KR20190075393A - Colored photosensitive composition, color filter and image display device - Google Patents

Abstract

The present invention relates to a colored photosensitive composition comprising: an alkali-soluble resin including at least two resins, wherein the resin has the glass transition temperature of less than 0°C; a colorant; and a solvent. A colored pattern which prevents film shrinkage and improves mechanical reliability is formed from the colored photosensitive composition.

Description

TECHNICAL FIELD [0001] The present invention relates to a colored photosensitive composition, a color filter, and an image display device.

The present invention relates to a colored photosensitive composition, a color filter, and an image display device. More particularly, the invention relates to a colored photosensitive composition, a color filter formed therefrom, and an image display device including the color filter.

For example, in an image display device such as a liquid crystal display (LCD) device using a separate light source such as a backlight, a color filter is used to realize a desired color for each pixel. The color filter may be formed by applying and patterning a photosensitive composition containing a colorant corresponding to each pixel of RGB. The colorant may comprise a dye and / or pigment and may have absorbing or absorbing properties for a particular wavelength.

In recent years, as the color reproduction characteristics of high resolution and high luminance are required, it is necessary to increase the content of the coloring agent. In this case, wrinkles and shrinkage of the film or pattern may occur during application and curing of the photosensitive composition, and mechanical properties such as a decrease in curability may be lowered.

In order to improve the process reliability at the time of forming the insulating film included in the image display apparatus in recent years, for example, a low temperature curing process of about 200 DEG C or less has been adopted. However, in the case of the low-temperature curing, adherence may be reduced due to insufficient curing, and pattern defects due to lack of sensitivity may be caused.

Therefore, it is necessary to develop a colored photosensitive composition for forming a colored pattern with high color reproducibility and high reliability even through low-temperature curing.

For example, Korean Patent Laid-Open No. 10-2009-0072754 discloses a composition for a color filter containing a pigment and a binder resin, but has limitations in satisfying both of the above-described high resolution color characteristics and mechanical properties.

Korean Patent Publication No. 10-2009-0072754

An object of the present invention is to provide a colored photosensitive composition having improved color reproduction characteristics and film-forming properties.

An object of the present invention is to provide a color filter formed from the colored photosensitive composition and having improved color reproduction characteristics and mechanical reliability.

An object of the present invention is to provide an image display device including the color filter.

1. A colored photosensitive composition comprising an alkali-soluble resin comprising at least two resins and a resin having a glass transition temperature of less than 0 占 폚, a colorant and a solvent.

2. The colored photosensitive composition of 1 above, wherein the alkali-soluble resin comprises a first resin having a glass transition temperature of less than 0 ° C and a second resin having a glass transition temperature different from that of the first resin.

3. The colored photosensitive composition according to 2 above, wherein the glass transition temperature difference between the first resin and the second resin is 30 DEG C or lower.

4. The colored photosensitive composition according to 2 above, wherein the first resin comprises a repeating unit represented by the following formula (1)

[Chemical Formula 1]

(Wherein R ₁ is hydrogen or a methyl group, and R ₂ is an alkyl group having 1 to 12 carbon atoms)

5. The colored photosensitive composition according to 4 above, wherein R < _{2 >} is a non-cyclic alkyl group.

6. The colored photosensitive composition according to 4 above, wherein the first resin or the second resin comprises a reactive repeating unit represented by the following formula (2):

(2)

(Wherein R ₃ is hydrogen or a methyl group).

7. The colored photosensitive composition according to 6 above, wherein the first resin or the second resin further comprises an aryl ring-containing unit or a carboxylic acid-containing unit.

8. The colored photosensitive composition according to 2 above, wherein the content of the first resin in the total weight of the alkali-soluble resin is 30% by weight or more.

9. A color filter comprising a coloring pattern formed from a colored photosensitive composition according to any one of claims 1 to 8.

10. An image display device comprising the above 9 color filters.

The colored photosensitive compositions according to embodiments of the present invention may include at least two alkali-soluble resins having different glass transition temperatures (Tg). The colored photosensitive composition includes an alkali-soluble resin having a glass transition temperature of less than 0 캜, whereby the flowability and coating property of the composition can be improved. Therefore, even when the content of the colorant is increased, film shrinkage and wrinkling can be prevented and a uniform coating film can be formed.

The glass transition temperature difference between any of the resins contained in the alkali-soluble resins contained in the colored photosensitive composition may be 30 DEG C or less. Therefore, it is possible to prevent deterioration of the pattern property due to the glass transition temperature deviation between the resins, and to secure the mechanical characteristics of the coloring pattern such as hardness, hardness, adhesion and the like.

By using the colored photosensitive composition, an image display device (for example, an LCD device) including the color filter of high luminance and high reliability and the color filter can be manufactured.

According to embodiments of the present invention, there is provided an ink composition comprising an alkali-soluble binder having at least two alkali-soluble resins having different glass transition temperatures (Tg) and having a glass transition temperature of less than 0 ° C, An improved colored photosensitive composition is provided. Further, a color filter and an image display device formed from the colored photosensitive composition are provided.

Hereinafter, embodiments of the present invention will be described in detail.

≪ Coloring Photosensitive composition >

The colored photosensitive composition according to the embodiments of the present invention may be a resin composition having developability. According to exemplary embodiments, the colored photosensitive composition may include an alkali-soluble resin, a colorant, and a solvent. In some embodiments, the colored photosensitive composition may further include a photopolymerization initiator, and may further include a photopolymerizable compound, other additives, and the like.

Alkali-soluble resin

The colored photosensitive composition may be used for forming a resin pattern through an exposure and development process, and may include an alkali-soluble resin that can be selectively removed by the developing process. The alkali-soluble resin may be provided as a binder resin of the colored photosensitive composition. For example, the alkali-soluble resin may include a negative tone photosensitive resin.

According to exemplary embodiments, the alkali-soluble resin may comprise at least two resins having different glass transition temperatures. At least one of the at least two resins may be a resin having a glass transition temperature of less than 0 ° C. Hereinafter, the resin having a glass transition temperature of less than 0 ° C is referred to as a first resin.

In some embodiments, the first resin may include a repeating unit having a structure represented by the following formula (1).

[Chemical Formula 1]

In the above formula (1), R ₁ may be hydrogen or a methyl group. R ₂ may be an alkyl group having 1 to 12 carbon atoms. R ₂ may be a linear or branched alkyl group and may contain heteroatoms (O, S or N) in the chain. In some embodiments, R ₂ may be a non-cyclic (non-nitrogen) alkyl group.

For example, the repeating unit of the above formula (1) may be derived from the monomer of the following formula (1-1).

[Formula 1-1]

In exemplary embodiments, R ₂ may be provided as a unit of adjustment of the glass transition temperature of the first resin.

For example, the longer the chain length of R ₂ , the lower the glass transition temperature of the first resin, and the flowability and coatability of the colored photosensitive composition can be improved.

Therefore, even when the amount of the coloring agent to be described later is increased, the film properties of the colored photosensitive composition can be maintained or improved to suppress film wrinkling and shrinkage.

In some embodiments, the glass transition temperature of the first resin is less than 0 占 폚, and may be greater than or equal to -30 占 폚. If the glass transition temperature of the first resin is less than -30 占 폚, the mechanical reliability (adhesion, hardness, etc.) of the coating film or pattern formed from the colored photosensitive composition may be excessively deteriorated.

The alkali-soluble resin may further comprise a resin different from the first resin. Hereinafter, the resin different from the first resin is referred to as a second resin.

According to exemplary embodiments, the second resin has a glass transition temperature different from that of the first resin, and the difference (based on the absolute value) of the glass transition temperature of the first resin and the second resin is 30 占 폚 or less have. If the glass transition temperature difference exceeds 30 占 폚, film shrinkage due to an increase in difference in hardness, hardness, etc. of the resins may be intensified.

The second resin may be included with the first resin to improve the mechanical reliability of the coating or pattern formed from the colored photosensitive composition. As described above, the flowability and coating property of the colored photosensitive composition can be ensured through the first resin, and the curing property and adhesion can be complemented through the second resin.

In one embodiment, the second resin may have a higher glass transition temperature than the first resin. In one embodiment, the second resin may have a glass transition temperature of 0 ° C or higher.

In exemplary embodiments, the second resin may include a reactive repeating unit represented by the following formula (2).

(2)

In the formula (2), R ₃ may be hydrogen or a methyl group. The repeating unit of the above-mentioned formula (2) contains a terminal (meth) acrylate group, so that it is possible to impart photocuring or thermosetting properties. Further, the adhesion of the coating film or pattern and the reactivity with the developing solution can be improved by the hydroxyl group contained in the repeating unit of the formula (2).

In some embodiments, the second resin may further comprise an aryl ring containing unit and / or a carboxylic acid containing unit. In this case, the adhesion to the substrate through the second resin and the heat resistance of the pattern can be further improved.

For example, the aryl ring-containing unit may be derived from a monomer of the following formula (3).

(3)

In Formula 3, R ₄ may be a hydrogen atom, or an alkoxy group having 1 to 6 carbon atoms, an alkyl group having 1 to 6 carbon atoms, or a cycloalkyl group having 4 to 8 carbon atoms.

For example, the carboxylic acid containing unit may be derived from a monomer such as acrylic acid or methacrylic acid.

In some embodiments, the first resin may also include a repeating unit represented by the formula (2), in which case the first resin may also exhibit curing reactivity. In one embodiment, the first resin may also comprise the aryl ring containing unit and / or the carboxylic acid containing unit.

In some embodiments, the second resin may also include a repeating unit of the above-described formula (1).

The content of the alkali-soluble resin is not particularly limited and may be, for example, about 5 to 50% by weight, and preferably about 10 to 20% by weight, based on the total weight of the composition. When the content of the alkali-soluble resin is less than about 5% by weight, pattern reliability and adhesion may be excessively lowered. When the content of the alkali-soluble resin is more than about 50% by weight, the viscosity of the composition may excessively increase and the coating property may be deteriorated.

Among the total weight of solids of the alkali-soluble resin, the content of the first resin may be about 30 wt%, preferably about 40 wt% or more. If the content of the first resin is less than about 30% by weight, the film shrinkage preventing effect may not be sufficiently realized when the content of the colorant is increased.

In some embodiments, the resins included in the alkali-soluble resin may all have a glass transition temperature of less than 0 ° C. In this case, the resin having the lowest glass transition temperature may be referred to as a first resin, and the glass transition temperature difference between the first resin and the other resin may be 30 캜 or less.

The alkali-soluble resin may be polymerized by further using at least one other monomer copolymerizable with the repeating unit or monomer described above. Non-limiting examples of such other monomers include styrene, vinyl toluene, methyl styrene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o- vinylbenzyl methyl ether, Aromatic vinyl compounds such as benzyl methyl ether, p-vinylbenzyl 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-based compounds such as methylphenyl maleimide, Np-methylphenyl maleimide, No-methoxyphenyl maleimide, Nm-methoxyphenyl maleimide and Np-methoxyphenyl maleimide; 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; (Meth) acrylate such as cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, 2-dicyclopentanyloxyethyl (Meth) acrylates; Aryl (meth) acrylates such as phenyl (meth) acrylate and benzyl (meth) acrylate; 3- (methacryloyloxymethyl) -2-trifluoromethyl oxetane, 3- (methacryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) 2- (methacryloyloxymethyl) oxetane, 2- (methacryloyloxymethyl) -4-trifluoromethyloxetane, and the like Unsaturated oxetane compounds; Unsaturated oxiranes such as glycidyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate and methyl glycidyl Compounds and the like. These may be used alone or in combination of two or more.

For example, the acid value of the alkali-soluble resin may be about 20 to 200 (KOH mg / g). The solubility in the developing solution can be improved in the acid value range, and thus the pattern resolution can be increased. And may be about 30 to 150 (KOH mg / g) in view of proper development, pattern characteristics, stability of the colorant, and the like.

The weight average molecular weight of the alkali-soluble resin (for example, Mw in terms of polystyrene measured by gel permeation chromatography (GPC)) may be about 3,000 to 50,000, preferably 3,000 to 10,000. The film loss and pattern stability in the developing process can be improved within the above molecular weight range.

The molecular weight distribution (weight average molecular weight (Mw) / number average molecular weight (Mn)) of the alkali-soluble resin may be about 1.5 to 6.0, preferably about 1.8 to 4.0 in consideration of development and pattern stability.

coloring agent

The colored photosensitive compositions according to exemplary embodiments may include at least one pigment, dye or mixtures thereof as a colorant.

The pigment may be an organic pigment or an inorganic pigment generally used in the art. Specific examples of the organic pigments include water-soluble azo pigments, insoluble azo pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, isoindolin pigments, perylene pigments, perinone pigments, Anthraquinone pigments, anthraquinone pigments, anthrapyrimidine pigments, anthanthrone pigments, indanthrone pigments, pravantron pigments, pyranthrone pigments, diketopyrrolopyrroles, Pigments, and the like.

The inorganic pigments may include metal compounds such as metal oxides and metal complex salts and may be oxides or complexes of metals such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, Metal oxides and the like.

As a specific example, the organic pigments and inorganic pigments include compounds classified as pigments in the color index (The society of Dyers and Colourists), and pigments of the color index (CI) number listed below can be used have.

The above C.I. Pigment pigments and the like, for example, C.I. Pigment Yellow 138, C.I. Pigment Yellow 139, C.I. Pigment Yellow 150, C.I. Pigment Yellow 185, C.I. Pigment Orange 38, C.I. Pigment Red 122, C.I. Pigment Red 166, C.I. Pigment Red 177, C.I. Pigment Red 208, C.I. Pigment Red 242, C.I. Pigment Red 254, C.I. Pigment Red 255, C.I. Pigment Violet 23, C.I. Pigment Blue 15: 3, Pigment Blue 15: 6, C.I. Pigment Green 7, C.I. Pigment Green 36, C.I. Pigment Green 58 and the like can be used. These may be used alone or in combination of two or more.

The examples of the above pigments are merely illustrative, and appropriate ones can be selected and combined in consideration of the desired chromaticity.

In some embodiments, a pigment dispersant may be included together for uniform dispersion of the pigment in the composition. For example, the pigment dispersion may be dispersed in the pigment dispersant to form a pigment dispersion having a uniform particle diameter, and the pigment dispersion may be mixed with the colored photosensitive composition.

Examples of the pigment dispersant include an acrylate-based dispersant such as BMA (butyl methacrylate) or DMAEMA (N, N-dimethylaminoethyl methacrylate), a polyester dispersant, a polyamine dispersant, a (meth) Styrene copolymers, resin type surfactants such as (meth) acrylic acid- (meth) acrylate ester copolymers, styrene-maleic acid copolymers, polyvinyl alcohol or polyvinylpyrrolidone. These may be used alone or in combination of two or more.

The dye may be selected in consideration of solubility and solvent resistance to an organic solvent and an alkaline developer, stability with time, and the like.

As the dye, an acidic dye having an acidic group such as a sulfonic acid or a carboxylic acid or a derivative thereof, an azoic acid, a xanthene-based acid, a phthalocyanine-based acidic dye or a derivative thereof may be used.

Such dyes may include, for example, compounds classified as dyes in the color index (The Society of Dyers and Colourists publication), or known dyes described in dyeing notes (color dyes).

Specific examples of the dye include C.I. Solvent series, also C.I. Acid series, C.I. Direct series, C.I. And dendritic dyes, which may be used alone or in combination of two or more.

The content of the colorant is not particularly limited, but may be about 3 to 60% by weight, preferably 5 to 50% by weight, based on the total weight of the solid matter of the colored photosensitive resin composition. The desired color reproducibility can be realized without causing the coloring agent to flow out in the above range.

Photopolymerizable compound

In some exemplary embodiments, the colored photosensitive composition may further comprise a photopolymerizable compound as an additional monomer, for example, to further crosslink or polymerize by the exposure process to improve the mechanical characteristics of the color pattern.

The photopolymerizable compound may be a monofunctional monomer, a bifunctional monomer or a polyfunctional monomer, and a bifunctional or higher functional monomer may be used for realizing sufficient curing characteristics.

Examples of the monofunctional monomer include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate, N-vinylpyrrolidone And the like. Examples of bifunctional monomers include 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, bisphenol A (Acryloyloxyethyl) ether, 3-methylpentanediol di (meth) acrylate, and the like.

Examples of other multifunctional monomers include trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, pentaerythritol tri Acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, ethoxylated dipentaerythritol hexa (meth) acrylate, propoxylated dipentaerythritol hexa (Meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like. These may be used alone or in combination of two or more.

The content of the photopolymerizable compound may be, for example, about 5 to 50% by weight based on the total weight of the solid composition. Within the above range, the strength and mechanical reliability of the color pattern can be improved without lowering the color reproducibility of the colorant, and preferably about 7 to 45% by weight.

Photopolymerization initiator

When the above-mentioned photopolymerizable compound is included, the colored photosensitive composition may further include a photopolymerization initiator to induce crosslinking or polymerization of the photopolymerizable compound by an exposure process.

For example, the photopolymerization initiator may be at least one compound selected from an acetophenone compound, a benzoin compound, a benzophenone compound, a triazine compound, a nonimidazole compound, a thioxanthone compound, an oxime ester compound, . ≪ / RTI > Preferably, the photopolymerization initiator may include an acetopetone-based compound.

Examples of the acetophenone-based compounds include diethoxyacetophenone, 2-methyl-2-morpholino-1- (4-methylthiophenyl) propan- 1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, (1-methylvinyl) phenyl] propane-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy- On oligomers and the like.

The content of the photopolymerization initiator may be, for example, about 1 to 30% by weight, preferably about 1 to 20% by weight, based on the total weight of the composition. The sensitivity to the exposure process can be increased without hindering the color reproduction characteristics of the colorant within the above range.

In one embodiment, a photopolymerization assistant may be used together with the photopolymerization initiator to promote the progress of polymerization after polymerization is initiated by the photopolymerization initiator. The photopolymerization assistant may include, for example, an amine compound or an alkoxyanthracene compound.

Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, Dimethylaminobenzoic acid, 2-ethylhexyl 4-dimethylaminobenzoate, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzophenone (Michler's ketone), 4,4'- , 4,4'-bis (ethylmethylamino) benzophenone, and the like.

Examples of the alkoxyanthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, .

Other additives

In some embodiments, the colored photosensitive composition may further include an additive for improving film properties such as coatability, adhesion, hardness, and the like. For example, other polymer compounds, a curing agent, a surfactant, an adhesion promoter, an antioxidant, an ultraviolet absorber, an anti-aggregation agent and the like may be added.

The other polymeric compound may be added in consideration of the hardness and adhesion of the color pattern, and examples thereof include thermosetting resins such as epoxy resin and maleimide resin, polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, A thermoplastic resin such as polyacrylate, polyacrylate, polyester, polyurethane, and the like.

The curing agent may be included for enhancing the strength through deep curing of the coloring pattern, and examples thereof include an epoxy compound, a polyfunctional isocyanate compound, a melamine compound, and an oxetane compound.

As the surfactant, a silicone surfactant, a fluorinated surfactant, a silicon surfactant having a fluorine atom, and the like can be used.

As the wetting agent, for example, glycerin, diethylene glycol, ethylene glycol and the like can be used.

Specific examples of the adhesion promoter include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- Aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- ( 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3- 3-isocyanatopropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, and the like.

Examples of the antioxidant include 2,2'-thiobis (4-methyl-6-t-butylphenol) and 2,6-di-t-butyl-4-methylphenol. Examples of the ultraviolet absorber include 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzothiazole and alkoxybenzophenone. Examples of the anti-aggregation agent include polyacrylic acid or a salt thereof.

solvent

The solvent may include an organic solvent which sufficiently dissolves the photopolymerizable compound and the alkali-soluble resin described above and does not cause precipitation of the colorant.

Examples of the solvent include glycol ethers, alcohols (methanol, ethanol, isopropanol, butanol, propylene glycol methoxy alcohol and the like), ketones (methyl ethyl ketone, methyl butyl ketone, methyl isobutyl ketone, diethyl ketone, di Methylcellosolve, ethylcellosolve and propylcellosolve), hydrocarbons (n-hexane, n-octane, n-hexane and the like) Esters such as ethyl acetate, methyl 3-methoxypropionate, and gamma-butyrolactone may be used. These solvents may be used alone or in combination of two or more kinds thereof. Can be used in combination.

An organic solvent having a boiling point of 100 占 폚 to 200 占 폚 may be used in consideration of the coating property and the drying property, and preferably an organic solvent such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, ethyl lactate, Ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, and the like can be used.

The solvent may be included in the balance excluding the components of the above-mentioned composition, for example, about 60 to 90% by weight of the total weight of the composition. When the above range is satisfied, a coating film can be easily formed through a coating method using a spin coater, a slit-and-spin coater, a slit coater, a die coater, a curtain flow coater, an ink jet or the like.

≪ Color filter and image display device >

A coloring pattern can be formed using the above-described colored photosensitive composition, and the coloring pattern can be used, for example, as a color filter of an image display device, as described later.

According to exemplary embodiments, for example, a black matrix may be formed on a glass substrate to define a pixel region for each color. Thereafter, the colored photosensitive composition is applied and cured on the glass substrate and the black matrix to form a pre-colored film.

In exemplary embodiments, the curing process may be performed at a temperature of about 200 ° C or less, or about 150 ° C or less. Since the colored photosensitive composition includes the first resin and the second resin according to the above-mentioned glass transition temperature, sufficient mechanical reliability can be realized even through the curing process at the low temperature condition.

Thereafter, the preliminary coloring film is exposed and developed to form a coloring pattern corresponding to each pixel.

The exposure process may include ultraviolet exposure using a mask that selectively exposes the pixel region. Thereafter, the colored pattern can be formed by selectively removing the non-exposed region using a developing solution.

The developing solution may contain, for example, an inorganic or organic alkaline compound. Examples of the inorganic alkaline compound include sodium hydroxide, potassium hydroxide, disodium hydrogen phosphate, sodium dihydrogen phosphate, ammonium dihydrogen phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, sodium silicate, potassium silicate, sodium carbonate, , Potassium hydrogencarbonate, sodium borate, potassium borate, and ammonia. Examples of the organic alkaline compound include tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropyl Amine, diisopropylamine, ethanolamine, and the like. These may be used alone or in combination of two or more.

After the development step, a post-baking process may be performed at, for example, 150 to 230 ° C.

Thereafter, an overcoat layer covering the black matrix and the coloring patterns may be formed, and an electrode layer may be formed on the overcoat layer. The electrode layer is formed using, for example, a transparent conductive oxide such as indium tin oxide (ITO), and may be provided as a common electrode of an image display device described later.

By the above processes, a color filter including a coloring pattern can be manufactured. As described above, even when the content of the colorant is increased by using the alkali-soluble resin satisfying the glass transition temperature condition, it is possible to form a color filter having high color reproducibility and high brightness with suppressed film shrinkage.

According to exemplary embodiments, an image display apparatus including the color filter is provided. In some embodiments, the image display device may be an LCD device including a backlight.

The LCD device may include a lower substrate on which a backlight unit, a lower polarizer, and a TFT array substrate are sequentially stacked. A pixel electrode is formed on the lower substrate, and a liquid crystal layer may be formed on the TFT array substrate on which the pixel electrode is formed.

Then, the above-described color filter can be disposed so as to face the TFT array substrate with the liquid crystal layer interposed therebetween. For example, the color filter may be laminated such that the electrode layer faces the pixel electrode.

An upper polarizer, a protective substrate, and the like may be stacked on the color filter.

In some embodiments, the color filter may be applied to a white organic light emitting diode (Whited OLED) device. For example, the color filter can be laminated on a white OLED element substrate, and the light resistance of the OELD to self-emission can also be improved.

Although the color filter using the colored photosensitive composition is exemplarily described, the colored photosensitive composition may be used for forming various insulating structures included in an image display device such as a black matrix, a spacer, and a pixel defining layer depending on the type of the colorant .

Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings. However, the present invention is not limited by the scope of the appended claims, It will be apparent to those skilled in the art that various changes and modifications can be made in the embodiments within the scope of the claims, and such variations and modifications are within the scope of the appended claims.

Experimental Example

Synthesis Example 1: Synthesis of alkali-soluble resin (A-1)

A flask equipped with a stirrer, a thermometer reflux condenser, a dropping funnel and a nitrogen inlet tube was charged with 120 parts of propylene glycol monomethyl ether acetate, 80 parts of propylene glycol monomethyl ether, 2 parts of AIBN, 10 parts of ethylhexyl methacrylate, 30 parts of methacrylate, 35 parts of acrylic acid and 25 parts of glycidyl methacrylate were charged and replaced with nitrogen. Thereafter, the temperature of the reaction solution was raised to 80 DEG C with stirring, and the reaction was carried out for 8 hours. Thereafter, the temperature of the reaction solution was lowered to room temperature. Through the above-described process, an alkali-soluble resin having a Tg of -4 캜, a solid content of 35.2 mgKOH / g and a weight-average molecular weight Mw of about 3560 as measured by GPC was obtained.

Synthesis Example 2: Synthesis of alkali-soluble resin (A-2)

A flask equipped with a stirrer, a thermometer reflux condenser, a dropping funnel and a nitrogen inlet tube was charged with 120 parts of propylene glycol monomethyl ether acetate, 80 parts of propylene glycol monomethyl ether, 2 parts of AIBN, 25 parts of ethylhexyl methacrylate, 25 parts of decylmethacrylate, 30 parts of acrylic acid and 20 parts of glycidyl methacrylate were charged and replaced with nitrogen. Thereafter, the temperature of the reaction solution was raised to 80 DEG C with stirring, and the reaction was carried out for 8 hours. Thereafter, the temperature of the reaction solution was lowered to room temperature. Through the above-mentioned process, an alkali-soluble resin having a Tg of -14 캜, a solid content of 32.0 mgKOH / g and a weight-average molecular weight Mw of about 3420 as measured by GPC was obtained.

Synthesis Example 3: Synthesis of alkali-soluble resin (A-3)

A flask equipped with a stirrer, a thermometer reflux condenser, a dropping funnel and a nitrogen inlet tube was charged with 120 parts of propylene glycol monomethyl ether acetate, 80 parts of propylene glycol monomethyl ether, 2 parts of AIBN, 25 parts of lauryl methacrylate, 25 parts of methacrylate, 30 parts of acrylic acid and 20 parts of glycidyl methacrylate were charged and replaced with nitrogen. Thereafter, the temperature of the reaction solution was raised to 80 DEG C with stirring, and the reaction was carried out for 8 hours. Thereafter, the temperature of the reaction solution was lowered to room temperature. Through the above-mentioned process, an alkali-soluble resin having a Tg of -28 캜, a solid content of 33.4 mgKOH / g and a weight-average molecular weight Mw of about 3658 as measured by GPC was obtained.

Synthesis Example 4: Synthesis of alkali-soluble resin (A-4)

A flask equipped with a stirrer, a thermometer reflux condenser, a dropping funnel and a nitrogen inlet tube was charged with 120 parts of propylene glycol monomethyl ether acetate, 80 parts of propylene glycol monomethyl ether, 2 parts of AIBN, 25 parts of styrene, 25 parts of acrylic acid, 30 parts of acrylic acid and 20 parts of glycidyl methacrylate were charged and replaced with nitrogen. Thereafter, the temperature of the reaction solution was raised to 80 DEG C with stirring, and the reaction was carried out for 8 hours. Thereafter, the temperature of the reaction solution was lowered to room temperature. Through the above-described process, an alkali-soluble resin having a Tg of +104 占 폚, a solid content of 31.7 mgKOH / g and a weight-average molecular weight Mw of about 3469 as measured by GPC was obtained.

Synthesis Example 5: Synthesis of alkali-soluble resin (A-5)

A flask equipped with a stirrer, a thermometer reflux condenser, a dropping funnel and a nitrogen inlet tube was charged with 120 parts of propylene glycol monomethyl ether acetate, 80 parts of propylene glycol monomethyl ether, 2 parts of AIBN, 25 parts of benzylmethacrylate, 25 parts of acrylate, 30 parts of acrylic acid and 20 parts of glycidyl methacrylate were charged and replaced with nitrogen. Thereafter, the temperature of the reaction solution was raised to 80 DEG C with stirring, and the reaction was carried out for 8 hours. Thereafter, the temperature of the reaction solution was lowered to room temperature. Through the above-mentioned process, an alkali-soluble resin having a Tg of + 58 占 폚, a solid content of 36.1 mgKOH / g and a weight average molecular weight Mw of about 3785 as measured by GPC was obtained.

Synthesis Example 6: Synthesis of alkali-soluble resin (A-6)

A flask equipped with a stirrer, a thermometer reflux condenser, a dropping funnel and a nitrogen inlet tube was charged with 120 parts of propylene glycol monomethyl ether acetate, 80 parts of propylene glycol monomethyl ether, 2 parts of AIBN, 25 parts of cyclohexyl methacrylate, 25 parts of methacrylate, 30 parts of acrylic acid and 20 parts of glycidyl methacrylate were charged and replaced with nitrogen. Thereafter, the temperature of the reaction solution was raised to 80 DEG C with stirring, and the reaction was carried out for 8 hours. Thereafter, the temperature of the reaction solution was lowered to room temperature. Through the above-described process, an alkali-soluble resin having a Tg of +12 DEG C, a solid content of 29.8 mgKOH / g and a weight-average molecular weight Mw of about 3027 as measured by GPC was obtained.

Examples and Comparative Examples

The colored photosensitive compositions of Examples and Comparative Examples were prepared with the components and the contents (parts by weight) shown in Tables 1 and 2 below.

Example One 2 3 4 5 6 alkali
Availability
Suzy A-1 1.96 1.96 - 1.96 - 1.3 A-2 2.56 - 1.96 - 1.96 - A-3 - 2.56 2.56 - - - A-4 - - - - - - A-5 - - - - - - A-6 - - - 2.56 2.56 3.22 Photopolymerization
compound B-1 3.12 3.12 3.12 3.12 3.12 3.12 Photopolymerization initiator C-1 1.34 1.34 1.34 1.34 1.34 1.34 coloring agent D-1 3.93 3.93 3.93 3.93 3.93 3.93 D-2 1.92 1.92 1.92 1.92 1.92 1.92 solvent E-1 85 85 85 85 85 85 additive F-1 0.05 0.05 0.05 0.05 0.05 0.05 F-2 0.05 0.05 0.05 0.05 0.05 0.05 F-3 0.20 0.20 0.20 0.20 0.20 0.20

Comparative Example One 2 3 4 5 alkali
Availability
Suzy A-1 1.96 1.96 - - - A-2 - - 1.96 - - A-3 - - - - 1.96 A-4 2.56 - - - - A-5 - 2.56 2.56 1.96 - A-6 - - - 2.56 2.56 Photopolymerization
compound B-1 3.12 3.12 3.12 3.12 3.12 Photopolymerization initiator C-1 1.34 1.34 1.34 1.34 1.34 coloring agent D-1 3.93 3.93 3.93 3.93 3.93 D-2 1.92 1.92 1.92 1.92 1.92 solvent E-1 85 85 85 85 85 additive F-1 0.05 0.05 0.05 0.05 0.05 F-2 0.05 0.05 0.05 0.05 0.05 F-3 0.20 0.20 0.20 0.20 0.20

The components shown in Table 1 and Table 2 are as follows.

A-1) The alkali-soluble resin of Synthesis Example 1

A-2) The alkali-soluble resin of Synthesis Example 2

A-3) The alkali-soluble resin of Synthesis Example 3

A-4) The alkali-soluble resin of Synthesis Example 4

A-5) The alkali-soluble resin of Synthesis Example 5

A-6) The alkali-soluble resin of Synthesis Example 6

B-1) dipentaerythritol hexaacrylate (KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.)

C-1) 2-Benzyl-2-dimethylamino-1 (4-morpholinophenyl) butan-1-one (Irgacure 369; Ciba Specialty Chemicals)

D-1) C.I. Pigment Green 58

D-2) C.I. Pigment Yellow 138

E-1) Propylene glycol monomethyl ether acetate

F-1) Surfactant (SH-8400 manufactured by Toray Silicone Co., Ltd.)

F-2) epoxy resin (SUMI-EPOXY ESCN-195XL; manufactured by Sumitomo Chemical Co., Ltd.)

F-3) 3-methacryloxypropyltrimethoxysilane

Manufacture of color filters

The colored photosensitive compositions prepared in Examples and Comparative Examples were applied on a glass substrate (# 1737, Corning) by spin coating, and then placed on a heating plate and held at a temperature of 100 ° C for 3 minutes to form a thin film.

A test photomask having a step-like pattern was placed on the thin film in a transmittance of 1 to 100%, and an ultra-high pressure mercury lamp (USH-250D, manufactured by Ushio DENKI Co., Ltd.) (365 nm) at 40 mJ / cm < 2 > in an air atmosphere. The thin film irradiated with ultraviolet rays was developed in a KOH aqueous solution of pH 12.5 for 70 seconds using a spray developing machine.

The glass substrate 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 20 minutes to prepare a color filter. The pattern (thin film) thickness of the manufactured color filter was 2.0 to 2.5 占 퐉.

(1) Development speed and sensitivity evaluation

During the above-described manufacturing process of the color filter, the time at which the removal / peeling of the non-exposed portion started at the time of development was measured to measure the developing speed. Further, during the manufacturing process of the color filter, the minimum exposure amount (mJ / cm 2) required to form a thin film without peeling of the pattern after development was measured to evaluate the sensitivity.

(2) Smear (Evaluation of film wrinkles)

The state of the surface of the fabricated color filter pattern was visually observed to determine whether vertical line unevenness due to film wrinkles occurred or not, and evaluated according to the following criteria.

○: Vertical line stains are not recognized on the pattern surface.

?: The unevenness of the vertical lines on the pattern surface is finely recognized.

X: Vertical stain on the pattern surface is clearly recognized.

(3) Evaluation of adhesion

The color filter prepared above was cut into 100 matrix structures in an area of 10 x 10 mm, and the adherence was evaluated by counting the number of matrices peeled off while vertically and strongly adhering the tape on the tape. / 100).

(4) Heat resistance

The color filters (heat resistance) before and after the heat treatment at 230 deg. C for 2 hours were compared and evaluated with respect to the color filters prepared above. Specifically, by using the following expression (1) representing the color change in the three-dimensional colorimeter defined by L *, a *, b *, the smaller the color change value, the higher the heat resistance.

[Equation 1]

? Eab * = [(? L *) ² + (? A *) ² + (? B *) ² ] ^1/2

(5) NMP content

The color filter prepared above was cut into 3 x 3 cm, and then immersed in 14.6 ml of NMP solution at 80 DEG C for 40 minutes. The absorbance of the re-collected NMP solution was then evaluated by UV-Vis spectrometer.

The evaluation results are shown in Tables 3 and 4 below.

Example
One Example
2 Example
3 Example
4 Example
5 Example
6 Sensitivity (mJ / cm ² ) 20 20 20 25 25 25 Development speed 18 13 21 23 25 21 Stain (vertical line) O O O O O △ Adhesiveness 100/100 100/100 95/100 95/100 95/100 97/100 Heat resistance 1.09 0.75 1.76 2.35 1.26 2.41 NMP
Solvent resistance 0.33 0.16 0.67 0.50 0.92 0.61

Comparative Example
One Comparative Example
2 Comparative Example
3 Comparative Example
4 Comparative Example
5 Sensitivity (mJ / cm ² ) 25 25 25 25 25 Development speed 24 10 20 28 14 Stain (vertical line) △ △ X X △ Adhesiveness 90/100 85/100 90/100 90/100 100/100 Heat resistance 1.34 0.75 2.60 2.26 1.42 NMP
Solvent resistance 1.93 0.16 2.26 2.77 0.16

Referring to Tables 3 and 4, the examples including the resin having a glass transition temperature of less than 0 占 폚, wherein the glass transition temperature difference between the resins was adjusted to 30 占 폚 or less, showed remarkably improved mechanical / No staining due to colorant or film shrinkage was observed while showing chemical reliability (adhesion, heat resistance, solvent resistance). In the case of Example 6, minute unevenness was observed as the content of the resin (first resin) having a glass transition temperature of less than 0 캜 was somewhat reduced.

When all of the glass transition temperatures of the resins exceeded 0 占 폚 as in Comparative Example 4, the smear phenomenon was intensified and the glass transition temperature between the resins exceeded 30 占 폚, .

Claims (10)

An alkali-soluble resin containing at least two resins and including a resin having a glass transition temperature of less than 0 占 폚;
coloring agent; And
Wherein the coloring photosensitive composition comprises a solvent.
The colored photosensitive composition according to claim 1, wherein the alkali-soluble resin comprises a first resin having a glass transition temperature of less than 0 ° C and a second resin having a glass transition temperature different from that of the first resin.
3. The colored photosensitive composition according to claim 2, wherein the glass transition temperature difference between the first resin and the second resin is 30 DEG C or lower.
The colored photosensitive composition according to claim 2, wherein the first resin comprises a repeating unit represented by the following formula (1):
[Chemical Formula 1]

(Wherein R ₁ is hydrogen or a methyl group, and R ₂ is an alkyl group having 1 to 12 carbon atoms)
5. The colored photosensitive composition according to claim 4, wherein R < _{2 >} is a non-cyclic alkyl group.
5. The colored photosensitive composition according to claim 4, wherein the first resin or the second resin comprises a reactive repeating unit represented by the following formula (2)
(2)

(Wherein R ₃ is hydrogen or a methyl group).
7. The colored photosensitive composition according to claim 6, wherein the first resin or the second resin further comprises an aryl ring-containing unit or a carboxylic acid-containing unit.
The colored photosensitive composition according to claim 2, wherein the content of the first resin in the total weight of the alkali-soluble resin is 30% by weight or more.
A color filter comprising a colored pattern formed from the colored photosensitive composition of any one of claims 1 to 8.
An image display device comprising the color filter of claim 9.