KR20170085687A - Colored photosensitive resin composition for red pixel - Google Patents

Abstract

The present invention relates to a red photosensitive resin composition comprising a red colorant, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator and a solvent, and is capable of high color reproduction and has excellent contrast ratio.

Description

[0001] The present invention relates to a red photosensitive resin composition,

The present invention relates to a red photosensitive resin composition, and more particularly, to a red photosensitive resin composition comprising a red colorant, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent.

BACKGROUND ART Color filters are widely used in imaging elements, liquid crystal display elements, and the like, and their application range is rapidly expanding. A color filter used for a color liquid crystal display element, an image pickup element, or the like is a system in which a colored photosensitive resin composition containing a coloring agent corresponding to each color of red, green and blue is applied uniformly by spin coating on a substrate on which a black matrix is pattern- The coating film formed by heating and drying (hereinafter also referred to as preliminary firing) may be exposed and developed, and if necessary, further heat curing (hereinafter also referred to as post-firing) may be repeated for each color, Color pixels are formed. In recent years, a color filter for a liquid crystal display (LCD) is required to reproduce a high color, and a color coordinate is required to be changed by changing the backlight. Accordingly, there is a demand for a colored photosensitive resin composition that has good color reproducibility and can easily change the color coordinates when the backlight is changed.

In a color liquid crystal display, a color reproduction range is a range expressed by a triangle connecting the chromatic coordinates of red, green, and blue in the XYZ color system, and is expressed as an area ratio to the National Television System Committee (NTSC) standard. The color reproduction range of the CRT is about 70% of the NTSC standard. The chromaticity coordinates (x, y) in the XYZ color system of red, green, blue, and each of the chromaticity coordinates (x, y) are in the range of 0.670, 0.330 ), Rust (0.210, 0.710), and blue (0.140, 0.080). The chromaticity coordinates (x, y) of the ITU-R BT.2020 broadcast standard are defined by DCI (Digital Cinema Initiatives), which are required by (0.708, 0.292), (0.170, 0.797) The chromaticity coordinates (x, y) in Adobe were 0.640 and 0.330, respectively. The chromaticity coordinates (x, y) were 0.680, 0.320, 0.265, 0.690 and 0.150, respectively. Rust (0.210, 0.710), and blue (0.150, 0.060).

In recent years, a color filter for a liquid crystal display is required to reproduce a high color, and thus the content of a coloring agent in a colored photosensitive resin composition used for manufacturing a color filter is continuously increasing. Further, in order to produce a high-quality color filter having excellent visibility, there is a continuing need for improvement of the contrast ratio.

However, in the conventional pigment dispersion system, the pigment content in the colored photosensitive resin composition reaches its limit, and the improvement of the contrast ratio through the atomization of the pigment has reached its limit.

Therefore, a method of simultaneously using a pigment and a dye as a coloring agent has been studied. However, when a color filter is manufactured using a colored photosensitive resin composition containing a dye as a coloring agent, the sensitivity is insufficient, This may cause a problem of peeling. In addition, when a color filter is prepared using a colored photosensitive resin composition containing the dye, the compatibility of the dye is poor in the hard bake process, and the dye is deposited on the surface to reduce the contrast ratio, so that it is very difficult to use a sufficient amount of dye .

It is an object of the present invention to provide a red photosensitive resin composition exhibiting high color reproduction and high contrast ratio.

Another object of the present invention is to provide a red photosensitive resin composition capable of solving the problem of peeling off a pattern in a developing process without lowering the sensitivity by a dye.

It is another object of the present invention to provide a color filter made of the red photosensitive resin composition and a display device including the color filter.

In order to achieve the above object,

The present invention relates to a red photosensitive resin composition comprising a red colorant, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator and a solvent,

Wherein the red colorant comprises a pigment and a dye,

Wherein the pigment comprises diketopyrrolopyrrole bromide,

Wherein the dye comprises at least one selected from the group consisting of xanthene dyes and azo dyes represented by the following formula (1)

Wherein the photopolymerization initiator comprises an oxime ester compound.

[Chemical Formula 1]

Each of R ₁ to R ₆ is independently hydrogen, an alkyl group having 1 to 5 carbon atoms, or a trialkoxysilylalkyl group having 1 to 5 carbon atoms,

Wherein R ₇ and R ₈ are each independently hydrogen, COOH, COO ^- _{is, COONa, SO 3 H, SO} 3 Na, COOCH 3 or ^{_{COOCH 2 CH 3 -, SO 3}} .

The present invention also provides a red color filter made of the red photosensitive resin composition.

Further, the present invention provides a display device including the red color filter.

The red photosensitive resin composition of the present invention has the effect of realizing high color reproduction and high contrast ratio.

Further, the red photosensitive resin composition of the present invention has an effect that no peeling of the pattern occurs in the development process without lowering the sensitivity by the dye.

Further, the color filter made of the red photosensitive resin composition of the present invention can exhibit high quality.

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

The present invention relates to a red photosensitive resin composition comprising a red colorant, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator and a solvent,

Wherein the red colorant comprises a pigment and a dye,

Wherein the pigment comprises diketopyrrolopyrrole bromide,

Wherein the dye comprises at least one selected from the group consisting of xanthene dyes and azo dyes represented by the following formula (1)

Wherein the photopolymerization initiator comprises an oxime ester compound.

[Chemical Formula 1]

Each of R ₁ to R ₆ is independently hydrogen, an alkyl group having 1 to 5 carbon atoms, or a trialkoxysilylalkyl group having 1 to 5 carbon atoms,

Wherein R ₇ and R ₈ are each independently hydrogen, COOH, COO ^- _{is, SO 3 H, COONa, SO} 3 Na, COOCH 3 or ^{_{COOCH 2 CH 3 -, SO 3}} .

Hereinafter, the red photosensitive resin composition of the present invention will be described in detail for each component.

(A) Red colorant

The red coloring agent of the present invention comprises a pigment and a dye, the pigment includes diketopyrrolopyrrole bromide, and the dye includes at least one selected from the group consisting of xanthene dyes and azo dyes represented by the following formula do.

[Chemical Formula 1]

Each of R ₁ to R ₆ is independently hydrogen, an alkyl group having 1 to 5 carbon atoms, or a trialkoxysilylalkyl group having 1 to 5 carbon atoms,

Wherein R ₇ and R ₈ are each independently hydrogen, COOH, COO ^- is, SO ₃ H, SO ₃ Na COONa, COOCH ₃ or ^{_{COOCH 2 CH 3 -, SO 3}} .

If R ₇ or R ₈ is the above-mentioned anion, it forms an inner salt with N ^{+ in the} above formula (1). When R ₇ or R ₈ is not an anion, it can bind with an inorganic or organic anion.

The red colorant is contained in an amount of 5 to 60% by weight, preferably 10 to 45% by weight based on the total solid weight of the red photosensitive resin composition of the present invention.

The red colorant is advantageous in that the color density of the pixel is sufficient at the time of forming the thin film in the range of 5 to 60 wt%, and the residue of the non-decomposed part is not lowered during development and no residue is generated.

In the present invention, the solid content in the red photosensitive resin composition means the total of the components from which the solvent has been removed.

(a1) pigment

The pigment used as the red colorant of the present invention contains diketopyrrolopyrrole bromide as an essential component.

As the product of the brominated diketopyrrolopyrrole, Irgaphor 占 Red S 3620 CF of BASF may be preferably used.

The brominated diketopyrrolopyrrole is contained in an amount of 5 to 95% by weight, preferably 30 to 80% by weight based on the total weight of the red colorant.

When the content of diketopyrrolopyrrolopyrrole is less than 5% by weight, the increase of the contrast ratio is insufficient. When the amount of the diketopyrrolopyrrole bromide is more than 95% by weight, the increase of the transmittance is insufficient.

In addition to the diketopyrrolopyrrole bromide, the pigment may further include a pigment.

The pigment may be an organic pigment or an inorganic pigment generally used in the art. The pigment may be subjected to a surface treatment using a pigment treatment, a pigment derivative into which an acidic group or a basic group is introduced, a graft treatment of the surface of the pigment with a polymer compound, an atomization treatment using a sulfuric acid atomization method or the like, A cleaning treatment with an organic solvent or water, or a treatment for removing ionic impurities by ion exchange or the like.

The organic pigments may be various pigments used in printing ink, ink jet ink, etc. Specific examples thereof include water-soluble azo pigments, insoluble azo pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, isoindoline pigments, A pyranthrone pigment, a diketopyrrolopyrrole pigment, an anthraquinone pigment, an anthraquinone pigment, an anthrone pigment, an anthrone pigment, an indanthrone pigment, a pravanthrone pigment, a pyranthrone pigment, a diketopyrrolopyrrole pigment And the like.

As the inorganic pigment, metal compounds such as metal oxides and metal complex salts can be used. Specific examples of the inorganic pigments include iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony, A black pigment, a titanium black, and an oxide of a metal such as a pigment that mixes red, green, and blue to give a black color, or a composite metal oxide.

Particularly, the organic pigments and inorganic pigments may be specifically classified into pigments in the Society of Dyers and Colourists, and more specifically, those having a color index (CI) number Pigments, but are not limited thereto.

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

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 Violet 14, 19, 23, 29, 32, 33, 36, 37 and 38, and the like.

These pigments may be used alone or in admixture of two or more thereof together with diketopyrrolopyrrole bromide.

The pigment is preferably a pigment dispersion in which the particle diameter of the pigment is uniformly dispersed. Examples of a method for uniformly dispersing the particle diameter of the pigment include a method of dispersing the pigment dispersion (a2) by containing the pigment dispersant (a2), and a pigment dispersion in which the pigment is uniformly dispersed in the solution can be obtained have.

(a2) pigment dispersant

The pigment dispersant is added for deaggregation of the pigment and maintenance of stability. Specific examples of the pigment dispersant include a cationic surfactant, an anionic surfactant, a nonionic surfactant, a positive surfactant, a polyester surfactant, and a polyamine surfactant. , Which may be used alone or in combination of two or more.

Specific examples of the cationic surfactant include amine salts such as stearylamine hydrochloride and lauryltrimethylammonium chloride, and quaternary ammonium salts.

Specific examples of the anionic surfactant include higher alcohol sulfuric acid ester salts such as sodium lauryl alcohol sulfate ester and sodium oleyl alcohol sulfate ester, alkylsulfates such as sodium laurylsulfate and ammonium laurylsulfate, sodium dodecylbenzenesulfonate, And alkylarylsulfonic acid salts such as sodium dodecylnaphthalenesulfonate.

Specific examples of the nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene aryl ethers, polyoxyethylene alkyl aryl ethers, other polyoxyethylene derivatives, oxyethylene / oxypropylene block copolymers, sorbitan fatty acid esters, Polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid esters, glycerin fatty acid esters, polyoxyethylene fatty acid esters, and polyoxyethylene alkylamines.

In addition, polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid modified polyesters, tertiary amine-modified polyurethanes, and polyethyleneimines have.

Also, the pigment dispersant preferably includes an acrylate-based dispersant (hereinafter referred to as an acrylate-based dispersant) containing butyl methacrylate (BMA) or N, N-dimethylaminoethyl methacrylate (DMAEMA). Examples of commercially available acrylate dispersants include DISPER BYK-2000, DISPER BYK-2001, DISPER BYK-2070 and DISPER BYK-2150. The acrylate dispersants may be used alone or in combination of two or more. .

As the pigment dispersant, other resin type pigment dispersants other than the acrylate dispersant may be used. The other resin type pigment dispersing agent may be a known resin type pigment dispersing agent, especially a polycarboxylic acid ester such as polyurethane, polyacrylate, unsaturated polyamide, polycarboxylic acid, polycarboxylic acid (partial) Amine salts of polycarboxylic acids, alkylamine salts of polycarboxylic acids, polysiloxanes, long chain polyaminoamide phosphate salts, esters of hydroxyl group-containing polycarboxylic acids and their modified products, or free ) Oil-based dispersants such as amides formed by reaction of a polyester having a carboxyl group with poly (lower alkyleneimine) or salts thereof; Soluble resin or water-soluble polymer compound such as (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylate ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol or polyvinylpyrrolidone; Polyester; Modified polyacrylates; Adducts of ethylene oxide / propylene oxide; And phosphate esters.

DISPER BYK-160, DISPER BYK-161, DISPER BYK-162, DISPER BYK-163, and DISPER BYK-160 available from BYK (Big) Chemie are examples of commercially available pigment dispersants of other resin types. BYK-164, DISPER BYK-166, DISPER BYK-171, DISPER BYK-182, DISPER BYK-184; EFKA-4060, EFKA-4060, EFKA-4055, EFKA-4055, EFKA-4055, EFKA-4020, EFKA-4015, EFKA-4060, EFKA- 4330, EFKA-4400, EFKA-4406, EFKA-4510, EFKA-4800; SOLSPERS-24000, SOLSPERS-32550, NBZ-4204/10 from Lubirzol; Hinoact T-6000, Hinoact T-7000, Hinoact T-8000; available from Kawaken Fine Chemicals; AJISPUR PB-821, Ajisper PB-822, Ajisper PB-823 manufactured by Ajinomoto; FLORENE DOPA-17HF, fluorene DOPA-15BHF, fluorene DOPA-33, and fluorene DOPA-44 are trade names of Kyoeisha Chemical Co.,

In addition to the acrylate-based dispersant, other resin-type pigment dispersants may be used alone or in combination of two or more, and may be used in combination with an acrylate-based dispersant.

The pigment dispersant is contained in the pigment in an amount of 5 to 60% by weight, preferably 15 to 50% by weight based on the total weight of the solid content. When the pigment dispersant is contained in an amount of less than 5% by weight, it is difficult to atomize the pigment and problems such as gelation may occur after dispersion. When the pigment dispersant is contained in an amount exceeding 60% by weight, the viscosity may be increased.

(a3) Dye

The dye used as the red colorant of the present invention includes at least one selected from the group consisting of xanthene dyes and azo dyes represented by the following formula (1).

[Chemical Formula 1]

Each of R ₁ to R ₆ is independently hydrogen, an alkyl group having 1 to 5 carbon atoms, or a trialkoxysilylalkyl group having 1 to 5 carbon atoms,

Wherein R ₇ and R ₈ are each independently hydrogen, COOH, COO ^- is, SO ₃ H, SO ₃ Na COONa, COOCH ₃ or ^{_{COOCH 2 CH 3 -, SO 3}} .

If R ₇ or R ₈ is the above-mentioned anion, it forms an inner salt with N ^{+ in the} above formula (1). When R ₇ or R ₈ is not an anion, it can bind with an inorganic or organic anion.

The organic or inorganic anion may specifically include, for example, at least one member selected from the group consisting of a halogen anion, a perhalogen acid anion, an alkylsulfate anion, a sulfonate anion and a sulfonimide anion, It is not.

In the present invention, at least one dye selected from the group consisting of the xanthene dyes and azo dyes of the formula (1) is contained in an amount of 5 to 95% by weight, preferably 10 to 60% by weight, based on the total weight of the red colorant .

If the content of the dye is less than 5% by weight, the increase of the transmittance is insignificant. If the content of the dye is more than 95% by weight, precipitation easily occurs in the coating film, and the contrast ratio is decreased, and the storage stability of the red photosensitive resin composition is decreased .

The xanthene dyes of formula (1) are excellent in transmittance and heat resistance, but have insufficient solubility and compatibility with solvents and thus can not be used in large quantities.

Accordingly, in the present invention, the xanthene dye of Formula 1 is contained in an amount of 3 to 50 wt%, preferably 5 to 20 wt%, based on the total weight of the red colorant.

When the content of the xanthene dye of Formula 1 is less than 3% by weight, the increase of the transmittance is insignificant. When the content of the xanthene dye is more than 50% by weight, precipitation easily occurs and the contrast ratio is decreased. The storage stability may be deteriorated.

Specific examples of the xanthene dyes of formula 1 include Acid Red 52, Basic Red 1, Basic Violet 10, Basic Violet 10, Violet 11, Rhodamine B, Rhodamine 6G, Rhodamine 123 and Sulforhodamine B, but the present invention is not limited thereto, May be used alone or in admixture of two or more.

The azo dyes are preferably azo dyes having a metal complex structure. This is because it is superior in heat resistance and solubility to general azo-type dyes, and thus has excellent contrast ratio, thereby increasing the dye content in the red photosensitive resin composition and exhibiting high brightness.

The azo dye is contained in an amount of 2 to 45% by weight, preferably 5 to 15% by weight based on the total weight of the red colorant.

 If the azo dye is contained in an amount of less than 2% by weight, the increase of the transmittance is insignificant. If it exceeds 45% by weight, reliability problems such as heat resistance and solvent resistance may occur.

The azo dyes specifically include, for example, C.I. Solvent Yellow 13, C.I. Solvent Yellow 19, C.I. Solvent Yellow 21, C.I. Solvent Yellow 25, C.I. Solvent Yellow 25: 1, C.I. Solvent Yellow 81, C.I. Solvent Yellow 82, C.I. Solvent Yellow 88, C.I. Solvent Yellow 89, C.I. Solvent Yellow 90, C.I. Solvent Orange 5, C.I. Solvent Orange 20, C.I. Solvent orange 40: 1, C.I. Solvent Orange 41, C.I. Solvent Orange 45, C.I. Solvent Orange 54, C.I. Solvent Orange 56, C.I. Solvent Orange 58, C.I. Solvent Orange 62, C.I. Solvent Orange 81, C.I. Solvent orange 99, C.I. Solvent Red 8, C.I. Solvent Red 83: 1, C.I. Solvent Red 84: 1, C.I. Solvent Red 90, C.I. Solvent Red 90: 1, C.I. Solvent Red 91, C.I. Solvent Red 118, C.I. Solvent Red 119, C.I. Solvent Red 122, C.I. Solvent Red 127, C.I. Solvent Red 130, C.I. Solvent Red 132, C.I. Solvent Red 160, C.I. Solvent Red 234, C.I. Solvent Red 243, C.I. Solvent Violet 21: 1, C.I. Solvent violet 58 and C.I. Solvent Blue 137, and the like, but the present invention is not limited thereto.

(B) an alkali-soluble resin

The alkali-soluble resin is prepared by copolymerizing an ethylenically unsaturated monomer containing a carboxyl group as an essential component in order to have solubility in an alkali developing solution used in a development processing step for forming a pattern.

Specific examples of the ethylenically unsaturated monomer containing 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; Anhydrides of dicarboxylic acids; mono (meth) acrylates of a polymer containing a carboxyl group and a hydroxyl group at both terminals such as? -carboxypolycaprolactone mono (meth) acrylate; And acrylic acid and methacrylic acid are preferable.

Further, a hydroxyl group may be added to the alkali-soluble resin in order to secure further developability.

Examples of the method for imparting the hydroxyl group include (1) a method of copolymerizing an ethylenically unsaturated monomer containing a carboxyl group and an ethylenically unsaturated monomer containing a hydroxyl group, (2) a method of producing an ethylenically unsaturated monomer containing a carboxyl group (3) a method of preparing a copolymer containing an ethylenically unsaturated monomer containing a carboxyl group and an ethylenically unsaturated monomer containing a hydroxyl group by further reacting a compound containing a glycidyl group with a glycidyl group, and And a method of reacting the compound with the compound of the present invention.

Specific examples of the ethylenically unsaturated monomer having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) 3-phenoxypropyl (meth) acrylate, N-hydroxyethyl acrylamide and the like. Of these, 2-hydroxyethyl (meth) acrylate is preferable, and the ethylenically unsaturated monomer containing a hydroxyl group Two or more species can be used in combination.

Specific examples of the compound containing the glycidyl group include butyl glycidyl ether, glycidyl propyl ether, glycidyl phenyl ether, 2-ethylhexyl glycidyl ether, glycidyl butylate, glycidyl methyl But are not limited to, ether, ethyl glycidyl ether, glycidyl isopropyl ether, t-butyl glycidyl ether, benzyl glycidyl ether, glycidyl 4-t-butyl benzoate, glycidyl stearate, Ethers and methacrylic acid glycidyl esters. Of these, preferred are butyl glycidyl ether, aryl glycidyl ether and methacrylic acid glycidyl ester, and the glycidyl group-containing compound may be at least two kinds Can be used in combination.

The unsaturated monomers copolymerizable with the ethylenic unsaturated monomer having a carboxyl group in the production of the alkali-soluble resin may be aromatic vinyl compounds, N-substituted maleimide compounds, alicyclic (meth) acrylates, hydroxyethyl (meth) Acrylates, aryl (meth) acrylates and unsaturated oxetane compounds, but are not limited thereto.

The aromatic vinyl compound is specifically exemplified by styrene, vinyltoluene,? -Methylstyrene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o- , m-vinylbenzyl methyl ether, p-vinylbenzyl methyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether and p-vinyl benzyl glycidyl ether.

The N-substituted maleimide compound is specifically exemplified by N-cyclohexylmaleimide, N-benzylmaleimide, N-phenylmaleimide, No-hydroxyphenylmaleimide, Nm-hydroxyphenylmaleimide, Np-hydroxyphenylmaleimide, N-methylphenylmaleimide, Nm-methylphenylmaleimide, Np-methylphenylmaleimide, No-methoxyphenylmaleimide, Nm-methoxyphenylmaleimide and Np-methoxyphenylmaleimide .

Specific examples of the alicyclic (meth) acrylates include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, Alkyl (meth) acrylates such as butyl (meth) acrylate, i-butyl (meth) acrylate, sec-butyl (meth) acrylate and t-butyl (meth) acrylate; (Meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 2,6] decan- Dicyclopentanyloxyethyl (meth) acrylate, and isobornyl (meth) acrylate.

Specific examples of the hydroxyethyl (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) 2-hydroxy-3-phenoxypropyl (meth) acrylate, and N-hydroxyethyl acrylamide.

Specific examples of the aryl (meth) acrylates include phenyl (meth) acrylate and benzyl (meth) acrylate.

Specific examples of the unsaturated oxetane compound include 3- (methacryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) -3-ethyloxetane, 3- (methacryloyloxymethyl 2- (methacryloyloxymethyl) oxetane and 2- (methacryloyloxymethyl) -2-trifluoromethyloxetane, 3- (methacryloyloxymethyl) ) -4-trifluoromethyloxetane, and the like.

The unsaturated monomers may be used alone or in combination of two or more.

The alkali-soluble resin preferably has an acid value of 30 to 150 mgKOH / g in order to ensure compatibility with the dye and storage stability of the red photosensitive resin composition. When the acid value of the alkali-soluble resin is less than 30 mgKOH / g, the development speed of the red photosensitive resin composition is slow, and when the acid value exceeds 150 mgKOH / g, the adhesion of the red photosensitive resin composition to the substrate is decreased, There is a problem that compatibility with dyes occurs and thus the dye in the red photosensitive resin composition is precipitated or the storage stability is lowered and the viscosity is increased.

The alkali-soluble resin is contained in an amount of 10 to 80% by weight, preferably 10 to 70% by weight, based on the total weight of solid components in the red photosensitive resin composition.

When the content of the alkali-soluble resin is in the range of 10 to 80% by weight, the solubility in the developing solution is sufficient and the formation of the pattern is easy. In the development, the reduction of the film thickness of the pixel portion of the exposed portion is prevented, have.

(C) Photopolymerizable compound

The photopolymerizable compound which is one of the red photosensitive resin compositions of the present invention should be a compound capable of polymerizing under the action of the photopolymerization initiator (D) to be described later.

As the photopolymerizable compound, monofunctional monomers, bifunctional monomers or polyfunctional monomers can be used, and preferably bifunctional monomers are used, but the present invention is not limited thereto.

Specific examples of the monofunctional monomer include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate or N- 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) , Bis (acryloyloxyethyl) ether of bisphenol A or 3-methylpentanediol di (meth) acrylate, but are not limited thereto.

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

The photopolymerizable compound is contained in an amount of 5 to 45% by weight, and preferably 7 to 45% by weight based on the total weight of the solid content of the red photosensitive resin composition of the present invention. The photopolymerizable compound can improve the strength and flatness of the pixel portion in the range of 5 to 45% by weight.

(D) a photopolymerization initiator

The photopolymerization initiator, which is a component of the red photosensitive resin composition of the present invention, essentially comprises an oxime ester compound.

The oxime ester compound is preferably selected from the group consisting of 1,2-octanedione, 1- [4- (phenylthio) phenyl] -, 2- (O- benzoyloxime) ) phenyl] -, 2- (O-benzoyloxime) and 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol- And at least one selected from the group consisting of 1- [9-Ethyl-6- (2-methylbenzoyl) -9H-carbazol-3- yl] ethanone 1- (O-acetyloxime). Examples of the products include Irgacure OXE 01, Irgacure OXE 02 and Irgacure OXE 03 manufactured by BASF. Since the absorbance and the kinds of radicals generated are various, it is preferable to use a mixture of two or more species .

The oxime ester compound is contained in an amount of 10 to 100% by weight, preferably 20 to 100% by weight based on the total weight of the photopolymerization initiator.

If the oxime ester compound is contained in an amount of less than 10% by weight, the sensitivity problem due to the dye can not be solved, and the pattern is likely to be short-circuited during the development process.

In addition to the above oxime ester compounds, the compounds of the present invention may further contain an acetophenone compound, a benzophenone compound, a triazine compound, a nonimidazole compound, and a thioxanone compound May be used.

Specific examples of the acetophenone compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 2- 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1 (2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] Propan-1-one and 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one.

Examples of the benzophenone 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.

Specific examples of the triazine-based compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4- (Trichloromethyl) -6-piperonyl-1,3,5-triazine, 2, 3-bis (Trichloromethyl) -6- [2- (5-methylfuran) -1,3,5-triazine, 2,4-bis Yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan- -Triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine and 2,4- Trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine.

Specific examples of the imidazole compound include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbimidazole, 2,2'- 4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (alkoxyphenyl) (2-chlorophenyl) -4,4 ', 5,5'-tetra (trialkoxyphenyl) biimidazole, 2,2-bis (2,6-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, or an imidazole compound in which the phenyl group at the 4,4', 5,5 'position is substituted by a carboalkoxy group . Among them, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3- , 5,5'-tetraphenylbiimidazole and 2,2-bis (2,6-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'- Is used.

The thioxanthone compound is specifically exemplified by 2-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone and 1-chloro-4- Santon et al.

These photopolymerization initiators may be used singly or in combination of two or more.

In the present invention, the photopolymerization initiator is contained in an amount of 0.1 to 40% by weight, preferably 1 to 10% by weight, based on the total weight of the solid content in the red photosensitive resin composition.

Since the red photosensitive resin composition has a high sensitivity within the range of 0.1 to 40% by weight, the exposure time is shortened, productivity is improved, and high resolution can be maintained. In addition, the strength of the pixel portion formed using the red photosensitive resin composition and the smoothness of the surface of the pixel portion can be improved.

The photopolymerization initiator (D) may further comprise a photopolymerization initiator (d1) to improve the sensitivity of the red photosensitive resin composition of the present invention. The red photosensitive resin composition according to the present invention contains the photopolymerization initiation auxiliary (d1), thereby further increasing the sensitivity and improving the productivity.

The photopolymerization initiator may include at least one member selected from the group consisting of an amine compound, a carboxylic acid compound and a polyfunctional thiol compound.

As the amine compound, an aromatic amine compound is preferably used, and specifically, aliphatic amine compounds such as triethanolamine, methyldiethanolamine and triisopropanolamine; 4-dimethylaminobenzoic acid ethyl, 4-dimethylaminobenzoic acid isoamyl, 4-dimethylaminobenzoic acid 2-ethylhexyl, benzoic acid 2-dimethylaminoethyl, N, N-dimethylparatoluidine, 4'-bis (dimethylamino) benzophenone (commonly known as Michler's ketone) and 4,4'-bis (diethylamino) benzophenone.

The carboxylic acid compound is preferably an aromatic heteroacetic acid, and more specifically, it is preferably an aromatic heteroaromatic acid such as phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthio Acetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, and naphthoxyacetic acid.

Examples of the polyfunctional thiol compound include tris- [(3-mercaptopropionyloxy) -ethyl] -isocyanurate (Tris - [(3-mercaptopropionyloxy) But are not limited to, trimethylolpropane tris-3-mercaptopropionate, pentaerythritol tetrakis-3-mercaptopropionate and dipentaerythritol hexa-3-mercaptopropionate Dipentaerythritol hexa-3-mercaptopropionate).

When the photopolymerization initiator is used, the photopolymerization initiator is contained in an amount of 0.1 to 40% by weight, preferably 1 to 30% by weight based on the total weight of the solid component in the red photosensitive resin composition of the present invention.

When the photopolymerization initiator is contained in an amount of 0.1 to 40% by weight, the sensitivity of the red photosensitive resin composition is increased and the productivity of the color filter manufactured using the photopolymerization initiator improves.

(E) Solvent

The solvent used in the conventional red photosensitive resin composition is not particularly limited so long as it is effective in dissolving the other components contained in the red photosensitive resin composition. In particular, the solvent may be selected from ethers, acetates, aromatic hydrocarbons, ketones, Alcohols or esters are preferred.

Examples of the ethers include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether;

And diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether and diethylene glycol dibutyl ether.

Examples of the acetates include methyl cellosolve acetate, ethyl cellosolve acetate, ethyl acetate, butyl acetate, amyl acetate, methyl lactate, ethyl lactate, butyl lactate, 3-methoxybutyl acetate, 3 Methoxy-1-butylacetate, methoxypentyl acetate, ethylene glycol monoacetate, ethylene glycol diacetate, methyl 3-methoxypropionate, propylene glycol methyl ether acetate, 3-methoxy- Butyl acetate, 1,2-propylene glycol diacetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, 1,3-butylene glycol diacetate, diethylene glycol monobutyl ether Acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, di Ethylene glycol monoacetate, diethylene glycol diacetate, diethylene glycol monobutyl ether acetate, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene carbonate and propylene carbonate. .

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

The ketones include, for example, methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, and cyclohexanone.

The alcohols include, for example, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, glycerin and 4-hydroxy-4-methyl-2-pentanone.

Examples of the esters include ethyl 3-ethoxypropionate, methyl 3-methoxypropionate and? -Butyrolactone.

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

It is preferable to use an organic solvent having a boiling point of 100 占 폚 to 200 占 폚 in terms of coatability and drying property, and among these, propylene glycol monomethyl ether acetate and 4-hydroxy-4-methyl- Is most preferable because it can dissolve the dye well.

The propylene glycol monomethyl ether acetate is contained in an amount of 15 to 80% by weight, preferably 30 to 60% by weight based on the total weight of the solvent. The viscosity stability of the red photosensitive resin composition can be ensured within the range of 15 to 80% by weight.

The 4-hydroxy-4-methyl-2-pentanone is contained in an amount of 20 to 85% by weight, preferably 20 to 40% by weight based on the total weight of the solvent. Within the range of 20 to 85% by weight, foreign matters are not generated by precipitation of the dyes of the red photosensitive resin composition, and the contrast ratio is not reduced. The dispersibility of the red photosensitive resin composition is appropriate, and the viscosity stability can be ensured.

In the present invention, the solvent is contained in an amount of 60 to 90% by weight, preferably 70 to 85% by weight based on the total weight of the red photosensitive resin composition. When the solvent is contained in the range of 60 to 90% by weight, when the solvent is applied by 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) .

(F) Additive

The additive may be optionally added as needed. For example, the additive may include at least one selected from the group consisting of fillers, other high molecular compounds, curing agents, surfactants, adhesion promoters, antioxidants, ultraviolet absorbers, can do.

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

Specific examples of the other polymer compound include a curable resin such as an epoxy resin and a maleimide resin, a thermoplastic resin such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, polyester and polyurethane .

The above-mentioned curing agent is used for enhancing deep curing and mechanical strength. Specific examples of the curing agent include an epoxy compound, a polyfunctional isocyanate compound, a melamine compound and an oxetane compound.

Specific examples of the epoxy compound in the curing agent include bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol F epoxy resin, hydrogenated bisphenol F epoxy resin, novolak epoxy resin, other aromatic epoxy resin, alicyclic epoxy resin Aliphatic, alicyclic or aromatic epoxy compounds, butadiene (co) polymeric epoxides, isoprene (co) polymers other than the brominated derivatives, epoxy resins and brominated derivatives of the above epoxy resins, glycidyl ester resins, glycidyl amine resins, (Co) polymer epoxides, glycidyl (meth) acrylate (co) polymers and triglycidyl isocyanurate.

Specific examples of the oxetane compound in the curing agent include carbonates bisoxetane, xylene bisoxetane, adipate bisoxetane, terephthalate bisoxetane, and cyclohexanedicarboxylic acid bisoxetane.

The curing agent may be used together with a curing agent 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.

The curing auxiliary compound includes, for example, polyvalent carboxylic acids, polyvalent carboxylic anhydrides and acid generators. The polyvalent carboxylic acid anhydrides may be those commercially available as an epoxy resin curing agent. Examples of the commercially available products include Adekahadona EH-700 (manufactured by Adeka Kogyo Co., Ltd.), Rikashido HH (manufactured by Shin-Nihon Ehwa Co., Ltd.), and MH-700 (manufactured by Shin-Etsu Chemical Co., Ltd.). The curing agents exemplified above may be used alone or in combination of two or more.

The surfactant may be used to further improve the film formation of the red photosensitive resin composition, and silicone, fluorine, ester, cationic, anionic, nonionic, amphoteric surfactant and the like may be preferably used.

Examples of the silicone surfactant include DC3PA, DC7PA, SH11PA, SH21PA and SH8400 of Dow Corning Toray Silicone Co., Ltd. as commercial products, and TSF-4440, TSF-4300, TSF-4445, TSF- -4460 and TSF-4452.

Examples of the fluorine-based surfactant include Megapis F-470, F-471, F-475, F-482 and F-489 commercially available from Dainippon Ink and Chemicals, Incorporated.

Other commercially available products include KP (Shinetsugaku Kagaku Kogyo Co., Ltd.), POLYFLOW (Kyoeisha Chemical Co., Ltd.), EFTOP (manufactured by TOKEM PRODUCTS CO., LTD.), MEGAFAC Asoui guard, Surflon (available from Asahi Glass Co., Ltd.), SOLSPERSE (Lubrisol) (available from Dainippon Ink and Chemicals Inc.), Flourad (Sumitomo 3M Co., Ltd.) , EFKA (EFKA Chemical), PB 821 (Ajinomoto), and Disperbyk-series (BYK-chemi).

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

The type of the adhesion promoter is not particularly limited and specific examples of the adhesion promoter that can be used include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl Aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, -Glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxy Propyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatepropyltrimethoxysilane, and 3-isocyanatepropyltriethoxysilane.

The adhesion promoters exemplified above may be used alone or in combination of two or more. The adhesion promoter may be contained in an amount of usually 0.01 to 10% by weight, preferably 0.05 to 2% by weight based on the total weight of the solid content of the red photosensitive resin composition.

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

The ultraviolet absorber is not particularly limited, but specific examples thereof include 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzothiazole and alkoxybenzophenone .

The kind of the anti-aggregation agent is not particularly limited, but specific examples that can be used include sodium polyacrylate and the like.

The process for producing the red photosensitive resin composition of the present invention is as follows.

First, the red pigment (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, part or all of the pigment dispersant (a1) and the alkali-soluble resin (B) may be dissolved or dispersed by mixing together with the dye (a3) and the solvent (E).

The remaining dispersion (a3) of the dye, the remainder of the alkali-soluble resin (B), the photopolymerizable compound (C), the photopolymerization initiator (D) and, if necessary, the additive (F) To prepare a red photosensitive resin composition according to the present invention.

The present invention also provides a red color filter made of a red photosensitive resin composition and a display device having the same.

First, a red photosensitive resin composition is coated on a substrate (usually glass) or a layer composed of a solid component of a red photosensitive resin composition formed in advance, followed by heating and drying to remove volatile components such as a solvent to obtain a smooth coated film.

The coating method can be carried out by, for example, a spin coating method, a flexible coating method, a roll coating method, a slit and spin coating method, a slit coating method or the like. After application, heating and drying (prebaking), or drying under reduced pressure to evaporate the volatile components such as solvent. Here, the heating temperature is usually 70 to 200 占 폚, preferably 80 to 130 占 폚. The thickness of the coating film after heat drying is usually about 1 to 8 mu m. The thus obtained coating film is irradiated with ultraviolet rays through a mask for forming a desired pattern. At this time, it is preferable to use an apparatus such as a mask aligner or a stepper so as to uniformly irradiate a parallel light beam onto the entire exposed portion and to precisely align the mask and the substrate. When ultraviolet light is irradiated, the site irradiated with ultraviolet light is cured.

The ultraviolet rays may be g-line (wavelength: 436 nm), h-line, i-line (wavelength: 365 nm), or the like. The dose of ultraviolet rays can be appropriately selected according to need, and the present invention is not limited thereto. When the coating film after curing is brought into contact with a developing solution to dissolve and develop the non-visible portion, a spacer having a desired pattern shape can be obtained.

The developing method is not particularly limited by a liquid addition method, a dipping method, a spraying method, or the like. Further, the substrate may be inclined at an arbitrary angle at the time of development. The developer is usually an aqueous solution containing an alkaline compound and a surfactant.

The alkaline compound is not particularly limited to an inorganic or organic alkaline compound. Examples of the inorganic alkaline compound include inorganic bases such as sodium hydroxide, potassium hydroxide, disodium hydrogenphosphate, sodium dihydrogenphosphate, ammonium dihydrogenphosphate, ammonium dihydrogenphosphate, potassium dihydrogenphosphate, sodium silicate, potassium silicate, Potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, sodium borate, potassium borate and ammonia.

The organic alkaline compound includes, for example, tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine , Monoisopropylamine, diisopropylamine, and ethanolamine.

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

As the surfactant in the developer, at least one selected from the group consisting of the nonionic surfactant, the anionic surfactant and the cationic surfactant can be used. The concentration of the surfactant in the developing solution is 0.01 to 10% by weight, preferably 0.05 to 8% by weight, more preferably 0.1 to 5% by weight based on the total weight of the developing solution. After development, the substrate is washed with water, and if necessary baked at 150 to 230 DEG C for 10 to 60 minutes.

The red photosensitive resin composition of the present invention can be used to form a specific pattern on a substrate through each of the above steps.

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail with reference to examples. However, the embodiments according to the present invention can be modified into various other forms, and the scope of the present invention should not be construed as being limited to the embodiments described below. The embodiments of the present invention are provided to enable those skilled in the art to more fully understand the present invention.

Synthetic example  1. Preparation of alkali-soluble resin

A flask equipped with a stirrer, a thermometer reflux condenser, a dropping funnel and a nitrogen inlet tube was charged with 120 parts by weight of propylene glycol monomethyl ether acetate, 80 parts by weight of propylene glycol monomethyl ether, 2 parts by weight of AIBN, 13 parts by weight of acrylic acid, 10 parts by weight of a styrene, 57 parts by weight of styrene, 20 parts by weight of methylmethacrylate and 3 parts by weight of n-dodecylmercapto were charged and replaced with nitrogen.

Thereafter, the temperature of the reaction solution was raised to 110 DEG C with stirring, and the reaction was carried out for 6 hours. The alkali-soluble resin thus synthesized had a solid dispersion value of 100.2 mgKOH / g and a weight average molecular weight Mw of about 15110 as measured by GPC.

≪ Preparation of red photosensitive resin composition &

Example  1 to 3 Comparative Example  1 to 6

The red photosensitive resin compositions of Examples 1 to 3 and Comparative Examples 1 to 6 were prepared with the compositions shown in Table 1 below.

(Unit: wt%) division Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Pigment A1 4.94 5.25 4.75 5.25 - - - 5.25 4.75 The pigment dispersant (A2) 2.19 2.19 2.1 2.19 - - - 2.19 2.1 dyes A3 0.31 - 0.29 - 7.67 - 3.83 - 0.29 A4 - 0.29 0.29 - - 7.67 3.83 - 0.29 The alkali-soluble resin (B) 10.32 10.32 10.32 10.32 10.32 10.32 10.32 10.32 10.32 The photopolymerizable compound (C) 3.44 3.44 3.44 3.44 3.44 3.44 3.44 3.44 3.44 Light curing
Initiator D1 0.69 0.69 0.69 0.69 0.69 0.69 0.69 - - D2 - - - - - - - 0.69 0.69 solvent E1 17 17 16.77 17 16.77 16.77 16.77 17 16.77 E2 61.11 60.82 61.35 61.11 61.11 61.11 61.12 61.11 61.35

A1: Irgaphor 占 Red S 3620 CF (manufactured by BASF)

A2: DISPERBYK-2001 (manufactured by BYK)

A3: Acid Red 52

A4: C.I. Solvent Red 122

B: The alkali-soluble resin prepared in Synthesis Example 1

C: KAYARAD DPHA (manufactured by Nippon Kayaku)

D1: Irgacure 占 OXE 02 (manufactured by BASF)

D2: Irgacure 占 369 (BASF)

E1: 4-Hydroxy-4-methyl-2-pentanone

E2: Propylene glycol monomethyl ether acetate

Experimental Example  1. Adhesion evaluation

Each of the red photosensitive resin compositions prepared in Examples 1 to 3 and Comparative Examples 1 to 6 was coated on a 2-inch glass substrate ("EAGLE XG", manufactured by Corning Incorporated) by spin coating, Lt; 0 > C for 3 minutes to form a thin film.

Then, a test photomask having a line / space pattern of 1 μm to 100 μm was placed on the thin film and irradiated with ultraviolet rays at a distance of 300 μm from the test photomask. At this time, the ultraviolet light source was irradiated at 60 mJ / cm 2 using a 1 kW high pressure mercury lamp containing g, h and i lines, and no special optical filter was used.

The thin film irradiated with ultraviolet rays was immersed in a KOH aqueous solution of pH 10.5 for 2 minutes to develop. 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 red color filter.

The thickness of the red color filter prepared above was 2.4 占 퐉.

The pattern of the red color filter was observed through an optical microscope, and the degree of the peeling phenomenon on the pattern was evaluated according to the following evaluation criteria, and the results are shown in Table 2 below.

<Adhesion Evaluation Standard>

○: No pattern peeling

B: 1 to 4 pattern peeling

×: 5 or more patterns peeled off

Experimental Example  2. Measurement of transmittance and contrast ratio

Test A red color filter without a pattern was prepared in the same manner as in Experimental Example 1 except that no pattern was formed without using a photomast.

The prepared red color filter was sandwiched between two polarizing plates, and the maximum and minimum values of the light intensity transmitted through the front side deflector plate were measured while being illuminated with a fluorescent lamp (wavelength of 380 to 780 nm) The contrast ratio of the red color filter was measured by measuring the luminance using a luminance meter (KONICA MINOLTA) and dividing the maximum value by the minimum value.

The transmittance was measured using a colorimeter (OSP-200, manufactured by Olympus Corporation), and the measured values of the contrast ratio and transmittance are shown in Table 2 below.

division Transmittance Contrast ratio Adhesiveness Example 1 16.75 8625 ○ Example 2 16.53 12850 ○ Example 3 16.66 10025 ○ Comparative Example 1 16.11 5940 △ Comparative Example 2 14.56 760 △ Comparative Example 3 15.88 13840 X Comparative Example 4 16.25 13470 X Comparative Example 5 16.39 11601 X Comparative Example 6 16.61 9960 X

In the results of Table 2, Examples 1 to 3, which are the red photosensitive resin compositions of the present invention, were excellent in transmittance, contrast ratio, and adhesion.

On the other hand, the red photosensitive resin composition of Comparative Example 1 in which no dye was used had a poor contrast ratio and poor adhesion.

Also, the red photosensitive resin compositions of Comparative Examples 2 to 4, which did not use pigments, had poor contrast and transmittance due to dye precipitation only in Comparative Example 2, and Comparative Examples 3 and 4 showed excellent contrast ratios. However, in Comparative Examples 2 to 4, adhesion was poor or normal due to a decrease in adhesion due to the dye.

The red photosensitive resin composition of Comparative Example 5 in which the dye and the oxime ester compound were not used as a photopolymerization initiator had poor adhesion and the red photosensitive resin composition of Comparative Example 6 in which the oxime ester compound was not used as a photopolymerization initiator, Showed poor results.

Therefore, the red photosensitive resin composition of the present invention can exhibit a high contrast ratio, and the pattern is not peeled off during the development process without lowering the sensitivity by the dye, so that the adhesion is very excellent.

Claims (11)

A red photosensitive resin composition comprising a red colorant, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator and a solvent,
Wherein the red colorant comprises a pigment and a dye,
Wherein the pigment comprises diketopyrrolopyrrole bromide,
Wherein the dye comprises at least one selected from the group consisting of xanthene dyes and azo dyes represented by the following formula (1)
Wherein the photopolymerization initiator comprises an oxime ester compound.
[Chemical Formula 1]

Each of R ₁ to R ₆ is independently hydrogen, an alkyl group having 1 to 5 carbon atoms, or a trialkoxysilylalkyl group having 1 to 5 carbon atoms,
Wherein R ₇ and R ₈ are each independently hydrogen, COOH, COO ^- is, SO ₃ H, SO ₃ Na COONa, COOCH ₃ or ^{_{COOCH 2 CH 3 -, SO 3}} . The ink composition according to claim 1, which comprises 5 to 95% by weight of the brominated diketopyrrolopyrrole pigment and 1 to 95% by weight of at least one dye selected from the group consisting of xanthene dyes and azo dyestuffs of the formula 1, based on the total weight of the red colorant, By weight based on the total weight of the red photosensitive resin composition. [4] The method of claim 2, further comprising 5 to 95% by weight of the brominated diketopyrrolopyrrole pigment, 3 to 50% by weight of the xanthene dye of the formula 1 and 2 to 45% by weight of the azo dye based on the total weight of the red colorant Wherein the red light-sensitive resin composition is a red light-sensitive resin composition. The photosensitive resin composition according to claim 1, which comprises 5 to 60% by weight of a red colorant, 10 to 80% by weight of an alkali-soluble resin, 5 to 45% by weight of a photopolymerizable compound and 0.1 to 40% by weight of a photopolymerization initiator based on the total weight of solid components in the red photosensitive resin composition Wherein the red photosensitive resin composition contains 60 to 90% by weight of a solvent based on the total weight of the red photosensitive resin composition. The oxime ester compound according to claim 1, wherein the oxime ester compound is 1,2- octadione, 1- [4- (phenylthio) phenyl] -, 2- (O- 2-methylbenzoyl) -9H-carbazol-3-yl] ethanone 1- (O-acetyloxime). The red photosensitive resin composition according to claim 1, wherein the oxime ester compound is contained in an amount of 10 to 100% by weight based on the total weight of the photopolymerization initiator. The red photosensitive resin composition according to claim 1, wherein the solvent comprises at least one selected from the group consisting of propylene glycol monomethyl ether acetate and 4-hydroxy-4-methyl-2-pentanone. The photosensitive resin composition according to claim 7, comprising 15 to 80 wt% of propylene glycol monomethyl ether acetate and 20 to 85 wt% of 4-hydroxy-4-methyl-2-pentanone based on the total weight of the solvent Composition. The red photosensitive resin composition according to claim 1, wherein the red photosensitive resin composition further comprises an additive. A red color filter made of the red photosensitive resin composition of claim 1. A display device comprising the red color filter of claim 10.