KR20200078978A - Photosensitive resin composition, and color filter and liquid crystal display device formed therefrom - Google Patents

Abstract

The present invention relates to a black photosensitive resin composition, a color filter prepared using the same, and a liquid crystal display device comprising the same. In particular, the black photosensitive resin composition comprises: a pigment; a binder resin; a photopolymerizable monomer; and a photopolymerization initiator, wherein the pigment comprises, with respect to the total weight of solids in the composition, 1.0-4.0 wt% of Orange 64, 20.0-30.0 wt% of Blue 60, and 10.0-15.0 wt% of Violet 29, and the absorbance ratio of a film prepared with the black photosensitive resin composition satisfies relation 1: 1.10 < [absorbance at 550 nm / absorbance at 650 nm] < 1.20.

Description

Black photosensitive resin composition and color filter and liquid crystal display device formed therefrom{PHOTOSENSITIVE RESIN COMPOSITION, AND COLOR FILTER AND LIQUID CRYSTAL DISPLAY DEVICE FORMED THEREFROM}

The present invention relates to a black photosensitive resin composition, a color filter formed therefrom, and a liquid crystal display device.

Displays are becoming the most common means of communication in modern society. Therefore, in many studies, development of a display device has been made, and a liquid crystal display (LCD) is one of the widely used flat panel display devices, which includes a thin film transistor substrate with a pixel electrode and a color filter substrate with a common electrode. They are opposed to each other, and a liquid crystal layer is inserted between them. Such a liquid crystal display device displays an image in such a way that the amount of light transmitted through the liquid crystal layer is controlled by rearranging the liquid crystal molecules of the liquid crystal layer by applying a voltage to the pixel electrode and the common electrode. In addition, the organic light emitting display (OLED), which is receiving attention as a next-generation display, has an advantage in developing a flexible display because it uses a self-luminous device instead of a liquid crystal as described above.

In general, in display elements such as thin film transistor (TFT) type liquid crystal display elements and organic EL (electroluminescent) elements, a patterned electrode protective film, a planarization film, an insulating film, and the like are provided. As a material for forming these films, among the photosensitive resin compositions, photosensitive resin compositions having a characteristic having sufficient flatness and a small number of steps for obtaining a required pattern shape have been widely used from the past.

Among them, the black photosensitive resin is an essential material such as a color filter, a liquid crystal display material, an organic light emitting device, and a display. For example, in the case of a color filter used in a liquid crystal display, pixels composed of red (R), green (G), and blue (B) colors are configured. In addition, in this case, in order to prevent mixing of different colors in each pixel or to hide the pattern of the electrode, a black matrix is also formed at the boundary between the black layers of each color. In addition, BCS (Black Colum Space) is a part that comes into contact with the liquid crystal, and requires excellent solvent resistance and free residue on the organic film. Accordingly, it is necessary to obtain a uniform optical film per μm of the black matrix and to form a uniform coating film, and a black photosensitive resin having excellent solvent resistance and no residue on the organic film.

On the other hand, in connection with this, in the case of the Republic of Korea Publication No. 10-2014-0096423, etc., discloses a black photosensitive resin composition formed by using a combination of black and blue pigments, such photosensitive resin compositions, etc., generally form a black matrix, etc. The purpose is to do this, there is a problem that can not solve the problem such as the occurrence of the reddish phenomenon when the black matrix is formed.

Republic of Korea Publication 10-2014-0096423

The present invention secures a uniform optical density per μm of the black matrix, forms a uniform coating film, has excellent solvent resistance and has no effect on the organic film, as well as the reddish phenomenon described above. It is to provide an excellently improved black photosensitive resin composition.

In addition, the present invention is to provide a color filter manufactured using the black photosensitive resin composition.

In addition, the present invention is to provide a display device including the color filter.

The present invention is a pigment; Binder resin; A black photosensitive resin composition comprising a photopolymerizable monomer and a photopolymerizable initiator,

The pigment comprises 1.0 to 4.0% by weight of Orange 64, 20.0 to 30.0% by weight of Blue 60, and 10.0 to 15.0% by weight of Violet 29, based on the total weight of the composition solids,

It provides a black photosensitive resin composition, the ratio of the absorbance at 550nm and 650nm for the coating film made of the black photosensitive resin composition satisfies the following equation (1).

[Equation 1]

1.10 <[absorbance at 550 nm/absorbance at 650 nm] <1.20

In addition, the present invention provides a color filter made of the above-described black photosensitive resin composition.

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

According to the black photosensitive resin composition of the present invention, it ensures a uniform optical density per μm of the black matrix, forms a uniform coating film, has excellent solvent resistance and has no effect of residue on the organic film. , It is possible to achieve an excellently improved effect, such as the reddish phenomenon described above.

In addition, by including a black matrix or the like made of the black photosensitive resin composition, it is possible to provide a color filter having excellent shielding properties and a liquid crystal display device including the same.

1 is a diagram of absorbance spectra of Examples 2 and 3 and Comparative Examples 1 and 3.

Hereinafter, specific embodiments of the present invention will be described in detail so that those skilled in the art to which the present invention pertains can easily practice them.

In the present invention, when the ratio of the absorbance at 550 nm and the absorbance at 650 nm of the prepared coating film while using a specific pigment in a specific content in the black photosensitive resin composition satisfies a specific condition, the coating film prepared from the composition or black photosensitive It secures a uniform optical density per µm of the resin black matrix, forms a uniform coating film, has excellent solvent resistance and has no effect on the organic film, and improves the reddish phenomenon described above. It was completed by experimentally confirming that it provided an effect.

The present invention includes a black photosensitive resin composition as described above, a color filter manufactured using the same, and a liquid crystal display device including the same.

<Black photosensitive resin composition>

Pigment

Pigments in the present invention are included to prevent the excellent optical density and reddish phenomenon.

The present invention includes 1.0 to 4.0% by weight of C.I pigment Orange 64, 20.0 to 30.0% by weight of C.I pigment Blue 60, and 10.0 to 15.0% by weight of C.I pigment Violet 29, based on the total weight of solids.

The Orange 64, may be included in 1.0 to 4.0% by weight. When Orange 64 is included in the range of less than 1.0% by weight, the problem that the unit OD decreases may occur, and when it is included in excess of 4.0% by weight, it is not preferable in that the problem that the NMP dissolution characteristics may deteriorate may occur.

The Blue 60 may be included in 20.0 to 30.0% by weight. When Blue 60 is included in the range of less than 20.0% by weight, the reddish problem of the substrate may occur, and when it is included in excess of 30.0% by weight, it is not preferable in that the problem of deteriorating NMP elution characteristics may occur.

The Violet 29 may be included in 10.0 to 15.0% by weight. When the Violet 29 is contained in an amount of less than 10.0% by weight, a problem that a unit OD may be lowered may occur, and when it is included in an amount exceeding 15.0% by weight, it is not preferable in that a reddish problem of the substrate may occur.

The absorbance ratio at 550 nm and 650 nm for the coating film made of the black photosensitive resin composition satisfies Equation 1 below, and when it satisfies Equation 1, it is preferable in that the reddish problem is improved. When the value of Equation 1 below is exceeded, a reddish phenomenon becomes unavoidable, and there is a problem in that the black matrix appears red, and thus there is a problem that the efficiency of contrast may decrease.

[Equation 1]

1.10 <[absorbance at 550 nm/absorbance at 650 nm] <1.20

In addition, the black photosensitive resin composition of the present invention may further include a black pigment to adjust optical properties. The black pigment may be appropriately selected from inorganic or organic pigments. Black black agents that can be used include carbon black, athenylene black, lamp black, bone black, graphite, iron black, aniline black, cyanine black, titanium black, lambtam black, perylene black, etc., depending on the purpose. Organic pigments may be used alone or in combination. Most preferably, carbon black can be used.

The black pigment content range may be 0 to 6%, more preferably 5 to 6%, based on the total weight of the solid content of the black photosensitive resin composition.

The pigment may be included in the total solid content of the black photosensitive resin composition at 31 to 55% by weight, and more preferably when it is included at 40 to 50% by weight. When the pigment is included within the above range, it is preferable in that it can exhibit sufficient shielding properties, excellent optical density (OD), and control the reddish phenomenon.

Binder resin

In the present invention, the binder resin usually makes the non-exposed portion of the photosensitive resin layer formed by using the photosensitive resin composition to be alkali-soluble, and can also act as a dispersion medium for the pigment. The binder resin may be selected from various polymers used in the field of application, but a binder resin containing an epoxy group may be more effective. This is because the binder resin containing the epoxy group may affect reliability. The molecular weight of the binder resin is not particularly limited, for example, the polystyrene-equivalent weight average molecular weight (hereinafter, weight average molecular weight) is 3,000 to 100,000, preferably 3,000 to 50,000, more preferably 5,000 to 50,000 . In addition, the acid value of the binder resin is preferably in the range of 50 to 200 mg·KOH/g on a solid basis. When the acid value of the alkali resin satisfies the above-mentioned range, there is an advantage that developability for alkali development is excellent, residue generation is suppressed, and adhesion of the pattern is improved.

The binder resin may be included in 18.8 to 32.9% by weight in the total solid content of the black photosensitive resin composition, and is more preferably included in 24.8 to 29.7% by weight. When the content of the binder resin is included within the above range, it is preferable in that the dispersibility of the black agent is increased, and the performance of the black agent can be excellently expressed.

Photopolymerizable compound

The photopolymerizable compound of the present invention contains an unsaturated bond and undergoes a photoreaction with a photoinitiator to form a photosensitive resin layer, and the polymerizable compound applied in the present invention includes a commonly used (meth)acrylate as a functional group It is possible to use, as long as it contains an unsaturated group and has photosensitivity, there are no restrictions on its use.

Specific examples of the photopolymerizable compound, ethylene glycol diacrylate, triethylene glycol diacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, pentaerythrate Litolacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, dipentaerythritol diacrylate, dipentaerythritol triacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate , Bisphenol A diacrylate, trimethylolpropane triacrylate, novolac epoxyacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, propylene glycol dimethacrylate, And 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, and the like. The photopolymerizable compounds illustrated above may be used alone or in combination of two or more.

The photopolymerizable compound may be included in an amount of 8.8 to 15.5% by weight, and more preferably 11.5 to 14.0% by weight in the total solid content of the black photosensitive resin composition. Pattern content when the content of the photopolymerizable compound is included within the above range It is preferable because it is formed satisfactorily.

Photopolymerization initiator

The photopolymerization initiator of the present invention initiates a radical reaction of the photosensitive resin composition, thereby causing curing and improving sensitivity. As the photopolymerization initiator generally used in the photosensitive resin composition, acetophenone-based, benzophenone-based, triazine-based, thioxanthone-based, oxime-based, benzoin-based, and biimidazole-based compounds may be used.

Examples of acetophenone-based compounds include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, and 2-hydroxy-1-[4-(2 -Hydroxyethoxy)phenyl]-2-methylpropan-1-one, 1-hydroxycyclohexylphenylketone, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropane-1- On, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, 2-hydroxy-2-methyl[4-(1-methylvinyl)phenyl]propane-1- Ong oligomers etc. are mentioned, Preferably 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one etc. are mentioned. In addition, photopolymerization initiators other than the above acetophenone system can be used in combination. Examples of the photopolymerization initiator other than acetophenone are active radical generators, sensitizers, and acid generators that generate active radicals by irradiating 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, and benzoisobutyl ether. Examples of the benzophenone-based compound include benzophenone, methyl o-benzoylbenzoate, 4-phenylzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3',4,4'-tetra( and t-butyl peroxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, and the like. As the thioxanthone-based compound, for example, 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-dichlorothioxanthone, 1-chloro- 4-propoxycity oxanthone; and the like. As the triazine-based compound, for example, 2,4-bis (trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4-bis (trichloromethyl) -6-(4-methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxystyryl)-1,3,5-tri Azine, 2,4-bis(trichloromethyl)-6-[2-(5-methylfuran-2-yl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl )-6-[2-(furan-2-yl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino- 2-methylphenyl)ethenyl]-1,3,5-triazine,2,4-bis(trichloromethyl)-6-[2-(3,4dimethoxyphenyl)ethenyl]-1,3,5 -Triazine and the like. 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-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, methyl phenylglyoxylate, titanocene Compounds and the like can be used. Examples of the acid generator include 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluenesulfo Nate, 4-acetoxyphenylmethylbenzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate, And onium salts such as diphenyl iodonium hexafluoroantimonate, nitrobenzyl tosylates, and benzointosylates. In addition, among the compounds as an active radical generator, there are also compounds which generate an acid simultaneously with the active radical, for example, a triazine-based photopolymerization initiator is also used as an acid generator.

The photopolymerization initiator may be included in an amount of 1.0 to 2.0% by weight, preferably 1.4 to 1.8% by weight based on the total weight of solids in the black photosensitive resin. When the photopolymerization initiator is included within the above range, the pattern formation is good, the black photosensitive resin composition is highly sensitive, and the intensity of the pixel portion formed using the composition or the smoothness on the surface of the pixel portion tends to be good, which is preferable. Do.

Furthermore, in the present invention, a photopolymerization initiation aid can be used. The photopolymerization initiator auxiliary is sometimes used in combination with a photopolymerization initiator, and is a compound used to accelerate polymerization of a photopolymerizable compound in which polymerization has been initiated by the photopolymerization initiator. Examples of the photopolymerization initiation aid include amine compounds, alkoxyanthracene compounds, thioxanthone compounds, carboxylic acid compounds, and sulfonic acid compounds.

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, N,N-dimethylparatoluidine, 4,4'-bis(dimethylamino)benzphenone (commonly known as Mihiler's Ketone), 4,4'-bis (diethyl Amino) benzophenone, 4,4'-bis(ethylmethylamino)benzophenone, and the like, and among these, 4,4'-bis(diethylamino)benzophenone is preferable.

Examples of the alkoxyanthracene-based compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, and 2-ethyl-9,10-diethoxyanthracene. And the like. As the thioxanthone-based compound, for example, 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-dichlorothioxanthone, 1-chloro- 4-propoxycity oxanthone; and the like.

Specific examples of the carboxylic acid compound include phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, and dichloro Aromatic heteroacetic acids such as phenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, and naphthoxyacetic acid.

These photopolymerization initiators (D) may be used alone or in combination. Moreover, what is marketed can be used as a photopolymerization start adjuvant, As a commercial photopolymerization start adjuvant, the brand name "EAB-F" (manufacturer: Hodogaya Chemical Industry Co., Ltd.) etc. are mentioned, for example.

When using these photoinitiator, the amount used is usually 10 mol or less per mole of the photopolymerization initiator, preferably 0.01 to 5 mol. If it is in the above range, the sensitivity of the black photosensitive resin composition becomes higher, and the productivity of the color filter formed using the composition tends to improve, which is preferable.

solvent

The solvent contained in the black photosensitive resin composition of the present invention is not particularly limited, but is compatible with the above-described configurations, but is preferably not reacted. Various organic solvents used in the field of black photosensitive resin compositions 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, mesitylene, and methyl ethyl ketone , Ketones such as acetone, methyl amyl ketone, methyl isobutyl ketone, cyclohexanone, alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol and glycerin, 3-ethoxypropionic acid ethyl, 3- And esters such as methyl methoxypropionate, and cyclic esters such as γ-butyrolactone. Among the above-mentioned solvents, organic solvents having a boiling point of 100°C to 200°C can be exemplified in terms of coatability and dryness, and more preferably, alkylene glycol alkyl ether acetates, ketones, and 3-ethoxy. And esters such as ethyl propionate and methyl 3-methoxypropionate. More preferably, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, 3-ethoxypropionate ethyl, 3- And methyl methoxypropionate. These solvents may be used alone or in combination of two or more, and organic solvents having different boiling points may be mixed and used.

The content of the solvent in the black photosensitive resin composition of the present invention may be 30 to 90% by weight, preferably 75 to 85% by weight, more preferably 79 to 83% by weight, based on the total weight of the black photosensitive resin composition containing it. . When the content of the solvent is within the above range, the coating properties are good, and it is preferable from the viewpoint of easy curing.

additive

The blue photosensitive resin composition of the black pattern layer according to the present invention may further include additives such as a filler, another polymer compound, a curing agent, a leveling agent, an adhesion enhancer, and an acid generator, if necessary.

Glass, silica, alumina, or the like may be used as the filler, and specific examples of the other polymer compound include curable resins such as epoxy resins and maleimide resins; And thermoplastic resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, polyester, and polyurethane.

The curing agent is used to increase the core hardening and mechanical strength, and specific examples of the curing agent include an epoxy compound, a polyfunctional isocyanate compound, a melamine compound, and an oxetane compound. Specific examples of the epoxy compound in the curing agent, bisphenol A-based epoxy resin, hydrogenated bisphenol A-based epoxy resin, bisphenol F-based epoxy resin, hydrogenated bisphenol F-based epoxy resin, no-block type epoxy resin, other aromatic epoxy resin, alicyclic epoxy resin, Glycidyl ester-based resins, glycidyl-amine-based resins, or brominated derivatives of these epoxy resins, aliphatic resins other than epoxy resins and brominated derivatives, alicyclic or aromatic epoxy compounds, butadiene (co)polymer epoxides, isoprene (co ) Polymer epoxides, glycidyl (meth) acrylate (co) polymers, triglycidyl isocyanurate, and the like. Specific examples of the oxetane compound in the curing agent include carbonate bisoxetane, xylene bisoxetane, adipate bisoxetane, terephthalate bisoxetane, and cyclohexanedicarboxylic acid bisoxetane. The curing agent may be used in combination with a curing agent, an epoxy group of the epoxy compound, a curing auxiliary compound capable of ring-opening polymerization of the oxetane skeleton of the oxetane compound.

As said hardening auxiliary compound, polyhydric carboxylic acids, polyhydric carboxylic anhydrides, an acid generator, etc. are mentioned, for example. As the carboxylic acid anhydride, commercially available ones can be used as the epoxy resin curing agent. As said epoxy resin curing agent, for example, a brand name (Adeka Hadona EH-700) (made by Adeka Industries Co., Ltd.), a brand name (Rikasitdo HH) (manufactured by Shin Nippon Ewha Co., Ltd.), a brand name (MH-700) ( Shin Nippon Ewha Co., Ltd.). The curing agents exemplified above can be used alone or in combination of two or more.

As an additive added in the present invention, an acid generator may be more preferable. It may be more preferable to use a thermal acid generator that generates acid when heat is applied to the acid generator. The thermal acid generator is a material that generates acid by heat, and refers to a component that generates acid by heat treatment (eg, post-baking, etc.) applied in the process of curing the black photosensitive resin composition to promote curing of the pattern. The thermal acid generator is more preferably a thermal acid generator represented by Formula 1 below.

[Formula 1]

In Chemical Formula 1,

R2 is a 3 to 8 cycloalkyl group,

R3 is a C1-C8 alkyl group or a C6-C10 aryl group.

In the present invention, the alkyl group is not particularly limited, but may be straight chain or branched chain, and preferably has 1 to 8 carbon atoms. Specific examples are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, n-pentyl, isopentyl, neo Pentyl, tert-pentyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, n-heptyl, 1-methylhexyl, n -Octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethylheptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl, and the like, but are not limited to these.

In the present invention, it is preferable that the cycloalkyl group has 3 to 8 carbon atoms. Specific examples include cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3,4,5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl, and the like, but is not limited thereto.

The cycloalkyl group may be substituted or unsubstituted with a hydroxy group, but is not limited thereto.

In the present invention, the aryl group is not particularly limited, but preferably has 6 to 8 carbon atoms, and may be a monocyclic aryl group or a polycyclic aryl group. The monocyclic aryl group may be a phenyl group, a biphenyl group, a terphenyl group, or a stilbenyl group, but is not limited thereto. The polycyclic aryl group may be a naphthyl group, anthracenyl group, phenanthryl group, pyrenyl group, perylenyl group, chrysenyl group, fluorenyl group, and the like, but is not limited thereto.

The aryl group may be substituted or unsubstituted with an alkyl group, specifically a methyl group.

Specifically, the thermal acid generator represented by Chemical Formula 1 may be represented by the following Chemical Formulas 1-1 to 1-3, and may be used alone or in combination of two or more.

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

When the thermal acid generator is included, the solution uniformity of the solvent is secured to improve solubility, and the black photosensitive resin composition is highly sensitive to strength of the pattern portion formed using the black photosensitive resin composition or smoothness on the surface of the pattern portion It is preferable because it tends to be good, and the solvent resistance can be excellent.

As said leveling agent, a commercially available surfactant can be used, For example, surfactants, such as silicone type, fluorine type, ester type, cationic type, anionic type, nonionic type, positive, etc. are mentioned, These are each independently You may use it in combination of 2 or more type. Examples of the surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid modified polyesters, tertiary amine modified polyurethanes, Besides polyethyleneimines, KP (manufactured by Shin-Etsu Chemical Industry Co., Ltd.), polyflow (manufactured by Kyoe Chemical Co., Ltd.), F-Top (manufactured by Tochem Products Co., Ltd.), Megapak (Dainippon ink chemical industry Manufactured), Florad (manufactured by Sumitomo 3M Co., Ltd.), Asahi Guard, Saffron (above, manufactured by Asahi Garas Co., Ltd.), Sorpas (manufactured by Geneca Corporation), EFKA ), PB821 (made by Ajinomoto Co., Ltd.), etc. are mentioned.

As the adhesion enhancer, a silane-based compound is preferable, specifically, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, N-(2-aminoethyl)- 3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycine Cydoxypropylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxy And propyl trimethoxysilane, 3-mercaptopropyl trimethoxysilane, and the like.

The additives can be used by appropriately added by those skilled in the art within a range that does not impair the effects 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, and more preferably 0.1 to 5 parts by weight based on 100 parts by weight of the black photosensitive resin composition, but is not limited thereto.

The black photosensitive resin composition according to the present invention may be prepared by, for example, the following method, but is not limited thereto. The black agent is mixed with a solvent and dispersed. If necessary, a dispersing agent may be further used, and part or all of the binder resin may be blended. The remainder of the binder resin, a photopolymerizable compound, a photopolymerization initiator, and other components used as necessary and additional solvents as necessary are further added to the obtained dispersion (hereinafter, sometimes referred to as a mill base) to a predetermined concentration. The desired black photosensitive resin composition can be obtained.

In the present invention, the coated film prepared from the black photosensitive resin composition may have an optical density of 1.24 or more per 1.0 μm of the film thickness at 550 nm. When the optical density range is satisfied, it is preferable in terms of preventing light leakage and mixing of neighboring pixels.

The coating film prepared from the black photosensitive resin composition of the present invention may have an optical density of 1.0 or more per 1.0 μm of the coating thickness at 650 nm. When the optical density range is satisfied, it is preferable in terms of preventing light leakage and mixing of neighboring pixels.

The peak absorbance of the coating film NMP solvent prepared from the black photosensitive resin composition of the present invention may be less than 7, and less than 5 may be more preferable. The peak absorbance is more specifically, the sum of 400 nm to 700 nm absorbance, and the measurement means measured at 1 nm intervals. When the peak absorbance range is satisfied, it is preferable from the viewpoint of chemical resistance, which is a solvent of the alignment layer and prevents color contamination in a post process. prevent.

<Color filter and liquid crystal display>

Another aspect of the present invention relates to a color filter comprising a black pattern layer comprising a cured product of the black photosensitive resin composition for forming a black pattern layer described above.

The color filter according to the present invention has an advantage of excellent reliability and excellent shielding property due to high optical density, minimized NMP elution by including green, orange, and purple black agents without excessive addition of black black agents to the black 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 located in 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, and the polymer substrate may be polyethersulfone (PES) or polycarbonate (PC).

The pattern layer is a layer containing the black photosensitive resin composition of the present invention, and may be a layer formed by applying the black photosensitive resin composition for forming the black pattern layer and exposing, developing, and heat-curing it in a predetermined pattern. It can be formed by performing a method commonly known in the art.

In another embodiment of the present invention, the color filter may further include one or more 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 may further include a partition formed between each pattern, 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 including a cured product of the above-described black photosensitive resin composition.

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

When the liquid crystal display includes the color filter including the pattern layer according to the present invention, it has an advantage of being excellent in shielding properties and reliability. In addition, the black photosensitive resin composition included in the color filter according to the present invention minimizes the reddish phenomenon by including the green colorant in addition to the orange and purple colorants, and the color filter comprising the photosensitive resin composition and the liquid crystal display device comprising the same It has the advantage of excellent color reproduction.

Hereinafter, examples will be described in detail to specifically describe the present specification. However, the embodiments according to the present specification may be modified in various other forms, and the scope of the present specification is not interpreted to be limited to the embodiments described below. The embodiments of the present specification are provided to more fully describe the present specification to those skilled in the art. In addition, "%" and "part" which represents content below are on a weight basis unless otherwise specified.

Synthesis Example: Synthesis of binder resin (B) and dispersion resin

After adding 277 g of methoxybutyl acetate to a 1-liter separable flask equipped with a stirrer, thermometer, reflux cooling tube, dropping funnel, and nitrogen introduction tube, heated to 80° C., and then heated to 3,4-epoxytricyclo[5.2.1.02 ,6]Decan-9-ylacrylate and 3,4-epoxytricyclo[5.2.1.02,6]decan-8-ylacrylate mixture [50:50 (molar ratio)] 301g, methacrylic acid 49g, And a mixture solution of 23 g of azobisdimethylvaleronitrile dissolved in 350 g of methoxybutyl acetate was added dropwise over 5 hours, and further aged for 3 hours to obtain copolymer solution A [solid content (NV) 35.0 wt%]. The obtained copolymer had an acid value of 69.8 KOH mg/g, a weight average molecular weight (Mw) of 12300, and a dispersion degree (Mw/Mn) of 2.1.

Production Example 1: Preparation of pigment dispersion (B-1)

C.I. Pigment Orange 64 (PO64) 15.0 parts by weight, dispersion resin 3 parts by weight of the dispersion resin synthesized under the above conditions (converted to solid content) [solid content (NV) 35.0% by weight], dispersant is acrylic polymer dispersant (DISPERBYK-2000) 7 parts by weight Part (converted to solid content) [Composition of solid content (NV) 40.0 wt%] and 75 parts by weight of propylene glycol monomethyl ether acetate as a solvent and a rigid milling medium (zirconia beads) having an average particle size of 0.1 mm in a weight ratio of 50:50 The mixture was added and mixed, followed by co-dispersion of four pigments for 4 to 6 hours with a bead mill to prepare a black dispersion (B-1).

Production Examples 2 to 4: Preparation of pigment dispersions (B-2) to (B-4)

C.I. in the same manner as in Production Example 1 of the pigment dispersion (B-1). Pigment Orange 64 (PO64) instead of C.I. Pigment Blue B60, C.I. Pigment Violet 29 and carbon black (CB) were respectively introduced and changed to prepare B-4 through B-4 in black dispersions according to the composition of Table 1.

[Table 1]

Examples 1 to 6 and Comparative Examples 1 to 10: Preparation of black photosensitive resin composition

According to the composition of Table 2, black photosensitive resin compositions of Examples 1 to 6 and Comparative Examples 1 to 10 were prepared.

[Table 2]

Substrate manufacturing

The 5 cm X 5 cm glass substrate (Corning) was washed with a neutral detergent and water and dried. Each of the black photosensitive resin compositions prepared in Examples 1 to 6 and Comparative Examples 1 to 10 was spin coated on the glass substrate so that the final film thickness was 3.0 µm, followed by pre-firing at 80 to 120° C. to 1 to 2 The solvent was removed by drying for a minute. Then, exposure was performed at an exposure amount of 25 to 35 mJ/cm ² to form a pattern, and an unexposed portion was removed using an aqueous alkali solution. Subsequently, a black substrate was prepared by baking at 200 to 250° C. for 10 to 30 minutes.

Experimental Example 1: Optical density evaluation

O.D. using the prepared coating films of Examples 1 to 6 and Comparative Examples 1 to 10. And the film thickness was measured to calculate O.D./μm. OD was measured using X-rite, and film thickness was measured using Dektak.

The results for O.D./μm of Examples 1 to 6 and Comparative Examples 1 to 10 are shown in Table 4 according to the evaluation criteria in Table 3 below.

Experimental Example 2: Evaluation of absorbance ratio

Using the prepared coating films of Examples 1 to 6 and Comparative Examples 1 to 10, absorbance at visible wavelength was measured using a Shimadzu UV-2600 device. The absorbance (@1 μm) of Examples 1 to 6 and Comparative Examples 1 to 10 was measured to calculate the absorbance ratio according to Equation 2 below, and the results are shown in Table 4.

[Equation 2]

Absorption ratio = absorbance at 550nm/absorbance at 650nm

Spectra related to the absorbance of the coating films produced using Examples 1 to 6 and Comparative Examples 1 to 10 are shown in FIG. 1.

Experimental Example 3: Near IR T% evaluation

Using the prepared coating films (film thickness of 3.2 um) of Examples 1 to 6 and Comparative Examples 1 to 10, transmittance at 880 nm was measured using a UV-2600 device manufactured by shimadzu.

Experimental Example 4: NMP dissolution evaluation

Reliability was determined by measuring solvent resistance using the prepared coating films of Examples 1 to 6 and Comparative Examples 1 to 10.

The solvent resistance measurement was performed by immersing the coating film (3*3) in an NMP 18g solution at 100 degrees for 60 minutes, and then extracting the NMP solvent and measuring the absorbance at the visible light wavelength of the NMP solvent after immersion using a Shimadzu UV-2600 instrument. . The peak absorbance of the NMP solvent (sum of 400 nm to 700 nm absorbance, measurement is measured at 1 nm intervals) after immersing the color filters of Examples 1 to 6 and Comparative Examples 1 to 10 is shown below.

Specifically, the black photosensitive resins of Examples 1 to 6 and Comparative Examples 1 to 10 were evaluated by the methods of Experimental Examples 1 to 4, and the values evaluated based on Table 3 are shown in Table 4 below.

Experimental Example 5: Evaluation of storage stability

The storage stability of the prepared black dispersions of Examples 1 to 6 and Comparative Examples 1 to 10 was measured for a viscosity change rate (viscosity after 1 week at 40°C/initial viscosity Х100), and the results are shown in Table 4 below.

The evaluation criteria were as follows.

<Evaluation criteria>

○: Viscosity change rate less than 105%

△: Viscosity change rate of more than 105%, less than 110%

×: viscosity change rate of 110% or more

[Table 3]

[Table 4]

As can be seen from the results of the experiment, it was confirmed that in Examples 1 to 6, which correspond to the claims of the present invention, by achieving a specific light absorption ratio, an excellent optical density and excellent solvent resistance and storage stability effect were achieved. . On the other hand, in the case of the black photosensitive resins of Comparative Examples 1 to 10 that did not satisfy the pigment range and/or the absorbance ratio, it was confirmed that the effect was poor in terms of optical density, solvent resistance and storage stability.

Claims (11)

Pigment; Binder resin; A black photosensitive resin composition comprising a photopolymerizable monomer and a photopolymerizable initiator,
The pigment comprises 1.0 to 4.0% by weight of Orange 64, 20.0 to 30.0% by weight of Blue 60, and 10.0 to 15.0% by weight of Violet 29, based on the total weight of the composition solids,
The black photosensitive resin composition, the ratio of absorbance at 550nm and 650nm to the coating film made of the black photosensitive resin composition satisfies the following formula (1).
[Equation 1]
1.10 <[absorbance at 550 nm/absorbance at 650 nm] <1.20
The black photosensitive resin composition according to claim 1, wherein the coating film prepared from the black photosensitive resin composition has an optical density of 1.24 or more per 1.0 μm of the film thickness at 550 nm.
The black photosensitive resin composition according to claim 1, wherein the coating film prepared from the black photosensitive resin composition has an optical density of 1.0 or more per 1.0 μm of the film thickness at 650 nm.
The black photosensitive resin composition according to claim 1, wherein the peak absorbance of the NMP solvent of the coating film prepared from the black photosensitive resin composition is less than 5.
The method according to claim 1, The pigment is a black photosensitive resin composition that further comprises a black pigment.
The black photosensitive resin composition of claim 5, wherein the black pigment includes carbon black.
The method according to claim 1, wherein the black photosensitive resin composition further comprises a solvent, the black photosensitive resin composition.
The method according to claim 1, wherein the black photosensitive resin composition further comprises an additive, black photosensitive resin composition.
The method according to claim 7, wherein the black photosensitive resin composition in the total solid content of the pigment 31 to 55% by weight; Binder resin 18.8 to 32.9 wt%; 8.8 to 15.5 wt% of a photopolymerizable compound; A black photosensitive resin composition comprising 1.0 to 2.0% by weight of a photopolymerization initiator and 75 to 85% by weight of a solvent relative to the total content of the black photosensitive resin composition.
A color filter made of the black photosensitive resin composition of any one of claims 1 to 9.
A liquid crystal display device comprising the color filter of claim 10.

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