TWI735817B - Colored photosensitive resin composition, pattern layer manufactured using the same, and color filter and display device including the pattern layer - Google Patents

Abstract

The present invention relates to a colored photosensitive resin composition comprising a colorant containing a blue pigment and an orange pigment, an alkali-soluble resin, a photo polymerizable compound, a photo polymerization initiator and a solvent, a pattern layer produced using the colored photosensitive resin composition, and a display device.

Description

Colored photosensitive resin composition and patterns manufactured using it Layer, color filter and display device including pattern layer

The present invention relates to a colored photosensitive resin composition, a pattern layer manufactured using the composition, and a color filter and a display device including the pattern layer.

Color filters are widely used in various display devices such as imaging elements and liquid crystal display devices (LCDs), and their application range is rapidly expanding. The color filters used in the above-mentioned imaging elements, liquid crystal display devices, etc. are formed of three color patterns of red (Red), green (Green) and blue (Blue), or are made of yellow (Yellow) and magenta (Magenta) The coloring patterns of the three colors and Cyan are formed.

Each colored pattern of the above-mentioned color filter is generally formed using a colored photosensitive resin composition containing a colorant such as a pigment or dye, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent. The coloring pattern processing using the above-mentioned colored photosensitive resin composition is usually performed by a photolithography process.

Colored photosensitive resins are necessary materials for color filters, liquid crystal display materials, organic light-emitting elements, displays, and the like. For example, used in liquid crystal displays In the case of the color filter, it contains pixels composed of red (Red), green (Green) and blue (Blue). In order to prevent the color mixing of these pixels or hide the electrode pattern, the The boundary portion between the colored layers forms a black matrix. In addition, the black column spacer (Black Colum Spacer, BCS) is the part that is in direct contact with the liquid crystal. It not only functions as a black matrix, but also functions as a spacer for cell gap maintenance. In addition to light shielding and solvent resistance In addition to sex, various characteristics such as elastic recovery rate are also required.

In recent years, the proportion of LCDs in the field of flat panel displays has been expanding, and as the screen area has become larger, bright backlights have been adopted. As the backlight becomes brighter, the black matrix is also required to have higher shading characteristics than before. However, when the content of pigments is increased in order to improve the shading characteristics, it is difficult to realize the basic characteristics of black matrix such as compression displacement and elastic recovery rate. When the content of carbon black is increased in order to reduce the content of pigments, the process characteristics continue Deteriorating, the defective rate becomes higher, and the problem of lowering the production yield rate occurs.

Korean Patent Publication No. 10-2011-0027079 relates to a black photosensitive composition and a light-shielding layer formed using the composition, and discloses a black photosensitive composition containing orange, blue, and violet pigments in a specific mixing ratio, but Improvements in solvent resistance, light transmittance, and elastic recovery rate are still insufficient.

In addition, Korean Patent Publication No. 10-2014-0121824 relates to a colored photosensitive composition, and similarly discloses a black photosensitive composition containing orange, blue, and purple pigments in a specific mixing ratio, but the optical density is different. The improvement is not yet sufficient.

Prior art literature Patent literature

Patent Document 1: Korean Published Patent No. 10-2011-0027079

Patent Document 2: Korean Published Patent No. 10-2014-0121824

The present invention was made to solve the above-mentioned problems of the prior art, and its object is to provide a colored photosensitive resin composition that is excellent in solvent resistance, optical density, light transmittance, color coordinates, and elastic recovery.

In addition, an object of the present invention is to provide a pattern layer made of the colored photosensitive resin composition, a color filter including the pattern layer, and a display device including the color filter.

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, the colorant includes a blue pigment and an orange pigment, and the blue pigment is a CI pigment Blue 16.

In addition, the present invention provides a color filter including a pattern layer manufactured from the above-mentioned colored photosensitive resin composition of the present invention. Furthermore, the present invention provides a color filter including a columnar spacer, a black matrix, or a black columnar spacer manufactured from the colored photosensitive resin composition of the present invention.

In addition, the present invention provides a display including the above-mentioned color filter of the present invention Device.

The colored photosensitive resin composition of the present invention contains CI Pigment Blue 16 together with an orange pigment, thereby having the following effects: not only improving optical density (OD/μm), light transmittance at 750nm, light transmittance at 950nm, and color coordinates Such as basic optical properties, and improve physical properties such as reliability and elastic recovery rate.

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

The present invention relates to a colored photosensitive resin composition comprising a colorant, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent. The colorant includes a blue pigment and an orange pigment, and the blue pigment is CI Pigment Blue 16.

<Colored photosensitive resin composition>

Hereinafter, the colored photosensitive resin composition of the present invention will be explained in detail in accordance with each component.

<Colorant>

In the present invention, the coloring agent uses a substance having light-shielding properties against visible light, and the coloring agent of the present invention contains a blue pigment and an orange pigment.

The present invention is characterized in that the above-mentioned blue pigment is C.I. Pigment Blue 16. When the above-mentioned C.I. Pigment Blue 16 is included, a more excellent optical density (O.D/μm) can be obtained, and the influence in a specific wavelength region can be reduced.

More specifically, CI Pigment Blue 16 is a blue pigment that does not contain a central metal. Compared with the case of CI Pigment Blue 15:6 containing the central metal, it can improve the electrical characteristics of the product, which is comparable to the case of CI Pigment Blue 60. Shows more excellent characteristics than in terms of color development.

The above-mentioned orange pigment functions to reduce the light transmittance in the region of 400 to 550 nm to increase the optical density. Although the type of the orange pigment is not particularly limited, it is preferable to use one or more selected from the group consisting of C.I. Pigment Orange 46, 62, 64, 68, 72, and 77, and it is most preferable to use C.I. Pigment Orange 64.

In addition, the content of the blue pigment may be 8 to 22% by weight, preferably 10 to 18% by weight, relative to the total weight of the solid content in the colored photosensitive resin composition. The content of the orange pigment may be 3 to 12% by weight, preferably 5 to 10% by weight, relative to the total weight of the solid content in the colored photosensitive resin composition. If the content of the blue pigment and the orange pigment is in the above range, it is possible to obtain a colored photosensitive resin composition excellent in reliability, optical density, and optical properties such as light transmittance.

In addition, the colored photosensitive resin composition of the present invention may further include a purple pigment as an additional coloring agent. The above-mentioned purple pigment has the function of reducing the light transmittance in the region of 400 to 600 nm and increasing the optical density (O.D). Furthermore, by using the aforementioned purple pigment, the content of the organic black pigment can be reduced, and the reliability of the colored photosensitive resin composition can be improved. Above purple Although the type of the pigment is not particularly limited, it is preferable to use one or more selected from the group consisting of C.I. Pigment Violet 14, 19, 23, 29, 32, 33, 36, and 37, and it is most preferable to use C.I. Pigment Violet 23.

In addition, the content of the purple pigment may be 3 to 18% by weight, preferably 5 to 15% by weight, relative to the total weight of the solid content in the colored photosensitive resin composition. If the content of the purple pigment is in the above range, a colored photosensitive resin composition having excellent optical density and color coordinates can be obtained.

Furthermore, the colored photosensitive resin composition of this invention may further contain a black pigment as an additional coloring agent. The type of the black pigment is not particularly limited as long as it has light-shielding properties to visible light, but it is preferable to use one or more selected from the group consisting of internal amide black, aniline black, perylene black, titanium black, and carbon black. The carbon black is not particularly limited as long as it is a pigment having light-shielding properties, and a known carbon black can be used. Specific examples of the carbon black of the black pigment include channel black, furnace black, thermal black, lamp black, and the like. The above-mentioned carbon black may be coated with a resin, and the resin-coated carbon black has lower conductivity than uncoated carbon black, and can impart excellent electrical insulation when forming a black matrix or columnar spacer.

In addition, the content of the black pigment may be 12% by weight or less, preferably 10% by weight or less, relative to the total weight of the solid content in the colored photosensitive resin composition. If the content of the black pigment is in the above range, it can have more excellent characteristics in terms of optical density (O.D/μm) and color development.

In the present invention, relative to the solid in the colored photosensitive resin composition The total weight of the components, the content of the colorant is 18 to 55% by weight, preferably 20 to 50% by weight. If the content of the colorant is 18 to 55% by weight, the optical density and reliability are excellent.

In the present invention, the solid content in the colored photosensitive resin composition means the total of the components after the solvent has been removed.

In addition, it is preferable to use a pigment dispersion liquid in which the particle diameter of the pigment is uniformly dispersed as the above-mentioned colorant. As an example of a method for uniformly dispersing the particle size of the pigment, a method of adding a dispersant and performing a dispersion treatment, etc. can be mentioned. By the above method, a pigment dispersion liquid in a state where the pigment is uniformly dispersed in a solution can be obtained.

<Alkali-soluble resin>

In the present invention, the alkali-soluble resin generally makes the non-exposed portion of the photosensitive resin layer formed from the photosensitive resin composition alkali-soluble, and can also function as a dispersion medium for the pigment. The alkali-soluble resin can be selected from various polymers used in the technical field of its application. Alkali-soluble resins containing epoxy groups can be more effective.

This is because the alkali-soluble resin containing the epoxy group can affect the improvement of reliability. In addition, regarding the molecular weight of the alkali-soluble resin used, the weight average molecular weight may be 3,000 to 40,000, and is preferably in the range of 5,000 to 30,000. In addition, the acid value of the alkali-soluble resin is preferably 50 to 200 mg on a solid basis. The range of KOH/g. If the acid value of the alkali-soluble resin satisfies the above range, it has advantages such as excellent developability for alkali development, suppression of residue generation, and improvement of pattern adhesion.

Relative to the total solid content in the colored photosensitive resin composition By weight, the content of the alkali-soluble resin is 5 to 60% by weight, preferably 20 to 50% by weight. If the content of the alkali-soluble resin is within this range, the dispersibility of the colorant is improved, the pattern is easily formed, and the resolution and film retention rate are improved, which is preferable.

<Photopolymerizable compound>

The photopolymerizable compound of the present invention contains an unsaturated bond and undergoes photoreaction with a photopolymerization initiator to form a photosensitive resin layer. The photopolymerizable compound used in the present invention may include a generally used (methyl) group in the functional group. As long as the acrylate contains an unsaturated group and exhibits photosensitivity, there are no restrictions on its use.

As specific examples of the aforementioned photopolymerizable compound, ethylene glycol diacrylate, triethylene glycol diacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, Neopentyl glycol diacrylate, pentaerythritol acrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, dipentaerythritol diacrylate, dipentaerythritol triacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, bisphenol A two Acrylate, trimethylolpropane triacrylate, novolac epoxy acrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, propylene glycol two Methacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, etc. The photopolymerizable compounds exemplified above can be used alone or in combination of two or more.

In the total solid content of the colored photosensitive resin composition, the content of the photopolymerizable compound may be 5 to 50% by weight, and more preferably 10 to 40% by weight. In the case where the content of the above-mentioned photopolymerizable compound is within the above-mentioned range, The sensitivity is excellent, and the pattern characteristics are formed well, which is preferable.

<Photoinitiator>

The photopolymerization initiator of the present invention has a function of initiating a radical reaction of the photosensitive resin composition to cause curing and improving sensitivity. The photopolymerization initiator is a photopolymerization initiator generally used for photosensitive resin compositions, and oxime, acetophenone, benzophenone, triazine, thioxanthone, benzoin, and combination can be used. Imidazole-based compounds, etc.

The oxime compound includes, for example, o-ethoxycarbonyl-α-oxyimino-1-phenylpropan-1-one and the like, and it is more preferable to include OXE01 and OXE02 of BASF, which are commercially available products.

Examples of acetophenone compounds include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, benzyl dimethyl ketal, 2-hydroxy -1-[4-(2-hydroxyethoxy)phenyl]-2-methylpropane-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1-(4-methylsulfide Phenyl)-2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, 2-hydroxy- Oligomers of 2-methyl[4-(1-methylvinyl)phenyl]propan-1-one, etc., preferably 2-benzyl-2-dimethylamino-1-(4- Morpholinophenyl) butan-1-one and the like. In addition, photopolymerization initiators other than the above-mentioned acetophenone-based photopolymerization initiators may be used in combination. Examples of photopolymerization initiators other than the acetophenone series include active radical generators, sensitizers, and acid generators that generate active radicals by irradiation with light. Examples of active radical generators include benzoin-based compounds, benzophenone-based compounds, thioxanthone-based compounds, and triazine-based compounds. Examples of benzoin-based compounds include benzoin, benzoin methyl ether, benzoin Inin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, etc.

Examples of benzophenone-based compounds include benzophenone, methyl phthalate, 4-phenylbenzophenone, 4-benzophenone-4'-methyl diphenyl sulfide Ether, 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone, 2,4,6-trimethylbenzophenone, etc. As the thioxanthone compound, for example, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone and so on.

Examples of triazine-based compounds include 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, and 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine Chloromethyl)-6-(4-methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxystyryl) -1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(5-methylfuran-2-yl)ethylene]-1,3,5-tri Oxazine, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)ethylene]-1,3,5-triazine, 2,4-bis(trichloromethyl) )-6-[2-(4-Diethylamino-2-methylphenyl)ethylene]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6- [2-(3,4-Dimethoxyphenyl)ethylene]-1,3,5-triazine and the like.

Specific examples of the thioxanthone compound include 2-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro- 4-Propoxythioxanthone and so on.

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

Specific examples of the biimidazole-based compound include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'- Double(2,3-two Chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(alkoxy) Phenyl) biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(trialkoxyphenyl)biimidazole, 2,2-bis(2, 6-Dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, or 4,4',5,5' phenyl group substituted by alkoxycarbonyl Biimidazole compounds and so on.

The above-mentioned photopolymerization initiators can be used alone or in combination of two or more.

The content of the photopolymerization initiator may be 0.1 to 40% by weight, preferably 1 to 30% by weight, relative to the total weight of the solid content in the colored photosensitive resin composition. When the content of the photopolymerization initiator is within the above range, the pattern formation is good, the colored photosensitive resin composition is increased in flexibility, the intensity of the pixel portion formed using the composition, and the smoothness of the surface of the pixel portion The tendency to become better is therefore preferred.

In addition, in the present invention, a photopolymerization initiator may be additionally used in the photopolymerization initiator.

The photopolymerization initiation aid is a compound used to promote the polymerization of a photopolymerizable compound whose polymerization is initiated by a photopolymerization initiator. Examples of the photopolymerization initiation aid include amine-based compounds and alkoxyanthracene-based compounds. , Thioxanthone compounds, carboxylic acid compounds and sulfonic acid compounds, etc.

As the amine compound, specifically, for example, triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4 -Dimethylaminobenzoic acid isoamyl ester, benzoic acid 2- Dimethylaminoethyl, 2-ethylhexyl 4-dimethylaminobenzoate, N,N-dimethyl-p-toluidine, 4,4'-bis(dimethylamino)benzophenone ( Commonly known as Michler’s ketone), 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(ethylmethylamino)benzophenone, etc., among which 4,4 is preferred '-Bis(diethylamino)benzophenone.

Specific examples of the above-mentioned alkoxyanthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, and 9,10-diethoxy Anthracene, 2-ethyl-9,10-diethoxyanthracene, etc.

As the thioxanthone compound, for example, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone and so on.

Such a photopolymerization initiator can be used alone or in combination of multiple types. In addition, a commercially available photopolymerization initiation aid can be used. As a commercially available photopolymerization initiation aid, for example, a brand name "EAB-F" (manufacturer: Hodogaya Chemical Industry Co., Ltd.) and the like can be mentioned.

In the case of using these photopolymerization initiation aids, the usage amount thereof is usually 10 mol or less, preferably 0.01 to 5 mol relative to 1 mol of the photopolymerization initiator. If it is in the above-mentioned range, the color density of the colored photosensitive resin composition is further improved, and the productivity of the color filter formed using the composition tends to be improved, so it is preferable.

<Solvent>

The above-mentioned solvent is not particularly limited as long as it is effective in dissolving other components contained in the colored photosensitive resin composition and does not react. The solvent used for the usual coloring photosensitive resin composition is used, and ethers, acetates, aromatic hydrocarbons, ketones, alcohols, esters, etc. are especially preferable.

Examples of the above-mentioned ethers include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether; Diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, and diethylene glycol dibutyl ether.

Examples of the above-mentioned acetates include methyl cellosolve acetate, ethyl cellosolve acetate, ethyl acetate, butyl acetate, pentyl acetate, methyl lactate, ethyl lactate, lactic acid Butyl ester, 3-methoxybutyl acetate, 3-methyl-3-methoxy-1-butyl acetate, methoxypentyl acetate, ethylene glycol monoacetate, Ethylene glycol diacetate, methyl 3-methoxypropionate, propylene glycol methyl ether acetate, 3-methoxy-1-butyl acetate, 1,2-propylene glycol diacetate, Ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, 1,3-butanediol diacetate, diethylene glycol monobutyl Base ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoacetate, diethylene glycol diacetate, diethylene glycol Monobutyl ether acetate, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene carbonate and propylene carbonate, etc.

As said aromatic hydrocarbons, benzene, toluene, xylene, mesitylene, etc. are mentioned, for example.

As said ketones, methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, cyclohexanone, etc. are mentioned, for example.

Examples of the above-mentioned alcohols include ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, glycerin, 4-hydroxy-4-methyl-2-pentanone, and the like.

Examples of the above-mentioned esters include ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, and γ-butyrolactone.

The above-mentioned solvents can be used alone or in a mixture of two or more.

From the viewpoint of coating properties and drying properties, it is preferable to use an organic solvent having a boiling point of 100 to 200° C. for the above-mentioned solvent, and it is also possible to mix and use solvents with 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, and preferably 65 to 85% by weight relative to the total weight of the colored photosensitive resin composition containing the solvent. If the content of the solvent is in the above range, the leveling properties and coating properties become good, and curing is easy, which is preferable from this point of view.

<Additives>

In the colored photosensitive resin composition of the present invention, in addition to the above-mentioned components, other additives may be contained in accordance with the needs of a person skilled in the art within a range that does not impair the purpose of the present invention.

With regard to the above-mentioned additives, specifically, one or more additives selected from the group consisting of, for example, a thermal initiator, a curing agent, an adhesion promoter, and a surfactant may be additionally included.

The above-mentioned thermal initiator plays a role of initiating a curing reaction caused by heat to maximize the initiation efficiency. The above-mentioned thermal initiator can be a peroxide-based compound Things.

The specific type of the thermal initiator is not particularly limited, and may be selected from tetramethylbutyl peroxyneodecanoate (for example, Perocta ND, manufactured by NOF Corporation), and bis(4-butylcyclohexyl) peroxydicarbonate. Ester (for example, Peroyl TCP, NOF company (manufactured)), di(2-ethylhexyl) peroxycarbonate, butyl peroxyneodecanoate (for example, Perbutyl ND, NOF company (manufactured)), diperoxydicarbonate Propyl ester (e.g. Peroyl NPP, NOF company (manufactured)), diisopropyl peroxydicarbonate (e.g. Peroyl IPP, NOF company (manufactured)), diethoxyethyl peroxydicarbonate (e.g. Peroyl EEP, NOF Company (manufactured by), diethoxyhexyl peroxydicarbonate (for example, Peroyl OEP, NOF company (manufactured by)), hexyl peroxydicarbonate (for example, Perhexyl ND, by NOF company (manufactured by)), peroxydicarbonate Dimethoxybutyl ester (for example, Peroyl MBP, NOF company (manufactured)), bis(3-methoxy-3-methoxybutyl) peroxydicarbonate (for example, Peroyl SOP, NOF company (manufactured)) , Dibutyl peroxydicarbonate, dicetyl peroxydicarbonate, dimyristyl peroxydicarbonate, 1,1,3,3-tetramethylbutyl peroxide Peroxypivalate (peroxypivalate), hexyl peroxypivalate (for example, Perhexyl PV, NOF company (manufactured)), butyl peroxypivalate (for example, Perbutyl, NOF company (manufactured)), trimethylhexyl Peroxide (e.g. Peroyl 355, NOF company (manufactured)), dimethyl hydroxybutyl peroxyneodecanoate (e.g. Luperox 610M75, Atofina (manufactured)), pentyl peroxyneodecanoate (e.g. Luperox 546M75, Atofina) (Manufactured), butyl peroxyneodecanoate (e.g. Luperox 10M75, Atofina (manufactured)), tert-butyl peroxyneoheptanoate, pentyl peroxypivalate (e.g. Luperox 546M75, Alofina (manufactured)), Tert-butyl peroxypivalate, tert-amyl peroxy-2-ethylhexanoate, tert-butyl peroxy-2-ethylhexanoate, laurel Base peroxide, dilauroyl peroxide (dilauroyl), didecyl peroxide, benzyl peroxide, dibenzyl peroxide, 2,2-bis(tert-butylperoxy)butane, 1, 1-bis(tert-butylperoxy)cyclohexane, 2,5-bis(butylperoxy)-2,5-dimethylhexane, 2,5-bis(tert-butylperoxy)-1 -Methylethyl)benzene, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, tert-butyl hydroperoxide, tert-butyl peroxide, peroxide Tert-butyl benzoate, tert-butyl peroxide isopropyl carbonate, cumene hydroperoxide, dicumyl peroxide, lauryl peroxide, 2,4-pentanedione peroxide, tert-butyl peracetate ( One or more of the group consisting of tert-butyl peracetate, peracetic acid, and potassium persulfate.

The content of the thermal initiator is preferably 1 to 10% by weight, and more preferably 1 to 5% by weight with respect to the total weight of the solid content in the colored photosensitive resin composition. When it is contained in this content, it is more preferable in terms of workability and undercutting.

The above-mentioned curing agent is used to achieve deep curing and improve mechanical strength. Specific examples include epoxy compounds, polyfunctional isocyanate compounds, melamine compounds, and oxetane compounds.

Among the above curing agents, specific examples of epoxy compounds include bisphenol A epoxy resins, hydrogenated bisphenol A epoxy resins, bisphenol F epoxy resins, hydrogenated bisphenol F epoxy resins, Novolac type epoxy resins, other aromatic epoxy resins, alicyclic epoxy resins, glycidyl ester resins, glycidylamine resins, or brominated derivatives of these epoxy resins, epoxy resins, and Aliphatic, alicyclic or aromatic epoxy compounds other than its brominated derivatives, butadiene (co)polymerization Compound epoxide, isoprene (co)polymer epoxide, glycidyl (meth)acrylate (co)polymer, triglycidyl isocyanurate, etc.

Specific examples of the oxetane compound in the above curing agent include carbonate dioxetane, xylene dioxetane, adipate dioxetane, and p-benzene. Diformate dioxetane, cyclohexane dicarboxylic acid dioxetane, etc.

The above-mentioned curing agent may be used in combination with a co-curing compound, which is 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 above-mentioned co-curing compound includes, for example, polycarboxylic acids, polycarboxylic anhydrides, acid generators, and the like. Commercially available epoxy resin curing agents can be used for the above-mentioned polycarboxylic acid anhydrides. As specific examples of the above-mentioned epoxy resin curing agent, ADEKA HARDENER EH-700 (trade name, manufactured by ADEKA Kogyo Co., Ltd.) and RIKACID HH (trade name, manufactured by Nippon Rika Co., Ltd.) are commercially available products. , MH-700 (trade name, manufactured by Nippon Rika Co., Ltd.), etc. The curing agents exemplified above can be used alone or in combination of two or more kinds.

The above-mentioned adhesion promoter is an additive used to enhance the coatability and adhesion to the substrate, and may contain a group selected from the group consisting of carboxyl group, methacryl group, isocyanate group, epoxy group, and combinations thereof. The reactive substituent of the silane coupling agent. Specific examples of the silane coupling agent include vinyl trimethoxy silane, vinyl triethoxy silane, vinyl tris(2-methoxyethoxy) silane, N-(2-amino) Ethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3- ring Oxypropoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3- Chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, trimethoxymethyl Silyl benzoic acid, vinyl triacetoxy silane, γ-isocyanate propyl triethoxy silane, etc.

The above-mentioned surfactants can be used to further improve the film-forming properties of the photosensitive resin composition. For example, surface active agents such as organosilicon, fluorine, ester, cationic, anionic, nonionic, and amphoteric can be used. As the agent, it is preferable to use organosilicon-based surfactants, fluorine-based surfactants, and the like.

The above-mentioned organosilicon-based surfactants include, for example, DC3PA, DC7PA, SH11PA, SH21PA, and SH8400 from Dow Corning Toray Organosilicon Co., Ltd., and TSF-4440, TSF-4300, TSF- 4445, TSF-4446, TSF-4460 and TSF-4452 etc. The above-mentioned fluorine-based surfactants include, for example, Megafac F-554, F-470, F-471, F-475, F-482 and F-489 (Dainippon Ink Chemical Industry Co., Ltd.), BM- 1000, BM-1100 (BM Chemie), Fluorad FC-135/FC-170C/FC-430 (Sumitomo 3M Co., Ltd.), etc.

As other examples of the above-mentioned surfactants, in addition to polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid modified polyesters In addition to KP (Shin-Etsu Chemical Co., Ltd.), POLYFLOW (Kyoeisha Chemical Co., Ltd.), and EFTOP (Tohkem Products Company), Megafac (Dainippon Ink Chemical Industry Co., Ltd.), Fluorad (Sumitomo 3M Co., Ltd.), Asahi guard, Surflon (above, Asahi Glass Co., Ltd.), SOLSPERSE (Zeneca Co., Ltd.), EFKA (EFKACHEMICALS Co., Ltd.), PB821 (Ajinomoto Co., Ltd.), etc.

The surfactants exemplified above can be used alone or in combination of two or more.

Those skilled in the art can appropriately use the above-mentioned additives in a range that does not impair the effects of the present invention. For example, with respect to 100 parts by weight of the entire colored photosensitive resin composition, the above-mentioned additives may be used in 0.05-10 parts by weight, preferably 0.1-10 parts by weight, more preferably 0.1-5 parts by weight, but not limited to this. .

The colored photosensitive resin composition of the present invention is produced by the following method, for example. The colorant and the solvent are mixed and dispersed. If necessary, a dispersant may be additionally used, or a part or all of the alkali-soluble resin may be blended. In the resulting dispersion (hereinafter, sometimes referred to as a mill base), the remaining alkali-soluble resin, photopolymerizable compound, photopolymerization initiator, and use as needed can be further added to achieve a predetermined concentration. Other components of, and additional solvents as necessary to obtain the desired colored photosensitive resin composition.

<Pattern layer containing columnar spacers, black matrix and/or black columnar spacers, color filters, and liquid crystal display devices>

The present invention also relates to a color filter including a pattern layer manufactured using the above-mentioned colored photosensitive resin composition.

The color filter of the present invention has the advantages of high optical density, excellent reliability and excellent shielding properties. The color filter includes a substrate and a substrate formed on the substrate The upper pattern layer.

As for the above-mentioned substrate, the above-mentioned color filter itself may be a substrate, or may be a part where the color filter is located in a display device or the like, and there is no particular limitation. The above-mentioned substrate may be glass, silicon (Si), silicon oxide (SiOx) or a polymer substrate, and the above-mentioned polymer substrate may be polyethersulfone (PES) or polycarbonate (PC) or the like.

The above-mentioned pattern layer is a layer containing a cured product of the colored photosensitive resin composition of the present invention, and may contain columnar spacers, black matrixes, and/or black columnar spacers.

The columnar spacer, black matrix, and/or black columnar spacer of the present invention has the advantages of high optical density, excellent reliability, and excellent shielding properties. In particular, the colored photosensitive resin composition of the present invention can preferably be used for the production of black columnar spacers (black matrix integrated spacers). The above-mentioned black columnar spacer means that the black matrix and the columnar spacers are One pattern is formed integrally instead of forming the black matrix and the column spacers separately.

The pattern layer may be a layer formed by applying the colored curable resin composition and performing exposure, development, and thermal curing in a predetermined pattern, and the pattern layer may be formed by implementing a method generally known in the art.

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

The present invention also relates to a display device including the above-mentioned color filter. for example, The liquid crystal display device of the present invention may include a color filter provided with a patterned layer containing a cured product of the above-mentioned colored photosensitive resin composition.

The color filter of the present invention can be applied not only to ordinary liquid crystal display devices, but also to various image display devices such as electroluminescence display devices, plasma display devices, and field emission display devices. When the above-mentioned liquid crystal display device includes a color filter provided with the patterned layer of the present invention, it has advantages of excellent shielding properties and reliability.

The usual patterning process for forming black matrixes, columnar spacers or black columnar spacers by photolithography includes: a) coating a colored photosensitive resin composition on a substrate; b) before drying the solvent Drying step; c) placing a photomask on the obtained film to irradiate active light to cure the exposed part; d) implementing a development process of dissolving the non-exposed part using an alkaline aqueous solution; and e) implementing drying and subsequent Baking steps.

The above-mentioned substrate uses a glass substrate or a polymer plate. As the glass substrate, it is particularly preferable to use soda lime glass, glass containing barium or strontium, lead glass, aluminosilicate glass, borosilicate glass, barium borosilicate glass, quartz, or the like. In addition, examples of the polymer plate include polycarbonate, acrylic, polyethylene terephthalate, polyether sulfide, or polysulfide.

At this time, the coating can be applied by using a roll coater, spin coater, slit type The wet coating method of a coating device such as a spin coater, a slit coater (also referred to as a die coater), and a sprayer is implemented so that the desired thickness can be obtained.

The pre-baking is performed by heating using an oven, a hot plate, or the like. At this time, the heating temperature and heating time in the pre-baking are appropriately selected according to the solvent used, for example, at a temperature of 80 to 150°C for 1 to 30 minutes.

In addition, the exposure performed after the pre-baking is performed using an exposure machine, and exposure is performed through a photomask, so that only the portion corresponding to the pattern is exposed to light. At this time, the irradiated light may be, for example, visible rays, ultraviolet rays, X-rays, electron rays, and the like.

The alkali development after exposure is performed to remove the colored photosensitive resin composition of the unremoved part which is a non-exposed part, and a desired pattern is formed by this development. As a developer suitable for this alkali development, for example, an aqueous solution of carbonates of alkali metals or alkaline earth metals can be used. In particular, it is performed using an alkaline aqueous solution containing 1 to 3% by weight of carbonates such as sodium carbonate, potassium carbonate, and lithium carbonate at a temperature of 10 to 50°C, preferably 20 to 40°C, using a developing machine, an ultrasonic cleaner, or the like.

Post-baking is performed to improve the adhesion between the patterned film and the substrate, and is performed by heat treatment under conditions of 80 to 220°C for 10 to 120 minutes. The post-baking is the same as the pre-baking, using an oven, a hot plate, etc.

At this time, the film thickness of the black matrix is preferably 0.2 μm to 20 μm, more preferably 0.5 μm to 10 μm, and particularly preferably 0.8 μm to 5 μm.

In addition, the film thickness of the columnar spacer and the black columnar spacer is preferably 0.1 μm to 8 μm, more preferably 0.1 μm to 6 μm, and particularly preferably 0.1μm~4μm.

The black matrix, columnar spacer, or black columnar spacer manufactured from the colored photosensitive resin composition of the present invention not only has excellent physical properties such as optical density, adhesion, electrical insulation, and light-shielding, but also has heat resistance and solvent resistance, etc. Excellent, so that the reliability of the liquid crystal display device can be improved.

In addition, the display device of the present invention includes a configuration known in the technical field in addition to the above-mentioned color filter.

Hereinafter, the present invention will be explained in more detail through examples. However, the following examples are used to explain the present invention more specifically, and the scope of the present invention is not limited by the following examples. Those skilled in the art can make appropriate modifications and changes to the following embodiments within the scope of the present invention.

<Synthesis example. Synthesis of alkali-soluble resin>

In a 1L separable flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel, and a nitrogen introduction tube, 277 g of methoxybutyl acetate was charged and heated to 80°C. Next, 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decane-9-yl acrylate and 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decane were prepared. A mixture of 301 g of -8-yl acrylate mixed at a molar ratio of 50:50, 49 g of methacrylic acid and 23 g of azobisdimethylvaleronitrile dissolved in 350 g of methoxybutyl acetate. Solution. The above-mentioned mixed solution was dropped into a flask over 5 hours using a dropping funnel, and then reacted for 3 hours to produce a dispersion resin [solid content (NV) 35.0% by weight]. The acid value (dry) of the dispersion resin produced above was 69.8 mgKOH/g, the weight average molecular weight (Mw) was 12,300, and the degree of dispersion (Mw/Mn) was 2.1.

<Examples 1 to 12 and Comparative Examples 1 to 2>

Based on the composition of Table 1 below, the colored photosensitive resin compositions of Examples 1 to 12 and Comparative Examples 1 to 2 were produced.

O64: C.I. Pigment Orange 64

B16: C.I. Pigment Blue 16

V23: C.I. Pigment Violet 23

CB: Carbon black

OBP: organic black pigment

B15: 6: C.I. Pigment Blue 15: 6

B60: C.I. Pigment Blue 60

B (dispersion resin): Alkali-soluble resin of synthesis example

M (photopolymerizable compound): Dipentaerythritol hexaacrylate (DPHA) (Nippon Kayaku Co., Ltd.)

PI (photopolymerization initiator): 1-[9-ethyl-6-(2-methylbenzyl)-9H-oxazol-3-yl]-ethanone-1-(O-acetoxime ) (Irgacure OXE-02: Ciba (Ciba))

D1 (Additive 1): SOLSPERSE 5000 (Lubrisol)

D2 (Additive 2): F554 (DIC Company)

S (solvent): propylene glycol monomethyl ether acetate (PGMEA)

<Production of substrate>

The 5cm×5cm glass substrate (Corning) was washed with neutral detergent and water and then dried. The colored photosensitive resin composition manufactured in Example 1 and Comparative Example was spin-coated on the glass substrate so that the final film thickness was 3.0 μm, and pre-fired at 80 to 120°C and dried for 1 to 2 minutes. Remove the solvent. After that, exposure was performed with an exposure amount of 25 to 35 mJ/cm ² to form a pattern, and the non-exposed part was removed using an alkaline aqueous solution. Next, post-firing is performed at 200 to 250°C for 10 to 30 minutes to produce a colored substrate.

<Experimental example>

<1. Reliability Evaluation>

In accordance with the above-mentioned production standard of the substrate, a colored substrate was produced by coating the entire surface with a black photosensitive resin without a pattern. Cut it into a size of 3cmx3cm, immerse it in NMP solvent, and then heat it at 100°C for 60 minutes. After that, only the NMP solvent was extracted. Regarding the degree of dissolution in the NMP solvent, the absorbance was measured using a UV-vis spectrometer and expressed as an integrated value of 300 to 800 nm. The specific evaluation criteria are as follows, and the measurement results are described in Table 2 below.

[Evaluation criteria]

Reliability (NMP dissolution reliability): 300~800nm Abs

Excellent ◎: 0.5 or less

Good ○: More than 0.5 and 1.0 or less

Insufficient △: greater than 1.0 and 1.2 or less

Deterioration X: greater than 1.2

<2. Optical characteristic evaluation>

In accordance with the manufacturing criteria of the substrate as described above, a colored substrate was prepared by coating the entire surface with a black photosensitive resin without a pattern, and the optical characteristics were evaluated using the substrate. An ultraviolet-visible spectrometer (UV-vis spectrometer, UV-2550, Shimadzu Corporation) was used. In the evaluation of optical characteristics, 400~650nm means optical density, 700~750nm and 950nm means near-infrared (Near-IR) region, confirm the measurement of each wavelength When the film thickness after curing is 2.5 μm, the light transmittance at the center wavelength of 510 nm is measured with an optical densitometer (361T, X-rite), and the optical density for the thickness of 1 μm is determined. The specific evaluation criteria are as follows, and the evaluation results are described in Table 2 below.

[Evaluation criteria]

(1) Optical density

Excellent ◎: 1.3 or more

Good ○: 1.1 or more and less than 1.3

Insufficient △: 1.0 or more and less than 1.1

Deterioration X: less than 1.0

(2) 750nm light transmittance

Excellent ◎: less than 10T%

Good ○: greater than 10T% and less than 12T%

Insufficient△: more than 12T% and less than 15T%

Deterioration X: more than 15T%

(3) 950nm light transmittance

Excellent ◎: 15T% or more

Good ○: 12T% or more and less than 15T%

Insufficient△: 10T% or more and less than 12T%

Deterioration X: less than 10T%

<3. Evaluation of color coordinates>

In accordance with the above-mentioned substrate manufacturing standards, a colored substrate was prepared by coating the entire surface with a black photosensitive resin without a pattern, and the color coordinates were measured. use Contrast Tester (Contrast Tester, CT-1, Tsubosak Company) to measure the x and y coordinate values. The specific evaluation criteria are as follows, and the evaluation results are described in Table 2 below.

[Evaluation criteria]

(1) x coordinate value

Excellent ◎: 0.1 or less

Good ○: More than 0.1 and 0.2 or less

Insufficient △: more than 0.2 and less than 0.4

Deterioration X: more than 0.4

(2) y coordinate value

Excellent ◎: 0.05 or less

Good ○: More than 0.05 and 0.15 or less

Insufficient △: more than 0.15 and less than 0.25

Deterioration X: greater than 0.25

<4. Evaluation of elastic recovery rate>

According to the above-mentioned production standard, a substrate having a columnar spacer pattern was produced. With respect to the substrate produced above, the thickness and height of the pattern in the reference state were measured using SNU (SIS-2000, SNU Corporation). After that, a hardness tester (Nano-indenter HM500, Fisher Company) was pressed using a flat indenter at a speed of 2 mN/sec until the pattern was deformed by 1 μm, and it was held at the position where the pattern was deformed by 1 μm for 5 seconds. After that, the thickness and height of the pattern were measured using SNU, and the elastic recovery rate was measured from the change in thickness of the pattern before and after. The specific evaluation criteria are as follows, and the evaluation results are described in Table 2 below.

[Evaluation criteria]

Excellent ◎: more than 98%

Good ○: more than 96% and less than 98%

Insufficient△: 94% or more and less than 96%

Deterioration X: less than 94%

Compared with Comparative Examples 1 and 2, Examples 1 to 12, which are the colored photosensitive resin composition of the present invention, exhibited reliability, optical density, light transmittance, and color. Both coordinates and elastic recovery rate are more excellent results. In addition, in the case of Example 2 which further contained a purple pigment, compared with Example 1, it showed more excellent results in terms of reliability and optical density, and the reliability and reliability of Examples 3 to 12 which further contained a black pigment The optical density characteristics are excellent, and other characteristics such as transmittance, color coordinates, and elastic recovery rate also show excellent results.

Claims (8)

A colored photosensitive resin composition comprising a colorant, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent. The colorant includes a blue pigment, an orange pigment, a purple pigment, and a black pigment. The pigment is CI Pigment Blue 16, the orange pigment is CI Pigment Orange 64, the purple pigment is CI Pigment Violet 23, wherein the alkali-soluble resin contains an epoxy group, and the pigmented photosensitive resin composition is formed by The elastic recovery rate of a pattern layer is above 96%. The coloring photosensitive resin composition according to claim 1, wherein the black pigment contains one or more selected from the group consisting of internal amide black, aniline black, perylene black, titanium black, and carbon black. The colored photosensitive resin composition according to the first item of the scope of patent application, wherein the coloring photosensitive resin composition contains 18 to 55% by weight of the colorant and 5 to 5% by weight of the alkali-soluble resin relative to the total weight of the solid content in the colored photosensitive resin composition. 60% by weight, 5-50% by weight of the photopolymerizable compound, 0.1-40% by weight of the photopolymerization initiator, and 60 to 90% by weight of the solvent with respect to the total weight of the colored photosensitive resin composition. The colored photosensitive resin composition according to the first item of the scope of the patent application, wherein the colored photosensitive resin composition further comprises a thermal initiator, a curing agent, an adhesion promoter, and a surfactant selected from the group consisting of More than one additive. A patterned layer, which is manufactured from the colored photosensitive resin composition described in any one of items 1 to 4 in the scope of patent application. The pattern layer according to item 5 of the scope of patent application, wherein the pattern layer is one or more selected from the group consisting of columnar spacers, black matrixes, and black columnar spacers. A color filter including the pattern layer described in item 5 of the scope of patent application. A display device including the color filter as described in item 7 of the scope of patent application.