JP2002162517A - Color filter for liquid crystal display - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a color filter having little deformation under high temperature and high pressure conditions, with a coloring layer of superior resistance to scuffing and wear and enabling manufacture of a liquid crystal display with superior display quality. SOLUTION: The color filter is manufactured, by forming a coloring layer which contains at least inorganic fine particles with an average particle diameter in 10-20 nm range, a coloring material and a resin component and consists of a plurality of colors on a substrate with a prescribed pattern.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a color filter capable of manufacturing a liquid crystal display having excellent display quality.

[0002]

2. Description of the Related Art In recent years, a color liquid crystal display has attracted attention as a flat display. As an example of a color liquid crystal display, a black matrix and a plurality of colors (normally, three primary colors of red (R), green (G), and blue (B))
A color filter comprising a colored layer, a transparent conductive layer (common electrode), and an alignment layer comprising a thin film transistor (TFT)
An element), a pixel electrode and a TFT array substrate provided with an alignment layer are opposed to each other with a predetermined gap, and a liquid crystal material is injected into the gap to form a liquid crystal layer. The coloring layer generally holds a coloring material with a resin component, and the R, G, and B patterns are formed by various methods such as a pigment dispersion method, a dyeing method, an electrodeposition method, a printing method, and an ink jet method. It is.

[0003]

However, in the conventional color filter, the colored layer is damaged during the rubbing treatment of the alignment layer, or the colored layer is subjected to a high temperature and a high pressure at the time of assembling with the TFT array substrate (cell compression bonding). Deformation is likely to occur, which causes a problem that color unevenness or the like occurs in a display image of the liquid crystal display, resulting in deterioration of image quality. The present invention has been made in view of the above-described circumstances, and has a color layer which has a small deformation under high temperature and high pressure and has a colored layer excellent in abrasion resistance, and is capable of producing a liquid crystal display excellent in display quality. The purpose is to provide.

[0004]

In order to achieve the above object, a color filter for a liquid crystal display according to the present invention comprises a substrate and a colored layer of a plurality of colors formed in a predetermined pattern on the substrate. The coloring layer contains at least a coloring material, an inorganic powder, and a resin component, and the inorganic powder has an average particle diameter in a range of 10 to 20 nm. In a preferred embodiment of the color filter for a liquid crystal display according to the present invention, the colored layer is formed by coating the inorganic powder with 5 to 5.
It was configured to be contained in the range of 20% by weight.

In the present invention, the hardness of the colored layer is increased by the contained inorganic powder, the amount of deformation of the colored layer under high temperature and high pressure during cell compression is reduced, and the abrasion resistance of the colored layer is reduced. The performance is improved.

[0006]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The preferred embodiments of the present invention will be described below with reference to the drawings. FIG. 1 is a longitudinal sectional view showing an example of an embodiment of the color filter of the present invention. FIG.
The color filter 1 of the present invention includes a substrate 2, a black matrix 3 and a coloring layer 4 formed on the substrate 2, and the coloring layer 4 preferably has a red pattern 4R, a green pattern 4G, and a blue pattern 4B. They are arranged in a pattern.

[0007] The substrate 2 constituting the above color filter 1
For example, a transparent rigid material having no flexibility such as quartz glass, Pyrex (registered trademark) glass, a synthetic quartz plate, or a transparent flexible material having flexibility such as a transparent resin film or an optical resin plate is used. be able to. Among them, Corning 1737 glass is a material having a low coefficient of thermal expansion, excellent dimensional stability and workability in high-temperature heat treatment, and is an alkali-free glass containing no alkali component in the glass. It is suitable for a color filter for a color liquid crystal display by the method.

The black matrix 3 constituting the color filter 1 is provided between the display pixel portions composed of the colored layers 4 and outside the region where the colored layers 4 are formed. Such a black matrix 3 is formed by forming a metal thin film of chromium or the like having a thickness of about 1000 to 2000 ° by a sputtering method, a vacuum evaporation method, or the like, and patterning the thin film, and containing light-shielding particles such as carbon fine particles. Forming a resin layer of polyimide resin, acrylic resin, epoxy resin, etc., and forming a photosensitive resin layer containing light-shielding particles such as carbon fine particles, metal oxides, etc. The photosensitive resin layer may be formed by patterning the photosensitive resin layer.

The coloring layer 4 contains at least an inorganic powder, a coloring material and a resin component. The inorganic powder used has an average particle diameter of 10 to 20 nm, and examples thereof include silicon oxide, germanium oxide, titanium oxide, aluminum oxide, zirconium oxide, and magnesium oxide.
If the average particle size of the inorganic powder is less than 10 nm, the effect of the present invention is hardly further improved and the cost of the inorganic powder increases, which is not preferable. When the average particle size of the inorganic powder exceeds 20 nm, the light transmittance of the colored layer 4 decreases.

The content of the inorganic powder in the colored layer 4 is 5 to 5.
It can be set in the range of 20% by weight, preferably 10 to 20% by weight. When the content of the inorganic powder exceeds 20% by weight, the accuracy of forming the colored pattern and the light transmittance are reduced. On the other hand, when the content of the inorganic powder is less than 5% by weight,
The hardness of the colored layer 4 becomes insufficient, the deformation amount becomes large, and the colored layer 4 is easily damaged, which is not preferable.

Here, the hardness of the colored layer will be described with reference to FIG. The load was applied to the colored layer with a triangular indenter for dynamic hardness (1150) in the thickness direction at a rate of 0.23 mN / sec up to 5 mN, and the deformation amount when held for 5 seconds was as shown in FIG. Is a graph showing the amount of deformation of the colored layer in the color filter of the present invention,
The broken line is a graph showing the deformation amount of the conventional colored layer containing no inorganic powder. In the present invention, the dynamic hardness (Pa) when a load is applied to 5 mN at a rate of 0.23 mN / sec in the thickness direction with a triangular indenter for dynamic hardness (1150) and held for 5 seconds is determined by Shimadzu Corporation. Measured with Shimadzu Dynamic Ultra Micro Hardness Tester. In the color filter 1 of the present invention, since the dynamic hardness of the coloring layer 4 is larger than the dynamic hardness of the coloring layer of the conventional color filter, the deformation amount of the coloring layer 4 is smaller than the deformation amount of the coloring layer of the conventional color filter. It is smaller than.

The coloring material contained in the coloring layer 4 includes red pigments such as C.I. I. No. 9, 97, 122, 12
3, 149, 168, 177, 180, 192, 215
As green pigments, C.I. I. No. 7, 36, etc. as blue pigments; I. No. 15, 20, 60, 64
As yellow pigments, C.I. I. No. 20, 24, 8
6, 93, 109, 110, 117, 125, 137,
138, 147, 148, 153, 154, 166, 1
68 and the like, as orange pigments, C.I. I. No. 36, 4
As violet pigments such as 3, 51, 55, 59 and 61, C.I. I. No. 19, 23, 29, 30, 37, 4
0, 50, etc. can be used. Of these, one
They may be used alone or in combination of two or more.
Often, three or more are used in combination. The content of the coloring material in the coloring layer 4 can be set in the range of 20 to 50% by weight.

The coloring layer 4 is formed by a known method such as a photolithography method, a printing method, a transfer method, and an ink-jet method using a photosensitive resin composition containing a desired coloring material and inorganic powder. Can be. The resin component obtained by curing the photosensitive resin functions as a binder for the inorganic powder and the coloring material. In addition, for example, by making the colored layer 4 thinnest in the red pattern 4R and thicker in the order of the green pattern 4G and the blue pattern 4B, the optimal liquid crystal layer thickness can be set for each color of the colored layer 4. Is also good.

In the color filter 1 of the present invention, since the coloring layer 4 contains an inorganic powder having an average particle diameter in the range of 10 to 20 nm as described above, the dynamic hardness is large, and the color filter 4 shown in FIG. As described, even under high temperature and high pressure during assembly (cell compression bonding) with the TFT array substrate,
The amount of deformation is small. Further, since the coloring layer 4 is excellent in transparency and has high hardness and excellent scratch resistance, generation of scratches due to rubbing treatment of the alignment layer is prevented.

Here, an example of a photosensitive resin composition that can be used for forming a colored layer of the color filter of the present invention will be described. The photosensitive resin composition has at least a polymer, a monomer, a photopolymerization initiator, and an average particle size of 10 to 20 n.
It contains an inorganic powder in the range of m.

The polymer constituting the photosensitive resin composition includes ethylene-vinyl acetate copolymer, ethylene-vinyl chloride copolymer, ethylene-vinyl copolymer, polystyrene, acrylonitrile-styrene copolymer, ABS resin, and polystyrene. Methacrylic acid resin, ethylene methacrylic acid resin, polyvinyl chloride resin, chlorinated vinyl chloride, polyvinyl alcohol, cellulose acetate propionate,
Cellulose acetate butyrate, nylon 6, nylon 66, nylon 12, polyethylene terephthalate,
Polybutylene terephthalate, polycarbonate, polyvinyl acetal, polyether ether ketone, polyether sulfone, polyphenylene sulfide, polyarylate, polyvinyl butyral, epoxy resin,
Phenoxy resin, polyimide resin, polyamide imide resin, polyamic acid resin, polyether imide resin, phenol resin, urea resin and the like, and polymerizable monomers methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-
Propyl acrylate, n-propyl methacrylate,
Isopropyl acrylate, isopropyl methacrylate, sec-butyl acrylate, sec-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, n-pentyl acrylate, n-pentyl methacrylate, n-hexyl acrylate, n-hexyl Methacrylate, 2-ethylhexyl acrylate, 2
-Ethylhexyl methacrylate, n-octyl acrylate, n-octyl methacrylate, n-decyl acrylate, n-decyl methacrylate, styrene, α-
One or more of methylstyrene, N-vinyl-2-pyrrolidone, glycidyl (meth) acrylate and acrylic acid;
Methacrylic acid, dimer of acrylic acid (for example, M-5600 manufactured by Toa Gosei Chemical Co., Ltd.), itaconic acid, crotonic acid, maleic acid, fumaric acid, vinyl acetic acid, and one or more of these acid anhydrides and the like. Polymers or copolymers.

Further, there may be mentioned, for example, polymers obtained by adding an ethylenically unsaturated compound having a glycidyl group or a hydroxyl group to the above copolymer, but the invention is not limited thereto. The content of such a polymer can be set in the range of 20 to 50% by weight based on the total solid content of the photosensitive resin composition.

As the monomer constituting the photosensitive resin composition, a compound having at least one polymerizable carbon-carbon unsaturated bond can be used. In particular,
Allyl acrylate, benzyl acrylate, butoxyethyl acrylate, butoxyethylene glycol acrylate, cyclohexyl acrylate, dicyclopentanyl acrylate, 2-ethylhexyl acrylate, glycerol acrylate, glycidyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, isobonyl acrylate , Isodexyl acrylate, isooctyl acrylate,
Lauryl acrylate, 2-methoxyethyl acrylate, methoxyethylene glycol acrylate, phenoxyethyl acrylate, stearyl acrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,
6-hexanediol diacrylate, 1,3-propanediol acrylate, 1,4-cyclohexanediol diacrylate, 2,2-dimethylolpropane diacrylate, glycerol diacrylate, tripropylene glycol diacrylate, glycerol triacrylate, trimethylol Propane triacrylate, polyoxyethylated trimethylolpropane triacrylate, pentaerythritol triacrylate,
Pentaerythritol tetraacrylate, triethylene glycol diacrylate, polyoxypropyltrimethylolpropane triacrylate, butylene glycol diacrylate, 1,2,4-butanetriol triacrylate, 2,2,4-trimethyl-1,3-pentanediol Diacrylate, diallyl fumarate,
1,10-decanediol dimethyl acrylate, dipentaerythritol hexaacrylate, and those obtained by substituting the acrylate group with a methacrylate group,
γ-methacryloxypropyltrimethoxysilane, 1-
Vinyl-2-pyrrolidone, 2-hydroxyethylacryloyl phosphate, tetrahydrofurfuryl acrylate, dicyclopentenyl acrylate, dicyclopentenyloxyethyl acrylate, 3-butanediol diacrylate, neopentyl glycol diacrylate, polyethylene glycol diacrylate, hydroxy Pivalic acid ester neopentyl glycol diacrylate, phenol-ethylene oxide modified acrylate, phenol-propylene oxide modified acrylate, N-vinyl-2-pyrrolidone, bisphenol A-ethylene oxide modified diacrylate, pentaerythritol diacrylate monostearate, tetraethylene Glycol diacrylate, polypropylene glycol diacrylate Acrylate monomers such as methacrylate, trimethylolpropane propylene oxide modified triacrylate, isocyanuric acid ethylene oxide modified triacrylate, trimethylolpropane ethylene oxide modified triacrylate, pentaerythritol pentaacrylate, pentaerythritol hexaacrylate, pentaerythritol tetraacrylate, And those in which these acrylate groups are substituted with methacrylate groups, urethane acrylate oligomers in which acrylate groups are bonded to oligomers having a polyurethane structure, polyester acrylate oligomers in which acrylate groups are bonded to oligomers having a polyester structure, and epoxy groups. Epoxy acrylates with acrylate groups bonded to oligomers Gomer, a urethane methacrylate oligomer in which a methacrylate group is bonded to an oligomer having a polyurethane structure, a polyester methacrylate oligomer in which a methacrylate group is bonded to an oligomer having a polyester structure, an epoxy methacrylate oligomer in which a methacrylate group is bonded to an oligomer having an epoxy group, Examples include polyurethane acrylate having an acrylate group, polyester acrylate having an acrylate group, epoxy acrylate resin having an acrylate group, polyurethane methacrylate having a methacrylate group, polyester methacrylate having a methacrylate group, and epoxy methacrylate resin having a methacrylate group. These are examples of monomers that can be used, but are not limited thereto. The content of such a monomer can be set in the range of 10 to 50% by weight based on the total solid content of the photosensitive resin composition.

As the photopolymerization initiator constituting the photosensitive resin composition, benzophenone, methyl o-benzoylbenzoate, 4,4-bis (dimethylamine) benzophenone, 4,4-bis (diethylamine) benzophenone,
α-amino acetophenone, 4,4-dichlorobenzophenone, 4-benzoyl-4-methyldiphenylketone, dibenzylketone, fluorenone, 2,2-diethoxyacetophonone, 2,2-dimethoxy-2-phenylacetophenone, -Hydroxy-2-methylpropiophenone, p-tert-butyldichloroacetophenone, thioxanthone, 2-methylthioxanthone, 2-
Chlorothioxanthone, 2-isopropylthioxanthone, diethylthioxanthone, benzyldimethylketal, benzylmethoxyethylacetal, benzoinmethylether, benzoinbutylether, anthraquinone, 2-tert-butylanthraquinone, 2-amylanthraquinone, β-chloroanthraquinone, anthrone, benzantrone , Dibenzsuberone, methyleneanthrone, 4-azidobenzylacetophenone, 2,6
-Bis (p-azidobenzylidene) cyclohexane,
2,6-bis (p-azidobenzylidene) -4-methylcyclohexanone, 2-phenyl-1,2-butadione-2- (o-methoxycarbonyl) oxime, 1-phenyl-propanedione-2- (o-ethoxy Carbonyl) oxime, 1,3-diphenyl-propanetrione-2- (o-ethoxycarbonyl) oxime, 1-phenyl-3-ethoxy-propanetrione-2- (o-benzoyl) oxime, Michler's ketone, 2-methyl-1
[4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone, naphthalenesulfonyl chloride, quinoline sulfonyl chloride, n- Phenylthioacridone, 4,4-azobisisobutyronitrile, diphenyl disulfide, benzothiazole disulfide, triphenylphosphine,
Examples include a combination of camphorquinone, N1717 manufactured by ADEKA CORPORATION, a photoreducing dye such as carbon tetrabromide, tribromophenylsulfone, benzoin peroxide, eosin, and methylene blue and a reducing agent such as ascorbic acid and triethanolamine. Can be In the present invention, one or more of these photopolymerization initiators can be used. The addition amount of such a photopolymerization initiator can be set in a range of 3 to 10% by weight based on the total solid content of the photosensitive resin composition.

The content of the inorganic powder in the photosensitive resin composition can be set in the range of 5 to 20% by weight, preferably 10 to 20% by weight based on the total solid content. When the content of the inorganic powder exceeds 20% by weight, the formability of the colored pattern and the light transmittance are reduced. On the other hand, if the content of the inorganic powder is less than 5% by weight, the amount of deformation of the formed colored pattern is undesirably large.

The photosensitive resin composition may further contain an epoxy resin. Examples of the epoxy resin to be used include an Epicoat series manufactured by Mitsubishi Yuka Shell Co., Ltd., a celoxide side series and an Epode series manufactured by Daicel Corporation, or bisphenol-A type epoxy resin, bisphenol-F type epoxy resin, and bisphenol-type. S type epoxy resin, novolak type epoxy resin, polycarboxylic acid glycidyl ester, polyol glycidyl ester, aliphatic or alicyclic epoxy resin, amine epoxy resin, triphenolmethane type epoxy resin, dihydroxybenzene type epoxy resin, glycidyl (meth) Copolymerized epoxy compounds of acrylates and radically polymerizable monomers can be exemplified. In the present invention, the above epoxy resins can be used alone or as a mixture of two or more. The addition amount of such an epoxy resin is 0 to 20 in the total solid content of the photosensitive resin composition.
It can be set in the range of weight%.

Examples of the solvent used in the photosensitive resin composition include alcohols such as methanol, ethanol, n-propanol, isopropanol, ethylene glycol and propylene glycol, terpenes such as α- and β-terpineol, and the like. Ketones such as acetone, methyl ethyl ketone, cyclohexanone, N-methyl-2-pyrrolidone, aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene, cellosolve, methyl cellosolve, ethyl cellosolve, carbitol, methyl carbitol, ethyl carbyl Tall, butyl carbitol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, Glycol ethers such as ethylene glycol monomethyl ether and triethylene glycol monoethyl ether, ethyl acetate, butyl acetate,
Cellosolve acetate, ethyl cellosolve acetate,
Examples thereof include acetates such as butyl cellosolve acetate, carbitol acetate, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate.

[0023]

Next, the present invention will be described in more detail with reference to examples.

Example 1 First, as a photosensitive resin composition for a red pattern, six kinds of photosensitive compositions having the following compositions in which the average particle diameter of the silicon oxide powder contained was changed as shown in Table 1 below Resin compositions RI, R-II, R-III, R-IV, R
-V and R-VI were prepared. Similarly, as the photosensitive resin composition for a green pattern, there are six kinds of photosensitive resin compositions GI, G-II, G-III, G-IV, G-V, and G-V having the following compositions.
I was prepared. Further, as a photosensitive resin composition for a blue pattern, six kinds of photosensitive resin compositions BI having the following compositions,
B-II, B-III, B-IV, BV and B-VI were prepared.

Composition of photosensitive resin composition for red pattern・ Silicon oxide (colloidal silica): 2 parts by weight (Snowtex NPC-ST manufactured by Nissan Chemical Industries, Ltd.) (solid content indication) ・ Coloring material (quinophthalene) Red pigment) 36 parts by weight Polymer 32 parts by weight (copolymer of styrene-methyl methacrylate-methacrylic acid) Monomer 16 parts by weight (dipentaerythritol pentaacrylate) Photopolymerization initiator 6 parts by weight (Irgacure 907 manufactured by Ciba Specialty Chemicals Co., Ltd.) Solvent: 200 parts by weight (propylene glycol monomethyl ether acetate)

Composition of photosensitive resin composition for green pattern : Silicon oxide (colloidal silica): 5 parts by weight (Snowtex NPC-ST manufactured by Nissan Chemical Industries, Ltd.) (solid content display) Coloring material (halogenated) Copper phthalocyanine pigment) 36 parts by weight Polymer 32 parts by weight (copolymer of styrene-methyl methacrylate-methacrylic acid) Monomer 16 parts by weight (dipentaerythritol pentaacrylate) Photopolymerization initiator 6 parts by weight Part (Irgacure 907 manufactured by Ciba Specialty Chemicals) ・ Solvent… 200 parts by weight (propylene glycol monomethyl ether acetate)

Composition of photosensitive resin composition for blue pattern : Silicon oxide (colloidal silica): 10 parts by weight (Snowtex NPC-ST manufactured by Nissan Chemical Industries, Ltd.) (solid content display) Coloring material (phthalocyanine blue) Pigment) 36 parts by weight Polymer 32 parts by weight (copolymer of styrene-methyl methacrylate-methacrylic acid) Monomer 16 parts by weight (dipentaerythritol pentaacrylate) Photopolymerization initiator 6 parts by weight (Ciba) Specialty Chemicals Co., Ltd. Irgacure 907) Solvent: 200 parts by weight (propylene glycol monomethyl ether acetate)

Next, the above-mentioned photosensitive resin compositions (I, II, III, IV, V, VI) for the respective colored patterns were applied on a glass substrate by a spin coater to provide openings of a predetermined shape. Exposure is performed through a photomask at an exposure amount of 100 mJ / cm ² , development, and heat treatment (200 ° C., 30 minutes)
Was done. Next, a dynamic hardness (Pa) when a load was applied to each pattern sample in the thickness direction at a rate of 0.23 mN / sec up to 5 mN and held for 5 seconds, was measured by Shimadzu Dynamic Ultra-Micro Hardness manufactured by Shimadzu Corporation. The dynamic hardness (Pa) shown in FIG. 2 is shown in Table 1 below.

Next, as a substrate for a color filter, 3
A glass substrate (Corning 1737 glass) having a size of 00 mm × 400 mm and a thickness of 0.7 mm was prepared. After washing the substrate according to a conventional method, a light-shielding layer (thickness: 0.1 μm) made of metallic chromium was formed on the entire surface of one side of the substrate by a sputtering method. Next, the light-shielding layer was subjected to photosensitive resist coating, mask exposure, development, etching, and resist layer peeling by a normal photolithography method to form a black matrix.

Next, the photosensitive resin composition (R-R) for the red pattern is coated on the entire surface of the substrate on which the black matrix is formed.
I) was applied by a spin coating method to form a red photosensitive resin layer, and prebaked (100 ° C., 3 minutes).
Thereafter, the red photosensitive resin layer is aligned and exposed using a predetermined colored pattern photomask, developed with a developing solution (aqueous potassium hydroxide solution), and then post-baked (200 ° C., 30 minutes). A red pattern (thickness: 1 μm) was formed at a predetermined position with respect to the black matrix pattern.

Similarly, a green pattern (thickness: 1 μm) was formed at a predetermined position with respect to the black matrix pattern by using the photosensitive resin composition (GI) for a green pattern. Further, a blue pattern (thickness: 1 μm) was formed at a predetermined position with respect to the black matrix pattern by using the photosensitive resin composition (BI) for a blue pattern. Next, indium tin oxide (ITO) is placed on the coloring layer.
Was formed. As a result, FIG.
A color filter (sample I) having a structure as shown in FIG.

In addition, except that the photosensitive resin compositions I, III, IV, V and VI of the respective colors were used instead of the photosensitive resin compositions I of the respective colors, the color filters ( Samples II, III, IV, V, VI) were obtained.

On the other hand, a transparent substrate of 300 mm × 400
mm, 0.7 mm thick glass substrate (Corning 1
737 glass). After washing the substrate according to a conventional method, thin film transistors (TFTs) are formed at a plurality of predetermined locations on the substrate, and the transparent pixel electrode is connected to indium tin oxide (I) so as to be connected to the drain electrode of each TFT.
TO) to form a counter electrode substrate.

Next, the color filters (samples I, I
I, III, IV, V, VI) to cover the common transparent electrode layer,
In addition, a polyimide resin paint (SE-7492 manufactured by Nissan Chemical Industries, Ltd.) was applied so as to cover the transparent pixel electrode of the counter electrode substrate, dried to form an alignment layer (0.07 μm in thickness), and rubbed. .

Next, a liquid crystal display was fabricated using these color filters and the counter electrode substrate (temperature at the time of cell compression = 180 ° C.), the presence or absence of color unevenness in the displayed image was measured, and the contrast ratio was measured. The results are shown in Table 1 below.

[0036]

[Table 1]

As shown in Table 1, the pattern samples formed by using the photosensitive resin compositions I, II, and III of each color have high dynamic hardness, and these photosensitive resin compositions are used. A liquid crystal display using a color filter having a colored layer formed thereon has a small amount of deformation of the colored layer, has no color unevenness, and can display an image with a high contrast ratio.

In the color filters formed using the photosensitive resin compositions IV and V, the amount of deformation of the colored layer during cell assembly was small, and no scratch was generated during the rubbing treatment. However, the light transmittance of the colored layer is poor, and the image quality of the liquid crystal display using the color filters IV and V has a low contrast ratio and is lower than the image quality of the liquid crystal display using the color filters I, II and III. Met. Further, in the color filter in which the colored layer is formed using the photosensitive resin composition VI containing no silicon oxide, the amount of deformation of the colored layer at the time of cell assembly is large, and a scratch is generated at the time of rubbing treatment, and image display is poor. It was difficult to produce a good liquid crystal display.

Example 2 First, a photosensitive resin composition for a red pattern such that silicon oxide having an average particle diameter of 20 nm is contained in the formed colored layer at the content shown in Table 2 below. The following five types of photosensitive resin compositions R-1 and R
-2, R-3, R-4 and R-5 were prepared. Note that a quinophthalene red pigment was used as a red color material.

Similarly, five types of photosensitive resin compositions G-1 having the following compositions were used as photosensitive resin compositions for green patterns.
G-2, G-3, G-4 and G-5 were prepared. Note that a halogenated copper phthalocyanine pigment was used as a green color material. Further, as a photosensitive resin composition for a blue pattern,
Five types of photosensitive resin compositions B-1, B-2, and B having the following compositions
-3, B-4 and B-5 were prepared. A phthalocyanine blue pigment was used as a blue color material.

Composition of photosensitive resin compositions R-1, G-1, B-1 Silicon oxide (colloidal silica): 3 parts by weight (Snowtex NPC-ST manufactured by Nissan Chemical Industries, Ltd.) Coloring material: 37 parts by weight Polymer: 35 parts by weight (copolymer of styrene-methyl methacrylate-methacrylic acid) Monomer: 18 parts by weight (dipentaerythritol pentaacrylate) Photopolymerization initiator: 7 parts by weight (Irgacure 907 manufactured by Ciba Specialty Chemicals Co., Ltd.) Solvent: 200 parts by weight (propylene glycol monomethyl ether acetate)

Composition of photosensitive resin compositions R-2, G-2, B-2: Silicon oxide (colloidal silica): 10 parts by weight (Snowtex NPC-ST manufactured by Nissan Chemical Industries, Ltd.) (solid content indication) Coloring material: 33 parts by weight Polymer: 34 parts by weight (copolymer of styrene-methyl methacrylate-methacrylic acid) Monomer: 17 parts by weight (dipentaerythritol pentaacrylate) Photopolymerization initiator: 6 parts by weight (Irgacure 907 manufactured by Ciba Specialty Chemicals Co., Ltd.) Solvent: 200 parts by weight (propylene glycol monomethyl ether acetate)

Composition of photosensitive resin compositions R-3, G-3 and B-3: Silicon oxide (colloidal silica) 20 parts by weight (Snowtex NPC-ST manufactured by Nissan Chemical Industries, Ltd.) (solid content indication) Coloring material: 32 parts by weight Polymer: 29 parts by weight (copolymer of styrene-methyl methacrylate-methacrylic acid) Monomer: 14 parts by weight (dipentaerythritol pentaacrylate) Photopolymerization initiator: 5 parts by weight (Irgacure 907 manufactured by Ciba Specialty Chemicals Co., Ltd.) Solvent: 200 parts by weight (propylene glycol monomethyl ether acetate)

Composition of photosensitive resin compositions R-4, G-4 and B-4: Silicon oxide (colloidal silica): 25 parts by weight (Snowtex NPC-ST manufactured by Nissan Chemical Industries, Ltd.) (solid content indication) Coloring material: 30 parts by weight Polymer: 26 parts by weight (copolymer of styrene-methyl methacrylate-methacrylic acid) Monomer: 14 parts by weight (dipentaerythritol pentaacrylate) Photopolymerization initiator: 5 parts by weight (Irgacure 907 manufactured by Ciba Specialty Chemicals Co., Ltd.) Solvent: 200 parts by weight (propylene glycol monomethyl ether acetate)

Composition of photosensitive resin compositions R-5, G-5, B-5: Silicon oxide (colloidal silica): 0 parts by weight (Snowtex NPC-ST manufactured by Nissan Chemical Industries, Ltd.) (solid content display) Coloring material: 40 parts by weight Polymer: 35 parts by weight (copolymer of styrene-methyl methacrylate-methacrylic acid) Monomer: 18 parts by weight (dipentaerythritol pentaacrylate) Photopolymerization initiator: 7 parts by weight (Irgacure 907 manufactured by Ciba Specialty Chemicals Co., Ltd.) Solvent: 200 parts by weight (propylene glycol monomethyl ether acetate)

Next, the dynamic hardness of the photosensitive resin composition (1, 2, 3, 4, 5) for each of the above colored patterns was measured in the same manner as in Example 1, and the results are shown in Table 2 below. Indicated.

Next, in the same manner as in Example 1, a black matrix and a colored layer were formed on a glass substrate, and a common transparent electrode layer made of indium tin oxide (ITO) was formed on the colored layer. Thus, a color filter (samples 1, 2, 3, 4, and 5) having a structure as shown in FIG. 1 was obtained.
Next, a liquid crystal display was produced using the above color filters in the same manner as in Example 1, and the presence or absence of color unevenness in the displayed image was observed. The results are shown in Table 2 below.

[0048]

[Table 2]

As shown in Table 2, the color filters 2 and 3 containing silicon oxide in the colored layer in the range of 5 to 20% by weight have a sufficiently large dynamic hardness of the colored layer.
For this reason, it was confirmed that the deformation amount of the colored layer at the time of cell assembly was small, no scratch was generated during the rubbing treatment, and it was possible to manufacture a liquid crystal display with good image display.

However, the color filter 1 containing 3% by weight of silicon oxide in the colored layer and the color filter 5 containing no silicon oxide in the colored layer have a small dynamic hardness of the colored layer. The amount of deformation of the colored layer during cell assembly is large, and rubbing treatment causes damage, making it difficult to produce a liquid crystal display with good image display. Further, the color filter 5 containing 25% by weight of silicon oxide in the coloring layer has a large dynamic hardness of the coloring layer, and therefore has a small deformation amount of the coloring layer at the time of cell assembly, but has a high precision of forming the coloring pattern. It was bad.

[0051]

As described above in detail, according to the present invention, the hardness of the colored layer is increased by the inorganic powder contained in the colored layer, so that the abrasion resistance of the colored layer is improved and the rubbing of the alignment layer is performed. The colored layer is prevented from being damaged during processing, and the amount of deformation of the colored layer under high temperature and high pressure during cell compression is reduced, so that a highly reliable liquid crystal display with excellent display quality can be provided.

[Brief description of the drawings]

FIG. 1 is a longitudinal sectional view showing an example of an embodiment of a color filter of the present invention.

FIG. 2 is a diagram illustrating a relationship between a load and a deformation amount.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 ... Color filter 2 ... Substrate 3 ... Black matrix 4 ... Coloring layer

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat ゛ (Reference) G03F 7/004 501 G03F 7/004 501 F term (Reference) 2H025 AA10 AA13 AB13 AC01 AD01 BC13 BC42 CC08 CC11 CC20 2H048 BA45 BA47 BA48 BB02 BB42 2H091 FA02Y FA35Y GA13 LA02 LA15 4J002 AB021 BB061 BB081 BB101 BC031 BC061 BD041 BD181 BE021 BF021 BG011 BG041 BG051 BG061 BH021 BN151 BQ001 CF01 CF1 CF1 CF11 001

Claims (2)

[Claims] 1. A substrate comprising: a substrate; and a colored layer having a plurality of colors formed in a predetermined pattern on the substrate, wherein the colored layer contains at least a coloring material, an inorganic powder, and a resin component. A color filter for a liquid crystal display, wherein an average particle diameter of the body is in a range of 10 to 20 nm. 2. The color filter according to claim 1, wherein the coloring layer contains the inorganic powder in a range of 5 to 20% by weight.