KR101912049B1 - Photosensitive resin composition, and pattern formed therefrom, color filter comprising thereof and liquid crystal display device comprigin the color filter - Google Patents

Abstract

The present invention relates to a colored photosensitive resin composition and a pattern layer formed therefrom, a color filter having the same and a liquid crystal display unit having the same, comprising: a colorant; alkali-soluble resins; photopolymerizable compounds; a photopolymerization initiator; and a solvent. The colorant includes a compound represented by a general formula 1.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a colored photosensitive resin composition, a pattern layer formed therefrom, a color filter including the same, and a liquid crystal display device including the same. BACKGROUND ART [0002]

A colored photosensitive resin composition and a pattern layer formed therefrom, a color filter including the same, and a liquid crystal display device including the same.

The black photosensitive resin is an essential material such as a color filter, a liquid crystal display material, an organic light emitting device, a display, a column spacer, a black matrix and / or a black column spacer. For example, a color filter of a color liquid crystal display is provided with a light-shielding layer using a black photosensitive composition at a boundary portion between coloring layers to enhance the contrast, coloring effect of red, green and blue. In recent years, a spacer for cell gap is formed not only as a black matrix but also on an array substrate, and is required to have various roles at a time. In order to achieve a high OD, the pigment absorbs light in the ultraviolet region contributing to photopolymerization in a colored spacer containing many coloring agents. Therefore, in a pattern having a small light transmittance of the opening portion, the shape of the desired spacer, It becomes difficult to achieve the characteristics such as the control of the step and the adhesion with the substrate.

A composition using a blue coloring agent, carbon black and / or organic black for improving optical properties in a conventional photosensitive resin composition has been known. Korean Patent Laid-Open No. 10-2014-0096423 also discloses a colored photosensitive resin composition for improving optical properties. . However, in the related art, the content of the coloring agent has been increased to increase the shielding ratio (optical density, OD), and as the content of the coloring agent is increased, the content of the pigment dispersing agent and the surface treating agent is increased, There was a drawback that the rate was low. In addition, it has been difficult to increase the optical density value of 0.1, and the content of carbon black has been increased to increase the optical density. However, as the content of carbon black increases, there is a problem with the dielectric constant. Further, when other organic black is used, the NMP elution also increases, which causes a problem in reliability. In the case of a colored photosensitive resin composition containing such a colorant in an excessive amount, the pigment dispersant and the surface treating agent are inevitably contained in an excessive amount, resulting in a problem of poor processability and optical properties. In particular, there is a problem that the development process becomes poor, and pattern defects such as the straightness of the pattern and the surface defects are generated, which makes it difficult to control the step to be designed, and the optical characteristics (light leakage, shielding ratio, etc.) become poor.

Korean Patent Publication No. 10-2014-0096423

Disclosure of the Invention The present invention provides a colored photosensitive composition capable of forming a black photo-spacer capable of improving optical properties (light-shielding property improvement), control of shape and level difference without increasing additional pigment, have.

In order to achieve the above object, the present invention provides a colored photosensitive resin composition comprising a colorant, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent, wherein the colorant comprises a compound represented by the general formula (1) to provide.

In general formula (1)

In the general formula (1), R ₁ to R ₁₈ each independently represent a hydrogen atom, a halogen atom, a monovalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, a nitro group or -SO ₂ R ₂₁

R ₂₁ represents -OH, -NHR ₂₂ or -R ₂₄ .

R ₂₂ represents a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, a cyclohexyl group optionally substituted with an alkyl group having 1 to 4 carbon atoms, -R ₂₃ -O-R ₂₄

, -R ₂₃ -COO-R ₂₃ , -R ₂₃ -O-CO-R ₂₄ , or an alkyl group having 7 to 10 carbon atoms.

R ₂₃ represents a divalent aliphatic hydrocarbon group having 1 to 8 carbon atoms.

R ₂₄ represents a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms.

R ₁₉ and R ₂₀ each independently represent a hydrogen atom, a methyl group, an ethyl group or an amino group.

The present invention also provides a pattern layer made of the above-mentioned colored photosensitive resin composition.

The present invention also provides a color filter comprising the above-described pattern layer.

Further, the present invention provides a liquid crystal display device including the color filter described above.

Disclosure of the Invention It is an object of the present invention to provide an ink composition for ink jet recording which has high optical density and NMP elution problem and is excellent in reliability effect without excessive use of the content of coloring agent and exhibits a high contrast ratio by improving the color purity at the same pigment concentration, Thereby providing an excellent colored photosensitive composition.

Also provided is a color filter having excellent shielding performance and excellent reliability, including the colored photosensitive resin composition, and a liquid crystal display device including the color filter.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in more detail with reference to the accompanying drawings.

The colored photosensitive resin composition of the present invention comprises a colored photosensitive resin composition having a high optical density and improved NMP eluting material by containing a specific coloring dye as a coloring agent and having excellent reliability, a color filter manufactured using the colored photosensitive resin composition, A display device can be provided. Further, the colored photosensitive resin composition of the present invention can more preferably provide a black photosensitive resin composition.

coloring agent

 In the present invention, the colorant is included to realize a high optical density. When a pigment of a different color is used in combination, the combination of colors is not particularly limited, but a high optical density and excellent reliability can be obtained even at the same concentration It may be preferred to include a coloring dye.

The colorant included in the present invention may specifically be a violet colorant, a green colorant, an orange colorant, a blue colorant, a black colorant, and the like.

As the purple colorant, C.I. Pigment Violet 1, 1: 1, 2, 2: 2, 3, 3: 1, 3: 3, 5, 5: 1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32 , 37, 39, 42, 44, 47, 49, 50, and the like, Pigment Violet 19, 23, and 29, and it is preferable that C.I. It is more preferable to include Pigment Violet 23, 29.

As the green colorant, C.I. Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55, 58, From the viewpoint of light shielding, CI Pigment Green 7, 36, 54, 58, 59, and more preferably, C.I. It is more preferable to include the pigment green 54.

As the orange colorant, C.I. Pigment Orange 1, 2, 5, 13, 16, 17, 19, 20, 21, 22, 23, 24, 34, 36, 38, 39, 43, 46, 48, 49, 61, 62, 64, 65 , 67, 69, 70, 71, 72, 73, 74, 75, 77, 78 and 79. From the viewpoint of light- Pigment Orange 38, 43, 64, 71, 72, and C.I. Pigment Orange 64 is more preferable.

Preferably, the blue colorant includes blue 16, 60, 61, 66 or the like in consideration of electrical characteristics, and blue 16 or 60 is more preferable.

As the black colorant, an inorganic or organic pigment can be appropriately selected. Examples of usable black colorants include carbon black, acetylene black, lamp black, black black, graphite, iron black, aniline black, cyanine black, titanium black, rhammet black and perylene black. The pigment may be used alone or in combination.

The colorant of the present invention may include a coloring dye, and it is preferable to include a coloring dye represented by the following general formula (1). It is preferable from the viewpoint of being advantageous to attainment.

In general formula (1)

Examples of the monovalent aliphatic hydrocarbon group having 1 to 10 carbon atoms in R1 to R18, R22 and R24 in the general formula (1) include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, n-hexyl, n-heptyl, n-octyl, decyl, 1-methylbutyl, 1,1,3,3-tetramethylbutyl, Dimethylhexyl group, 1,6-dimethylheptyl group, 2-ethylhexyl group, and 1,1,5,5-tetramethylhexyl group.

Examples of the alkyl group having 1 to 4 carbon atoms in the general formula (1) include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl and tert-butyl.

Examples of the divalent aliphatic hydrocarbon group having 1 to 8 carbon atoms in the general formula (1) include a methylene group, an ethylene group, a propane-1,3-diyl group, a propane-1,2-diyl group, Diethyl group, pentane-1, 5-diyl group, hexane-1, 6-diyl group, heptane-1, 7-diyl group, octane- have.

In the general formula (1), examples of the cyclohexyl group which may be substituted with an alkyl group having 1 to 4 carbon atoms include a 2-methylcyclohexyl group, a 2-ethylcyclohexyl group, a 2-propylcyclohexyl group, A cyclohexyl group, a 4-methylcyclohexyl group, a 4-ethylcyclohexyl group, a 4-propylcyclohexyl group, a 4-isopropylcyclohexyl group and a 4-butylcyclohexyl group.

Examples of -R23-O-R24 in the general formula (1) include a methoxymethyl group, ethoxymethyl group, propoxymethyl group, methoxyethyl group, ethoxyethyl group, propoxyethyl group, methoxypropyl group, ethoxypropyl group, A 2-oxo-4-methoxybutyl group, an octyloxypropyl group, a 3-ethoxypropyl group and a 3- (2-ethylhexyloxy) propyl group.

In the general formula (1), examples of -R23-CO-O-R24 include methoxycarbonylmethyl, methoxycarbonylethyl, ethoxycarbonylmethyl, ethoxycarbonylethyl, propoxycarbonylmethyl, A butoxycarbonylmethyl group, a butoxycarbonylethyl group, and the like can be given

Examples of -R23-O-CO-R24 in the general formula (1) include an acetyloxymethyl group, an acetyloxyethyl group, an ethylcarbonyloxymethyl group, an ethylcarbonyloxyethyl group, a propylcarbonyloxymethyl group, a propylcarbonyloxyethyl group, A carbonyloxymethyl group, and a butylcarbonyloxyethyl group.

In the general formula (1), examples of -SO2R21 include a sulfo group; a sulfamoyl group;

N-isopropylsulfamoyl group, N-methylsulfamoyl group, N-methylsulfamoyl group, N-ethylsulfamoyl group, N-propylsulfamoyl group, N-isopropylsulfamoyl group, (1, 1-dimethylpropyl) sulfamoyl group, N- (1, 2-dimethylpropyl) sulfamoyl group, N- (2-methylpropyl) sulfamoyl group, N- (2-methylbutyl) sulfamoyl group, N- (3,3-dimethylbutyl) sulfamoyl group, an N-cyclopentylsulfamoyl group, an N-hexylsulfamoyl group, N- (1,3-dimethylbutyl) sulfamoyl group, N- N-heptylsulfamoyl group, N- (1-methylhexyl) sulfamoyl group, N- (1,4-dimethylpentyl) sulfamoyl group, N-octylsulfamoyl group, N- (2-ethylhexyl) Sulfamoyl

Group, an N- (1,5-dimethyl) hexylsulfamoyl group, N- (1,1,2,2-tetramethylbutyl) sulfamoyl group,

A sulfamoyl group substituted by an aliphatic hydrocarbon group such as a diaryl group or an N-allyl sulfamoyl group;

(2-methoxyethyl) sulfamoyl group, N- (2-ethoxyethyl) sulfamoyl group, N- (1-methoxypropyl) sulfamoyl group, N- (3-ethoxypropyl) sulfamoyl group, N- (3-ethoxypropyl) sulfamoyl group, N- ) -Si (O) 2 group such as a sulfamoyl group, an N- (2-ethylhexyloxypropyl) sulfamoyl group, an N- (3-tert-butoxypropyl) sulfamoyl group, A sulfamoyl group substituted with -O-R24;

(Methoxycarbonylmethyl) sulfamoyl group, N- (methoxycarbonylethyl) sulfamoyl group, N- (methoxycarbonylethyl) sulfamoyl group, N- (ethoxycarbonylethyl) sulfamoyl group, N- (Propoxycarbonylmethyl) sulfamoyl group, N- (propoxycarbonylethyl) sulfamoyl group, N- (butoxycarbonylmethyl) sulfamoyl group, N- (butoxycarbonylethyl) (Acetyloxymethyl) sulfamoyl group, N- (acetyloxyethyl) sulfamoyl group, N- (ethylcarbonyloxymethyl) sulfamoyl group, sulfamoyl group substituted with -R23-CO-O- ), Sulfamoyl group, N- (ethylcarbonyloxyethyl) sulfamoyl group, N- (propylcarbonyloxymethyl) sulfamoyl group, N- (propylcarbonyloxyethyl) sulfamoyl group, N- Oxymethyl) sulfamoyl group, N- (butylcarbonyloxyethyl) sulfamoyl group and the like; - a sulfamoyl group substituted with -R23-O-CO-R24;

(2-methylcyclohexyl) sulfamoyl group, N- (3-methylcyclohexyl) sulfamoyl group, N- (4-methylcyclohexyl) sulfamoyl group, N- 4-butylcyclohexyl) sulfamoyl group and the like; a sulfamoyl group substituted with a cyclohexyl group having a substituent;

(2-phenylethyl) sulfamoyl group, N- (3-phenylpropyl) sulfamoyl group, N- (4-phenylbutyl) sulfamoyl group, N- ) Sulfamoyl group, N- (2- (2-naphthyl) ethyl] sulfamoyl group, N- [2- (4-methylphenyl) Pamoyl group, and sulfamoyl group substituted with an aralkyl group such as N- (3-phenyl-1-methylpropyl) sulfamoyl group.

In the general formula (1), examples of -SO2R24 include a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, an isopropylsulfonyl group, an n-butylsulfonyl group, a sec-butylsulfonyl group, a tert- butylsulfonyl group, Hexylsulfonyl group, heptylsulfonyl group, octylsulfonyl group, 1-methylbutylsulfonyl group, 1,1,3,3-tetramethylbutylsulfonyl group, 1,5-dimethylhexylsulfonyl group, 1,6-dimethylheptylsulfonyl group , 2-ethylhexylsulfonyl group, and 1,1,5,5-tetramethylhexylsulfonyl group. Among them, a methylsulfonyl group and an ethylsulfonyl group are preferable, and a methylsulfonyl group is more preferable.

It is preferable that at least one of R 1 to R 18 is a nitro group since there is a tendency to form a pattern or the like with superior heat resistance.

It is preferable that at least one of R ₁ to R ₅ and at least one of R ₆ to R ₁₀ is -SO ₂ R ₂₁ . When a plurality of -SO ₂ R _{21 s} are present, a plurality of R 21 s may be the same or different.

-SO ₂ R ₂₁ is -SO ₃ H, -SO ₂ NHR ₂₂ or -SO ₂ R ₂₄ , preferably -SO ₂ R ₂₄ . Among them, it is preferably -SO ₂ CH _3.

If the compounds of the invention having a -SO ₂ R _24, it is preferable that at least one of R ₁₁ ~ R ₁₄ and at least one of R ₁₅ ~ R ₁₈ is -SO ₂ R _24.

-SO case having 2 ₂ R _24, a plurality of R ₂₄ may be the same or may be different from each other.

Preferable examples of the anion moiety of the compound 1 include anions represented by the formulas (B-1) to (B-12).

The content of the coloring dye in the general formula (1) may be 0.01 to 5%, more preferably 0.03 to 3%, in 100% of the total coloring agent. When the coloring dye is contained in the colorant within the above-mentioned range, it is preferable from the viewpoint of securing an effect of increasing color purity and excellent reliability (solvent resistance and electrical characteristics).

  The coloring agent may comprise a black coloring agent, a blue coloring agent, a purple coloring agent and a coloring dye, wherein the coloring agent may comprise from 20% to 55% of the total solids content of the colored photosensitive composition, Lt; / RTI > It is preferable that a high OD (OD: not less than 1.3 / um) can be achieved when the colorant is contained within the above range.

The black colorant may be appropriately selected from inorganic or organic pigments. Examples of usable black colorants include carbon black, atelieren black, lamp black, black black, graphite, iron black, aniline black, cyanine black, titanium black, rhammet black and perylene black. The organic pigments may be used alone or in combination. The content of the carbon black may be 0 to 13%, more preferably 4 to 10%, in the solid content. In addition, organic black among the black pigments may be added, preferably 3 to 25% by weight based on the solid content. If the organic black is less than 3% in the solid content of the colorant, the optical density may be ineffective. If it exceeds 25%, the product reliability may be affected. In the present invention, the black colorant may be mixed with a black oil / inorganic pigment as the case may be.

More specifically, since it contains no metallic element and contains Blue 60 (Blue 60, B60), Blue 16 (Blue 16, B16), Violet 23 (Violet 23, V23), Violet 29 The organic coloring agent is preferably contained in the solid content in an amount of 5 to 25% by weight in view of minimizing the effect, the curability and the defective step.

In the present invention, red 179 (R179), orange 64 (Or64) and green 54 (G54) may be added in addition to the organic and inorganic pigments.

Alkali-soluble resin

In the present invention, an alkali-soluble resin usually makes the non-exposed portion of the photosensitive resin layer formed using the photosensitive resin composition alkali-soluble and can also act as a dispersion medium for the pigment. The alkali-soluble resin may be selected from a variety of polymers used in the applicable application fields. More preferably, a binder resin containing an epoxy group may be more effective. This is because the alkali-soluble resin containing the epoxy group may affect the reliability improvement by thermal curing. The molecular weight of the alkali-soluble resin used may be in the range of 3,000 to 40,000 and preferably in the range of 5,000 to 30,000. In addition, the acid value of the alkali-soluble resin is preferably in the range of 50 to 200 mgKOH / g based on the solid content. When the acid value of the alkali resin satisfies the above-described range, there is an advantage that the developability against alkali development is excellent, the occurrence of residue is suppressed, the adhesion of the pattern, the leveling property, and the residual film ratio are improved.

The alkali-soluble resin may be contained in an amount of 20 to 45% by weight based on the total solid content of the colored photosensitive resin composition, more preferably 25 to 40% by weight. When the content of the alkali-soluble resin is within the above range, it is preferable from the viewpoint that the developing property, the residual film ratio and the dispersibility of the coloring agent are improved and the performance of the coloring agent can be excellently expressed.

Photopolymerizable compound

Photopolymerizable compound

The photopolymerizable compound of the present invention contains an unsaturated bond and undergoes a photoreaction with the photoinitiator to form a photosensitive resin layer. The polymerizable compound to be used in the present invention includes a commonly used (meth) acrylate in a functional group When the composition contains an unsaturated group and is photosensitive, there is no limitation in use.

Specific examples of the photopolymerizable compound include ethylene glycol diacrylate, triethylene glycol diacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, pentaerythritol diacrylate, But are not limited to, glycol acrylate, glycol acrylate, glycol acrylate, glycol acrylate, lithol acrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, dipentaerythritol diacrylate, dipentaerythritol triacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate , Bisphenol A diacrylate, trimethylolpropane triacrylate, novolak epoxy acrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, and the like. . The above-mentioned photopolymerizable compounds may be used alone or in combination of two or more thereof.

The photopolymerizable compound may be included in the total solid content of the colored photosensitive resin composition in an amount of 5 to 50% by weight, more preferably 10 to 40% by weight. When the content of the photopolymerizable compound is within the above range, So that a good pattern property can be formed.

Photopolymerization initiator

The photopolymerization initiator of the present invention initiates a radical reaction of the photosensitive resin composition to cause curing and improve the sensitivity. The photopolymerization initiator is a photopolymerization initiator generally used in a photosensitive resin composition, and may be an acetophenone based, benzophenone based, triazine based, thioxanthone based, oxime based, benzoin based, or imidazole based compound.

Examples of the acetophenone compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 2- 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1- Methyl [4- (1-methylvinyl) phenyl] propane-1-one, 2-benzyl-2-dimethylamino- 2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, and the like. In addition, photopolymerization initiators other than the acetophenone-based photopolymerization initiator may be used in combination. Photopolymerization initiators other than acetophenone-based photopolymerization initiators include active radical generators, sensitizers, and acid generators that generate active radicals upon irradiation with light. Examples of the active radical generator include benzoin-based compounds, benzophenone-based compounds, thioxanthone-based compounds, and triazine-based compounds. Examples of the benzoin-based compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoisobutyl ether and the like. Examples of the benzophenone-based compound include benzophenone, methyl o-benzoylbenzoate, 4-phenylphenazine, 4-benzoyl-4'-methyldiphenylsulfide, 3,3 ', 4,4'-tetra t-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, and the like. Examples of the thioxanthone compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1- Propanedioxanthone, and the like. Examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) (Trichloromethyl) -6- (4-methoxystyryl) -1,3,5-triazine, 2,4-bis Azine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) ethenyl] -1,3,5-triazine, 2,4- Yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino- Methylphenyl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5 -Triazine, and the like. As the oxime-based compound, for example, -ethoxycarbonyl-α-oximino-1-phenylpropan-1-one and the like are exemplified. OXE01 and OXE02 of BASF Co. are typical examples of commercially available products. Examples of the active radical generator include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,2-bis (o-chlorophenyl) -4,4 ', 5,5'-tetra Phenyl-1,2'-biimidazole, 10-butyl-2-chloroacridone, 2-ethyl anthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, methyl phenylglyoxylate, Compounds and the like can be used. Examples of the acid generator include 4-hydroxyphenyldimethylsulfonium p-toluene sulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluene sulfone 4-acetoxyphenylmethylbenzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate, diphenyliodonium p-toluenesulfonate, Diphenyl iodonium hexafluoroantimonate and the like, and nitrobenzyl tosylates, benzoin tosylates and the like. Also, as the active radical generator, there are compounds which generate an acid at the same time as an active radical, and for example, a triazine-based photopolymerization initiator is also used as an acid generator.

The photopolymerization initiator may be contained in an amount of 0.1 to 40% by weight, preferably 1 to 30% by weight based on the total weight of the solid content in the colored photosensitive resin. When the photopolymerization initiator is contained within the above range, the pattern formation becomes favorable, the colored photosensitive resin composition becomes highly sensitive, and the strength of the pixel portion formed by using the composition and the smoothness on the surface of the pixel portion tend to be favorable, Do.

Further, in the present invention, a photopolymerization initiator may be used. The photopolymerization initiator is sometimes used in combination with a photopolymerization initiator and is a compound used for promoting the polymerization of the photopolymerizable compound initiated by the photopolymerization initiator. Examples of the photopolymerization initiator include an amine compound, an alkoxyanthracene compound, a thioxanthone compound, a carboxylic acid compound, and a sulfonic acid compound.

 Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylamino benzoate Ethyl (4-dimethylaminobenzoic acid), 2-ethylhexyl 4-dimethylaminobenzoate, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzphenone Amino) benzophenone, and 4,4'-bis (ethylmethylamino) benzophenone. Of these, 4,4'-bis (diethylamino) benzophenone is preferable. Examples of the alkoxyanthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene And the like. Examples of the thioxanthone compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1- Propanedioxanthone, and the like. These photopolymerization initiators (D) may be used singly or in combination of two or more thereof. Commercially available photopolymerization initiators may be used as the photopolymerization initiator. Commercially available photopolymerization initiators include, for example, trade names "EAB-F" (manufactured by Hodogaya Chemical Industry Co., Ltd.) and the like.

 When these photopolymerization initiators are used, the amount of the photopolymerization initiator is usually 10 moles or less, preferably 0.01 to 5 moles per mole of the photopolymerization initiator. Within the above range, the sensitivity of the colored photosensitive resin composition becomes higher, and the productivity of the color filter formed using the composition tends to be improved, which is preferable.

solvent

The solvent contained in the colored photosensitive resin composition of the present invention is not particularly limited and various organic solvents used in the field of the colored photosensitive resin composition can be used. Specific examples of the solvent include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether and ethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, Diethylene glycol dialkyl ethers such as diethylene glycol dipropyl ether and diethylene glycol dibutyl ether, ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, Alkylene glycol alkyl ether acetates such as propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate and methoxypentyl acetate, aromatic hydrocarbons such as benzene, toluene, xylene and mesitylene , Ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone and cyclohexanone, alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol and glycerin, Ethyl and methyl 3-methoxypropionate, and cyclic esters such as? -Butyrolactone. Among the above solvents, organic solvents having a boiling point of 100 占 폚 to 200 占 폚 in the solvent are preferably used from the viewpoint of coatability and dryness, more preferably alkylene glycol alkyl ether acetates, ketones, 3-ethoxy Propylene glycol monomethyl ether acetate, cyclohexanone, ethyl 3-ethoxypropionate, 3-ethoxypropionate, and 3-methoxypropionate are more preferable. Examples of the solvent include propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, Methyl methoxypropionate, and the like. These solvents may be used alone or in admixture of two or more, or mixed with organic solvents having different boiling points.

The content of the solvent in the colored photosensitive resin composition of the present invention may be 60 to 90% by weight, preferably 65 to 85% by weight, based on the total weight of the colored photosensitive resin composition containing the colored photosensitive resin composition. When the content of the solvent is within the above range, it is preferable that the leveling property and the coating property are good and curing is easy.

additive

The blue photosensitive resin composition of the colored pattern layer according to the present invention may further contain an additive such as a silane coupling agent and a surfactant in order to improve the coating property and the adhesive property as required.

The silane coupling agent for improving adhesion to a substrate may include a silane coupling agent having a reactive substituent selected from the group consisting of a carboxyl group, a methacryloyl group, an isocyanate group, an epoxy group, and a combination thereof. Examples of the silane coupling agent include trimethoxysilylbenzoic acid,? -Methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane,? -Isocyanatepropyltriethoxysilane, r-glycidoxypropyl Trimethoxysilane, and? - (3,4-epoxycyclohexyl) ethyltrimethoxysilane. These may be used alone or in combination of two or more.

The surfactant may be further added to improve coatability. Specifically, fluorine surfactants such as BM-1000, BM-1100 (BM Chemie) and Proride FC-135 / FC-170C / FC-430 (Sumitomo 3M Co.) can be used.

The colored photosensitive resin composition of the present invention includes other additives according to the needs of those skilled in the art, as long as the objects of the present invention are not impaired, in addition to the above-mentioned components.

The additive may further include at least one additive selected from the group consisting of, for example, another polymer compound, a curing agent, a surfactant, an adhesion promoter, an antioxidant, an ultraviolet absorber and an anti-

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

The curing agent is used for increasing the curing depth and mechanical strength, and specific examples thereof include an epoxy compound, a polyfunctional isocyanate compound, a melamine compound and an oxetane compound.

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

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

The curing agent may be used together with a curing assistant 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. The curing assistant compound includes, for example, polyvalent carboxylic acids, polyvalent carboxylic anhydrides, and acid generators. The polyvalent carboxylic acid anhydrides may be those commercially available as an epoxy resin curing agent. Specific examples of the above-mentioned epoxy resin curing agents include commercial products such as ADEKA HARDONA EH-700 (ADEKA INDUSTRIAL CO., LTD.), Trade name (RICACIDO HH) (manufactured by New Japan Chemical Co., Ltd.) Manufactured by Shin-Etsu Chemical Co., Ltd.). The curing agents exemplified above may be used alone or in combination of two or more.

The surfactant may be used for further improving the film-forming property of the photosensitive resin composition, and a silicone surfactant or a fluorine surfactant may be preferably used.

TS-4440, TSF-4300, TSF-4445, TSF-4446, and TSF-4400 of GE Toshiba Silicones such as DC3PA, DC7PA, SH11PA, SH21PA and SH-8400 from Dow Corning Toray Silicone Co., 4460 and TSF-4452. F-482, F-489 and F-554 (manufactured by Dainippon Ink and Chemicals, Incorporated), BM-1000, BM -1100 (BM Chemie), Proride FC-135 / FC-170C / FC-430 (Sumitomo 3M Co., Ltd.). The above-exemplified surfactants may be used alone or in combination of two or more.

The adhesion promoter is an additive which is used for improving coatability and adhesion to a substrate, and is a silane coupling agent containing a reactive substituent selected from the group consisting of a carboxyl group, a methacryloyl group, an isocyanate group, an epoxy group, . Specific examples of the silane coupling agent include trimethoxysilylbenzoic acid,? -Methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane,? -Isocyanatepropyltriethoxysilane, r- Glycidoxypropyltrimethoxysilane, and? - (3,4-epoxycyclohexyl) ethyltrimethoxysilane.

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

Specific examples of the ultraviolet absorber include 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzothiazole and alkoxybenzophenone.

Specific examples of the anti-aggregation agent include sodium polyacrylate and the like.

The additive can be suitably added and used by those skilled in the art within a range not hindering the effect of the present invention. For example, the additive may be used in an amount of 0.05 to 10 parts by weight, preferably 0.1 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the total of the colored photosensitive resin composition.

The colored photosensitive resin composition according to the present invention can be produced, for example, by the following method. The colorant is mixed with a solvent and dispersed. If necessary, a dispersant may be further used, and some or all of the alkali-soluble resin may be blended. The remaining amount of the alkali-soluble resin, the photopolymerizable compound, the photopolymerization initiator, other components to be used if necessary, and, if necessary, the additional solvent are further added to the obtained dispersion (hereinafter, also referred to as mill base) To obtain a desired colored photosensitive resin composition.

Color filters and liquid crystal displays

Another aspect of the present invention relates to a color filter comprising a colored pattern layer including a cured product of the above-mentioned colored photosensitive resin composition for forming a colored pattern layer.

The color filter according to the present invention has advantages of minimizing NMP elution and having high optical density and excellent reliability and shielding property by including green, orange, and purple coloring agents, without adding an excessive amount of black coloring agent to the colored photosensitive resin composition.

The color filter includes a substrate and a pattern layer formed on the substrate.

The substrate may be the substrate of the color filter itself, or may be a portion where a color filter is placed on a display device or the like, and is not particularly limited. The substrate may be glass, silicon (Si), silicon oxide (SiOx), or a polymer substrate. The polymer substrate may be polyethersulfone (PES) or polycarbonate (PC).

The pattern layer may be a layer containing the colored photosensitive resin composition of the present invention, and may be a layer formed by applying the colored photosensitive resin composition for forming a colored pattern layer and exposing, developing and thermally curing the colored photosensitive resin composition in a predetermined pattern, Can be formed by carrying out a method commonly known in the art.

In still another embodiment of the present invention, the color filter may further include at least one selected from the group consisting of a red pattern layer and a green pattern layer.

The color filter including the substrate and the pattern layer as described above may further include a partition wall formed between the respective patterns, and may further include a black matrix, but is not limited thereto.

Another aspect of the present invention relates to a liquid crystal display device including the color filter described above. In short, the liquid crystal display device according to the present invention may include a color filter including a pattern layer containing a cured product of the above-mentioned colored photosensitive resin composition.

The color filter of the present invention is applicable not only to a general liquid crystal display device but also to various image display devices such as an electroluminescence display device, a plasma display device, and a field emission display device.

When the liquid crystal display device includes the color filter including the pattern layer according to the present invention, there is an advantage that the shielding property and the reliability are excellent. The colored photosensitive resin composition included in the color filter according to the present invention minimizes the reddish phenomenon by including a green coloring agent in addition to orange and purple coloring agents. Thus, a color filter including the photosensitive resin composition and a liquid crystal display device There is an advantage of excellent color reproduction.

A pattern layer including a column spacer, a black matrix and / or a black column spacer, a color filter, and a liquid crystal display

The color filter according to the present invention has an advantage of high reliability due to high optical density and excellent shielding property. The color filter includes a substrate and a pattern layer formed on the substrate.

The substrate may be the substrate of the color filter itself, or may be a portion where a color filter is placed on a display device or the like, and is not particularly limited. The substrate may be glass, silicon (Si), silicon oxide (SiOx), or a polymer substrate. The polymer substrate may be polyethersulfone (PES) or polycarbonate (PC).

The pattern layer may include a column spacer, a black matrix and / or a black column spacer as a layer containing a cured product of the colored photosensitive resin composition of the present invention.

The column spacer, the black matrix and / or the black column spacer according to the present invention has an advantage of high reliability and excellent shielding due to high optical density.

The pattern layer may be a layer formed by applying the above-mentioned colored photosensitive resin composition and exposing, developing, and thermosetting in a predetermined pattern, and the pattern layer may be formed by performing a method commonly known in the art.

In still another embodiment of the present invention, the color filter may further include at least one selected from the group consisting of a red pattern layer and a green pattern layer.

The color filter including the substrate and the pattern layer as described above may further include a partition wall formed between the respective patterns, and may further include a black matrix, but is not limited thereto.

Another aspect of the present invention relates to a liquid crystal display device including the color filter described above. In short, the liquid crystal display device according to the present invention may include a color filter including a pattern layer containing a cured product of the above-mentioned colored photosensitive resin composition.

The color filter of the present invention is applicable not only to a general liquid crystal display device but also to various image display devices such as an electroluminescence display device, a plasma display device, and a field emission display device.

When the liquid crystal display device includes the color filter including the pattern layer according to the present invention, there is an advantage that the shielding property and the reliability are excellent

Hereinafter, the present invention will be described in detail by way of examples to illustrate the present invention. However, the embodiments according to the present disclosure can be modified in various other forms, and the scope of the present specification is not construed as being limited to the above-described embodiments. Embodiments of the present disclosure are provided to more fully describe the present disclosure to those of ordinary skill in the art. In the following, "% " and " part " representing the content are by weight unless otherwise specified.

Manufacturing example

Production Example 1. Preparation of Binder Resin (B)

277 g of methoxybutyl acetate was added to a 1-liter separable flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen inlet tube, and the mixture was heated to 80 DEG C, and 3,4-epoxytricyclo [5.2. (50: 50 (molar ratio)) of 3,4-epoxytricyclo [5.2.1.0,2,6] decane-8-yl acrylate , A mixed solution obtained by dissolving 301 g of the compound represented by the formula (11), Ra '= H], 49 g of methacrylic acid and 23 g of azobisdimethyl valeronitrile in 350 g of methoxybutyl acetate was added dropwise over 5 hours , And further aged for 3 hours to obtain a copolymer solution (solid content (NV) 35.0% by weight). The obtained copolymer had an acid value (dry) of 69.8 KOH mg / g, a weight average molecular weight (Mw) of 12,300 and a dispersion degree (Mw / Mn) of 2.1.

Production Example 2. Preparation of colored dyes

After adding 65 parts of water to 7.5 parts of 2-amino-4-methylsulfonyl-6-nitrophenol (CAS No.101861-04-5), 1.3 parts of sodium hydroxide was added and dissolved. Under ice cooling, 6.1 parts of 35% aqueous solution of sodiumacetate (manufactured by Wako Pure Chemical Industries, Ltd.) was added. Then, 19.4 parts of 35% hydrochloric acid was added portionwise to dissolve and the mixture was stirred for 2 hours, A suspension (suspension) containing the ammonium salt was obtained. Subsequently, an aqueous solution prepared by dissolving 5.6 parts of amide sulfuric acid (manufactured by Wako Pure Chemical Industries, Ltd.) in 26 parts of water was slowly added thereto to inactivate excess sodium acetates. Subsequently, 5.6 parts of 3-methyl-1-phenyl-5-pyrazolone (manufactured by Wako Pure Chemical Industries, Ltd.) was suspended in 70 parts of water, and the pH was adjusted to 8.0 using sodium hydroxide. The suspension containing the diazonium salt was added dropwise over 15 minutes while appropriately adding a 10% sodium hydroxide solution so that the pH was stabilized in the range of 7 to 7.5. After completion of dropwise addition, stirring was further continued for 30 minutes to obtain a yellow suspension. And stirred for 1 hour. The yellow solid obtained by filtration was dried at 60 ° C under reduced pressure to obtain 11.7 parts (yield: 87%) of the compound represented by the formula (A-1).

 (A-1)

10 parts of the compound of the formula (A-1) were dissolved in 100 parts of dimethylformamide (manufactured by Tokyo Kasei Kogyo Co., Ltd.) and ammonium chromate (III) sulfate hydrate (Wako Pure Chemical Industries, , 1.1 parts of sodium acetate (manufactured by Wako Pure Chemical Industries, Ltd.) was added, and the mixture was heated to reflux for 4 hours and a half. After cooling to room temperature, the reaction solution was poured into 1500 parts of 20% saline, and the resulting red-orange solid after filtration was dried at 60 캜 to obtain 13.6 parts (yield: 63%) of the compound represented by the formula (A-2).

 (A-2)

Examples 1 to 5 and Comparative Examples 1 to 4: Preparation of colored photosensitive resin composition

The colored photosensitive resin compositions of Examples 1 to 7 and Comparative Examples 1 to 5 were prepared according to the composition shown in Table 1 below.

 [Table 1]

Binder resin (B): Refer to Production Example 1

Coloring dye formula (A-2): See Production Example 2

Color Dye-B: Acid Red 52 (TCI)

Coloring dye -C: Rhodamine B from TCI (TCI)

Monomer (M): DPHA (Nippon Kayaku Co., Ltd.)

Photopolymerization initiator (PI): 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -ethanone- 1- (O- acetyloxime) (Irgacure OXE- four)

Additive (D1): F554 (DIC)

Additive (D2): Sol Spurs 5000 (manufactured by Lubrisol)

Solvent (S): Propylene glycol monomethyl ether acetate (PGMEA)

Fabrication of Substrate

A 5 cm x 5 cm glass substrate (Corning) was cleaned with a neutral detergent and water and dried. Each of the colored photosensitive resin compositions prepared in Example 1 and Comparative Example was spin-coated on the glass substrate to a final film thickness of 3.0 占 퐉, prebaked at 80 to 120 占 폚 and dried for 1 to 2 minutes to prepare a solvent Respectively. Then, exposure was performed at an exposure amount of 25 to 35 mJ / cm 2 to form a pattern, and an unexposed area was removed using an aqueous alkaline solution. Followed by baking at 200 to 250 DEG C for 10 to 30 minutes to prepare a colored substrate.

Experimental Example 1. Evaluation of optical characteristics

 Based on the above manufacturing standards, the optical characteristics are evaluated with a substrate made to be coated with a black photosensitive resin on the entire surface without a pattern. UV-vis (UV-2550, manufactured by Shimadzu) is used. In the evaluation of optical characteristics, the optical density was measured at 400 to 650 nm, and the measured values at each wavelength were confirmed in the near-IR region at 700 to 750 nm and 950 nm. 361T, X-rite) was used to measure the transmittance at a center wavelength of 510 nm, and the optical density to a thickness of 1 mu m was determined. The specific evaluation criteria are as follows, and the evaluation results are shown in Table 2 below.

[Evaluation standard]

1. Optical characteristics (optical density, 700 to 750 nm, 950 nm transmittance)

(1) Optical density (400 to 650 nm)

?: Excellent, less than 0.032 T%

Good: 0.032 T% or more to 0.04 T% or less

?: Insufficient, more than 0.04T% to less than 0.05T%

X: deterioration, exceeding 0.05T%

(2) 700 to 750 nm transmittance

⊚: excellent, 10T% or less

Good: 10T% to 12T% or less

?: Insufficient, more than 12T% to less than 15T%

X: worsening, exceeding 15T%

(3) Transmittance at 950 nm

◎: Excellent, 18T% or more

Good: 15T% or more to less than 18T%

△: insufficient, 12T% or more to less than 15T%

X: worse, less than 12T%

Experimental Example 2. Reliability Evaluation

 A substrate is manufactured so that a black photosensitive resin is applied to the entire surface without a pattern, on the basis of the above-described production standards. It is cut into a size of 3 x 3 cm, immersed in NMP solvent, and heated at 100 캜 for 60 minutes. Thereafter, only the NMP solvent is extracted, and the degree of elution in the NMP solvent is measured using an UV-vis spectrometer, and the absorbance is expressed as an integral value of 400 to 700 nm.

*. The formed substrate is checked by checking the measurement conditions of each item

The line width was made by using a line pattern mask, and the evaluation progressed.

The scope of the evaluation result is as follows.

[Evaluation standard]

Reliability (NMP elution reliability): 400 to 700 nm Abs integral value

◎: Excellent, less than 5

Good: 5 or more to less than 8

△: insufficient, 8 or more to less than 12

X: worse, 12 or more

[Table 2]

The substrates prepared in Examples 1 to 5, which were the colored photosensitive resin compositions of the present invention, showed not only high optical density and excellent optical characteristics, but also less NMP elution and good pattern reliability.

On the other hand, in the case of Comparative Example 2 or 4 containing other colored dyes in place of the colored dyes of the general formula 1, it was confirmed that the optical density was lowered and the reliability was also significantly lowered. When the carbon black or the organic black was increased to increase the optical density, the optical density was excellent, but the pattern straightness and the NMP elution reliability were poor.

Claims (12)

coloring agent; Alkali-soluble resins; Photopolymerizable compounds; A photopolymerization initiator; And a solvent,
Wherein the colorant comprises a compound represented by the general formula (1), further comprising a black colorant comprising carbon black and organic black:
[Formula 1]

In the general formula (1), R ₁ to R ₁₈ each independently represent a hydrogen atom, a halogen atom, a monovalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, a nitro group or -SO ₂ R ₂₁ ,
R ₂₁ represents -OH, -NHR ₂₂ or -R ₂₄ ,
R ₂₂ represents a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, a cyclohexyl group optionally substituted with an alkyl group having 1 to 4 carbon atoms, -R ₂₃ -O-R ₂₄ , -R ₂₃ -COO-R ₂₃ , -R ₂₃ -O-CO-R ₂₄ , or an aralkyl group having 7 to 10 carbon atoms,
R ₂₃ represents a divalent aliphatic hydrocarbon group having 1 to 8 carbon atoms,
R ₂₄ represents a monovalent aliphatic hydrocarbon group of 1 to 8 carbon atoms,
R ₁₉ and R ₂₀ independently represent a hydrogen atom, a methyl group, an ethyl group or an amino group,
M ₁ represents Cr or Co,
Y represents Na or K.
The black photosensitive resin composition according to claim 1, wherein the colorant further comprises at least one selected from the group consisting of a blue colorant and a purple colorant.
The method according to claim 1,
Wherein the alkali-soluble resin comprises an epoxy group.
The method according to claim 1,
Wherein the photopolymerization initiator comprises at least one selected from the group consisting of acetophenone, benzophenone, triazine, thioxanthone, oxime, benzoin and nonimidazole compounds. .
The black photosensitive resin composition according to claim 1, wherein the solvent of the black photosensitive resin composition comprises an organic solvent having a boiling point of 100 ° C to 200 ° C.
The black photosensitive resin composition according to claim 1, wherein the black photosensitive resin composition further comprises an additive.
The black photosensitive resin composition according to claim 1, wherein the formula (1) is at least one selected from the group consisting of the following formulas.

The method according to claim 1,
20 to 55% by weight of a colorant relative to the total solid content in the black photosensitive resin composition; 20 to 45% by weight of an alkali-soluble resin; 5 to 50% by weight of photopolymerizable compound; 0.1 to 40% by weight of a photopolymerization initiator; And 60 to 90% by weight of a solvent based on the total content of the black photosensitive resin composition.
A pattern layer made of the black photosensitive resin composition according to any one of claims 1 to 8.
The pattern layer according to claim 9, wherein the pattern layer is at least one selected from the group consisting of a column spacer, a black matrix and a black column spacer.
A color filter comprising the patterned layer of claim 9.
A liquid crystal display device comprising the color filter of claim 11.