KR102363755B1 - Colored photosensitive resin composition and color filter using the same - Google Patents

Abstract

The present invention includes a colorant, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, a silsesquioxane-based compound having a specific structure, and a solvent; The colorant includes a pigment or dye combined with at least one insolubilizing agent selected from phosphotungstic acid and molybdic acid, and the photopolymerization initiator includes an oxime ester-based photopolymerization initiator. It relates to a color filter manufactured using

Description

Colored photosensitive resin composition, and color filter manufactured using the same {COLORED PHOTOSENSITIVE RESIN COMPOSITION AND COLOR FILTER USING THE SAME}

The present invention relates to a colored photosensitive resin composition and a color filter manufactured using the same.

Color filters are widely used in various display devices such as imaging devices, liquid crystal displays (LCDs), and organic light emitting diodes (OLEDs), and their application range is rapidly expanding.

The color filter used in the above-described display device is composed of a coloring pattern of three colors of red, green, and blue, or yellow, magenta, and cyan. It consists of a coloring pattern of three colors.

The coloring pattern of each of the color filters is generally formed using a colored photosensitive resin composition including a colorant such as a pigment or dye, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent. The coloring pattern processing using the colored photosensitive resin composition is generally performed by a lithography process.

Recently, as a flat panel display device proposed to replace a conventional cathode ray tube display device, a liquid crystal display device, a field emission display device, and a plasma display device are used. Display panels (Plasma Display Panel) and organic light emitting diodes (Organic Light-Emitting Diode Display, OLED Display), and the like.

Recently, the market demand for a high-quality display with high color reproducibility is increasing. Accordingly, the content of the colorant included in the colored photosensitive resin composition used for manufacturing the color filter is continuously increasing, and the use of a colorant having a better coloring power is being considered.

However, when the content of the colorant is increased, problems such as a decrease in sensitivity, line tearing of a pattern, and a decrease in straightness may occur. In addition, there is a problem such as lack of reliability in the case of a colorant having superior coloring power compared to the conventional one.

The present invention has been devised to solve the problems of the prior art,

An object of the present invention is to provide a colored photosensitive resin composition having excellent reliability, such as solvent resistance, while having characteristics of high coloring power, high transmittance, and high adhesion.

Another object of the present invention is to provide a color filter manufactured using the colored photosensitive resin composition.

The present invention is

It contains a colorant, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, a silsesquioxane-based compound of the following formula (1), and a solvent,

The colorant comprises a pigment or dye combined with at least one insolubilizing agent selected from phosphotungstic acid and Molybdic acid,

The photopolymerization initiator provides a colored photosensitive resin composition comprising an oxime ester-based photopolymerization initiator.

<Formula 1>

In Formula 1, R ₁ and R ₂ are each independently a C1-C30 aliphatic hydrocarbon, a C1-C30 aromatic hydrocarbon; may contain oxygen, silicon or sulfur;

It may form a ring with or independently of oxygen, silicon or sulfur.

Also, the present invention

It provides a color filter manufactured by using the colored photosensitive resin composition.

The present invention can provide a highly reliable colored photosensitive resin composition excellent in coloring power, transmittance, adhesiveness and solvent resistance.

In addition, it is possible to provide a color filter manufactured using the composition.

While the present inventors were researching a highly reliable colored photosensitive resin composition having excellent colorability, transmittance, adhesion and solvent resistance,

A colorant including a pigment or dye combined with a specific insolubilizing agent, an alkali-soluble resin, a photopolymerizable compound, an oxime ester-based photopolymerization initiator, a colored photosensitive resin composition comprising a silsesquioxane-based compound of a specific structure and a solvent It was confirmed to provide and completed the present invention.

The present invention is

It contains a colorant, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, a silsesquioxane-based compound of the following formula (1), and a solvent,

The colorant comprises a pigment or dye combined with at least one insolubilizing agent selected from phosphotungstic acid and molybdic acid,

The photopolymerization initiator provides a colored photosensitive resin composition comprising an oxime ester-based photopolymerization initiator.

<Formula 1>

In Formula 1, R ₁ and R ₂ are each independently a C1-C30 aliphatic hydrocarbon, a C1-C30 aromatic hydrocarbon; may contain oxygen, silicon or sulfur;

It may form a ring with or independently of oxygen, silicon or sulfur.

Hereinafter, each component which comprises the coloring photosensitive resin composition of this invention is demonstrated.

(A) Colorant

The colorant included in the colored photosensitive resin composition of the present invention includes a pigment or dye combined with at least one insolubilizing agent selected from phosphotungstic acid and molybdic acid. The pigment or dye combined with at least one insolubilizing agent selected from phosphotungstic acid and molybdic acid has an advantage in that it exhibits excellent colorability and can exhibit various colors.

The above-mentioned bond may be more specifically a coordination bond, and a pigment or dye may exhibit insolubility by combining with an insolubilizing agent. In this case, the insoluble means, for example, not being dissolved in propylene glycol monomethyl ether acetate (PGMEA).

As an example, a pigment or dye combined with at least one insolubilizing agent selected from phosphotungstic acid and molybdic acid may be prepared by mixing and reacting a pigment or dye with phosphotungstic acid and/or molybdic acid as an insolubilizing agent.

The pigment or dye is not particularly limited, and those commonly used in the art may be appropriately selected and used.

pigment

As the pigment, organic or inorganic pigments generally used in the art may be used. As the pigment, various pigments used in printing ink, inkjet ink, etc. may be used, and more specifically, as the pigment, a water-soluble azo pigment, an insoluble azo pigment, a phthalocyanine pigment, a quinacridone pigment, an isoindolinone pigment, isoin Doline pigment, perylene pigment, perinone pigment, dioxazine pigment, anthraquinone pigment, dianthraquinonyl pigment, anthrapyrimidine pigment, anthanthrone pigment, indanthrone pigment, prabanthrone pigment, pyran and pyranthrone pigments and diketopyrroropyrrole pigments.

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

As the pigment, red, yellow, orange, purple, and magenta pigments may be preferable, and in particular, the organic and inorganic pigments are specifically classified as pigments in the color index (published by The Society of Dyers and Colorists). CI among the compounds in Pigment Red, C.I. Pigment Yellow, C.I. Pigment Violet and C.I. At least one selected from pigment orange may be used, but the present invention is not limited thereto. More preferably, C.I. Pigment Red or C.I. Pigment yellow can be used.

It is also possible to use, as the colorant of the present invention, at least one of the above-mentioned pigments not combined with an insolubilizing agent.

dyes

The dye may be used without limitation as long as it has solubility in organic solvents or is dispersible. Preferably, it is preferable to use a dye capable of securing reliability such as solubility in alkali developer, heat resistance and solvent resistance.

As described above, the dye may be used in combination with at least one insolubilizing agent selected from phosphotungstic acid and molybdic acid.

The dye is not particularly limited, and specifically, compounds classified as dyes in the color index (published by The Society of Dyers and Colorists) or known dyes described in the dyeing notes (color dyes) may be mentioned, but the present invention is not limited thereto. does not

Pigments or dyes combined with one or more insolubilizing agents selected from phosphotungstic acid and molybdic acid as a colorant, or pigments are used in the form of a dispersion having uniformly dispersed particle diameters. desirable. As an example of a method for uniformly dispersing the particle size of the pigment or dye or pigment combined with the insolubilizing agent, a method of dispersing treatment by containing a dispersing agent may be mentioned, and according to this method, the colorant is uniformly dispersed in a solution A dispersed solution can be obtained.

dispersant

The dispersing agent is added to deagglomerate the colorant and maintain stability, and those generally used in the art may be used without limitation. Commercially available dispersants include BYK's Disperbyk-101, 103, 107, 108, 110, 111, 112, 116, 130, 140, 142, 154, 161, 162, 163, 164, 165, 166, 167, 168, 170 , 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2009, 2010, 2020, 2025, 2050, 2070, 2095, 2150, 2155, 2163, 2164 and LPN-6919 Lubrizol's SOLSPERSE-3000, 9000, 13000, 13240, 13650,13940, 16000, 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 56000 and 76500.

These may be used alone or in combination of two or more, more preferably BYK's Disperbyk-2000, 2001, BYK's LPN-6919, Lubrizol's SOLSPERSE-3000, 21000, 26000, which are dispersants having an acidic functional group, 36600, 41000, etc. may be used, but is not limited thereto.

The dispersant is preferably used in an amount of 5 to 50 parts by weight, more preferably 15 to 50 parts by weight, based on 100 parts by weight of the solid content of the colorant used. When the content of the dispersant is less than 5 parts by weight based on the above-mentioned basis, it may cause problems such as difficulty in atomization or gelation after dispersion. On the other hand, when the content exceeds 50 parts by weight, the viscosity may increase.

In the present invention, specific examples of pigments or dyes combined with at least one insolubilizing agent selected from phosphotungstic acid and molybdic acid include C.I. Pigment Red 81, C.I. Pigment Red 81:3, C.I. Pigment Red 81:4, C.I. Pigment Violet 1, C.I. Pigment Violet 2, C.I. Pigment Violet 2:2, C.I. Pigment Violet 3, C.I. Pigment Violet 39, C.I. Pigment Blue 1, C.I. Pigment Blue 9, C.I. Pigment Blue 14, C.I. Pigment Green 1, C.I. Pigment Green 2 and C.I. Pigment Green 4 and the like may be mentioned, but the present invention is not limited thereto.

In addition, the pigment or dye combined with at least one insolubilizing agent selected from phosphotungstic acid and molybdic acid of the present invention, based on the total weight of solids in the composition 5 to 40% by weight It is preferably included, and it is more preferably included in an amount of 5 to 20% by weight. When the content is less than 5% by weight based on the above criteria, the increase in the contrast ratio is not high. On the other hand, when it exceeds 40% by weight, reliability problems are likely to occur.

The colorant is preferably included in an amount of 5 to 50 wt%, more preferably 5 to 30 wt%, based on the total weight of the solid content in the colored photosensitive resin composition of the present invention. If the content is less than 5% by weight as described above, there is a problem that the color concentration of the pixel is not sufficient, and if it exceeds 50% by weight, the viscosity is high, the storage stability is poor, and the dispersion efficiency is low, which may adversely affect the contrast ratio.

(B) alkali-soluble resin

The alkali-soluble resin contained in the colored photosensitive resin composition of the present invention is not particularly limited as long as it is a resin having solubility in an alkali developer used in the developing treatment step at the time of forming a pattern, and an ethylenically unsaturated monomer containing a carboxyl group It is preferable to prepare by copolymerization.

Specific examples of the ethylenically unsaturated monomer having a carboxyl group include monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; dicarboxylic acids such as fumaric acid, mesaconic acid, and itaconic acid; and anhydrides of their dicarboxylic acids; polymer mono(meth)acrylates having a carboxyl group and a hydroxyl group at both terminals, such as ω-carboxypolycaprolactone mono(meth)acrylate; and the like. Among these, acrylic acid and methacrylic acid are preferable.

When preparing the alkali-soluble resin, polymerization may be performed by adding an ethylenically unsaturated monomer copolymerizable with the ethylenically unsaturated monomer having a carboxyl group.

Specific examples of the copolymerizable unsaturated monomer include glycidyl methacrylate, which is an unsaturated monomer having a glycidyl group; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, N -ethylenically unsaturated monomers having a hydroxyl group, such as hydroxyethyl (meth)acrylates such as hydroxyethyl acrylamide; Styrene, vinyltoluene, α-methylstyrene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinylbenzylmethyl ether, m-vinylbenzylmethyl ether, p-vinyl Aromatic vinyl compounds, such as benzyl methyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, and p-vinyl benzyl glycidyl ether; N-cyclohexylmaleimide, N-benzylmaleimide, N-phenylmaleimide, No-hydroxyphenylmaleimide, Nm-hydroxyphenylmaleimide, Np-hydroxyphenylmaleimide, No-methylphenylmaleimide, Nm -N-substituted maleimide compounds, such as methylphenylmaleimide, Np-methylphenylmaleimide, No-methoxyphenylmaleimide, Nm-methoxyphenylmaleimide, and Np-methoxyphenylmaleimide; 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 ] decan-8-yl (meth) acrylate, 2- alicyclic (meth)acrylates such as dicyclopentanyloxyethyl (meth)acrylate and isobornyl (meth)acrylate; aryl (meth)acrylates such as phenyl (meth)acrylate and benzyl (meth)acrylate; 3-(methacryloyloxymethyl)oxetane, 3-(methacryloyloxymethyl)-3-ethyloxetane, 3-(methacryloyloxymethyl)-2-trifluoromethyloxetane; 3-(methacryloyloxymethyl)-2-phenyloxetane, 2-(methacryloyloxymethyl)oxetane, 2-(methacryloyloxymethyl)-4-trifluoromethyloxetane, etc. of unsaturated oxetane compounds.

The above-described monomers may be used alone or in combination of two or more, but are not necessarily limited thereto.

The alkali-soluble resin preferably has an acid value of 30 to 150 mgKOH/g in order to secure the developability of the colored photosensitive resin composition. When the acid value of the alkali-soluble resin is less than 30 mgKOH/g, it is difficult for the colored photosensitive resin composition to secure a sufficient development rate. On the other hand, when it exceeds 150 mgKOH/g, the adhesion to the substrate is reduced, so that a short circuit of the pattern is likely to occur.

The alkali-soluble resin is preferably contained in an amount of 10 to 80% by weight, more preferably in an amount of 10 to 70% by weight, based on the solid content in the colored photosensitive resin composition. When the content of the alkali-soluble resin is within the range of 10 to 80% by weight based on the above criteria, the solubility in the developer is sufficient to facilitate pattern formation, and the film reduction of the pixel portion of the exposed portion is prevented during development, so that the non-pixel portion It is preferable because the omission property of

(C) photopolymerization compound

The photopolymerizable compound contained in the colored photosensitive resin composition of the present invention is a compound that can be polymerized by the action of a photopolymerization initiator described later, and may be a monofunctional monomer, a difunctional monomer, or a polyfunctional monomer. Among them, it may be more preferable to use a polyfunctional monomer having a bifunctional or higher function.

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

Specific examples of the bifunctional monomer include 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and triethylene glycol di (meth) acrylate. , bis(acryloyloxyethyl) ether of bisphenol A and 3-methylpentanediol di(meth)acrylate, but is not limited thereto.

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

The photopolymerizable compound is preferably contained in an amount of 5 to 45% by weight, more preferably in an amount of 7 to 45% by weight, based on the solid content in the colored photosensitive resin composition of the present invention. When the photopolymerizable compound is included in the range of 5 to 45% by weight based on the above-mentioned basis, it is preferable because the strength or smoothness of the pixel portion is improved.

(D) light curing initiator

The photoinitiator contained in the coloring photosensitive resin composition of this invention contains an oxime ester type photoinitiator.

Specific examples of the oxime ester-based photopolymerization initiator include 1,2-octanedione, 1-[4-(phenylthio)phenyl]-,2-(O-benzoyloxime) (1,2-Octanedione, 1-[4) -(phenylthio)phenyl]-,2-(O-benzoyloxime)), 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone 1-(O-acetyl oxime) (1-[9-Ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone 1-(O-acetyloxime)) and 1-[4-(phenylthio)phenyl)]-3 -Cyclohexyl-propane-1,2-dione-2-(O-acetyloxime) (1-[4-(phenylthio)phenyl)]-3-cyclohexyl-propane-1,2-dione-2-(O -acetyloxime)) and the like. Further, commercially available products include PBG-327 from Tronley, Irgacure® OXE 01, Irgacure® OXE 02 and Irgacure® OXE 03 from BASF.

The above-described oxime-based ester-based photopolymerization initiators may be used alone or in combination of two or more.

The oxime ester-based photopolymerization initiator is preferably included in an amount of 10 to 100 wt%, more preferably 20 to 100 wt%, based on the total weight of the photopolymerization initiator. When the content of the oxime ester-based photopolymerization initiator is less than 10% by weight based on the above-mentioned basis, the problem of sensitivity degradation due to the colorant cannot be solved, and short circuit of the pattern during development is easy to occur.

In addition, the composition of the present invention may further include other photopolymerization initiators in addition to the oxime ester-based photopolymerization initiator as a photopolymerization initiator within a range that does not impair the effects of the present invention. Representative examples of the other photopolymerization initiator include an acetophenone-based compound, a benzophenone-based compound, a triazine-based compound, a biimidazole-based compound, and a thioxanthone-based compound. can

Specific examples of the acetophenone-based 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-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, 0-benzoylbenzoate methyl, 4-phenylbenzophenone, 4-benzoyl-4′-methyldiphenylsulfide, 3,3′,4,4′-tetra( tert-butylperoxycarbonyl)benzophenone, 2,4,6-trimethylbenzophenone, etc. are mentioned.

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-tri azine, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)ethenyl]-1,3,5-triazine and 2,4-bis(trichloro methyl)-6-[2-(3,4-dimethoxyphenyl)ethenyl]-1,3,5-triazine;

Specific examples of the biimidazole-based compound include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3) -Dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(alkoxyphenyl)bi Imidazole, 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; there is.

Among them, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-dichlorophenyl)-4,4' ,5,5'-tetraphenylbiimidazole, 2,2-bis(2,6-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole is preferably can be used

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

The photopolymerization initiator is preferably contained in an amount of 5 to 40% by weight, more preferably in an amount of 10 to 30% by weight, based on the total weight of the solid content in the colored photosensitive resin composition of the present invention. When the content of the photopolymerization initiator is within the range of 5 to 40 wt % based on the above-mentioned basis, the colored photosensitive resin composition is highly sensitive and the exposure time is shortened, so that productivity is improved and high resolution can be maintained. In addition, the intensity of the pixel portion and smoothness on the surface of the pixel portion may be improved.

In addition, the photoinitiator may further include a photoinitiator 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 contains a photopolymerization initiation adjuvant, thereby further increasing the sensitivity and improving productivity.

As the photopolymerization initiation adjuvant, for example, at least one compound selected from an amine compound, a carboxylic acid compound, and a polyfunctional thiol compound may be preferably used.

It is preferable to use an aromatic amine compound as the amine compound, and specifically, an aliphatic amine compound such as triethanolamine, methyldiethanolamine, and triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4- Dimethylaminobenzoic acid isoamyl, 4-dimethylaminobenzoic acid 2-ethylhexyl, benzoic acid 2-dimethylaminoethyl, N,N-dimethylparatoluidine, 4,4'-bis(dimethylamino)benzophenone (common name: Michler ketone) ), 4,4'-bis(diethylamino)benzophenone, etc. are mentioned.

The carboxylic acid compound is preferably aromatic heteroacetic acid, specifically phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthio Acetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthoxyacetic acid, etc. are mentioned.

The polyfunctional thiol compound includes tris-[(3-mercaptopropionyloxy)-ethyl]-isocyanurate (Tris-[(3-mercaptopropionyloxy)-ethyl]-isocyanurate), trimethylopropane tris-3- Mercaptopropionate (Trimethylolpropane tris -3-mercaptopropionate), pentaerythritol tetrakis-3-mercaptopropionate (Pentaerythritol tetrakis-3-mercaptopropionate), dipentaerythritol hexa-3-mercaptopropionate (Dipentaerythritol hexa-3-mercaptopropionate) and the like.

When using the photopolymerization initiation adjuvant, the photopolymerization initiation adjuvant is preferably contained in an amount of 5 to 40 wt%, more preferably 5 to 30 wt%, based on the total weight of the solid content in the colored photosensitive resin composition of the present invention. Do. When the content is within the range of 5 to 40% by weight based on the above-mentioned basis, the sensitivity of the colored photosensitive resin composition is higher, and productivity of a color filter formed by using the composition is improved.

(E) of the following formula (1) Silsesquioxane type compound

The colored photosensitive resin composition of the present invention includes a silsesquioxane-based compound of Formula 1 below. The silsesquioxane-based compound suppresses penetration of a solvent into a coating film formed of the colored photosensitive resin composition in a subsequent process due to its inherent bulky structure. Accordingly, in the case of using a colorant in the coating film, particularly a pigment or dye combined with at least one insolubilizing agent selected from phosphotungstic acid and Molybdic acid included in the composition of the present invention , serves to prevent the dissolution of these colorants.

<Formula 1>

In Formula 1, R ₁ and R ₂ are each independently a C1-C30 aliphatic hydrocarbon, a C1-C30 aromatic hydrocarbon; may contain oxygen, silicon or sulfur;

It may form a ring with or independently of oxygen, silicon or sulfur.

Wherein R ₁ and R ₂ are each independently, more specifically, a substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C1-C30 cycloalkyl group, a substituted or unsubstituted C1-C30 aryl group, substituted Or an unsubstituted C1-C30 arylalkyl group, a substituted or unsubstituted C1-C30 alkenyl group, a substituted or unsubstituted C1-C30 alkynyl group, a substituted or unsubstituted C1-C30 acrylate group, a substituted or At least one selected from an unsubstituted C1-C30 epoxy group, a substituted or unsubstituted C1-C30 ester group, a substituted or unsubstituted C1-C30 alcohol group, and a substituted or unsubstituted C1-C30 thiol group is a group.

In this case, the substituted substituent may include, but is not limited to, an alkyl group, an alkylene group, an alkynyl group, a benzyl group, and a phenyl group.

In particular, in terms of being able to more effectively prevent the dissolution of the color material in the subsequent process, R ₁ and R ₂ are more preferably selected from an aryl group, a vinyl group, a (meth)acrylic group, an epoxy group, and a thiol group. It is preferable to include more than one species.

More specifically, R ₁ and R ₂ may each independently be one or more groups selected from the following Chemical Formulas 1-1 to 1-17, but are not limited thereto.

Specific examples of the silsesquioxane-based compound of Formula 1 include PSS-Allyl-Heptaisobutyl substituted, PSS-[2-(3,4-Epoxycyclohexyl)ethyl]-Heptaisobutyl substituted, PSS-(3-Glycidyl)propoxy-Heptaisobutyl substituted, PSS-Octa[(3-glycidyloxypropyl)dimethylsiloxy] substituted, PSS-(3-Mercapto)propyl-Heptaisobutyl substituted, PSS-Methacryl substituted, PSS-Octa[(1,2-epoxy-4-ethylcyclohexyl)dimethylsiloxy] substituted , PSS-Octa[(3-glycidyloxypropyl)dimethylsiloxy] substituted, PSS-Octavinyl substituted, PSS-(1-Propylmethacrylate)-Heptaisobutyl substituted, PSS-Trivinylsilyloxy-Heptacyclopentyl substituted, PSS-Vinyl-Heptacyclopentyl substituted-HeptaisobutylVinyl-Heptacyclopentyl substituted-Heptaisobutyl substituted and PSS-Vinyl substituted and the like.

More preferably, PSS-[2-(3,4-Epoxycyclohexyl)ethyl]-Heptaisobutyl substituted, PSS-(3-Glycidyl)propoxy-Heptaisobutyl substituted as an example containing a (meth)acryl, epoxy or thiol group having excellent reactivity , PSS-Octa[(3-glycidyloxypropyl)dimethylsiloxy] substituted, PSS-(3-Mercapto)propyl-Heptaisobutyl substituted, PSS-Methacryl substituted, PSS-Octa[(1,2-epoxy-4-ethylcyclohexyl)dimethylsiloxy] substituted and PSS-Octa[(3-glycidyloxypropyl)dimethylsiloxy] substituted, and the like, but is not limited thereto.

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

The silsesquioxane-based compound of Formula 1 is preferably included in an amount of 1 wt% to less than 10 wt%, and is more preferably included in an amount of 1 to 5 wt%, based on the total weight of the solid content in the colored photosensitive resin composition of the present invention. desirable. When the content of the silsesquioxane-based compound is less than 1% by weight based on the above-mentioned basis, the penetration of the solvent cannot be effectively suppressed. On the other hand, when it is 10% by weight or more, the development speed of the colored photosensitive resin composition is lowered, and residues are easily generated.

(F) solvent

As long as the solvent contained in the colored photosensitive resin composition of the present invention is effective for dissolving other components contained in the colored photosensitive resin composition, a solvent commonly used in the art may be used without particular limitation.

As a specific example of the solvent, at least one selected from ethers, acetates, aromatic hydrocarbons, ketones, alcohols, esters, and amides may be used, but is not limited thereto.

The ether solvent is specifically ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether;

diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, and diethylene glycol dibutyl ether; and the like.

The acetate solvents are specifically ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate;

alkylene glycol alkyl ether acetates such as propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate, and methoxypentyl acetate; and the like.

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

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

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

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

3-ethoxy ethyl propionate, 3-methoxy methyl propionate, etc. are mentioned.

Specific examples of the amide solvent include dimethylformamide and dimethylacetamide.

The solvent may be more preferably an organic solvent having a boiling point of 100 to 200° C. in terms of applicability and dryness. More preferably, at least one selected from propylene glycol monoethyl ether acetate, cyclohexanone, ethyl lactate, butyl lactate, ethyl 3-ethoxypropionate, and methyl 3-methoxypropionate may be used.

The solvent is preferably included in an amount of 60 to 90 wt%, more preferably 70 to 85 wt%, based on the total weight of the colored photosensitive resin composition of the present invention. When the content of the solvent is within the range of 60 to 90 wt% based on the above-mentioned criteria, the application is performed using a roll coater, a spin coater, a slit and spin coater, a slit coater (sometimes referred to as a die coater), or an inkjet coating device. When it does, the effect that applicability|paintability becomes favorable can be provided.

(G) additives

The colored photosensitive resin composition of the present invention may contain additives such as dispersants, antioxidants, fillers, other high molecular compounds, curing agents, adhesion promoters, ultraviolet absorbers, and anti-aggregation agents, according to the needs of those skilled in the art, in the range that does not impair the purpose of the present invention on the above components. It is also possible to further include one or more additives selected from.

As a specific example of the antioxidant, commercially available products include ADK STAB AO-30, ADK STAB AO-40, ADK STAB AO-50F, ADK STAB AO-60, ADK STAB AO-80, ADK STAB 1178, ADK STAB from Adeka. TPP, ADK STAB 1500, ADK STAB 135A and ADK STAB 3010, and the like.

As a specific example of the filler, glass, silica, alumina, etc. may be used, but the present invention is not limited thereto.

Specific examples of the other high molecular compound include a curable resin such as an epoxy resin and a maleimide resin, a thermoplastic resin such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, polyester, polyurethane, etc. may be mentioned, but is not limited thereto.

The curing agent is used for deep curing and mechanical strength improvement, and specific examples thereof include, but are not limited to, an epoxy compound, a polyfunctional isocyanate compound, a melamine compound, and an oxetane compound.

Specifically, the epoxy compound is a bisphenol A-based epoxy resin, a hydrogenated bisphenol A-based epoxy resin, a bisphenol F-based epoxy resin, a hydrogenated bisphenol F-based epoxy resin, a novolak-type epoxy resin, other aromatic epoxy resins, alicyclic epoxy resins, gly Cidyl ester-based resins, glycidylamine-based resins, or brominated derivatives of these epoxy resins, aliphatic, alicyclic or aromatic epoxy compounds other than epoxy resins and brominated derivatives thereof, butadiene (co)polymer epoxide, isoprene (co) Polymer epoxide, glycidyl (meth) acrylate (co) polymer, triglycidyl isocyanurate, and the like may be used, but is not limited thereto.

Specifically, the oxetane compound may include carbonate bisoxetane, xylenebisoxetane, adipate bisoxetane, terephthalate bisoxetane, cyclohexanedicarboxylic acid bisoxetane, and the like, but is limited thereto. it is not

The curing agent may be used in combination with a curing auxiliary compound capable of ring-opening polymerization of the epoxy group of the epoxy compound and the oxetane skeleton of the oxetane compound together with the curing agent. Specifically, as the curing auxiliary compound, polyhydric carboxylic acids, polyhydric carboxylic acid anhydrides, acid generators, and the like may be used. As the carboxylic acid anhydride, a commercially available epoxy resin curing agent may be used. The commercially available epoxy resin curing agent includes, for example, a trade name (Adecahadona EH-700) (manufactured by Adeka Industrial Co., Ltd.), a trade name (Rikasiddo HH) (manufactured by Shin-Nippon Ewha Co., Ltd.), trade name (MH-700) (manufactured by Nippon Ewha Co., Ltd.); and the like.

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

The adhesion promoter is specifically, vinyltrimethoxysilane, vinyltriethoxysilane, vinyl tris(2-methoxyethoxy)silane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N -(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltri At least one selected from methoxysilane, 3-isocyanatepropyltrimethoxysilane and 3-isocyanatepropyltriethoxysilane may be used.

The adhesion promoter is preferably included in an amount of 0.01 to 10 wt%, more preferably 0.05 to 2 wt%, based on the total weight of the solid content in the composition.

Specifically, the UV absorber may include, but is not limited to, 2-(3-tert-butyl-2-hydroxy-5-methylphenyl)-5-chlorobenzotyrazole, alkoxybenzophenone, and the like.

The aggregation inhibitor may specifically include, but is not limited to, sodium polyacrylate.

<Color filter>

In order to achieve another object of the present invention, the present invention provides a color filter comprising a color layer formed by applying the colored photosensitive resin composition according to the present invention on a substrate, and exposing and developing it in a predetermined pattern. to provide.

The color filter of the present invention includes a substrate and a colored pattern made of the colored photosensitive resin composition of the present invention on the substrate. The substrate is a transparent material, and a material having sufficient strength and support for the stability of the color filter may be used. Preferably, a glass having excellent chemical stability and high strength may be used.

That is, the present invention provides a color filter including a colored pattern made of the colored photosensitive resin composition of the present invention, and a conventional method well known in the art may be used for the method of manufacturing the color filter.

Hereinafter, the present invention will be described in more detail using examples. However, the following examples are intended to illustrate the present invention, and the present invention is not limited by the following examples, and may be variously modified and changed within the scope of the present invention. The scope of the present invention will be determined by the technical spirit of the claims to be described later.

< Synthesis example > Synthesis of alkali-soluble resin

120 parts by weight of propylene glycol monomethyl ether acetate, 80 parts by weight of propylene glycol monomethyl ether, 2 parts by weight of Azobisisobutyronitrile (AIBN), 13.0 parts by weight of acrylic acid, 10 parts by weight of benzyl methacrylate, 57.0 parts by weight of 4-methylstyrene, 20 parts by weight of methyl methacrylate, and 3 parts by weight of n-dodecyl mercapto were added, followed by nitrogen substitution. Then, while stirring, the temperature of the reaction solution was raised to 110° C. and reacted for 6 hours. The alkali-soluble resin thus synthesized had a solid content acid value of 100.2 mgKOH/g, and a weight average molecular weight Mw measured by GPC of about 15,110.

< production example >

Preparation of pigment dispersion composition

<Pigment dispersion composition M1>

As a colorant combined with at least one insolubilizing agent selected from phosphotungstic acid and molybdic acid, C.I. Pigment Blue 14 12.0 parts by weight, LPN-6919 (manufactured by BYK) 6.0 parts by weight as a dispersant, and 80.0 parts by weight of propylene glycol methyl ether acetate as a solvent were mixed and dispersed for 12 hours by a bead mill to prepare a pigment dispersion composition M1.

<Pigment dispersion composition M2>

As a colorant, C.I. Pigment Blue 15:6 12.0 parts by weight, 6.0 parts by weight of LPN-6919 (manufactured by BYK) as a dispersant, and 80.0 parts by weight of propylene glycol methyl ether acetate as a solvent were mixed and dispersed by a bead mill for 12 hours to prepare a pigment dispersion composition M2 did

Preparation of colored photosensitive resin composition

A colored photosensitive resin composition was prepared by combining the compositions and contents described in Examples 1 to 2 and Comparative Examples 1 to 5 below.

< Example 1>

25.00 parts by weight of the pigment dispersion composition M1, 13.36 parts by weight of the resin of the above synthesis example, 4.45 parts by weight of KAYARAD DPHA (Nippon Kayaku) as a photopolymerizable compound, PSS-(3-Glycidyl) propoxy as a silsesquioxane-based compound -Heptaisobutyl substituted (Aldrich) 0.27 parts by weight, PBG-327 (Tronly) 1.34 parts by weight as a photopolymerization initiator, 17.00 parts by weight of diacetone alcohol, and 38.58 parts by weight of propylene glycol monomethyl ether acetate were mixed to prepare a colored photosensitive resin composition did

< Example 2>

12.50 parts by weight of the pigment dispersion M1, 12.50 parts by weight of the pigment dispersion M2, 13.36 parts by weight of the resin of the above synthesis example, 4.45 parts by weight of KAYARAD DPHA (Nippon Kayaku) as a photopolymerizable compound, silsesquioxane-based compound 0.27 parts by weight of PSS-(3-Glycidyl)propoxy-Heptaisobutyl substituted (Aldrich), 1.34 parts by weight of PBG-327 (manufactured by Tronly) as a photopolymerization initiator, 17.00 parts by weight of diacetone alcohol, 38.58 parts by weight of propylene glycol monomethyl ether acetate The parts were mixed to prepare a colored photosensitive resin composition.

< comparative example 1>

25.00 parts of the pigment dispersion composition M1, 13.36 parts by weight of the resin of the above synthesis example, 4.45 parts by weight of KAYARAD DPHA (Nippon Kayaku) as a photopolymerizable compound, 1.34 parts by weight of PBG-327 (manufactured by Tronly) as a photopolymerization initiator, 17.00 parts by weight of diacetone alcohol A colored photosensitive resin composition was prepared by mixing 38.58 parts by weight of propylene glycol monomethyl ether acetate by weight.

< comparative example 2>

12.50 parts by weight of the pigment dispersion composition M1, 12.50 parts by weight of the pigment dispersion composition M2, 13.36 parts by weight of the resin of the above synthesis example, 4.45 parts by weight of KAYARAD DPHA (Nippon Kayaku) as a photopolymerizable compound, PBG-327 (manufactured by Tronly) as an initiator ) 1.34 parts by weight, 17.00 parts by weight of diacetone alcohol, and 38.58 parts by weight of propylene glycol monomethyl ether acetate were mixed to prepare a colored photosensitive resin composition.

< comparative example 3>

25.00 parts by weight of the pigment dispersion composition M1, 13.36 parts by weight of the resin of the above synthesis example, 4.45 parts by weight of KAYARAD DPHA (Nippon Kayaku) as a photopolymerizable compound, PSS-(3-Glycidyl) propoxy as a silsesquioxane-based compound -Heptaisobutyl substituted (Aldrich) 0.27 parts by weight, 1.34 parts by weight of Irgacure® 369 (BASF) as a photopolymerization initiator, 17.00 parts by weight of diacetone alcohol, and 38.58 parts by weight of propylene glycol monomethyl ether acetate were mixed to prepare a colored photosensitive resin composition did

< comparative example 4>

12.50 parts by weight of the pigment dispersion M1, 12.50 parts by weight of the pigment dispersion M2, 13.36 parts by weight of the resin of the above synthesis example, 4.45 parts by weight of KAYARAD DPHA (Nippon Kayaku) as a photopolymerizable compound, silsesquioxane-based compound 0.27 parts by weight of PSS-(3-Glycidyl)propoxy-Heptaisobutyl substituted (Aldrich), 1.34 parts by weight of Irgacure® 369 (BASF) as a photopolymerization initiator, 17.00 parts by weight of diacetone alcohol, 38.58 parts by weight of propylene glycol monomethyl ether acetate The parts were mixed to prepare a colored photosensitive resin composition.

< comparative example 5>

25.00 parts by weight of the pigment dispersion composition M2, 13.36 parts by weight of the resin of the above synthesis example, 4.45 parts by weight of KAYARAD DPHA (Nippon Kayaku) as a photopolymerizable compound, PSS-(3-Glycidyl) propoxy as a silsesquioxane-based compound -Heptaisobutyl substituted (Aldrich) 0.27 parts by weight, PBG-327 (Tronly) 1.34 parts by weight as a photopolymerization initiator, 17.00 parts by weight of diacetone alcohol, and 38.58 parts by weight of propylene glycol monomethyl ether acetate were mixed to prepare a colored photosensitive resin composition did

< Experimental example >

Experimental example 1. Adhesion evaluation

A color filter was prepared using the colored photosensitive resin composition prepared in Examples 1 to 2 and Comparative Examples 1 to 5.

Specifically, each of the colored photosensitive resin compositions was coated on a 2-inch square glass substrate ("EAGLE XG", manufactured by Corning) by spin coating, placed on a heating plate, and maintained at a temperature of 100° C. for 3 minutes to form a thin film made it Then, a test photomask having a line/space pattern of 1 µm to 100 µm was placed on the thin film, and ultraviolet rays were irradiated with an interval of 300 µm from the test photomask. At this time, the UV light source was irradiated at 50 mJ/cm ² using a 1KW high-pressure mercury lamp containing all of the g, h, and i lines, and no special optical filter was used. The thin film irradiated with ultraviolet light was developed by immersing it in a developing solution of a KOH aqueous solution having a pH of 10.5 for 2 minutes. The glass plate coated with the thin film was washed with distilled water, dried by blowing nitrogen gas, and heated in a heating oven at 230° C. for 25 minutes to prepare a color filter.

At this time, the generated pattern was evaluated for tearing on the pattern as follows using an optical microscope, and the results are shown in Table 1 below.

<Adhesiveness evaluation criteria>

○: No tearing in pattern

△: 1-4 pieces torn in pattern

×: 5 or more torn patterns

Experimental example 2. Transmittance evaluation

Except that the test photomask was not used, a color filter was prepared in the same manner as in Experimental Example 1, and transmittance was measured using a colorimeter (manufactured by Olympus, OSP-200). The results are shown in Table 1 below.

Experimental example 3. solvent resistance evaluation

A substrate was prepared in the same manner as in Experimental Example 2, and the color coordinates of the substrate, whose chromaticity and transmittance were measured, were measured with a colorimeter (manufactured by Olympus, OSP-200). The substrate on which the color coordinate measurement was completed was immersed in N-methylpyrrolidone at 90° C. for 2 minutes. After taking out the substrate, it was washed with distilled water to measure the chromaticity again, and the color difference before and after immersion in N-methylpyrrolidone was calculated as ΔE*ab, and evaluated according to the following criteria.

<Equation 1>

<Evaluation criteria>

○: ΔE*ab is 3.0 or less

Δ: ΔE*ab greater than 3.0 to 5.0 or less

X: ΔE*ab greater than 5.0

division transmittance solvent resistance adhesion Example 1 10.30 ○ ○ Example 2 10.01 ○ ○ Comparative Example 1 10.32 Ⅹ ○ Comparative Example 2 10.05 △ ○ Comparative Example 3 10.18 Ⅹ Ⅹ Comparative Example 4 9.94 △ △ Comparative Example 5 9.72 ○ ○

As can be seen from the results in Table 1, the compositions of Examples 1 and 2 corresponding to the compositions of the present invention showed excellent results in reliability and adhesion evaluation such as transmittance and solvent resistance.

On the other hand, Comparative Examples 1 to 5 showed poor results in one or more of the above evaluations.

In detail, Comparative Examples 1 and 2 not including the silsesquioxane-based compound had poor solvent resistance evaluation results. In the case of Comparative Examples 3 to 4 not containing the oxime ester-based photopolymerization initiator, the evaluation of solvent resistance and adhesion was poor.

In addition, in the case of Comparative Example 5, which did not include a pigment or dye combined with at least one insolubilizing agent selected from phosphotungstic acid and molybdic acid, the transmittance was poor.

Claims (8)

A colorant, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, a silsesquioxane-based compound represented by the following formula (1) and a solvent,
the colorant comprises a pigment or dye combined with at least one insolubilizing agent selected from phosphotungstic acid and molybdic acid;
The photopolymerization initiator is a colored photosensitive resin composition comprising an oxime ester-based photopolymerization initiator:

<Formula 1>

In Formula 1, R ₁ and R ₂ are each independently one or more groups selected from Formulas 1-1 to 1-12 and Formulas 1-14 to 1-17.

The method according to claim 1,
with respect to the total weight of solids in the composition,
The pigment or dye combined with at least one insolubilizing agent selected from phosphotungstic acid and molybdic acid is contained in an amount of 5 to 40% by weight of the colored photosensitive resin composition. The method according to claim 1,
The oxime ester-based photopolymerization initiator is a colored photosensitive resin composition, characterized in that it is included in an amount of 10 to 100% by weight based on the total weight of the photopolymerization initiator. The method according to claim 1,
with respect to the total weight of solids in the composition
The colored photosensitive resin composition, characterized in that the silsesquioxane-based compound of Formula 1 is included in an amount of 1 to less than 10 wt%. delete The method according to claim 1,
Colored photosensitive resin composition, characterized in that it further comprises one or more additives selected from dispersants, antioxidants, fillers, other high molecular compounds, curing agents, adhesion promoters, ultraviolet absorbers and anti-aggregation agents. The method according to claim 1,
with respect to the total weight of solids in the composition
5 to 50% by weight of a colorant, 10 to 80% by weight of an alkali-soluble resin, 5 to 45% by weight of a photopolymerizable compound, and 5 to 40% by weight of a photoinitiator includes;
A colored photosensitive resin composition comprising 60 to 90 wt% of a solvent based on the total weight of the composition. A color filter manufactured using the colored photosensitive resin composition of claim 1.