KR102172686B1 - A color photosensitive resin composition, color filter and display device comprising the same - Google Patents

Abstract

The present invention relates to a colored photosensitive resin composition comprising a colorant, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, a solvent, and an additive, wherein the additive comprises an epoxy compound. The photosensitive resin composition has a hard curing density, so that the reliability of the color filter can be improved.

Description

A color photosensitive resin composition, color filter and display device comprising the same}

The present invention relates to a colored photosensitive resin composition, a color filter including the same, and a display device, and more particularly, to a colored photosensitive resin composition including the epoxy compound, a color filter and a display device including the same.

Color filters are widely used in imaging devices, liquid crystal displays (LCDs), and the like, and their application range is rapidly expanding. A color filter used in a color liquid crystal display device or an image pickup device is generally applied by spin coating a colored photosensitive resin composition containing a pigment corresponding to each color of red, green and blue on a patterned substrate with a black matrix. After that, the coating film formed by heat drying (hereinafter, sometimes referred to as'pre-baking') is exposed and developed, and further heat-cured (hereinafter, referred to as'post-baking') as necessary. It is manufactured by repeatedly forming pixels of each color. Here, the black matrix on which the pattern is formed is usually formed of a black photosensitive resin composition.

Such a colored thin film is usually formed by a dyeing method, a printing method, an electrodeposition method, a pigment dispersion method, an inkjet method, or the like.

In the case of dyeing, an image with a dyeing base such as natural photosensitive resin such as gelatin, amine-modified polyvinyl alcohol, and amine-modified acrylic binder resin is formed on a glass substrate in advance, and then dyed with a dye such as direct dye to form a colored thin film. However, in order to form a multi-colored thin film on the same substrate, it is necessary to perform a flame-proofing process every time the color is changed, so the process is very complicated and the time is delayed. In addition, although the clarity and dispersibility of commonly used dyes and resins themselves are good, there are disadvantages of poor light resistance, moisture resistance, and heat resistance, which is the most important characteristic.

In the printing method, a colored thin film is formed by performing printing using an ink in which a pigment is dispersed in a thermosetting or photocurable resin, and then curing with heat or light. According to this method, material cost can be reduced compared to other methods, but it is difficult to form highly precise and detailed images, and there are disadvantages in that the formed thin film layer is not uniform. Republic of Korea Patent Publication No. 1996-0011513 proposes a method of manufacturing a color filter using an inkjet method. Since the colored resin composition sprayed from the nozzle is a dye type for printing delicate and accurate pigments, it is durable as in the dyeing method. And heat resistance deteriorates.

In contrast, Korean Patent Laid-Open No. 1996-0029904 proposes an electrodeposition method using an electroprecipitation method. The electrodeposition method can form a precise colored thin film and has excellent heat resistance and light resistance because it uses a pigment, but in the future When the pixel size becomes precise and the electrode pattern becomes fine, colored spots due to electric resistance appear at both ends or the thickness of the colored thin film becomes thick, making it difficult to apply to a color filter requiring high precision.

Meanwhile, the pigment dispersion method repeats a series of processes in which a photopolymerizable composition containing a colorant is coated on a transparent substrate provided with a black matrix, exposed in the form of a pattern to be formed, and then thermally cured by removing the unexposed part with a solvent. By doing this, a colored thin film is formed. The pigment dispersion method has the advantage of improving heat resistance and durability, which are the most important properties of a color filter, and maintaining a uniform film thickness. The colored resin composition used for manufacturing the color filter according to the pigment dispersion method is generally composed of an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, a pigment and a solvent.

However, when forming a colored thin film by the pigment dispersion method has a problem that reliability is weak, there is a need to improve reliability by maximizing the curing density of the colored thin film by additionally including other additives in addition to the composition. .

Republic of Korea Patent Publication No. 1996-0011513 Republic of Korea Patent Publication No. 1996-0029904 Korean Patent Registration No. 10-0364241

An object of the present invention is to provide a colored photosensitive resin composition excellent in curing density and reliability by including an epoxy compound as an additive.

In addition, an object of the present invention is to provide a colored photosensitive resin composition having high concentration, high transmittance and excellent dispersion stability.

Another object of the present invention is to provide a color filter having excellent driving characteristics and a display device including the color filter by using the colored photosensitive resin composition for manufacturing a color filter.

To achieve the above object,

The present invention is a colored photosensitive resin composition comprising a colorant, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, a solvent and an additive,

The additive provides a colored photosensitive resin composition comprising the epoxy compound of the following formula (1).

[Formula 1]

R is hydrogen or an alkyl group having 1 to 3 carbon atoms,

N is 1 to 6.

In addition, the present invention provides a color filter containing the colored photosensitive resin composition.

In addition, the present invention provides a display device including the color filter.

The colored photosensitive resin composition of the present invention includes an epoxy compound as an additive to maximize curing density and has excellent reliability.

In addition, the colored photosensitive resin composition of the present invention has advantages of high concentration, high transmittance, and excellent dispersion stability.

In addition, a color filter having excellent driving characteristics and a display device including the same can be manufactured by using the colored photosensitive resin composition of the present invention.

1 is a graph measuring the solvent resistance of Example 1, Example 3, and Comparative Example 1.

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

The present invention is a colored photosensitive resin composition comprising a colorant, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, a solvent and an additive,

The additive relates to a colored photosensitive resin composition comprising an epoxy compound of the following formula (1).

[Formula 1]

R is hydrogen or an alkyl group having 1 to 3 carbon atoms,

N is 1 to 6.

The colored photosensitive resin composition of the present invention may prepare a colored photosensitive resin composition having improved curing density and reliability by including the epoxy compound of Formula 1 as an additive.

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

(A) colorant

The colorant is characterized in that it contains at least one pigment, at least one dye, or a mixture thereof.

(A1) Pigment dispersion composition

The pigment dispersion composition includes a pigment (a1) and a pigment dispersant (a2), and may further include a dispersion aid (a3), a dispersion solvent (a4), and a dispersion resin (a5).

( a1 ) Pigment

As the pigment, organic or inorganic pigments generally used in the art may be used. In addition, the pigment is a resin treatment, surface treatment using a pigment derivative into which an acidic group or a basic group is introduced, a grafting treatment on the pigment surface with a polymer compound, atomization treatment by sulfuric acid atomization, etc., to remove impurities. Washing treatment with an organic solvent, water, or the like, or removal treatment of ionic impurities by an ion exchange method or the like may be performed.

The organic pigment may be a variety of pigments used in printing ink, inkjet ink, etc., specifically water-soluble azo pigment, insoluble azo pigment, phthalocyanine pigment, quinacridone pigment, isoindolinone pigment, isoindoline pigment, Ferriene Pigment, Perinone Pigment, Dioxazine Pigment, Anthraquinone Pigment, Dianthraquinonyl Pigment, Anthrapyrimidine Pigment, Antantrone Pigment, Indanthrone Pigment, Pravantron Pigment, Pyrantrone Pigment, Diketopyrropyrrole Pigment And the like.

In addition, as the inorganic pigment, metal compounds such as metal oxides or metal complex salts may be used. Specifically, iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony, carbon black, organic And oxides of metals such as black pigments, titanium blacks, and pigments in which red, green, and blue are mixed to give a black color or complex metal oxides.

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

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

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

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

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

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

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

C.I Pigment Brown 28;

Pigments such as C.I pigment black 1 and 7 are mentioned.

Preferably C.I pigment yellow 138, 139, 150, 185; C.I Pigment Orange 38; C.I Pigment Red 255; C.I pigment violet 23; C.I Pigment Blue 15:3, 15:6; And at least one selected from the group consisting of C.I pigment green 7, 36, and 58.

In the present invention, the pigment is contained in an amount of 20 to 90% by weight, preferably 30 to 70% by weight, based on the total weight of the solid content in the pigment dispersion composition. When the content of the pigment is out of 20 to 90% by weight, viscosity increases, storage stability decreases, and dispersion efficiency decreases, which adversely affects the contrast ratio.

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

( a2 ) Pigment Dispersant

The pigment dispersant is added for deagglomeration and stability of the pigment. Specific examples of the pigment dispersant include surfactants such as cationic, anionic, nonionic, amphoteric, polyester, and polyamine. And these may be used alone or in combination of two or more.

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

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

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

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 are listed. have.

In addition, the pigment dispersant preferably includes an acrylate-based dispersant (hereinafter, an acrylate-based dispersant) including butyl methacrylate (BMA) or N,N-dimethylaminoethyl methacrylate (DMAEMA). Commercially available products of the acrylate-based dispersant include DISPER BYK-2000, DISPER BYK-2001, DISPER BYK-2070, or DISPER BYK-2150, and the acrylate-based dispersants are used alone or in combination of two or more. I can.

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

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

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

The pigment dispersant is included in an amount of 5 to 50 parts by weight, preferably 15 to 50 parts by weight, based on 100 parts by weight of the solid content in the pigment. If the content of the pigment dispersant exceeds 50 parts by weight, the viscosity increases, and if it is less than 5 parts by weight, it may be difficult to atomize the pigment or cause problems such as gelation after dispersion.

( a3 ) Dispersion aid

The dispersion aid refers to a formulation that serves to prevent reaggregation when the pigment is dispersed into fine particles. The dispersion aid is effective in constructing a color filter having a high contrast ratio and excellent transmittance.

Dispersion aids that may be further included in the pigment dispersion composition of the present invention include a compound represented by the following formula (2).

[Formula 2]

The R ₁ to R ₄ are each independently hydrogen, -OH or -NH-R ⁹ ,

The R ₅ to R ₈ are each independently hydrogen, a halogen atom or SO ₃ ^- ,

R ₉ is hydrogen, an alkyl group having 1 to 8 carbon atoms, or a compound represented by the following formula (3),

[Formula 3]

The R ₁₀ to R ₁₄ are each independently hydrogen, an alkyl group having 1 to 4 carbon atoms, SO ₃ ^- or a compound represented by the following formula (4),

[Formula 4]

R ₁₅ is hydrogen, COR ₁₆ , an alkyl group having 1 to 8 carbon atoms, a cyclic saturated hydrocarbon, a cyclic unsaturated hydrocarbon or an aromatic hydrocarbon,

R ₁₆ is hydrogen or an alkyl group having 1 to 8 carbon atoms.

Specific examples of the compound corresponding to Formula 2 include 1,8-diamino-4,5-dihydroxyanthraquinone, 1,5-bis{[2-(diethylamino)ethyl]amino} Anthra-9,10-quinone, 1,8-bis(benzamido)anthraquinone, 1,4-bis{[2-(4-hydroxyphenyl)ethyl]amino}anthra-9,10-quinone, 1 ,4-bis{[2-(dimethylamino)ethyl]amino}-5,8-dihydroxyanthra-9,10-quinone, 1,8-dihydroxy-4-[4-(2-hydro Roxyethyl)anilino]-5-nitroanthra-9,10-quinone, 1,4-dihydroxyanthraquinone, 1,4-bis(4-butylanilino)-5,8-dihydroxyanthra Quinone, 4'-(4-hydroxy-1-anthraquinonylamino)-acetanilide, 1,4-bis[(2,6-diethyl-4-methylphenyl)amino]anthraquinone, 1,4- Bis(butylamino)-9,10-anthracendione, 1,4-bis(4-butylanilino)-5,8-dihydroxyanthraquinone, 1,5-bis[(3-methylphenyl)amino] -9,10-anthracendione, 1,5-dicyclohexylaminoanthraquinone, 1,4-bis(isopropylamino)anthraquinone, 1,4-bis(methylamino)anthraquinone, 1,4-bis (2,6-diethyl-4-methylanilino) anthraquinone, 2,2'-(9,10-dioxoanthracene-1,4-diyldiimino)bis(5-methylsulfonate), 1 -Anilino-4-hydroxyanthraquinone, 1-hydroxy-4-[(4-methylphenyl)amino]-9,10-anthracenedione, 1,4-bis(para-tolylamino)anthraquinone, 1 -Amino-4-fetylaminoanthraquinone, N-[4-[(4-hydroxy-anthraquino-1-yl)amino]phenyl]acetamide, 1-(methylamino)-4-(4-methylanyl Rhino) anthracene-9,10-dione and 1,4,5,8-tetrahydroxyanthraquinone.

In addition, in addition to the dispersion aid, a commercially available dispersion aid may be further included if necessary. Specifically, for example, Lubrizol's SOLSPERSE-5000, SOLSPERSE-12000, SOLSPERSE-22000, BYK's BYK-SYNERGIST 2100, BYK-SINERGIST 2105, BASF's EFKA-6745 or EFKA-6750.

The dispersion aid is included in an amount of 1 to 30 parts by weight based on 100 parts by weight of the solid content of the pigment. If the content of the dispersion aid exceeds 30 parts by weight, the inherent color of the pigment is deteriorated, and discoloration due to hard baking occurs during the color filter manufacturing process.

( a4 ) Dispersion solvent

The dispersion solvent is not particularly limited, but various organic solvents used in the art may be used.

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

Preferably, alkylene glycol alkyl ether acetates; Ketones; Esters such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate can be used, more preferably propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, 3-ethoxy ethyl propionate And methyl 3-methoxypropionate.

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

In addition, the dispersion solvent is included in an amount of 60 to 90% by weight, preferably 70 to 85% by weight, based on the total weight of the pigment dispersion composition. If the content of the dispersion solvent is out of the range of 60 to 90% by weight, there is a problem that the storage stability of the pigment dispersion composition is deteriorated.

( a5 ) Dispersion balance

The dispersion resin acts as a dispersion medium for the pigment (a1), and may be optionally added. In the case of using the dispersion resin, it is possible to prepare a more excellent pigment dispersion composition compared to the single use of the pigment dispersant (a2).

The dispersion resin can be used without limitation as long as it can act as a dispersion medium, but it is preferable to use an acid value in order to have solubility in an alkaline developer in consideration of the developability of the colored photosensitive resin composition made of the pigment dispersion composition.

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

Dispersion resin having an acid value can be prepared by copolymerizing an ethylenically unsaturated monomer having a carboxyl group and an unsaturated monomer capable of copolymerization with the ethylenically unsaturated monomer having a carboxyl group.

Specifically, examples of the ethylenically unsaturated monomer having a carboxyl group include monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; Dicarboxylic acids such as fumaric acid, mesaconic acid and itaconic acid; And an anhydride of dicarboxylic acid of the compound; And mono (meth) acrylates of a polymer having a carboxyl group and a hydroxyl group at both ends, such as ω-carboxypolycaprolactone mono (meth) acrylate, among others, acrylic acid and methacrylic acid are preferable. Each of the above compounds may be used alone or in combination of two or more.

In addition, the unsaturated monomer copolymerizable with the ethylenically unsaturated monomer having a carboxyl group is specifically, for example, styrene, vinyltoluene, α-methylstyrene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinylbenzylmethyl ether, m-vinylbenzylmethyl ether, p-vinylbenzylmethyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether and p-vinylbenzylgly Aromatic vinyl compounds such as cidyl ether;

Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, alkyl (meth)acrylates such as sec-butyl (meth)acrylate and t-butyl (meth)acrylate;

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

Aryl (meth)acrylates such as phenyl (meth)acrylate and benzyl (meth)acrylate;

Hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate;

N-cyclohexylmaleimide, N-benzylmaleimide, N-phenylmaleimide, No-hydroxyphenylmaleimide, Nm-hydroxyphenylmaleimide, Np-hydroxyphenylmaleimide, No-methylphenylmaleimide, Nm -N-substituted maleimide compounds such as methylphenylmaleimide, Np-methylphenylmaleimide, No-methoxyphenylmaleimide, Nm-methoxyphenylmaleimide and Np-methoxyphenylmaleimide;

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

3-(methacryloyloxymethyl)oxetane, 3-(methacryloyloxymethyl)-3-ethyloxetane, 3-(methacryloyloxymethyl)-2-trifluoromethyloxetane, 3-(methacryloyloxymethyl)-2-phenyloxetane, 2-(methacryloyloxymethyl)oxetane and 2-(methacryloyloxymethyl)-4-trifluoromethyloxetane, etc. And unsaturated oxetane compounds.

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

The dispersion resin is included in an amount of 5 to 60 parts by weight, preferably 10 to 50 parts by weight, based on 100 parts by weight of the pigment (a1). When the content of the dispersion resin exceeds 60 parts by weight, the viscosity may increase due to the dispersion resin, and when it is included in less than 5 parts by weight, the amount of the dispersion resin is insufficient, and thus a finely divided pigment dispersion composition cannot be obtained.

( a6 )dyes

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

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

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

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

C.I. Solvent Blue 5, 35, 36, 37, 44, 45, 59, 67 and 70;

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

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

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

C.I. And dyes such as Solvent Green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34 and 35.

The C.I. Among solvent dyes, C.I. Solvent Red 8, 49, 89, 111, 122, 132, 146 and 179; C.I. Solvent blue 35, 36, 44, 45 and 70; C.I. Solvent violet 13 has excellent solubility in organic solvents, preferably C.I. Solvent Red 8, 122 and 132.

Also, C.I. As an acid dye

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

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

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

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

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

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

C.I. Acid Red 92 among the above C.I. acid dyes; C.I. acid blue 80, 90; And C.I. acid violet 60 has excellent solubility in organic solvents.

In addition, as a C.I. direct dye,

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

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

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

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

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

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

In addition, as a C.I. modanto dye,

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

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

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

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

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

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

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

The content of the dye in the colorant is 0.5 to 80% by weight, preferably 0.5 to 60% by weight, and more preferably 1 to 50% by weight based on the total weight of the solids in the colorant. When the content of the dye in the colorant is 0.5 to 80% by weight, it is possible to prevent the problem of reducing the reliability of the dye eluting by the organic solvent after pattern formation, and the sensitivity is increased.

The content of the colorant is included in 5 to 60% by weight, preferably 10 to 45% by weight, based on the total weight of the solids in the colored photosensitive resin composition. When the colorant is included in an amount of 5 to 60% by weight, the color density of the pixel is sufficient when the thin film is formed, and the omission property of the non-pixel part is not lowered during development, so that it is difficult to generate a residue.

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

(B) alkali-soluble resin

The alkali-soluble resin of the present invention includes one or more selected from the group consisting of a compound containing a monomer of the following formula (5) or a compound containing a monomer of the following formula (6).

[Formula 5]

[Formula 6]

R ₁₇ is hydrogen or a methyl group,

R ₁₈ is hydrogen or a methyl group,

R ₁₉ is hydrogen, a carboxyl group or a methyl group.

When the alkali-soluble resin includes a compound containing the monomer of Formula 5, the compound containing the monomer of Formula 5 is included in an amount of 3 to 80 mol% based on the total number of moles of the alkali-soluble resin, preferably 5 to It is contained in 70 mol%. When the content is contained in an amount of 3 to 80 mol%, the sensitivity and adhesion of the colored photosensitive resin composition become excellent, so that peeling of the pattern does not occur during the development process.

In addition, when the alkali-soluble resin includes a compound containing the monomer of Formula 6, the compound containing the monomer of Formula 6 is included in an amount of 3 to 80 mol% based on the total number of moles of the alkali-soluble resin, preferably Is contained in 5 to 70 mol%. When it is contained in an amount of 3 to 80 mol%, the sensitivity and adhesion of the colored photosensitive resin composition become excellent, so that peeling of the pattern does not occur during the development process, and the solvent resistance is excellent.

In addition, the alkali-soluble resin further includes a compound containing a monomer of the following formula 7 together with at least one selected from the group consisting of a compound containing a monomer of formula 5 or a compound containing a monomer of formula 6 can do.

[Formula 7]

On the other hand, the alkali-soluble resin containing at least one selected from the group consisting of the compound containing the monomer of Formula 5 or the compound containing the monomer of Formula 6 is an ethylenically unsaturated monomer having a glycidyl group (b1) Ethylenically unsaturated having a glycidyl group in the polymer (B2) obtained by further reacting the copolymer (B1) of the ethylenically unsaturated monomer (b2) having a carboxyl group or the copolymer of the ethylenically unsaturated monomer (b2) having a carboxyl group It may be a polymer (B2) obtained by further reacting a monomer (b1).

The ethylenically unsaturated monomer (b1) having a glycidyl group includes glycidyl methacrylate.

Specific examples of the ethylenically unsaturated monomer (b2) having a carboxyl group include acrylic acid, methacrylic acid, itaconic acid, maleic acid, maleic anhydride, fumaric acid, or maleic acid alkyl ester. The maleic acid compounds include monomethylmaleic acid, ethylmaleic acid, n-propylmaleic acid, isopropylmaleic acid, n-butyl maleic acid, n-hexylmaleic acid, n-octylmaleic acid, 2-ethylhexylmaleic acid, n-nonylmaleic acid, and n-dode Silmaleic acid, etc. are mentioned. Each of the above compounds may be used alone or in combination of two or more.

In addition, in the preparation of the alkali-soluble resin, in addition to the ethylenically unsaturated monomer (b1) having a glycidyl group and the ethylenically unsaturated monomer (b2) having a carboxyl group, a copolymerizable unsaturated monomer (b3) may be added to perform polymerization. The copolymerizable monomers (b3) are exemplified below, but are not limited thereto.

Specifically, for example, styrene, vinyltoluene, α-methylstyrene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinylbenzylmethyl ether, m-vinylbenzyl Aromatic vinyl compounds such as methyl ether, p-vinylbenzyl methyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, and p-vinylbenzyl glycidyl ether;

Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, alkyl (meth)acrylates such as sec-butyl (meth)acrylate and t-butyl (meth)acrylate;

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

Aryl (meth)acrylates such as phenyl (meth)acrylate and benzyl (meth)acrylate;

Hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate;

N-cyclohexylmaleimide, N-benzylmaleimide, N-phenylmaleimide, No-hydroxyphenylmaleimide, Nm-hydroxyphenylmaleimide, Np-hydroxyphenylmaleimide, No-methylphenylmaleimide, Nm -N-substituted maleimide compounds such as methylphenylmaleimide, Np-methylphenylmaleimide, No-methoxyphenylmaleimide, Nm-methoxyphenylmaleimide, and Np-methoxyphenylmaleimide;

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

3-(methacryloyloxymethyl)oxetane, 3-(methacryloyloxymethyl)-3-ethyloxetane, 3-(methacryloyloxymethyl)-2-trifluoromethyloxetane, 3-(methacryloyloxymethyl)-2-phenyloxetane, 2-(methacryloyloxymethyl)oxetane, 2-(methacryloyloxymethyl)-4-trifluoromethyloxetane, etc. And unsaturated oxetane compounds.

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

In addition, the alkali-soluble resin of the present invention may be used by further mixing other known alkali-soluble resins generally used in the art, if necessary.

The alkali-soluble resin has a weight average molecular weight in terms of polystyrene of 3,000 to 100,000, preferably 5,000 to 50,000. When the weight average molecular weight of the alkali-soluble resin exceeds 3,000 to 100,000, film reduction is not prevented during development, and thus pattern portions may be omitted.

The acid value of the alkali-soluble resin is 50 to 150 KOH mg/g, preferably 60 to 140 KOH mg/g, more preferably 80 to 135 KOH mg/g, and most preferably 80 to 130 KOH mg/g. When the acid value of the alkali-soluble resin is 50 to 150 (KOH mg/g), the solubility in the developer is improved and the residual film rate is improved.

In addition, the alkali-soluble resin is contained in 10 to 80% by weight, preferably 10 to 70% by weight, based on the total weight of the solid content of the colored photosensitive resin composition of the present invention. When the content of the alkali-soluble resin is 10 to 80% by weight, the solubility of the developer is sufficient to facilitate pattern formation, and film reduction in the pixel portion of the exposed portion is prevented during development, thereby improving the omission of non-pixel portions.

(C) Photopolymerization compound

The photopolymerizable compound, which is one of the colored photosensitive resin compositions of the present invention, must be a compound capable of polymerization by the action of a photopolymerization initiator (D) described later. A monofunctional photopolymerizable compound, a bifunctional photopolymerizable compound or a trifunctional photopolymerizable compound, and the like, but is not limited thereto.

The monofunctional monomer is specifically, for example, nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate, N- Vinylpyrrolidone, etc., and commercially available products include Aaronix M-101 (Doagosei), KAYARAD TC-110S (Nippon Kayaku), or Biscotti 158 (Osaka Yuki Kagaku High School).

Specifically, the bifunctional monomer is, for example, 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) Acrylate, bis(acryloyloxyethyl) ether of bisphenol A, 3-methylpentanedioldi(meth)acrylate, etc., and commercially available products include Aaronix M-210, M-1100, 1200 (Toagosei) , KAYARAD HDDA (Nippon Kayaku), Viscot 260 (Osaka Yuki Kagaku High School), AH-600, AT-600 or UA-306H (Kyoeisha Kagakusa).

The trifunctional or higher polyfunctional photopolymerizable compound is specifically, for example, trimethylolpropane tri (meth) acrylate, ethoxylated trimethylol propane tri (meth) acrylate, propoxylated trimethylol propane tri (meth) )Acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, thipentaerythritol penta(meth)acrylate, ethoxylated dipentaerythritol hexa(meth)acrylate, Propoxylated dipentaerythritol hexa(meth)acrylate, dipentaerythritol hexa(meth)acrylate, etc., and commercially available products include Aaronix M-309, TO-1382 (Doagosei), KAYARAD TMPTA, KAYARAD DPHA or KAYARAD DPHA-40H (Nippon Kayaku).

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

The photopolymerizable compound is included in an amount of 5 to 45% by weight, and preferably 7 to 45% by weight, based on the total weight of the solids in the colored 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) Light polymerization Initiator

The photopolymerization initiator may be used without particular limitation on its kind as long as it can polymerize the photopolymerizable compound (C).

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

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

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

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

Specific examples of the biimidazole compound include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-dichloro Phenyl)-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, And imidazole compounds in which the phenyl group at the 4',5,5'-tetraphenyl-1,2'-biimidazole and the 4,4',5,5' position is substituted with a carboalkoxy group. Among the above compounds, 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 desirable.

Specific examples of the oxime compound include o-ethoxycarbonyl-α-oxyimino-1-phenylpropan-1-one, and commercially available products include BASF's OXE01 and OXE02.

Specific examples of the thioxanthone compound include 2-isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-dichloro thioxanthone, and 1-chloro-4-propoxythioxanthone. have.

Further, a photopolymerization initiator other than the above may be further used within a range that does not impair the effects of the present invention. For example, a benzoin-based compound or an anthracene-based compound may be mentioned, and these may be used alone or in combination of two or more.

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

Specific examples of the anthracene-based compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, and 2-ethyl-9,10-diethoxyanthracene. .

In addition to the above compounds, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, campoquinone, phenylclioxyl Acid methyl and titanocene compounds and the like can be further used as a photoinitiator.

In addition, the photopolymerization initiator may further include a photopolymerization initiation aid in order to improve the sensitivity of the colored photosensitive resin composition of the present invention. The colored photosensitive resin composition according to the present invention includes a photopolymerization initiation aid, so that sensitivity can be further improved and productivity can be increased.

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

Examples of the amine compound include aliphatic amine compounds such as triethanolamine, methyldiethanolamine, and triisopropanolamine; 4-dimethylaminobenzoic acid methyl, 4-dimethylaminobenzoic acid ethyl, 4-dimethylaminobenzoic acid isoamyl, 4-dimethylaminobenzoic acid 2-ethylhexyl, benzoic acid 2-dimethylaminoethyl, N,N-dimethylparatoluidine, 4,4 And aromatic amine compounds such as'-bis(dimethylamino)benzophenone (common name: Michler's ketone) and 4,4'-bis(diethylamino)benzophenone, and the aromatic amine compound is used as the amine compound. It is desirable.

The carboxylic acid compound is, for example, 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 aromatic heteroacetic acid such as naphthoxyacetic acid.

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

In the present invention, the photopolymerization initiator may be contained in an amount of 0.1 to 30% by weight, preferably 1 to 20% by weight, based on the total weight of solids in the colored photosensitive resin composition of the present invention. When the photopolymerization initiator is in the range of 0.1 to 30% by weight, the sensitivity of the colored photosensitive resin composition is increased to shorten the exposure time, thereby improving productivity and maintaining high resolution. Further, the strength of the pixel portion formed by using the colored photosensitive resin composition and smoothness on the surface of the pixel portion can be improved.

In addition, when the photopolymerization initiation aid is additionally used, the photopolymerization initiation aid may be contained in an amount of 0.1 to 30% by weight, preferably 1 to 20% by weight, based on the total weight of solids in the colored photosensitive resin composition of the present invention. When the content of the photopolymerization initiation aid is in the range of 0.1 to 30% by weight, the sensitivity of the colored photosensitive resin composition is further increased, and the productivity of the color filter formed using the colored photosensitive resin composition can be improved.

(E) solvent

As long as the solvent is effective in dissolving other components included in the colored photosensitive resin composition, the solvent used in the usual colored photosensitive resin composition may be used without particular limitation, and in particular, ethers, aromatic hydrocarbons, ketones, alcohols, esters And amides are preferred.

As the ethers, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol di Propyl ether and diethylene glycol dibutyl ether, and the like.

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, and glycerin.

Examples of the esters include ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, methyl cellosolve acetate, ethyl cellosolve acetate, ethyl acetate, butyl acetate, amyl acetate, methyl lactate, ethyllac Tate, 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, 2-amino-2-methyl-1,3-propanediol, 2-amino-2-ethyl-1,3-propanediol, ethyl lactate, propylene glycol, n- Propyl ether, ethyl-3-ethoxypropionate, propylene glycol monobutyl ether, 3-methoxy-1-butyl acetate, ethylene glycol monobutyl ether, diethylene glycol methyl ethyl ether, 1, 2-propylene glycol diacetate, dipropylene glycol monomethyl ether, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether, gamma butyrolactone, diethylene glycol monoethyl ether acetate, Dipropylene glycol methyl ether acetate, diethylene glycol monobutyl ether, 1,3-butylene glycol diacetate, diethylene glycol monobutyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate , Diethylene glycol monoacetate, diethylene glycol diacetate, diethylene glycol monobutyl ether acetate, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene carbonate, propylene carbonate And γ-butyrolactone.

Among the solvents exemplified above, organic solvents having a boiling point of 100 to 200°C in terms of applicability and drying properties are preferable, for example, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, ethyl lactate , Butalactate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, and the like are used.

The solvents illustrated above may be used alone or in combination of two or more. In addition, the solvent is included in an amount of 60 to 90% by weight, preferably 70 to 85% by weight, based on the total weight of the colored photosensitive resin composition of the present invention. When the solvent is included in the range of 60 to 90% by weight, roll coater, spin coater, slit and spin coater, slit coater (sometimes referred to as die coater), spray coater, reverse printing, gravure printing, screen printing, pad printing And when applied with a coating device such as an ink jet, the coating property becomes good.

(F) additive

The colored photosensitive resin composition of the present invention is characterized by containing an epoxy compound represented by the following formula (1) as an additive. The colored photosensitive resin composition comprising the following Formula 1 can improve reliability by maximizing the curing density of the coating film.

[Formula 1]

R is hydrogen or an alkyl group having 1 to 3 carbon atoms,

N is 1 to 6.

Formula 1 is contained in an amount of 0.1 to 10% by weight based on the total weight of solids in the colored photosensitive resin composition of the present invention. When included in the above range, the pattern formation is good and the reliability is improved.

In addition, the additive may be selectively added as needed, and may include, for example, one or more selected from the group consisting of other polymer compounds, curing agents, surfactants, adhesion promoters, ultraviolet absorbers, and anti-aggregation agents. .

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

The curing agent is used to increase 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, noblock type epoxy resin, other aromatic epoxy resins, alicyclic epoxy resins , Glycidyl ester resins, glycidylamine resins, or brominated derivatives of the above epoxy resins, aliphatic, alicyclic or aromatic epoxy compounds other than the epoxy resins and brominated derivatives thereof, butadiene (co)polymer epoxides, isoprene ( Co)polymer epoxidation products, glycidyl (meth)acrylate (co)polymer, triglycidyl isocyanurate, and the like.

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

The curing agent may be used in combination with a curing agent and 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.

Examples of the curing auxiliary compound include polyvalent carboxylic acids, polyvalent carboxylic anhydrides, and acid generators. The polyhydric carboxylic anhydrides may be commercially available as an epoxy resin curing agent. Examples of the commercially available products include Adeka Hadona EH-700 (manufactured by Adeka Industries Co., Ltd.), Rika Shiddo HH (manufactured by Shin Nippa Ewha Corporation), and MH-700 (manufactured by Shin Nihon Ewha Corporation). The curing agent 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 colored photosensitive resin composition, and silicone-based, fluorine-based, ester-based, cationic, anionic, nonionic, amphoteric surfactants, etc. may be preferably used.

The silicone-based surfactants include, for example, DC3PA, DC7PA, SH11PA, SH21PA, and SH8400 of Dow Corning Toray Silicones as commercial products, and TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF of GE Toshiba Silicones. -4460 and TSF-4452.

Examples of the fluorine-based surfactant are commercially available products such as Megapieces F-470, F-471, F-475, F-482, and F-489 manufactured by Dai Nippon Ink Chemical Co., Ltd.

In addition, other commercially available products include KP (Shin-Etsu Chemical Co., Ltd.), POLYFLOW (Kyoeisha Chemical Co., Ltd.), EFTOP (Tochem Products), and MEGAFAC. (Dai Nippon Ink Kagaku High School Co., Ltd.), Flourad (Sumitomo 3M Co., Ltd.), Asahi guard, Surflon (above, Asahi Glass Co., Ltd.), SOLSPERSE (Lubrisol) , EFKA (EFKA Chemicals), PB 821 (Ajinomoto), Disperbyk-series (BYK-chemi), and the like.

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

The type of adhesion promoter is not particularly limited, and specific examples of the adhesion promoter that can be used include vinyl trimethoxysilane, vinyl triethoxysilane, vinyl tris (2-methoxyethoxy) silane, N-(2-aminoethyl) )-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3 -Glycidoxypropylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxy And propyl trimethoxysilane, 3-mercaptopropyl trimethoxysilane, 3-isocyanate propyl trimethoxy silane, and 3-isocyanate propyl triethoxy silane. The adhesion promoters exemplified above may be used alone or in combination of two or more. The adhesion promoter may be included in a range of usually 0.01 to 10% by weight, preferably 0.05 to 2% by weight, based on the total weight of the solid content in the colored photosensitive resin composition.

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

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

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

First, in the colorant (A), the pigment (a1) is mixed with the solvent (E) and dispersed using a bead mill or the like until the average particle diameter of the pigment becomes about 0.2 μm or less. At this time, if necessary, a pigment dispersant (a2), part or all of the alkali-soluble resin (B), or a dye (a6) may be mixed with a solvent (E) to dissolve or disperse.

Formula 1 (F) and solvent (E) as a dye (a6), the remainder of the alkali-soluble resin (B), a photopolymerizable compound (C), a photopolymerization initiator (D) and an additive to the mixed dispersion to a predetermined concentration. It can be further added to prepare the colored photosensitive resin composition according to the present invention.

In addition, the present invention provides a color filter made of a colored photosensitive resin composition and a display device including the same.

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

As the coating method, for example, it can be performed by spin coating, casting coating, roll coating, slit and spin coating, or slit coating. After application, heat-drying (pre-baking) or drying under reduced pressure is performed, followed by heating to volatilize volatile components such as a solvent. Here, the heating temperature is usually 70 to 200°C, preferably 80 to 130°C. The thickness of the coating film after heating and drying is usually about 1 to 8 µm. The thus obtained coating film is irradiated with ultraviolet rays through a mask for forming a target pattern. At this time, it is preferable to use a device such as a mask aligner or a stepper so that parallel light rays are uniformly irradiated to the entire exposed portion and accurate positioning of the mask and the substrate is performed. When ultraviolet rays are irradiated, curing of the ultraviolet rays is irradiated.

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

The developing method is not particularly limited to a liquid addition method, a dipping method, a spray method, or 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 hydrogen carbonate, potassium hydrogen carbonate, sodium borate, potassium borate, ammonia, and the like.

In addition, as an organic alkaline compound, for example, tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine , Monoisopropylamine, diisopropylamine, and ethanolamine.

The inorganic or organic alkaline compounds 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.

The surfactant in the developer may be at least one selected from the group consisting of the above-described nonionic surfactants, anionic surfactants, and cationic surfactants. The concentration of the surfactant in the developer is included in an amount of 0.01 to 10% by weight, preferably 0.05 to 8% by weight, and more preferably 0.1 to 5% by weight, based on the total weight of the developer. After image development, it can wash with water and post-baking for 10 to 60 minutes at 150-230 degreeC as needed can also be performed.

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

Hereinafter, examples will be described in detail to illustrate the present invention in detail. However, the embodiments according to the present invention may be modified in various other forms, and the scope of the present invention should not be construed as being limited to the embodiments described below. Embodiments of the present invention are provided to more completely describe the present invention to those of ordinary skill in the art.

<Synthesis of alkali-soluble resin>

Synthesis example One.

A flask equipped with a stirrer, a thermometer reflux condenser, a dropping lot and a nitrogen introduction tube was prepared. As a monomer dropping lot, a mixture of 3,4-epoxytricyclodecane-8-yl (meth)acrylate and 3,4-epoxytricyclodecane-9-yl (meth)acrylate in a molar ratio of 50:50 40 Parts by weight, 50 parts by weight of methyl methacrylate, 40 parts by weight of acrylic acid, 70 parts by weight of vinyl toluene, 4 parts by weight of t-butylperoxy-2-ethylhexanoate, 40 parts by weight of propylene glycol monomethyl ether acetate (PGMEA) It was added and stirred. As a chain transfer agent dropping tank, 6 parts by weight of n-dodecanethiol and 24 parts by weight of PGMEA were added and stirred.

Thereafter, 395 parts by weight of PGMEA was added to the flask, the atmosphere in the flask was exchanged from air to nitrogen, and the temperature of the flask was raised to 90°C while stirring.

Thereafter, dropping of the monomer and the chain transfer agent was started from the dropping lot. The dropping was maintained at 90°C for 2 hours, and the temperature was raised to 110°C after 1 hour and maintained for 5 hours.The weight average molecular weight in terms of polystyrene was 17,000, the molecular weight distribution (Mw/Mn) was 2.3, and the solid content acid value An alkali-soluble resin (B-1), which is a compound containing the monomer of Formula 5, was obtained with 75 mgKOH/g.

Synthesis example 2.

A flask equipped with a stirrer, a thermometer reflux condenser, a dropping lot and a nitrogen introduction tube was prepared. As a monomer dropping lot, 40 parts by weight of styrene, 60 parts by weight of maleic anhydride, 4 parts by weight of t-butylperoxy-2-ethylhexanoate, and 40 parts by weight of propylene glycol monomethyl ether acetate (PGMEA) were added and stirred. .

As a chain transfer agent dropping tank, 6 parts by weight of n-dodecanethiol and 24 parts by weight of PGMEA were added and stirred.

Thereafter, 400 parts by weight of PGMEA was added to the flask, the atmosphere in the flask was exchanged from air to nitrogen, and the temperature of the flask was raised to 90°C while stirring.

Thereafter, dropping of the monomer and the chain transfer agent was started from the dropping lot. The dropping was maintained at 90°C for 2 hours, and the temperature was raised to 110°C after 1 hour and maintained for 5 hours.The weight average molecular weight in terms of polystyrene was 7,000, the molecular weight distribution (Mw/Mn) was 2.1, and the solid content acid value An alkali-soluble resin (B-2) was obtained, which is a compound containing the monomers of Formula 6 and Formula 7 wherein is 105 mgKOH/g.

In addition, the weight average molecular weight (Mw) and number average molecular weight (Mn) of the alkali-soluble resins of Synthesis Example 1 and Synthesis Example 2 were measured using gel permeation chromatography, and were measured under the following conditions.

Gel permeation chromatography: HLC-8120GPC (manufactured by Tosoh Corporation)

Column: Use by connecting TSK-GELG4000HXL and TSK-GELG2000HXL columns in series

Column temperature: 40℃

Mobile phase solvent: tetrahydrofuran

Flow rate: 1.0mL/min

Concentration of measurement sample: 0.6% by weight

Measurement sample injection volume: 50μL

Detector: RI detector

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

<Preparation of colored photosensitive resin composition>

The colored photosensitive resin compositions of Examples 1 to 3 and Comparative Examples 1 to 2 were prepared in the composition ratio of Table 1 below.

(Unit: parts by weight) division Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 (A) colorant A-1 20 - 20 20 - A-2 - 18 - - 18 (a2) Pigment dispersant 4 - 4 4 - (B) alkali solubility
Suzy B-1 30 30 - 30 30 B-2 - - 30 - - (C) photopolymerizable compound 30 30 30 30 30 (D) photopolymerization initiator 2 3 2 2 3 (E) solvent 150 150 150 150 150 (F) additive One 2 2 - -

(A) Colorant:

A-1: C.I. Pigment Blue 15:6 (EP-193, manufactured by DIC)

A-2: C.I. Solvent Blue 45 (manufactured by Clariant)

(a2) Pigment dispersant: DiperBYK-163 (manufactured by BYK)

(B) Alkali-soluble resin:

B-1: Alkali-soluble resin of Synthesis Example 1

B-2: Alkali-soluble resin of Synthesis Example 2

(C) Photopolymerizable compound: dipentaerythritol hexaacrylate (Kayarad DPHA: Nippon Kayaku Co., Ltd.)

(D) Photoinitiator: Ethanone-1-[9-ethyl-6-(2-methyl-4-tetrahydropyranyloxybenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime )(Irgacure OXE-02: Ciba company)

(E) Solvent: Propylene glycol monomethyl ether acetate

(F) Additive: Compound of Formula 1 (n=1, R=H)

Experimental example 1. Color filter manufacturing and Solvent resistance evaluation

Each of the colored photosensitive resin compositions of Examples 1 to 3 and Comparative Examples 1 to 2 was coated on a 2-inch glass substrate (manufactured by Corning, "EAGLE XG") by spin coating, and then placed on a heating plate at a temperature of 100°C. Hold for 3 minutes to form a thin film.

Then, ultraviolet rays were irradiated. At this time, the ultraviolet light source was irradiated with an illuminance of 40 mJ/cm 2 using a high-pressure mercury lamp of 1 kW containing all g, h, and i-rays.

The UV-irradiated thin film was developed by immersing it in a developing solution of a KOH solution having a pH of 10.5 for 2 minutes. The glass plate on which the thin film was applied was washed with distilled water, dried by blowing nitrogen gas, and heated in a heating oven at 230° C. for 25 minutes to prepare each color filter. The film thickness of the color filter prepared above was 2.3 μm.

Reliability was determined by measuring solvent resistance with each of the color filters prepared above.

The solvent resistance measurement was performed by immersing the color filter in the NMP solution at room temperature for 30 minutes, extracting the NMP solvent, and measuring the absorbance at the visible wavelength of the NMP solvent after immersion using a shimadzu UV-2600 instrument, and the results are shown in the table below. It is shown in 2.

division Absorbance Example 1 0.38 Example 2 0.28 Example 3 0.22 Comparative Example 1 0.62 Comparative Example 2 0.52

In the results of Table 2, the color filters of Comparative Examples 1 to 2 that do not include Formula 1 exhibited high degree of detection due to the high elution of pigments or dyes in the NMP solvent, whereas the colors of Examples 1 to 3 The filter showed a low degree of detection due to less elution of the pigment or dye in the NMP solvent (Fig. 1).

In addition, in Example 2 and Comparative Example 2 using a dye, a result similar to that of Example 1 and Comparative Example 1 using a pigment was shown.

In addition, in the case of Example 3, it was possible to confirm a more improved result compared to Example 1.

Therefore, the colored photosensitive resin composition of the present invention has excellent curing density, and thus a hardly cured coating film can be prepared, and thereby, a color filter with improved reliability can be manufactured using the colored photosensitive resin composition of the present invention. .

Claims (10)

A colored photosensitive resin composition containing a colorant, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, a solvent and an additive,
The additive is a colored photosensitive resin composition, characterized in that it contains an epoxy compound of the formula (1).
[Formula 1]

R is hydrogen or an alkyl group having 1 to 3 carbon atoms,
N is 1 to 6. The colored photosensitive resin composition according to claim 1, wherein the colorant comprises at least one pigment, at least one dye, or a mixture thereof. The method according to claim 1, wherein the alkali-soluble resin is a colored photosensitive resin composition comprising at least one selected from the group consisting of a compound containing a monomer represented by the following formula (5) or a compound containing a monomer represented by the following formula (6).
[Formula 5]

[Formula 6]

R ₁₇ is hydrogen or a methyl group,
R ₁₈ is hydrogen or a methyl group,
R ₁₉ is hydrogen, a carboxyl group or a methyl group. The method according to claim 3, wherein the compound containing the monomer of Formula 5 is contained in an amount of 3 to 80 mol% based on the total number of moles of the alkali-soluble resin,
The compound containing the monomer of Formula 6 is a colored photosensitive resin composition, characterized in that it is contained in an amount of 3 to 80 mol% based on the total number of moles of the alkali-soluble resin. The colored photosensitive resin composition according to claim 3, wherein the alkali-soluble resin further contains a compound containing a monomer represented by the following formula (7).
[Formula 7]

The colored photosensitive resin composition according to claim 1, wherein the alkali-soluble resin has a weight average molecular weight in terms of polystyrene of 3,000 to 100,000. The colored photosensitive resin composition according to claim 1, wherein the alkali-soluble resin has an acid value of 50 to 150 KOHmg/g. The method according to claim 1, based on the total weight of the solid content in the colored photosensitive resin composition, 5 to 60% by weight of a colorant, 10 to 80% by weight of an alkali-soluble resin, 5 to 45% by weight of a photopolymerizable compound, 0.1 to 30% by weight of a photopolymerization initiator, and A colored photosensitive resin composition comprising 0.1 to 10% by weight of an additive containing the epoxy compound of Formula 1, and comprising 60 to 90% by weight of a solvent based on the total weight of the colored photosensitive resin composition. A color filter comprising the colored photosensitive resin composition of claim 1. A display device comprising the color filter of claim 9.

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