoroethyl group, 2,2-dibromoethyl group, 2,2,3,3-tetrafluoropropyl group, 2-ethoxyethyl group, 2-butoxyethyl group, 2-nitropropyl group, benzyl group, 4-methylbenzyl group, 4-tert-butylbenzyl group, 4 Alkyl groups having substituents such as -methoxybenzyl group, 4-nitrobenzyl group, and 2,4-dichlorobenzyl group are mentioned.

In addition, examples of the alkoxy group which may have a substituent include methoxy group, ethoxy group, propoxy group, isopropoxy group, n-butoxy group, isobutyloxy group, tert-butyloxy group, neopentyloxy group, 2,3 In addition to linear or branched alkoxyl groups such as -dimethyl-3-pentoxy, n-hexyloxy group, n-octyloxy group, stearyloxy group, and 2-ethylhexyloxy group, trichloromethoxy group and trifluoromethoxy group , 2,2,2-trifluoroethoxy group, 2,2,3,3-tetrafluoropropyloxy group, 2,2-ditrifluoromethylpropoxy group, 2-ethoxyethoxy group, And an alkoxyl group having a substituent such as a 2-butoxyethoxy group, a 2-nitropropoxy group, and a benzyloxy group.

In addition, as an aryl group which may have a substituent, in addition to an aryl group such as a phenyl group, a naphthyl group, and an anthranyl group, p-methylphenyl group, p-bromophenyl group, p-nitrophenyl group, p-methoxyphenyl group, 2,4- Dichlorophenyl group, pentafluorophenyl group, 2-aminophenyl group, 2-methyl-4-chlorophenyl group, 4-hydroxy-1-naphthyl group, 6-methyl-2-naphthyl group, 4,5,8-trichloro- An aryl group having a substituent such as a 2-naphthyl group, an anthraquinonyl group, and a 2-aminoanthraquinonyl group is mentioned. Further, examples of the acidic group include -SO ₃ H and -COOH, and examples of the monovalent to trivalent metal salts of these acid groups include sodium salt, potassium salt, magnesium salt, calcium salt, iron salt, aluminum salt, and the like. have. In addition, as an acidic alkyl ammonium salt, an ammonium salt of a long-chain monoalkylamine such as octylamine, laurylamine, and stearylamine, a quaternary alkyl ammonium salt such as palmityltrimethylammonium, dilauryldimethylammonium, and distearyldimethylammonium salt. Can be lifted.

Examples of the substituents in the phthalimidomethyl group (C ₆ H ₄ (CO) ₂ N-CH ₂ -) which may have a substituent and the sulfamoyl group (H ₂ NSO ₂ -) which may have a substituent include the above halogen atom and a substituent. Alkyl group which may have, an alkoxyl group which may have a substituent, an aryl group which may have a substituent, etc. are mentioned.

The compound of Formula 1 is preferably included in an amount of 5 to 75% by weight, more preferably 10 to 70% by weight, and more preferably 20 to 60% by weight, based on the solid content in the colorant (A) of the present invention. It is more preferable to be included as. When the compound of Formula 1 is included in an amount of 5 to 75% by weight, the content of the colorant is reduced, thereby preventing the problem of reducing reliability in which the colorant is eluted by an organic solvent, and is preferable because of its excellent sensitivity.

The colorant (A) may be used as the pigment (a1) by adding an organic or inorganic pigment generally used in the art. As the pigment, various pigments used in printing ink, inkjet ink, etc. may be used, and more specifically, as the organic pigment, water-soluble azo pigment, insoluble azo pigment, phthalocyanine pigment, quinacridone pigment, isoindolinone pigment, iso Indoline Pigment, Ferriene Pigment, Perinone Pigment, Dioxazine Pigment, Anthraquinone Pigment, Dianthraquinonyl Pigment, Anthrapyrimidine Pigment, Antanthrone Pigment, Indanthrone Pigment, Pravantron Pigment, And a pyranthrone pigment, a diketopyrropyrrole pigment, and the like.

Examples of the inorganic pigment include metal compounds such as metal oxides and metal complex salts, and more specifically, metals such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony, and carbon black. Oxides or composite metal oxides.

Pigments included in the colored photosensitive resin composition for red or green pixels of the present invention are preferably green, yellow, blue, purple, and magenta-based pigments, and the organic and inorganic pigments are specifically color index (The Society of Dyers and Colourists (published by Dyers and Colourists), among the compounds classified as pigments, CI pigment red, CI pigment green, CI pigment yellow, CI pigment orange, CI pigment violet, and CI pigment blue are mentioned. More specifically, pigments having a color index (CI) number as follows, but are not limited thereto, may be used alone or in combination of two or more.

CI Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265, etc. Pigment;

Green pigments such as CI Pigment Green 7, 10, 15, 25, 36, 47, 58, 59

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

Orange pigments such as CI Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, and 71;

CI pigment violet 1, 14, 19, 23, 29, 32, 33, 36, 37 and 38 violet color pigments;

Blue pigments such as CI Pigment Blue 15 (15:3, 15:4, 15:6, etc.), 21, 28, 60, 64 and 76;

Pigment dispersant ( a2 )

The pigment (a1) is preferably used in the form of a pigment dispersion in which the particle diameter is uniformly dispersed. An example of a method for uniformly dispersing the particle diameter of the pigment includes a method of dispersing by containing a pigment dispersant (a2), and according to this method, a pigment dispersion in which the pigment is uniformly dispersed in a solution can be obtained. have.

Specific examples of the pigment dispersant (a2) include surfactants such as cationic, anionic, nonionic, amphoteric, polyester, and polyamine, and these may be used alone or in combination of two or more. I can.

The pigment dispersant (a2) is added for deagglomeration and stability maintenance of the pigment, and those generally used in the art may be used without limitation. It is preferable to contain an acrylate-based dispersant (hereinafter referred to as an acrylic dispersant) including BMA (butyl methacrylate) or DMAEMA (N,N-dimethylaminoethyl methacrylate). At this time, it is preferable to apply the acrylate-based dispersant manufactured by the living control method as suggested in Korean Patent Application Laid-Open No. 2004-0014311. As a commercial item of the acrylate-based dispersant manufactured through the living control method, DISPER BYK-2000, DISPER BYK-2001, DISPER BYK-2070, DISPER BYK-2150, and the like.

The acrylate-based pigment dispersants exemplified above may be used alone or in combination of two or more.

As the pigment dispersant (a2), other resin type pigment dispersants may be used in addition to the acrylate-based dispersant. As the pigment dispersant of the other resin type, a known resin type pigment dispersant, in particular, of a polycarboxylic acid ester typified by polyurethane, polyacrylate, unsaturated polyamide, polycarboxylic acid, polycarboxylic acid (partial) 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 pigment dispersant such as an amide formed by 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. As a commercial item of the above resin type pigment dispersant, 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 Chemicals' brand name: FLORENE DOPA-17HF, Floren DOPA-15BHF, Floren DOPA-33, Floren DOPA-44, and the like. In addition to the above acrylic pigment dispersants, other resin type pigment dispersants may be used alone or in combination of two or more, and may be used in combination with acrylic lake pigment dispersants.

The pigment dispersant (a2) is preferably contained in an amount of 5 to 60 parts by weight based on 100 parts by weight of the solid content of the pigment (a1) to be used, more preferably 15 to 50 parts by weight. If the content of the pigment dispersant (a2) is less than 5 parts by weight based on the above, it may be difficult to atomize the pigment or cause problems such as gelation after dispersion, and if it exceeds 60 parts by weight, the viscosity may increase. Not desirable.

dyes( a3 )

The colorant (A) of the present invention may further contain a dye (a3). The dye may be used without limitation as long as it has solubility in an organic solvent or is dispersible. 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. In the case of a dye that is not soluble in an organic solvent, it is also possible to disperse and use.

As the dye (a3), at least 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 may be used. In addition, it is also possible to select from azo-based, xanthene-based, phthalocyanine-based acid dyes and derivatives thereof.

As the dye (a3), a compound classified as a dye in the color index (published by The Society of Dyers and Colorists), or a known dye described in a dyeing note (color dyeing company) are preferably mentioned. As the color, green, yellow, blue, purple, and magenta dyes are preferable. More specifically, although the following dyes are mentioned, it is not necessarily limited to these.

C.I. Solvent Green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, 35

C.I. Solvent Yellow 4, 14, 15, 16, 21, 23, 24, 38, 56, 62, 63, 68, 79, 82, 93, 94, 98, 99, 151, 162, 163

C.I. Solvent Blue 18, 35, 36, 45, 58, 59, 59: 1, 63, 68, 69, 78, 79, 83, 94, 97, 98, 100, 101, 102, 104, 105, 111, 112, 122, 128, 132, 136, 139

CI solvent violet 11, 13, 14, 26, 31, 38, 47, 48, 51, 59, 60

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

The colorant (A) is preferably contained in an amount of 5 to 60% by weight, more preferably 10 to 45% by weight based on the solid content in the colored photosensitive resin composition for red or green pixels of the present invention. When the colorant (A) is contained in an amount of 5 to 60% by weight, the color density of the pixel is sufficient even when the thin film is formed, and the omission property of the non-pixel portion does not decrease during development, so that the residue is difficult to occur, so it is preferable.

In the present invention, the solid content in the colored photosensitive resin composition for red and green pixels means the total content of the remaining components excluding the solvent from the colored photosensitive resin composition for red and green pixels.

(B) alkali-soluble resin

The alkali-soluble resin (B) contained in the colored photosensitive resin composition for red or green pixels of the present invention is a component that imparts solubility to the alkali developer used in the developing step.

In the present invention, the alkali-soluble resin (B) is characterized in that it contains a repeating unit represented by the following formula (2).

[Formula 2]

In Chemical Formula 2,

The methyl group (-CH ₃ ) bonded to the benzene ring may be positioned at an ortho, meta, or para site.

In the present invention, if the alkali-soluble resin (B) contains the repeating unit of Formula 2, it is preferable because it has an advantage in coloring.

The repeating unit of Formula 2 is preferably contained in an amount of 10 to 60% by weight, more preferably 10 to 45% by weight, based on the total weight of the alkali-soluble resin (B) of the present invention. When the repeating unit of Formula 2 is included in the above range, it is preferable because it has advantageous advantages in coloring.

The alkali-soluble resin (B) of the present invention may further include other resins in addition to the repeating unit of Formula 2, and the resin is prepared by copolymerizing an ethylenically unsaturated monomer having a carboxyl group or an acid in a resin copolymer having a hydroxyl group. It can be produced by reacting an anhydride to give an acid value.

The ethylenically unsaturated monomer having a carboxyl group is a component that imparts solubility to an alkali developer used in a developing process when forming a pattern. Specific examples of the ethylenically unsaturated monomer having a carboxyl group include monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; Dicarboxylic acids such as fumaric acid, mesaconic acid, and itaconic acid; And anhydrides of the dicarboxylic acids; Mono (meth) acrylates of a polymer having a carboxyl group and a hydroxyl group at both ends, such as ω-carboxypolycaprolactone mono (meth)acrylate, and the like, and acrylic acid and methacrylic acid are more preferable. These can be used by selecting one or more.

As a method of giving an acid value by reacting an acid anhydride to the resin copolymer having a hydroxyl group, there is a method of giving an acid value by additionally reacting an anhydride to a hydroxy (meth) acrylate copolymer, but is not limited thereto. .

The hydroxy (meth) acrylates are specific examples, such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxy -3-phenoxypropyl (meth)acrylate, N-hydroxyethyl acrylamide, and the like, but are not limited thereto.

The alkali-soluble resin (B) can be prepared by further copolymerizing a copolymerizable unsaturated monomer.

As a specific example of the copolymerizable unsaturated monomer,

Styrene, vinyltoluene, α-methylstyrene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinylbenzylmethylether, m-vinylbenzylmethylether, p-vinyl Aromatic vinyl compounds such as 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;

Unsaturated amide compounds such as (meth)acrylamide and N,N-dimethyl (meth)acrylamide;

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, tricyclo[5.2.1.0 2,6]decane-8-yl (meth)acrylate, 2- Alicyclic (meth)acrylates such as dicyclopentanyloxyethyl (meth)acrylate and isobornyl (meth)acrylate;

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. Unsaturated oxetane compounds of, but are not limited thereto, and one or more may be selected and used therefrom.

The acid value of the alkali-soluble resin (B) is preferably 30 to 200 mgKOH/g based on solid content, and when the acid value of the alkali-soluble resin (B) is less than 30 mgKOH/g, the colored photosensitive resin composition secures a sufficient development speed. It is difficult to follow, and if the acid value exceeds 200 mgKOH/g, the adhesion with the substrate is reduced, which is likely to cause a short circuit in the pattern, and a problem in compatibility with the colorant occurs, causing the colorant in the colored photosensitive resin composition to precipitate or color. The storage stability of the photosensitive resin composition may decrease and the viscosity may increase, which is not preferable.

In addition, the alkali-soluble resin (B) is preferably contained in a weight fraction of 10 to 80% by weight, more preferably 10 to 70% by weight based on the solid content in the colored photosensitive resin composition for red or green pixels of the present invention. It is good. If the content of the alkali-soluble resin (B) is 10 to 80% by weight based on the above, it has sufficient solubility in a developer to facilitate pattern formation, and a film reduction in the pixel portion of the exposed portion during development is prevented, and thus the non-pixel portion It is preferable because the omission property of is improved.

(C) Photopolymerization compound

The photopolymerizable compound (C) contained in the colored photosensitive resin composition for red or green pixels of the present invention is a compound that can be polymerized by the action of a photopolymerization initiator (D) described below, and is a monofunctional monomer, a bifunctional monomer, or others. A functional monomer can be used, and more preferably, a polyfunctional monomer having a bifunctional or higher function is preferably used.

Specific examples of the monofunctional monomer include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate or N-vinylpi Rolidone and the like, but are not limited thereto.

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 or 3-methylpentanediol di(meth)acrylate, but are not limited thereto.

Specific examples of the polyfunctional monomer include trimethylol propane tri (meth) acrylate, ethoxylated trimethylol propane tri (meth) acrylate, propoxylated trimethylol propane tri (meth) acrylate, pentaerythritol tri (Meth)acrylate, pentaerythritol tetra (meth)acrylate, dipentaerythritol penta (meth)acrylate, ethoxylated dipentaerythritol hexa (meth) acrylate, propoxylated dipentaerythritol hexa (meth) ) Acrylate or dipenta erythritol hexa (meth) acrylate, and the like, but are not limited thereto.

The photopolymerizable compound (C) is preferably contained in an amount of 5 to 45% by weight, more preferably 7 to 45% by weight, based on the solid content in the colored photosensitive resin composition for red or green pixels of the present invention. Do. When the photopolymerizable compound (C) is contained in an amount of 5 to 45% by weight based on the above, it is preferable because the strength and smoothness of the pixel portion become good.

(D) Light polymerization Initiator

The photopolymerization initiator (D) contained in the colored photosensitive resin composition for red or green pixels of the present invention is the photopolymerizable compound (C) described above by exposure to radiation such as visible light, ultraviolet rays, far ultraviolet rays, electron rays, and X-rays. It is a compound that generates a radical capable of initiating the polymerization of. The photopolymerization initiator may include an acetophenone compound, a benzophenone compound, a biimidazole compound, a triazine compound, an oxime ester compound, and a thioxanthone compound, but are not limited thereto. You can select and use more than one type. In the present invention, the use of at least one oxime ester compound as the photoinitiator is more preferable in that the sensitivity is sufficient and short circuit of the pattern is difficult to occur in the developing step.

Examples of the acetophenone 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, 2-(4-methylbenzyl)-2-(dimethylamino)-1-(4-morpholinophenyl)butan-1-one, and the like.

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

Examples of the biimidazole-based compound 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) Biimidazole, 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 or imidazole compounds in which the phenyl group at the 4,4',5,5' position is substituted by a carboalkoxy group. have. Among these, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole and/or 2,2-bis(2,6-dichlorophenyl)-4,4'5,5'-tetraphenyl-1,2'-biimidazole is more It is preferably used.

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, 2,4-bis(trichloro Methyl)-6-[2-(3,4-dimethoxyphenyl)ethenyl]-1,3,5-triazine, and the like.

Examples of the oxime ester compound include 1,2-octanedione (1,2-Octanedione), 1-[4-(phenylthio)phenyl]-,2-(O-benzoyloxime)(1-[ 4-(phenylthio) phenyl]-,2-(O-benzoyloxime)), 1-[9-ethyll-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone 1-(O -Acetyloxime)(1-[9-Ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone 1-(O-acetyloxime)) and the like.

Examples of the thioxanthone compound include 2-isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-dichloro thioxanthone, 1-chloro-4-propoxy thioxanthone, etc. Can be mentioned.

The photopolymerization initiator (D) is preferably contained in an amount of 0.1 to 40% by weight based on the solid content in the colored photosensitive resin composition for red or green pixels of the present invention, more preferably 1 to 30% by weight. It is good. When the content of the photopolymerization initiator is within the above range, the colored photosensitive resin composition is highly sensitive and thus the exposure time is shortened, so that productivity is improved and high resolution can be maintained. Further, it is preferable because the intensity of the pixel portion and smoothness on the surface of the pixel portion can be improved.

Meanwhile, according to an embodiment of the present invention, the photopolymerization initiator (D) may further include a photopolymerization initiation auxiliary agent (d1) in order to improve the sensitivity of the colored photosensitive resin composition for red and green pixels of the present invention. The colored photosensitive resin composition for red and green pixels according to the present invention contains a photopolymerization initiation aid, so that the sensitivity is further increased and the productivity can be improved.

The photopolymerization initiation aid (d1) may preferably be one or more compounds selected from the group consisting of an amine compound, a carboxylic acid compound, and an organic sulfur compound having a thiol group.

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

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

Specific examples of the organic sulfur compound having a thiol group include 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), pentaerythritol tetrakis (3-mercaptobutyl) Rate), pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptopropionate), tetraethylene glycolbis (3-mercaptopropionate), etc. I can.

When the photopolymerization initiation aid (d1) is further used, the photopolymerization initiation aid is 0.1 to 40% by weight, more preferably 1 to 30% by weight, based on the solid content in the colored photosensitive resin composition for red and green pixels of the present invention. Can be included. When the content of the photopolymerization initiation aid is in the range of 0.1 to 40% by weight, the sensitivity of the colored photosensitive resin composition is further increased, and the productivity of the color filter formed using the composition may be improved.

The photopolymerization initiation aid (d1) is preferably contained in an amount of 10 to 90% by weight, more preferably 20 to 90% by weight, based on the total weight of the photopolymerization initiator. When the photopolymerization initiator is included in an amount of less than 10% by weight based on the total weight of the photopolymerization initiator, the decrease in sensitivity due to the dye cannot be overcome, and a short circuit of the pattern may easily occur during the development process.

(E) solvent

As long as the solvent (E) contained in the colored photosensitive resin composition for red or green pixels of the present invention is effective in dissolving other components included in the colored photosensitive resin composition, the solvent commonly used in the field may be used without particular limitation. have. As a specific example, the solvent may be used by selecting one or more from ethers, acetates, aromatic hydrocarbons, ketones, alcohols and esters, but is not limited thereto.

Specifically, the ether solvents 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; And the like.

Specifically, the acetate solvents include ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate;

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; And the like.

Specific examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene, and mesitylene.

Specific examples of the ketone solvent include methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, and cyclohexanone.

Specific examples of the alcohol solvent include ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, and glycerin.

Specifically, the ester solvents include cyclic esters such as γ-butyrolactone;

Ethyl lactate, butyl lactate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, and the like.

The solvent (E) is preferably an organic solvent having a boiling point of 100° C. to 200° C. in terms of coating properties and drying properties, more preferably propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, and ethyl Lactate, butyl lactate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, and the like can be used.

The solvent (E) contained in the colored photosensitive resin composition for red or green pixels of the present invention is preferably contained in an amount of 60 to 90% by weight based on the total weight of the colored photosensitive resin composition for red and green pixels of the present invention, More preferably, it may be included in 70 to 85% by weight. When the solvent (E) is included in the above-described range, the coating property is good when applied with a coating device such as a roll coater, a spin coater, a slit and spin coater, a slit coater (sometimes referred to as a die coater), or inkjet. It can provide a debilitating effect.

(F) additive

In addition to the above components, the colored photosensitive resin composition for red and green pixels of the present invention includes fillers, other polymer compounds, curing agents, adhesion promoters, ultraviolet absorbers, and anti-aggregation agents, as required by those skilled in the art within the scope of not impairing the object of the present invention. It may further include an additive (F).

Specific examples of the filler may include glass, silica, alumina, and the like, but are not limited thereto.

As a specific example of the other polymer compound, thermoplastic resins such as epoxy resin, thermosetting resin such as maleimide resin, polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, polyester, polyurethane, etc. Can be used, but is not limited thereto.

The curing agent is used to increase deep curing and mechanical strength, and as specific examples, an epoxy compound, a polyfunctional isocyanate compound, a melamine compound, an oxetane compound, etc. may be used, but the present invention is not limited thereto.

As specific examples of the epoxy compound, bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol F epoxy resin, hydrogenated bisphenol F epoxy resin, noblock epoxy resin, other aromatic epoxy resin, alicyclic epoxy resin, Glycidyl ester resins, glycidylamine resins, or brominated derivatives of these epoxy resins, aliphatic, alicyclic or aromatic epoxy compounds other than epoxy resins and brominated derivatives thereof, butadiene (co)polymer epoxides, isoprene (co ) Polymer epoxidation, glycidyl (meth) acrylate (co) polymer, triglycidyl isocyanurate, and the like, but are not limited thereto.

Specific examples of the oxetane compound include carbonate bisoxetane, xylene bisoxetane, adipate bisoxetane, terephthalate bisoxetane, cyclohexane dicarboxylic acid bisoxetane, etc., but limited thereto. It does not become.

The curing agent may be used in combination with a curing auxiliary compound capable of ring-opening polymerization of the epoxy group of the epoxy compound and the oxetane skeleton of the oxetane compound. Specifically, as the curing auxiliary compound, polyvalent carboxylic acids, polyvalent carboxylic anhydrides, acid generators, and the like can be used. The carboxylic anhydrides may be commercially available as an epoxy resin curing agent. Examples of the commercially available epoxy resin curing agent include a brand name (Adeka Hadona EH-700) (manufactured by Adeka Industries Co., Ltd.), a brand name (Rika Shiddo HH) (manufactured by Shin Nippon Ewha Corporation), and a brand name (MH-700) (Manufactured by Shin-Japan Ewha Corporation) and the like.

The curing agent and the curing auxiliary compound exemplified above may be used alone or in combination of two or more.

As specific examples of the adhesion promoter, vinyl trimethoxysilane, vinyl triethoxysilane, vinyl tris(2-methoxyethoxy)silane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2 -(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyl Trimethoxysilane, 3-isocyanatepropyltrimethoxysilane, and 3-isocyanatepropyltriethoxysilane alone or a mixture thereof may be used.

The adhesion promoter may be included in an amount of 0.01 to 10% by weight, more preferably 0.05 to 2% by weight, based on the solid content in the colored photosensitive resin composition for red or green pixels of the present invention.

Specific examples of the ultraviolet absorber include, but are not limited to, 2-(3-tert-butyl-2-hydroxy-5-methylphenyl)-5-chlorobenzotyrazole, alkoxybenzophenone, and the like.

Specific examples of the anti-aggregation agent may include sodium polyacrylate, but are not limited thereto.

The manufacturing method of the colored photosensitive resin composition for red or green pixels of the present invention will be described as follows.

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

In the mixed dispersion, the dye (a3), the rest of the alkali-soluble resin (B), the photopolymerizable compound (C) and the photopolymerization initiator (D), and the additive (F) and the solvent (E), if necessary, are added to a predetermined concentration. By further adding, the colored photosensitive resin composition for red or green pixels according to the present invention may be prepared.

In addition, the present invention includes a color filter including a pattern formed by forming the colored photosensitive resin composition for red or green pixels in a predetermined pattern, then exposing and developing. The manufacturing method of the color filter may use a conventional method well known in the art.

When a red pixel is formed using the colored photosensitive resin composition for a red pixel of the present invention, when expressed by chromaticity coordinates (x, y) in the XYZ color system, x of the chromaticity coordinate is 0.620<x<0.73, and y is 0.25 <y<0.36.

In the conventional case, in order to implement the chromaticity coordinates in the above range, the film thickness of the pixel had to exceed 3.3 μm. However, in the present invention, since the chromaticity can be realized with a film thickness of preferably 1.5 to 3.3 µm, more preferably 1.5 to 3.0 µm, it is possible to form a red pixel having excellent transmittance and no residue.

When a green pixel is formed using the colored photosensitive resin composition for a green pixel of the present invention, when expressed by chromaticity coordinates (x, y) in the XYZ color system, x of the chromaticity coordinate is 0.15<x<0.33, and y is 0.62. <y<0.80.

In the conventional case, in order to implement the chromaticity coordinates in the above range, the film thickness of the pixel had to exceed 3.5 µm. However, in the present invention, it is possible to implement the chromaticity with a film thickness of preferably 1.5 to 3.5 µm, more preferably 1.5 to 2.8 µm, so that a green pixel having excellent transmittance and no residue, etc. can be formed.

That is, the colored photosensitive resin composition for red or green pixels of the present invention can produce a color filter capable of high color reproduction even with a thin thickness.

In addition, the present invention includes a liquid crystal display device including the color filter. The liquid crystal display device includes a configuration known to a person skilled in the art except for the color filter, that is, the present invention includes a liquid crystal display to which the color filter of the present invention can be applied. .

Hereinafter, the present invention will be described in more detail using Examples and Comparative Examples. However, the following examples are intended to illustrate the present invention, and the present invention is not limited by the following examples, and various modifications and changes can be made within the scope of the present invention. The scope of the present invention will be determined by the technical idea of the claims to be described later.

In addition, "%" and "parts" indicating the content in the following Preparation Examples, Examples, and Comparative Examples are based on weight unless otherwise noted.

< Manufacturing example >

Preparation of pigment dispersion composition

<Pigment dispersion composition M1>

12.0 parts by weight of CI Pigment Red 254 as a pigment, 4.0 parts by weight of DISPERBYK-2001 (manufactured by BYK) as a pigment dispersant, 84 parts by weight of propylene glycol methyl ether acetate as a solvent were mixed/dispersed for 12 hours by a bead mill, and pigment dispersion M1 Was prepared.

<Pigment dispersion composition M2>

12.0 parts by weight of CI Pigment Red 177 as a pigment, 4.0 parts by weight of DISPERBYK-2001 (manufactured by BYK) as a pigment dispersant, 84 parts by weight of propylene glycol methyl ether acetate as a solvent were mixed/dispersed for 12 hours by a bead mill, and pigment dispersion M2 Was prepared.

<Pigment dispersion composition M3>

Pigment dispersion M3 by mixing/dispersing 12.0 parts by weight of a pigment of the following [Formula 3], 4.0 parts by weight of DISPERBYK-2001 (manufactured by BYK) as a pigment dispersant, 84 parts by weight of propylene glycol methyl ether acetate as a solvent for 12 hours by a bead mill Was prepared.

[Formula 3]

<Pigment dispersion composition M4>

12.0 parts by weight of CI Pigment Green 7 as a pigment, 4.0 parts by weight of DISPERBYK-2001 (manufactured by BYK) as a pigment dispersant, 84 parts by weight of propylene glycol methyl ether acetate as a solvent were mixed/dispersed for 12 hours with a bead mill, and pigment dispersion M4 Was prepared.

<Pigment dispersion composition M5>

12.0 parts by weight of CI Pigment Yellow 138 as a pigment, 4.0 parts by weight of DISPERBYK-2001 (manufactured by BYK) as a pigment dispersant, 84 parts by weight of propylene glycol methyl ether acetate as a solvent were mixed/dispersed for 12 hours with a bead mill, and pigment dispersion M5 Was prepared.

<Pigment dispersion composition M6>

12.0 parts by weight of CI Pigment Yellow 129 as a pigment, 4.0 parts by weight of DISPERBYK-2001 (manufactured by BYK) as a pigment dispersant, 84 parts by weight of propylene glycol methyl ether acetate as a solvent were mixed/dispersed for 12 hours with a bead mill, and pigment dispersion M6 Was prepared.

Synthesis of alkali-soluble resin

< Synthesis example 1>

Propylene glycol monomethyl ether acetate 120 parts by weight, propylene glycol monomethyl ether 80 parts by weight, AIBN 2 parts by weight, acrylic acid 13.0 parts by weight, vinyl toluene 60.0 parts by weight Part by weight, 10 parts by weight of benzyl methacrylate, 17 parts by weight of methyl methacrylate, and 3 parts by weight of n-dodecylmercaptan were added, followed by nitrogen substitution. After that, while stirring, the temperature of the reaction solution was raised to 80° C. and reacted for 8 hours. The acid value of the solid content of the thus synthesized alkali-soluble resin was 100.2 mgKOH/g, and the weight average molecular weight Mw measured by GPC was about 15,700.

< Synthesis example 2>

Propylene glycol monomethyl ether acetate 120 parts by weight, propylene glycol monomethyl ether 80 parts by weight, AIBN 3 parts by weight, acrylic acid 9.0 parts by weight, vinyl toluene 45.0 parts by weight Part by weight, 25.0 parts by weight of benzyl methacrylate, 21 parts by weight of methyl methacrylate, and 3 parts by weight of n-dodecylmercaptan were added, followed by nitrogen substitution. After that, while stirring, the temperature of the reaction solution was raised to 80° C. and reacted for 8 hours. The acid value of the solid content of the thus synthesized alkali-soluble resin was 72.4 mgKOH/g, and the weight average molecular weight Mw measured by GPC was about 12,380.

< Synthesis example 3>

Propylene glycol monomethyl ether acetate 120 parts by weight, propylene glycol monomethyl ether 80 parts by weight, AIBN 3 parts by weight, acrylic acid 13.0 parts by weight, vinyl toluene 30.0 parts by weight Part by weight, 25 parts by weight of benzyl methacrylate, 32 parts by weight of methyl methacrylate, and 3 parts by weight of n-dodecylmercaptan were added, followed by nitrogen substitution. After that, while stirring, the temperature of the reaction solution was raised to 80° C. and reacted for 8 hours. The acid value of the solid content of the thus synthesized alkali-soluble resin was 103.8 mgKOH/g, and the weight average molecular weight Mw measured by GPC was about 11,901.

< Synthesis example 4>

Propylene glycol monomethyl ether acetate 120 parts by weight, propylene glycol monomethyl ether 80 parts by weight, AIBN 2 parts by weight, acrylic acid 13.0 parts by weight, vinyl toluene 15.0 parts by weight Part by weight, 40.0 parts by weight of benzyl methacrylate, 32 parts by weight of methyl methacrylate, and 3 parts by weight of n-dodecylmercaptan were added, followed by nitrogen substitution. After that, while stirring, the temperature of the reaction solution was raised to 80° C. and reacted for 8 hours. The acid value of the solid content of the thus synthesized alkali-soluble resin was 98.6 mgKOH/g, and the weight average molecular weight Mw measured by GPC was about 13,901.

< Synthesis example 5>

Propylene glycol monomethyl ether acetate 120 parts by weight, propylene glycol monomethyl ether 80 parts by weight, AIBN 2 parts by weight, the methacrylic acid 13.0 parts by weight, vinyl 50.0 parts by weight of toluene, 10 parts by weight of benzyl methacrylate, 10 parts by weight of methyl methacrylate, and 3 parts by weight of n-dodecylmercaptan were added, followed by nitrogen substitution. After that, while stirring, the temperature of the reaction solution was raised to 80° C. and reacted for 8 hours. Then, the temperature of the reaction solution was lowered to room temperature, the atmosphere of the flask was replaced with air from nitrogen, and then 0.2 parts by weight of triethylamine, 0.1 parts by weight of 4-methoxy phenol, and 10 parts by weight of glycidyl methacrylate were added thereto, and at 100° C. It reacted for 6 hours. The acid value of the solid content of the thus synthesized alkali-soluble resin was 70.6 mgKOH/g, and the weight average molecular weight Mw measured by GPC was about 16,380.

< Synthesis example 6>

Propylene glycol monomethyl ether acetate 120 parts by weight, propylene glycol monomethyl ether 80 parts by weight, AIBN 2 parts by weight, the methacrylic acid 13.0 parts by weight, vinyl 55.0 parts by weight of toluene, 10 parts by weight of benzyl methacrylate, 10 parts by weight of methyl methacrylate, and 3 parts by weight of n-dodecylmercaptan were added, followed by nitrogen substitution. After that, while stirring, the temperature of the reaction solution was raised to 80° C. and reacted for 8 hours. Then, the temperature of the reaction solution was lowered to room temperature, the atmosphere of the flask was replaced with air from nitrogen, and then 0.2 parts by weight of triethylamine, 0.1 parts by weight of 4-methoxy phenol, and 10 parts by weight of glycidyl methacrylate were added thereto, and at 100° C. It reacted for 6 hours. Thereafter, the temperature of the reaction solution was lowered to room temperature, 2.0 parts by weight of succinic anhydride was added and reacted at 80° C. for 12 hours. Subsequently, the acid value of the solid content of the thus synthesized alkali-soluble resin was 75.3 mgKOH/g, and the weight average molecular weight Mw measured by GPC was about 12,874.

< Comparative Synthesis Example 1>

Propylene glycol monomethyl ether acetate 120 parts by weight, propylene glycol monomethyl ether 80 parts by weight, AIBN 2 parts by weight, acrylic acid 13.0 parts by weight, benzyl methacrylic in a flask equipped with a stirrer, thermometer reflux condenser, dropping lot and nitrogen inlet tube 45 parts by weight of rate, 42 parts by weight of methyl methacrylate, and 3 parts by weight of n-dodecylmercaptan were added, followed by nitrogen substitution. After that, while stirring, the temperature of the reaction solution was raised to 80° C. and reacted for 8 hours. The acid value of the solid content of the thus synthesized alkali-soluble resin was 99.6 mgKOH/g, and the weight average molecular weight Mw measured by GPC was about 14,700.

< Comparative Synthesis Example 2>

Propylene glycol monomethyl ether acetate 120 parts by weight, propylene glycol monomethyl ether 80 parts by weight, AIBN 3 parts by weight, acrylic acid 9.0 parts by weight, benzyl methacrylic in a flask equipped with a stirrer, thermometer reflux condenser, dropping lot and nitrogen inlet tube 15.0 parts by weight of rate, 76 parts by weight of methyl methacrylate, and 3 parts by weight of n-dodecylmercaptan were added, followed by nitrogen substitution. After that, while stirring, the temperature of the reaction solution was raised to 80° C. and reacted for 8 hours. The acid value of the solid content of the thus synthesized alkali-soluble resin was 75.4 mgKOH/g, and the weight average molecular weight Mw measured by GPC was about 13,380.

Preparation of colored photosensitive resin composition

A colored photosensitive resin composition was prepared by adjusting the proportion and content of the pigment dispersion so that the colored photosensitive resin compositions of Examples 1 to 12 and Comparative Examples 1 to 7 below exhibit the same color coordinates.

Example One.

31.91 parts by weight of the <pigment dispersion composition M4>, 14.34 parts by weight of the <pigment dispersion composition M3>, 9.90 parts by weight of the resin of <Synthesis Example 1>, KAYARAD DPHA (manufactured by Nippon Kayaku) 3.45 parts by weight, Irgacure OXE01 (manufactured by BASF) ) 0.69 parts by weight and 39.71 parts by weight of propylene glycol monomethyl ether acetate were mixed to prepare a colored photosensitive resin composition.

Example 2.

A photosensitive resin composition was prepared in the same manner as in Example 1, except that the resin used in <Example 1> was changed to the resin of <Synthesis Example 2>.

Example 3.

A colored photosensitive resin composition was prepared in the same manner as in Example 1, except that the resin used in <Example 1> was changed to the resin of <Synthesis Example 3>.

Example 4.

A colored photosensitive resin composition was prepared in the same manner as in Example 1, except that the resin used in <Example 1> was changed to the resin of <Synthesis Example 4>.

Example 5.

A colored photosensitive resin composition was prepared in the same manner as in Example 1, except that the resin used in <Example 1> was changed to the resin of <Synthesis Example 5>.

Example 6.

A colored photosensitive resin composition was prepared in the same manner as in Example 1, except that the resin used in <Example 1> was changed to the resin of <Synthesis Example 6>.

Example 7.

The <pigment dispersion composition M1> 18.29 parts by weight, <pigment dispersion composition M2> 11.67 parts by weight, <pigment dispersion composition M3> 16.29 parts by weight, <Synthesis Example 1> resin 9.9 parts by weight, KAYARAD DPHA (manufactured by Nippon Kayaku) 3.45 parts by weight, 0.69 parts by weight of Irgacure OXE01 (manufactured by BASF), and 39.71 parts by weight of propylene glycol monomethyl ether acetate were mixed to prepare a colored photosensitive resin composition.

Example 8.

A colored photosensitive resin composition was prepared in the same manner as in Example 1, except that the resin used in <Example 7> was changed to the resin of <Synthesis Example 2>.

Example 9.

A colored photosensitive resin composition was prepared in the same manner as in Example 1, except that the resin used in <Example 7> was changed to the resin of <Synthesis Example 3>.

Example 10.

A colored photosensitive resin composition was prepared in the same manner as in Example 1, except that the resin used in <Example 7> was changed to the resin of <Synthesis Example 4>.

Example 11.

A colored photosensitive resin composition was prepared in the same manner as in Example 1, except that the resin used in <Example 7> was changed to the resin of <Synthesis Example 5>.

Example 12.

A colored photosensitive resin composition was prepared in the same manner as in Example 1, except that the resin used in <Example 7> was changed to the resin of <Synthesis Example 6>.

Comparative example One.

A photosensitive resin composition was prepared in the same manner as in Example 1, except that the resin used in <Example 1> was changed to the resin of <Comparative Synthesis Example 1>.

Comparative example 2.

A photosensitive resin composition was prepared in the same manner as in Example 1, except that the resin used in <Example 1> was changed to the resin of <Comparative Synthesis Example 2>.

Comparative example 3.

25.98 parts by weight of the <pigment dispersion composition M4>, 40.86 parts by weight of the <pigment dispersion composition M5>, 5.61 parts by weight of the resin of <Synthesis Example 1>, KAYARAD DPHA (manufactured by Nippon Kayaku) 1.96 parts by weight, Irgacure OXE01 (manufactured by BASF) ) 0.39 parts by weight and 25.20 parts by weight of propylene glycol monomethyl ether acetate were mixed to prepare a colored photosensitive resin composition.

Comparative example 4.

The <pigment dispersion composition M4> 32.51 parts by weight, <pigment dispersion composition M6> 11.44 parts by weight, 10.38 parts by weight of the resin of <Synthesis Example 1>, KAYARAD DPHA (manufactured by Nippon Kayaku) 3.62 parts by weight, Irgacure OXE01 (manufactured by BASF) ) 0.72 parts by weight and 39.71 parts by weight of propylene glycol monomethyl ether acetate were mixed to prepare a colored photosensitive resin composition.

Comparative example 5.

A photosensitive resin composition was prepared in the same manner as in Example 1, except that the resin used in <Example 7> was changed to the resin of <Comparative Synthesis Example 1>.

Comparative example 6.

A photosensitive resin composition was prepared in the same manner as in Example 1, except that the resin used in <Example 7> was changed to the resin of <Comparative Synthesis Example 2>.

Comparative example 7.

The <pigment dispersion composition M1> 20.24 parts by weight, <pigment dispersion composition M2> 8.50 parts by weight, <pigment dispersion composition M5> 17.51 parts by weight, <Comparative Synthesis Example 1> resin 9.9 parts by weight, KAYARAD DPHA (manufactured by Nippon Kayaku ) 3.45 parts by weight, 0.69 parts by weight of Irgacure OXE01 (manufactured by BASF), and 39.71 parts by weight of propylene glycol monomethyl ether acetate were mixed to prepare a colored photosensitive resin composition.

< Experimental example >

Experimental example 1. Outgas Discharge evaluation

Using the colored photosensitive resin composition prepared in Examples 1 to 6 and Comparative Examples 1 to 4, the color coordinates at the C light source were x = 0.1972, y = 0.6514, prepared in Examples 7 to 12 and Comparative Examples 5 to 7 Using the colored photosensitive resin composition, a color filter was prepared so that the color coordinates of the C light source were x=0.6234 and y=0.3520.

Specifically, each of the above colored photosensitive resin compositions is coated on a 2-inch-angled glass substrate (manufactured by Corning, 「EAGLE XG」) by spin coating, and then placed on a heating plate and held at a temperature of 100° C. for 3 minutes to form a thin film. Made it. Subsequently, a test photomask having a 3cm * 3cm square pattern was placed on the thin film, and ultraviolet rays were irradiated with the distance between the test photomask at 300 µm. ^{At this time, the ultraviolet light source was irradiated with an illuminance of 100 mJ/cm 2} using a 1KW high-pressure mercury lamp containing all g, h, and i lines, and no special optical filter was used. The UV-irradiated thin film was developed by immersing it in a developing solution of a KOH solution having a pH of 10.5 for 80 seconds. The glass plate coated with the thin film was washed with distilled water, dried by blowing nitrogen gas, and heated in a heating oven at 230° C. for 25 minutes to prepare a color filter.

The prepared substrate was heat-treated at 230° C. for 30 minutes using Pyrolized GC/MS to measure the amount of outgas discharged.

Experimental example 2. Transmittance measurement

Using the colored photosensitive resin composition prepared in Examples 1 to 6 and Comparative Examples 1 to 4, the color coordinates at the C light source were x = 0.1972, y = 0.6514, prepared in Examples 7 to 12 and Comparative Examples 5 to 7 Using the colored photosensitive resin composition, a color filter was prepared so that the color coordinates of the C light source were x=0.6234 and y=0.3520.

Specifically, each of the above colored photosensitive resin compositions is coated on a 2-inch-angled glass substrate (manufactured by Corning, 「EAGLE XG」) by spin coating, and then placed on a heating plate and held at a temperature of 100° C. for 3 minutes to form a thin film. Made it. Subsequently, a test photomask having a pattern for changing the transmittance in a stepwise shape in the range of 1 to 100% and a line/space pattern of 1 µm to 100 µm was placed on the thin film, and the distance from the test photo mask was set to 300 µm. Was investigated. ^{At this time, the ultraviolet light source was irradiated with an illuminance of 100 mJ/cm 2} using a 1KW high-pressure mercury lamp containing all g, h, and i lines, and no special optical filter was used. The UV-irradiated thin film was developed by immersing it in a developing solution of a KOH solution having a pH of 10.5 for 80 seconds. The glass plate coated with the thin film was washed with distilled water, dried by blowing nitrogen gas, and heated in a heating oven at 230° C. for 25 minutes to prepare a color filter.

At this time, the transmittance of the 100 μm pattern of the prepared substrate was measured with a colorimeter (Olympus, OSP-200), and the results are shown in Table 1 below.

Experimental example 3. Color coordinates And Film thickness Measure

A color filter was manufactured using the colored photosensitive resin composition prepared in Examples 1 to 12 and Comparative Examples 1 to 7.

Specifically, each of the above colored photosensitive resin compositions is coated on a 2-inch-angled glass substrate (manufactured by Corning, 「EAGLE XG」) by spin coating, and then placed on a heating plate and held at a temperature of 100° C. for 3 minutes to form a thin film. Made it.

Subsequently, a test photomask having a pattern and a line/space pattern of 1 µm to 100 µm was placed on the thin film, and ultraviolet rays were irradiated with a distance of 300 µm to the test photo mask. ^{At this time, the ultraviolet light source was irradiated with an illuminance of 60 mJ/cm 2} using a 1KW high-pressure mercury lamp containing all g, h, and i lines, and no special optical filter was used. The UV-irradiated thin film was developed by immersing it in a developing solution of a KOH solution having a pH of 10.5 for 2 minutes. The glass plate coated with the thin film was washed with distilled water, dried by blowing nitrogen gas, and heated in a heating oven at 230° C. for 25 minutes to prepare a color filter.

At this time, the film thickness of the 100 μm pattern of the manufactured substrate was measured using a contact type thin film thickness meter (product name: DEKTAK 6M, manufacturer: Veeco), and the color coordinate was measured with a colorimeter (manufactured by Olympus, OSP-200). And the results are shown in Table 1 below.

Experimental example 4. Development time and Residue Measure

A color filter was manufactured using the colored photosensitive resin composition prepared in Examples 1 to 12 and Comparative Examples 1 to 7.

Specifically, each of the above colored photosensitive resin compositions is coated on a 2-inch-angled glass substrate (manufactured by Corning, 「EAGLE XG」) by spin coating, and then placed on a heating plate and held at a temperature of 100° C. for 3 minutes to form a thin film. Made it. The thin film was developed by immersing it in a developing solution of a KOH solution having a pH of 10.5 for 80 seconds. The development time was measured by measuring the time at which the glass substrate was exposed.

The glass substrate was washed with distilled water, and then dried by blowing nitrogen gas, and then the residue was evaluated according to the following criteria using a colorimeter (manufactured by Olympus, OSP-200), and is shown in Table 1 below.

<Residual evaluation criteria>

○: 99.7% or more

△: 99.5% or more to less than 99.7%

Ⅹ: less than 99.5%

Experimental example 5. Pattern adhesion evaluation

A color filter was manufactured in the same manner as in Experimental Example 1, and when the generated pattern was evaluated through an optical microscope, the degree of tearing on the pattern as follows was evaluated and shown in Table 1 below.

<Adhesion evaluation criteria>

○: No tearing of patterns larger than 30㎛

△: 1 to 3 tears in a pattern with a size of 30㎛ or more

Ⅹ: 4 or more tears in a pattern with a size of 30㎛ or more

Item Outgas
Discharge volume evaluation Transmittance
(%) Film thickness
(㎛) Color coordinates (x, y) Development time
(sec) Adhesion Residue Example 1 2606128 35.44 3.0 (0.197, 0.651) - 12 ○ ○ Example 2 2364722 36.01 3.03 14 ○ ○ Example 3 2751962 35.78 3.0 11 ○ ○ Example 4 2621236 35.64 3.0 13 ○ ○ Example 5 2840792 35.21 2.95 15 ○ ○ Example 6 2337087 35.49 3.05 8 ○ ○ Example 7 1418956 25.35 2.5 - (0.623, 0.352) 11 ○ ○ Example 8 1313911 25.68 2.6 13 ○ ○ Example 9 1577973 24.96 2.5 10 ○ ○ Example 10 1440187 26.64 2.7 14 ○ ○ Example 11 1308943 25.98 2.5 15 ○ ○ Example 12 1167524 26.15 2.5 6 ○ ○ Comparative Example 1 3606128 25.99 3.1 (0.197, 0.651) - 22 △ △ Comparative Example 2 4364722 25.54 3.0 23 △ X Comparative Example 3 6704444 31.42 4.0 21 Ⅹ △ Comparative Example 4 6431096 30.66 3.6 30 Ⅹ X Comparative Example 5 3348761 23.1 3.2 - (0.623, 0.352) 24 △ △ Comparative Example 6 3061754 22.64 3.1 26 △ X Comparative Example 7 4560241 23.21 3.4 35 Ⅹ X

As can be seen from the results shown in Table 1, the colored photosensitive resin composition of the present invention not only exhibited excellent adhesion and residue evaluation results, but also exhibited suitable results in evaluating transmittance and development time. In addition, it can be seen that, based on the same color coordinates, it has a thin film thickness compared to the comparative example that does not contain the compound of Formula 1, so that excellent chromaticity is exhibited even at a thin thickness. In the evaluation of the outgas discharge amount, it can be seen that a significantly smaller level of outgas is generated compared to the composition of the comparative example.

That is, the colored photosensitive resin composition of the present invention may exhibit excellent chromaticity even though it is thin, and may provide advantages such as less outgassing and excellent transmittance, adhesion, and development speed.

Claims (9)

A colorant (A), an alkali-soluble resin (B), a photopolymerizable compound (C), a photoinitiator (D), and a solvent (E),
The colorant (A) contains a compound represented by the following formula (3),
The alkali-soluble resin (B) is a colored photosensitive resin composition for red or green pixels, characterized in that it contains a repeating unit of the following formula (2).

[Formula 2]

[Formula 3]

The method according to claim 1,
The compound of formula (3) is a colored photosensitive resin composition for red or green pixels, characterized in that it is contained in an amount of 5 to 75% by weight based on the solid content in the colorant (A). The method according to claim 1,
As a weight fraction with respect to the solid content in the colored photosensitive resin composition for red or green pixels,
5 to 60% by weight of the colorant (A); And
A colored photosensitive resin composition for red or green pixels, comprising 10 to 80% by weight of an alkali-soluble resin (B). The method according to claim 1,
The repeating unit of Formula 2 is a colored photosensitive resin composition for red or green pixels, characterized in that it is contained in an amount of 10 to 60 wt% based on the total weight of the alkali-soluble resin (B). The method according to claim 1,
The acid value of the alkali-soluble resin (B) is 30 to 200 mgKOH / g based on the solid content, characterized in that the colored photosensitive resin composition for red or green pixels. The method according to claim 1,
The photopolymerization initiator (D) is an oxime ester-based photopolymerization initiator, wherein the colored photosensitive resin composition for red or green pixels. The method according to claim 1,
When pixels are formed using the colored photosensitive resin composition, in the XYZ color system, x of chromaticity coordinates is 0.620<x<0.73, and y is 0.25<y<0.36; or
The color photosensitive resin composition for red or green pixels, wherein x in chromaticity coordinates is 0.15<x<0.33, and y is 0.62<y<0.80. A color filter comprising a pattern formed by forming the colored photosensitive resin composition for red or green pixels according to any one of claims 1 to 7 in a predetermined pattern, then exposing and developing. A liquid crystal display device comprising the color filter of claim 8.