JP2017126058A - Red photosensitive resin composition, color filter manufactured using the same, and display device having color filter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a red photosensitive resin composition, a color filter manufactured using the same, and a display device having the color filter.SOLUTION: There are provided: a red photosensitive resin composition which contains a red colorant, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator and a solvent, and thereby enables high color reproduction, and is excellent in a contrast ratio; a color filter manufactured using the composition; and a display device having the color filter.SELECTED DRAWING: None

Description

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

Color filters are widely used for image sensors, 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 usually a colored photosensitive resin composition containing a colorant corresponding to each color of red, green and blue on a substrate on which a black matrix is patterned. After coating uniformly by spin coating, the coating film formed by heating and drying (hereinafter sometimes referred to as pre-baking) is exposed and developed, and if necessary, further heat-cured (hereinafter also referred to as post-baking). ) Is repeated for each color to form pixels of each color. In recent years, a color filter for a liquid crystal display (LCD) is required to reproduce high colors, and a change in color coordinates is required even when a backlight is changed. For this reason, there is a demand for a colored photosensitive resin composition having good color reproducibility and capable of easily changing the color coordinates when the backlight is changed.

In a color liquid crystal display, the color reproduction range is a range represented by a triangle in which chromaticity coordinates of red, green, and blue are connected in the XYZ color system, and is an area ratio with respect to the NTSC (National Television System Committee) standard. expressed. The color reproduction range of CRT is about 70% of the NTSC standard. The color reproducibility is wider than the EBU (European Broadcasting Union) standard, and the above-mentioned NTSC standard is a good standard. The chromaticity coordinates (x, y) in the XYZ color system of red, green, blue, and each color are respectively , Red (0.670, 0.330), green (0.210, 0.710), and blue (0.140, 0.080). ITU-R BT. The chromaticity coordinates (x, y) of the 2020 broadcast standard are required by red (0.708, 0.292), green (0.170, 0.797), and blue (0.131, 0.046), respectively. The chromaticity coordinates (x, y) in DCI (Digital Cinema Initiatives) are red (0.680, 0.320), green (0.265, 0.690), and blue (0.150, 0.060), respectively. The chromaticity coordinates (x, y) in Adobe are red (0.640, 0.330), green (0.210, 0.710), and blue (0.150, 0.060), respectively. is there.

In recent years, color filters for liquid crystal displays are required to have high color reproduction, and as a result, the content of the colorant in the colored photosensitive resin composition used in the production of the color filter is continuously increased. Further, in order to produce a high-quality color filter with excellent visibility, there is a continuous demand for improvement in contrast ratio.

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

Therefore, currently, a method of simultaneously using a pigment and a dye as a colorant has been studied. However, when a color filter is produced using a colored photosensitive resin composition containing a dye as a colorant, the sensitivity is insufficient and alkali development is performed. There may be a problem that the developed pattern is peeled off during the developing process using the liquid. In addition, when a color filter is produced with the colored photosensitive resin composition containing the dye, the compatibility of the dye may be insufficient in the hard baking process, and the dye may precipitate on the surface to reduce the contrast ratio. It is very difficult to use an amount of dye.

An object of this invention is to provide the red photosensitive resin composition which shows high color reproduction and a high contrast ratio.

Another object of the present invention is to provide a red photosensitive resin composition that can solve the problem of pattern peeling in the development process without a decrease in sensitivity due to a dye.

Furthermore, an object of this invention is to provide the display apparatus containing the color filter manufactured with the said red photosensitive resin composition, and the said color filter.

To achieve the above objective,
The present invention is a red photosensitive resin composition comprising a red colorant, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent,
The red colorant includes a pigment and a dye,
The pigment comprises brominated diketopyrrolopyrrole,
The dye includes one or more selected from the group consisting of a xanthene dye and an azo dye of the following chemical formula 1,
The photopolymerization initiator includes an oxime ester compound and provides a red photosensitive resin composition.

R _{1 to} R ₆ are each independently hydrogen, an alkyl group having 1 to 5 carbon atoms, or a trialkoxysilylalkyl group having 1 to 5 carbon atoms,
R ₇ and R ₈ are each independently hydrogen, COOH, COO ⁻ , SO ₃ ⁻ , COONa, SO ₃ H, SO ₃ Na, COOCH ₃ , or COOCH ₂ CH ₃ .

Moreover, this invention provides the red color filter manufactured with the said red photosensitive resin composition.

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

The red photosensitive resin composition of the present invention has an effect that high color reproduction and high contrast ratio can be realized.

In addition, the red photosensitive resin composition of the present invention exhibits the effect that the pattern is not peeled off during the development process without a decrease in sensitivity due to the dye.

Furthermore, the color filter manufactured with the red photosensitive resin composition of this invention can show high quality.

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

The present invention is a red photosensitive resin composition comprising a red colorant, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent,
The red colorant includes a pigment and a dye,
The pigment comprises brominated diketopyrrolopyrrole,
The dye includes one or more selected from the group consisting of a xanthene dye and an azo dye of the following chemical formula 1,
The photopolymerization initiator relates to a red photosensitive resin composition comprising an oxime ester compound.

R _{1 to} R ₆ are each independently hydrogen, an alkyl group having 1 to 5 carbon atoms, or a trialkoxysilylalkyl group having 1 to 5 carbon atoms,
R ₇ and R ₈ are each independently hydrogen, COOH, COO ⁻ , SO ₃ ⁻ , SO ₃ H, COONa, SO ₃ Na, COOCH ₃ , or COOCH ₂ CH ₃ .

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

(A) Red colorant The red colorant of the present invention contains a pigment and a dye, the pigment contains brominated diketopyrrolopyrrole, and the dye is composed of a xanthene dye and an azo dye of the following chemical formula 1. 1 type or more selected from a group is included.

R _{1 to} R ₆ are each independently hydrogen, an alkyl group having 1 to 5 carbon atoms, or a trialkoxysilylalkyl group having 1 to 5 carbon atoms,
R ₇ and R ₈ are each independently hydrogen, COOH, COO ⁻ , SO ₃ ⁻ , SO ₃ H, COONa, SO ₃ Na, COOCH ₃ , or COOCH ₂ CH ₃ .

If R ₇ or R ₈ is the anion, it forms an inner salt with N ^{+ of} Formula 1, and if it is not an anion, it may bind to an inorganic or organic anion. Good.

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

The red colorant has the advantage that when forming a thin film in the range of 5 to 60% by weight, the color density of the pixel is sufficient, the omission of non-pixel portions does not deteriorate during development, and no residue is generated. is there.

In this invention, solid content in a red photosensitive resin composition means the sum total of the component which removed the solvent.

(A1) Pigment The pigment used as the red colorant of the present invention contains brominated diketopyrrolopyrrole as an essential component.

As a product of the brominated diketopyrrolopyrrole, Irgaphor (R) Red S3620CF manufactured by BASF is 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 brominated diketopyrrolopyrrole is contained in an amount of less than 5% by weight, the contrast ratio is not sufficiently increased. When the brominated diketopyrrolopyrrole is contained in an amount exceeding 95% by weight, the transmittance is not sufficiently increased and high color reproduction is exhibited. I can't.

The pigment may contain a pigment in addition to brominated diketopyrrolopyrrole.

As the pigment, an organic pigment or an inorganic pigment generally used in the art can be used. In addition, the pigment is obtained by resin treatment, surface treatment using a pigment derivative having an acidic group or basic group introduced, graft treatment of the pigment surface with a polymer compound, sulfuric acid atomization method, or the like, if necessary. Atomization treatment, washing treatment with an organic solvent or water for removing impurities, or removal treatment of ionic impurities by an ion exchange method or the like may be performed.

As the organic pigment, various pigments used for printing ink, inkjet ink, and the like can be used. Specifically, a water-soluble azo pigment, an insoluble azo pigment, a phthalocyanine pigment, a quinacridone pigment, an isoindolinone pigment, Examples thereof include isoindoline pigments, perylene pigments, perinone pigments, dioxazine pigments, anthraquinone pigments, dianthraquinonyl pigments, anthrapyrimidine pigments, anthronetron pigments, indanthrone pigments, flavantron pigments, pyranthrone pigments, diketopyrrolopyrrole pigments.

Further, as the inorganic pigment, metal compounds such as metal oxides and metal complex salts can be used. Specifically, iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, Examples thereof include antimony, carbon black, organic black pigments, titanium black, and metal oxides or composite metal oxides such as pigments that are mixed with red, green, and blue to exhibit black.

In particular, examples of the organic pigment and the inorganic pigment include compounds classified as pigments in the color index (published by The Society of Dyers and Colorists). More specifically, the following colors are listed. Examples include, but are not necessarily limited to, pigments having index (CI) numbers.

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. And CI pigment violet 14, 19, 23, 29, 32, 33, 36, 37, and 38.

The pigment can be used alone or in admixture of two or more with brominated diketopyrrolopyrrole.

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

(A2) Pigment dispersant The pigment dispersant is added to disaggregate and maintain stability of the pigment. Specific examples of the pigment dispersant include cationic, anionic, nonionic, and amphoteric. These include surfactants such as polyesters, polyesters, and polyamines, and these can 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, or quaternary ammonium salts.

Specific examples of the anionic surfactants include higher alcohol sulfate salts such as sodium lauryl alcohol sulfate and sodium oleyl alcohol sulfate, alkyl sulfates such as sodium lauryl sulfate and ammonium lauryl sulfate, and sodium dodecylbenzenesulfonate. And alkylaryl sulfonates such as sodium dodecylnaphthalene sulfonate.

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

Other examples include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid-modified polyesters, tertiary amine-modified polyurethanes, and polyethyleneimines.

The pigment dispersant preferably contains an acrylate dispersant (hereinafter referred to as an acrylate 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. Can be used as a mixture.

In addition to the acrylate-based dispersant, other resin-type pigment dispersants may be used as the pigment dispersant. Examples of the other resin-type pigment dispersants include known resin-type pigment dispersants, in particular, polycarboxylic acid esters represented by polyurethane and polyacrylate, unsaturated polyamides, polycarboxylic acids, and polycarboxylic acid (partial). ) Amine salts, ammonium salts of polycarboxylic acids, alkylamine salts of polycarboxylic acids, polysiloxanes, long chain polyaminoamide phosphate salts, esters of hydroxyl-containing polycarboxylic acids and their modified products, or free ( free) Oily dispersants such as amides or salts thereof formed by the reaction of polyesters with carboxyl groups and poly (lower alkyleneimines); (meth) acrylic acid-styrene copolymers, (meth) acrylic acid- ( (Meth) acrylate ester copolymer, styrene-ma Ynoic acid copolymers, polyvinyl alcohol or water-soluble resin or a water-soluble polymeric compounds such as polyvinyl pyrrolidone; polyesters; modified polyacrylate; addition products of ethylene oxide / propylene oxide; and the like and phosphate esters.

As a commercial product of the pigment dispersant of the other resin type, as the cationic resin dispersant, for example, trade names of BYK (Big) Chemie: 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 Corporation trade 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 Lubilzol: SOLPERS-24000, SOLSPERS-32550, NBZ-4204 / 10; trade names of Kawaken Fine Chemicals: HINOACT T-6000, Hinoact T-7000, Hinoact T-8000; Ajinomoto brand names: AJISPUR PB-821, Ajisper PB-822, Azisper PB-823; Kyoeisha Chemical brand names: FLORENE DOPA-17HF, FLOREN DOPA-15BHF, FLOREN DOPA -33, florene DOPA-44 and the like.

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 an amount of 5 to 60% by weight, preferably 15 to 50% by weight, based on the total solid content in the pigment. If 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 after dispersion may occur. If the pigment dispersant is contained in excess of 60% by weight, the viscosity may be increased. .

(A3) Dye The dye used as the red colorant of the present invention includes one or more selected from the group consisting of xanthene dyes and azo dyes of the following chemical formula 1.

R _{1 to} R ₆ are each independently hydrogen, an alkyl group having 1 to 5 carbon atoms, or a trialkoxysilylalkyl group having 1 to 5 carbon atoms,
R ₇ and R ₈ are each independently hydrogen, COOH, COO ⁻ , SO ₃ ⁻ , SO ₃ H, COONa, SO ₃ Na, COOCH ₃ , or COOCH ₂ CH ₃ .

If R ₇ or R ₈ is the anion, it forms an inner salt with N ^{+ of} Formula 1, and if it is not an anion, it may bind to an inorganic or organic anion. Good.

The organic or inorganic anion is specifically selected from the group consisting of, for example, a halogen anion, a perhalogenate anion, an alkyl sulfate anion, a sulfonate anion, and a sulfonimide anion. Although 1 or more types can be included, it is not limited to this.

In the present invention, the one or more dyes selected from the group consisting of the xanthene dye and the azo dye of Formula 1 are included in an amount of 5 to 95% by weight based on the total weight of the red colorant, preferably 10 to 60% by weight is contained.

When the content of the dye is less than 5% by weight, the increase in transmittance is slight, and when the content exceeds 95% by weight, precipitation tends to occur in the coating film, and the contrast ratio decreases. The storage stability of the red photosensitive resin composition may be lowered.

The xanthene dye of the chemical formula 1 is excellent in transmittance and heat resistance, but has a problem that the solubility and compatibility with a solvent are insufficient, and a large amount cannot be used.

Therefore, in this invention, it is preferable to contain 3-50 weight% of the xanthene dye of the said Chemical formula 1 with respect to the total weight of a red coloring agent, More preferably, 5-20 weight% is contained.

When the content of the xanthene dye of the chemical formula 1 is less than 3% by weight, the increase in the transmittance is slight, and when it exceeds 50% by weight, the coating tends to cause precipitation in the coating film. The ratio may decrease, and the storage stability of the red photosensitive resin composition may decrease.

Specific examples of the xanthene dyes represented by the chemical formula 1 include, for example, Acid Red 52, Basic Red 1, Basic Violet 10, Basic Violet 11 and Rhodamine. B (Rhodamine B), rhodamine 6G (Rhodamine 6G), rhodamine 123 (Rhodamine 123), sulforhodamine B (Sulforhodamine B), and the like, but are not limited to these, and the dye is used alone or in combination of two or more. Can be used in combination.

The azo dye is preferably an azo dye having a metal complex structure. This is because the heat resistance and solubility are excellent and the contrast ratio is excellent as compared with general azo dyes, the content of the dye in the red photosensitive resin composition can be increased, and high brightness can be exhibited. It is.

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.

When the azo dye is contained in an amount of less than 2% by weight, the transmittance is slightly increased, and when it exceeds 45% by weight, reliability problems such as heat resistance and solvent resistance may occur. is there.

Specific examples of the azo dye include C.I. I. Solvent Yellow 13, C.I. I. Solvent Yellow 19, C.I. I. Solvent Yellow 21, C.I. I. Solvent Yellow 25, C.I. I. Solvent Yellow 25: 1, C.I. I. Solvent Yellow 81, C.I. I. Solvent Yellow 82, C.I. I. Solvent Yellow 88, C.I. I. Solvent Yellow 89, C.I. I. Solvent Yellow 90, C.I. I. Solvent Orange 5, C.I. I. Solvent Orange 20, C.I. I. Solvent orange 40: 1, C.I. I. Solvent Orange 41, C.I. I. Solvent Orange 45, C.I. I. Solvent Orange 54, C.I. I. Solvent Orange 56, C.I. I. Solvent Orange 58, C.I. I. Solvent Orange 62, C.I. I. Solvent Orange 81, C.I. I. Solvent Orange 99, C.I. I. Solvent Red 8, C.I. I. Solvent Red 83: 1, C.I. I. Solvent Red 84: 1, C.I. I. Solvent Red 90, C.I. I. Solvent Red 90: 1, C.I. I. Solvent Red 91, C.I. I. Solvent Red 118, C.I. I. Solvent Red 119, C.I. I. Solvent Red 122, C.I. I. Solvent Red 127, C.I. I. Solvent Red 130, C.I. I. Solvent Red 132, C.I. I. Solvent Red 160, C.I. I. Solvent Red 234, C.I. I. Solvent Red 243, C.I. I. Solvent Violet 21: 1, C.I. I. Solvent Violet 58, and C.I. I. Solvent Blue 137 etc. are mentioned, However, it is not limited to these.

(B) Alkali-soluble resin The alkali-soluble resin has an ethylenically unsaturated monomer containing a carboxyl group as an essential component in order to be soluble in an alkali developer used in a development processing step when forming a pattern. As a copolymer.

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; mono (meth) acrylates of a polymer containing a carboxyl group and a hydroxyl group at both ends, such as ω-carboxypolycaprolactone mono (meth) acrylate; acrylic acid and methacrylic acid are preferred.

In addition, a hydroxyl group can be added to the alkali-soluble resin in order to ensure additional developability.

The method for imparting the hydroxyl group includes (1) a method of copolymerizing and producing an ethylenically unsaturated monomer containing a carboxyl group and an ethylenically unsaturated monomer containing a hydroxyl group, and (2) carboxyl. A method of additionally reacting a copolymer of a glycidyl group with a copolymer of an ethylenically unsaturated monomer containing a group, and (3) an ethylenically unsaturated monomer containing a carboxyl group and a hydroxyl group. Examples thereof include a method in which a copolymer having an ethylenically unsaturated monomer is additionally reacted with a compound having a glycidyl group.

Specific examples of the ethylenically unsaturated monomer containing a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxy-3- There are phenoxypropyl (meth) acrylate, N-hydroxyethyl acrylate, etc., among which 2-hydroxyethyl (meth) acrylate is preferable, and the ethylenically unsaturated monomer containing the hydroxyl group is a combination of two or more. Can be used.

Specific examples of the compound containing a glycidyl group include butyl glycidyl ether, glycidyl propyl ether, glycidyl phenyl ether, 2-ethylhexyl glycidyl ether, glycidyl butyrate, glycidyl methyl ether, ethyl glycidyl ether, glycidyl isopropyl ether, t-butyl glycidyl. Ether, benzyl glycidyl ether, glycidyl 4-t-butylbenzoate, glycidyl stearate, aryl glycidyl ether, and glycidyl methacrylate, preferably butyl glycidyl ether, aryl glycidyl ether, and glycidyl methacrylate are The compound containing a glycidyl group can be used in combination of two or more.

Further, during the production of the alkali-soluble resin, the unsaturated monomer copolymerizable with the ethylenically unsaturated monomer containing a carboxyl group may be an aromatic vinyl compound, an N-substituted maleimide compound, an alicyclic (meta ) Acrylates, hydroxyethyl (meth) acrylates, aryl (meth) acrylates, and unsaturated oxetane compounds, but are not limited thereto.

Specific examples of the aromatic vinyl compound include styrene, vinyltoluene, α-methylstyrene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, and o-vinylbenzyl methyl ether. M-vinyl benzyl methyl ether, p-vinyl benzyl methyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, and the like.

Specific examples of the N-substituted maleimide compound include N-cyclohexylmaleimide, N-benzylmaleimide, N-phenylmaleimide, N-o-hydroxyphenylmaleimide, Nm-hydroxyphenylmaleimide, and Np. -Hydroxyphenylmaleimide, N-o-methylphenylmaleimide, Nm-methylphenylmaleimide, Np-methylphenylmaleimide, N-o-methoxyphenylmaleimide, Nm-methoxyphenylmaleimide, and Np- And methoxyphenylmaleimide.

Specifically, the alicyclic (meth) acrylates include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl ( Alkyl (meth) acrylates such as (meth) acrylate, i-butyl (meth) acrylate, sec-butyl (meth) acrylate, t-butyl (meth) acrylate; cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2- Methyl cyclohexyl (meth) acrylate, tricyclo [5.2.1.02,6] decan-8-yl (meth) acrylate, 2-dicyclopentanyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, etc. Can be mentioned.

Specifically, the hydroxyethyl (meth) acrylates are, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxy-3- Examples include 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, and 3- (methacryloyloxymethyl) -2-trifluoromethyloxetane. , 3- (methacryloyloxymethyl) -2-phenyloxetane, 2- (methacryloyloxymethyl) oxetane, 2- (methacryloyloxymethyl) -4-trifluoromethyloxetane, and the like.

The unsaturated monomers can be used alone or in admixture 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 it exceeds 150 mgKOH / g, the adhesion of the red photosensitive resin composition to the substrate decreases. A short circuit of the pattern is likely to occur, a problem of compatibility with the dye occurs, and the dye in the red photosensitive resin composition is precipitated, or a problem that the storage stability is lowered and the viscosity is increased occurs.

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

If the content of the alkali-soluble resin is from 10 to 80% by weight, the solubility in the developer is sufficient and the pattern can be easily formed. The lack of is improved.

(C) Photopolymerizable compound The photopolymerizable compound that is one of the red photosensitive resin compositions of the present invention must be a compound that can be polymerized by the action of the photopolymerization initiator (D) described later.

As the photopolymerizable compound, a monofunctional monomer, a bifunctional monomer, or a polyfunctional monomer can be used, and a bifunctional monomer is preferably used, but is not limited thereto. is not.

Specific examples of the monofunctional monomer include nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl acrylate, and N-vinyl pyrrolidone. However, it is not limited to these.

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, Examples include, but are not limited to, bis (acryloyloxyethyl) ether of bisphenol A or 3-methylpentanediol di (meth) acrylate.

Specific examples of the polyfunctional monomer include trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, and pentaerythritol tri (meth). Acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, ethoxylated dipentaerythritol hexa (meth) acrylate, propoxylated dipentaerythritol hexa (meth) acrylate, or dipentaerythritol hexa (meth) Examples include, but are not limited to, acrylates.

The photopolymerizable compound is contained in an amount of 5 to 45% by weight, preferably 7 to 45% by weight, based on the total solid content in 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) Photopolymerization initiator The photopolymerization initiator which is one component of the red photosensitive resin composition of the present invention contains an oxime ester compound as an essential component.

The oxime ester-based compound includes 1,2-octanedione, 1- [4- (phenylthio) phenyl]-, 2- (O-benzoyloxime) (1,2-Octanedione, 1- [4- (phenylthio) phenyl). ]-, 2- (O-benzoyloxime)), and 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone 1- (O-acetyloxime) (1- [ It is preferable to include one or more selected from the group consisting of 9-Ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanolone 1- (O-acetylloxime)). In addition, examples of products include Irgacure (R) OXE01, Irgacure (R) OXE02, and Irgacure (R) OXE03 manufactured by BASF. It is preferable to use a mixture.

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.

When the oxime ester-based compound is contained in an amount of less than 10% by weight, the problem of sensitivity reduction due to the dye cannot be solved, and a pattern short circuit is likely to occur during the development process.

Further, within the range not impairing the effect of the present invention, in addition to the oxime ester compound, in addition, from the group consisting of acetophenone compound, benzophenone compound, triazine compound, biimidazole compound, and thioxanthone compound One or more selected compounds can be used.

Specific examples of the acetophenone compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 2-hydroxy-1- [4- (2- Hydroxyethoxy) phenyl] -2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 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] propan-1-one, and 2- (4- Methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one and the like. .

Specific examples of the benzophenone compound include benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, 3,3 ′, 4,4′-tetra ( tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, and the like.

Specifically, the triazine compound is, for example, 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl)- 6- (4-Methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4-bis (trichloromethyl) -6 -(4-methoxystyryl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) ethenyl] -1,3,5- Triazine, 2,4-bis (trichloromethyl) -6- [2- (furan-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-me Ruphenyl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine and the like It is done.

Specifically, the biimidazole compound includes, for example, 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 an imidazole compound in which the phenyl group at the 4,4 ′, 5,5 ′ position is substituted with a carboalkoxy group. Of these, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2,3-dichlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole and 2,2-bis (2,6-dichlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole are preferably used.

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

The said photoinitiator can be used individually or in mixture of 2 or more types.

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 solid content in the red photosensitive resin composition.

Within the range of 0.1 to 40% by weight, the sensitivity of the red photosensitive resin composition is increased and the exposure time is shortened, so that 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 on the surface of the pixel portion are improved.

In addition, the photopolymerization initiator (D) may further include a photopolymerization initiation auxiliary agent (d1) in order to improve the sensitivity of the red photosensitive resin composition of the present invention. When the red photosensitive resin composition according to the present invention contains the photopolymerization initiation auxiliary agent (d1), the sensitivity is further increased and the productivity can be improved.

The photopolymerization initiation auxiliary agent can include, for example, one or more selected from the group consisting of amine compounds, carboxylic acid compounds, and polyfunctional thiol compounds.

As the amine compound, an aromatic amine compound is preferably used. Specifically, aliphatic amine compounds such as triethanolamine, methyldiethanolamine, and triisopropanolamine; methyl 4-dimethylaminobenzoate, 4- Ethyl dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, N, N-dimethylparatoluidine, 4,4′-bis (dimethylamino) Benzophenone (common name: Michler's ketone), 4,4′-bis (diethylamino) benzophenone, and the like 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, 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] -isocynurate (tris-[(3-mercaptopropionyloxy) -ethyl] -isocyclicate), trimethylopropane tris-3-mercaptopropio. Nitrate (Trimethylolpropane tris-3-mercaptopropionate), Pentaerythritol Tetrakis-3-mercaptopropionate (Pentaerythritol tetrakis-3-mercaptopropionate), and Dipentaerythritol Hex-3-mercaptopropiol propionate Etc., and the like.

When the photopolymerization initiation auxiliary agent is used, the photopolymerization initiation auxiliary agent is included in an amount of 0.1 to 40% by weight, preferably based on the total solid content in the red photosensitive resin composition of the present invention. 1-30 wt% is included.

When the photopolymerization initiation auxiliary agent 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 a color filter produced using this is improved.

(E) Solvent As long as the solvent is effective for dissolving other components contained in the red photosensitive resin composition, the solvent used in the normal red photosensitive resin composition is used without particular limitation. In particular, 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-methyl-3-methoxy-1- Butyl acetate, methoxypentyl acetate, ethylene glycol monoacetate, ethylene glycol diacetate, methyl 3-methoxypropionate, propylene glycol methyl ether acetate, 3-methoxy-1-butyl acetate, 1,2-propylene glycol diacetate, ethylene Glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate 1,3-butylene glycol diacetate, diethylene glycol monobutyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoacetate, diethylene glycol diacetate, diethylene glycol monobutyl ether acetate, propylene glycol monoacetate, propylene glycol Examples thereof include 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.

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

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

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

The said solvent can be used individually or in mixture of 2 or more types, respectively.

The solvent is preferably an organic solvent having a boiling point of 100 ° C. to 200 ° C. in terms of coating properties and drying properties, among which propylene glycol monomethyl ether acetate and 4-hydroxy-4-methyl-2-pentanone. It is most preferable that the dye can be dissolved 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 secured 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, the occurrence of foreign matter due to the precipitation of the dye of the red photosensitive resin composition and the reduction of the contrast ratio do not appear, and the dispersibility of the red photosensitive resin composition is appropriate and ensures viscosity stability. can do.

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 coated with a coating apparatus such as a roll coater, a spin coater, a slit and spin coater, a slit coater (sometimes referred to as a die coater), and an inkjet, Coating properties are good.

(F) Additive The additive can be selectively added as necessary. For example, a filler, other polymer compound, a curing agent, a surfactant, an adhesion promoter, an antioxidant, One or more selected from the group consisting of an ultraviolet absorber and an aggregation inhibitor can be included.

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

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

The curing agent is used to enhance deep curing and mechanical strength, and 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, novolac epoxy resin, and other aromatics. Epoxy resins, alicyclic epoxy resins, glycidyl ester resins, glycidyl amine resins, or brominated derivatives of the above epoxy resins, epoxy resins, and aliphatic, alicyclic or aromatic epoxies other than brominated derivatives thereof Examples thereof include compounds, butadiene (co) polymer epoxidized products, isoprene (co) polymer epoxidized products, glycidyl (meth) acrylate (co) polymers, and triglycidyl isocyanurate.

In the curing agent, specific examples of the oxetane compound include carbonate bisoxetane, xylene bisoxetane, adipate bisoxetane, terephthalate bisoxetane, and bisoxetane cyclohexanedicarboxylate.

The said hardening | curing agent can use together the hardening auxiliary compound which makes ring opening polymerization possible the epoxy group of an epoxy compound, and the oxetane skeleton of an oxetane compound with a hardening | curing agent.

Examples of the curing auxiliary compound include polyvalent carboxylic acids, polyvalent carboxylic acid anhydrides, and acid generators. As the polyvalent carboxylic acid anhydride, a commercially available epoxy resin curing agent can be used. Examples of the commercially available products include ADEKA HARDNER EH-700 (manufactured by ADEKA INDUSTRY CO., LTD.), RIKACID HH (manufactured by Shin Nippon Rika Co., Ltd.), and MH-700 (manufactured by Nippon Nippon Rika Co., Ltd.). The exemplified curing agents can be used alone or in admixture of two or more.

The surfactant can be used to further improve the film formation of the red photosensitive resin composition, and is based on silicone, fluorine, ester, cation, anion, nonionic, and amphoteric interfaces. An activator or the like is preferably used.

Examples of the commercially available silicone surfactant include DC3PA, DC7PA, SH11PA, SH21PA, and SH8400 manufactured by Dow Corning Toray Silicone, Inc., and TSF-4440, TSF-4300, and TSF-4445 manufactured by GE Toshiba Silicone. , TSF-4446, TSF-4460, and TSF-4442.

Examples of the fluorosurfactant include Megapis F-470, F-471, F-475, F-482, and F-489 manufactured by Dainippon Ink & Chemicals, Inc. as commercially available products.

Other commercially available products include KP (Shin-Etsu Chemical Co., Ltd.), Polyflow (POLYFLOW) (Kyoeisha Chemical Co., Ltd.), FTOP (EFTOP) (Tochem Products), MegaFac (MEGAFAC) (Dainippon Ink Chemical Co., Ltd.), Florad (Sumitomo 3M Co., Ltd.), Asahi guard, Surflon (above, Asahi Glass Co., Ltd.), SULPERSE (Lubrisol) , EFKA (EFKA Chemicals), PB821 (Ajinomoto Co., Inc.), Disperbyk-series (BYK-chemi), and the like.

The exemplified surfactants can be used alone or in combination of two or more.

The kind 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, and N- (2-aminoethyl). ) -3-Aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxy Propylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltri Methoxysilane Such as 3-isocyanate propyl trimethoxysilane and 3-isocyanate propyl triethoxysilane, and the like.

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

The kind of the antioxidant is not particularly limited, and examples thereof include 2,2'-thiobis (4-methyl-6-tert-butylphenol), 2,6-di-tert-butyl-4-methylphenol.

The type of the ultraviolet absorber is not particularly limited, and specific examples that can be used include 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzotriazole, alkoxybenzophenone, and the like. It is done.

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

The manufacturing method of the red photosensitive resin composition of this invention is as follows.

First, the red pigment (a1) is mixed with the solvent (E) and dispersed using a bead mill or the like until the average particle size of the pigment is about 0.2 μm or less. At this time, if necessary, part or all of the pigment dispersant (a2) and the alkali-soluble resin (B) can be mixed with the dye (a3) and the solvent (E) to be dissolved or dispersed.

In the mixed dispersion, the remainder of the dye (a3), the remainder of the alkali-soluble resin (B), the photopolymerizable compound (C), the photopolymerization initiator (D), and, if necessary, an additive (F ) And solvent (E) can be further added to a predetermined concentration to produce the red photosensitive resin composition according to the present invention.

Moreover, this invention provides the red color filter manufactured with the red photosensitive resin composition, and a display apparatus provided with the same.

First, after applying the red photosensitive resin composition on a substrate (usually glass) or a layer made of the solid content of the previously formed red photosensitive resin composition, it is dried by heating to remove volatile components such as a solvent. Remove to obtain a smooth coating.

As a coating method, for example, spin coating, casting coating method, roll coating method, slit and spin coating, or slit coating method is performed. After application, drying by heating (pre-baking) or drying after reduced pressure is performed to volatilize volatile components such as solvent. Here, heating temperature is 70-200 degreeC normally, Preferably it is 80-130 degreeC. The coating thickness after heat drying is usually about 1 to 8 μm. The coating film thus obtained is irradiated with ultraviolet rays through a mask for forming a target pattern. At this time, it is preferable to use an apparatus such as a mask aligner or a stepper so that parallel light rays are uniformly irradiated on the entire exposure unit and accurate alignment between the mask and the substrate is performed. When the ultraviolet ray is irradiated, the portion irradiated with the ultraviolet ray is cured.

As the ultraviolet rays, g-line (wavelength: 436 nm), h-line, i-line (wavelength: 365 nm) and the like can be used. The irradiation amount of ultraviolet rays is appropriately selected as necessary, and is not limited in the present invention. When the cured coating film is brought into contact with a developing solution to dissolve the non-exposed portion and developed, a spacer having a target pattern shape can be obtained.

The developing method is not particularly limited to the liquid addition method, dipping method, spray method and the like. Further, the substrate may be tilted at an arbitrary angle during 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 sodium hydroxide, potassium hydroxide, disodium hydrogen phosphate, sodium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, sodium silicate. Potassium silicate, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium borate, potassium borate, and ammonia.

Examples of the organic alkaline compound include tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, and ethanolamine. Etc.

The inorganic or organic alkaline compounds can 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, one or more selected from the group consisting of the above-described nonionic surfactants, anionic surfactants, and cationic surfactants can be used. The concentration of the surfactant in the developer 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 developer. It is. After the development, it is washed with water and may be post-baked at 150 to 230 ° C. for 10 to 60 minutes as necessary.

Using the red photosensitive resin composition of the present invention, a specific pattern can be formed on the substrate through the above steps.

Hereinafter, the present invention will be described in detail with reference to examples. However, the embodiments of the present invention can be modified into various different forms, and the scope of the present invention should not be construed as being limited to the embodiments described in detail below. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the concept of the invention to those skilled in the art.

Synthesis Example 1 Production of alkali-soluble resin In a flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel and nitrogen inlet tube, 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 Parts, 13 parts by weight of acrylic acid, 10 parts by weight of benzyl methacrylate, 57 parts by weight of styrene, 20 parts by weight of methyl methacrylate, and 3 parts by weight of n-dodecyl mercapto were substituted with nitrogen.

Thereafter, the mixture was stirred, and the temperature of the reaction solution was raised to 110 ° C. to react for 6 hours. The solid content acid value of the alkali-soluble resin thus synthesized was 100.2 mgKOH / g, and the weight average molecular weight Mw measured by GPC was about 15,110.

<Production of red photosensitive resin composition>
Examples 1-3, Comparative Examples 1-6
The red photosensitive resin composition of Examples 1-3 and Comparative Examples 1-6 was manufactured with the composition of following Table 1.

Experimental Example 1 Adhesion evaluation Each of the red photosensitive resin compositions produced in Examples 1 to 3 and Comparative Examples 1 to 6 was spin-coated by a 2-inch square glass substrate (manufactured by Corning, "EAGLE XG"). )) After being coated on, it was placed on a heating plate and maintained at a temperature of 100 ° C. for 3 minutes to form a thin film.

Next, a test photomask having a line / space pattern of 1 μm to 100 μm was placed on the thin film, and an ultraviolet ray was irradiated at an interval 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 including all g, h, and i rays, and no special optical filter was used.

The thin film irradiated with ultraviolet rays was developed by immersing in a KOH aqueous solution developing 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 produce a red color filter.

The manufactured red color filter had a thickness of 2.4 μm.

The pattern of the red color filter was observed with an optical microscope, the degree of peeling phenomenon on the pattern was evaluated according to the following evaluation criteria, and the results are shown in Table 2 below.
<Adhesion evaluation criteria>
○: No pattern on the pattern Δ: 1-4 patterns on the pattern ×: Pattern on the pattern 5 or more patterns

Experimental Example 2. Measurement of transmittance and contrast ratio A red color filter without a pattern was manufactured in the same manner as in Experimental Example 1 except that no test photomask was used and no pattern was formed.

The manufactured red color filter is sandwiched between two deflecting plates, and the front side deflecting plate is rotated and illuminated while illuminating with a fluorescent lamp (wavelength 380 to 780 nm) from the rear side. The value was measured using a CS-2000 luminance meter (KONICA MINOLTA). Thereafter, the maximum value was divided by the minimum value, and the contrast ratio of the red color filter was measured.

Further, transmittance was measured using a chromaticity meter (manufactured by Olympus, OSP-200), and measured values of contrast ratio and transmittance are shown in Table 2 below.

From the result of the said Table 2, Examples 1-3 which are the red photosensitive resin compositions of this invention were excellent in all of the transmittance | permeability, contrast ratio, and adhesiveness.

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

Further, the red photosensitive resin compositions of Comparative Examples 2 to 4 which do not use a pigment have poor contrast ratio and transmittance due to precipitation of the dye only in Comparative Example 2, and Comparative Examples 3 and 4 are excellent in contrast ratio. Results are shown. However, Comparative Examples 2 to 4 showed a result of normal or poor adhesion due to a decrease in adhesion due to the dye.

The red photosensitive resin composition of Comparative Example 5 that does not use a dye and an oxime ester compound as a photopolymerization initiator has poor adhesion, and the red color of Comparative Example 6 that does not use an oxime ester compound as a photopolymerization initiator. The photosensitive resin composition showed poor contrast ratio and adhesion.

Therefore, the red photosensitive resin composition of the present invention can exhibit a high contrast ratio, and there is no decrease in sensitivity due to the dye, no peeling of the pattern occurs during the development process, and the excellent adhesion is achieved. .

Claims (10)

A red photosensitive resin composition comprising a red colorant, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent,
The red colorant includes a pigment and a dye,
The pigment comprises brominated diketopyrrolopyrrole,
The dye includes one or more selected from the group consisting of a xanthene dye and an azo dye of the following chemical formula 1,
The photopolymerization initiator contains an oxime ester compound, and is a red photosensitive resin composition.

Wherein R _{1 to} R ₆ are each independently hydrogen, an alkyl group having 1 to 5 carbon atoms, or a trialkoxysilylalkyl group having 1 to 5 carbon atoms,
R ₇ and R ₈ are each independently hydrogen, COOH, COO ⁻ , SO ₃ ⁻ , SO ₃ H, COONa, SO ₃ Na, COOCH ₃ , or COOCH ₂ CH ₃ . ) 5 to 95% by weight of the brominated diketopyrrolopyrrole pigment, and one or more dyes selected from the group consisting of the xanthene dyes and azo dyes of Formula 1 with respect to the total weight of the red colorant The red photosensitive resin composition according to claim 1, comprising -95% by weight. 5 to 95% by weight of the brominated diketopyrrolopyrrole pigment, 3 to 50% by weight of the xanthene dye of the chemical formula 1, and 2 to 45% by weight of the azo dye, based on the total weight of the red colorant. The red photosensitive resin composition according to claim 2, wherein the composition is a red photosensitive resin composition. 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 a photopolymerization initiator 0 based on the total solid content in the red photosensitive resin composition 2. The red photosensitive resin composition according to claim 1, comprising 1 to 40% by weight and containing 60 to 90% by weight of a solvent based on the total weight of the red photosensitive resin composition. The oxime ester compounds include 1,2-octanedione, 1- [4- (phenylthio) phenyl]-, 2- (O-benzoyloxime), and 1- [9-ethyl-6- (2-methylbenzoyl). 2) -9H-carbazol-3-yl] ethanone 1- (O-acetyloxime). The red photosensitive resin composition according to claim 1, comprising at least one selected from the group consisting of 1- (O-acetyloxime). 2. 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 contains one or more selected from the group consisting of propylene glycol monomethyl ether acetate and 4-hydroxy-4-methyl-2-pentanone. . 8. The red light-sensitive property according to claim 7, comprising 15 to 80% by weight of propylene glycol monomethyl ether acetate and 20 to 85% by weight of 4-hydroxy-4-methyl-2-pentanone based on the total weight of the solvent. Resin composition. The red color filter manufactured with the red photosensitive resin composition of any one of Claims 1-8. A display device comprising the red color filter according to claim 9.