JP2001013311A - Heat-resistant color filter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a heat-resistant color filter having a fine pattern and a flat surface with which a display having excellent display quality can be obtained with significantly excellent effects as a color filter such as color separation, color correction, antireflection and improvement in the display contrast while correction of colors developed by a phosphor is not limited by the inorganic pigments used. SOLUTION: Patterns 2, 3, 4, 5 consisting of only coloring pigments of a plurality of colors are formed by using photosensitive color compositions by calcining on a transparent substrate. Then a single layer or a plurality of layers of colored glass or glass dyed with colloid to supplement the spectral characteristics of the coloring pigments is formed as an overcoat layer 6 on the coloring pigments to fix the coloring pigments.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is applied to a display device such as a field emission display, a plasma discharge display panel, a fluorescent display device and a solid-state image pickup device, and mainly reduces a reflectance, improves a contrast, and improves spectral characteristics. The present invention relates to a heat-resistant color filter used for control.

[0002]

2. Description of the Related Art In a color liquid crystal display, a color filter having a spectral characteristic of a desired color is often used for displaying a color image. This color filter is formed by forming a resin layer colored with an organic pigment or an organic dye as a color filter by a dyeing method, a pigment dispersion method, a printing method, or the like. (M. Tani, et al: "LC
D Color Filters: Character
issues and Future Issues ",
SID 95 SEMINAR LECTURE (19
95) etc.)

Also, it has been proposed to use a color filter to reduce the reflectance and to improve the contrast of a displayed image in a cathode ray tube display (CRT), a low-speed electron beam fluorescent display panel, and the like (T. Ito, et al: "Microfilte").
rTM "Color CRT, SID 95 Dige
st, p. 25 (1995)), and using a color filter to reduce the reflectance and control the spectral characteristics of an image display device is a useful means for improving the display image quality.

In the production of plasma discharge display panels and field emission displays, a heating process at 400 ° C. or higher for melting low-melting glass and sealing two glass substrates is indispensable. Even if a color filter for display is applied, conventional organic pigments for coloring will burn and decompose in a high-temperature heating process, so exhibit color filter characteristics such as improving display contrast, reducing reflectance, and controlling spectral characteristics. Is difficult.

As one method for solving this problem, it has been proposed that a color filter using a coloring material in which an inorganic pigment is dispersed in a low-melting glass is adapted to a high-temperature manufacturing process. (Sakai et al .: "Ultra-low reflectivity color display discharge panel (3)" Technical Report of the Institute of Television Engineers of Japan, ED993, IPD113-8 (1986-11)
Etc.)

According to this method, a paste comprising a low-melting glass powder, an inorganic pigment, and a resin binder for temporarily fixing these materials to a transparent substrate is screen-printed on pixel portions on the transparent substrate, and the printed pixels are printed. About 6 patterns
Baking at 00 ° C. burns off organic components such as a resin binder, and melts the low-melting glass powder to coat and fix the inorganic pigment on the transparent substrate to form each color pattern of the color filter. Each of the constituted colored patterns has durability to a high-temperature heating process involved in manufacturing.

However, in the screen printing method, generally, factors such as the ambient temperature of the printing press, the humidity, the squeegee pressure, and the moving speed of the squeegee induce the expansion and contraction of the screen plate to easily cause distortion of the printing pattern. There is a disadvantage that it is difficult to print a fine pattern due to the limit of the opening. Further, in order to satisfy the spectral characteristics required as a color filter, the thickness of the low-melting glass and the pigment constituting the color filter is increased to about 10 μm, so that a step corresponding to the thickness of each color is formed on the transparent substrate. Occurs. This step is likely to cause a disconnection of a conductive thin film or the like formed as a drive electrode of a plasma discharge display panel, a field emission display, or the like later. Therefore, in addition to the resolution and dimensional accuracy required for the colored pattern, Problems tend to occur in image quality such as display defects.

As a method of solving this problem, a photosensitive coloring composition having an acrylic resin, a polyfunctional acrylic monomer, a photopolymerization initiator and a coloring pigment as constituents, pattern exposure, development and the like are repeated for the required number of colors. After heating and baking, after forming only the pigment in a predetermined shape pattern on the transparent substrate, a method of flattening by providing an overcoat layer having a light transmitting property on the patterned pigment and its peripheral portion has been proposed. ing. (See Japanese Patent Application No. 7-298200)

This transparent overcoat layer is used to prevent the colored pigment layer, which is a pattern of only the heated and baked pigment, from being damaged mechanically, and to drive the conductive thin film or the like to a plasma discharge display panel or a field emission display. It functions to protect the electrode from damage when formed by a chemical method.

The color filter produced by this method utilizes a good resolution characteristic of the photolithography system, and has a thickness of about several μm formed in a fine pattern having predetermined spectral characteristics. It is composed of a coloring pigment and a light-transmitting overcoat material provided on the upper part and the peripheral part. Further, since the thickness difference of about several μm for each color pattern caused by the coloring power difference inherent to the color pigment of each color is absorbed by the thickness of the overcoat layer, the step on the color filter is reduced, and Even with a configuration in which an electrode is formed under the filter, unevenness due to the dielectric layer formed on the color filter can be smoothed,
In either case, a driving electrode such as a conductive thin film can be favorably formed, so that display defects occurring in a display can be reduced.

However, this overcoat layer is mainly composed of low-melting glass, and although it depends on the composition and particle size of the low-melting glass fine powder material to be used, it has a thickness of about several μm and is easily formed. When the thickness is more than the above, there is a problem that the display is darkened by light absorption and scattering.
On the other hand, if the thickness is too small, the overcoat layer tends to cause pinholes, and there is a problem that durability in an etching process used for forming a conductive thin film for a drive electrode or the like is insufficient.

On the other hand, a method of forming a metal oxide film from an alkoxide compound such as silicon or titanium, which is known as a sol-gel method, uses an appropriate compound to select and use, thereby obtaining optical transparency and mechanical strength. Thus, it is possible to form an overcoat layer having good chemical resistance. Generally, when a metal oxide film formed by a sol-gel method is formed thickly, cracks and the like are liable to occur. The step is almost left as it is. However, for example, a method of adjusting the thickness of the pigment layer after baking with a photosensitive coloring composition containing a transparent barium sulfate fine powder by using a bulky colored pigment coated on the surface with a transparent inert layer, or the like. If used, the unevenness on the color filter can be reduced while suppressing the influence on the spectral characteristics.

On the other hand, the inherent spectral characteristics of the coloring pigment used in the heat-resistant color filter affect the image quality of the image display device such as the transmittance and contrast of each color of RGB. Inorganic pigments having high-temperature durability have lower transparency and coloring power than organic pigments for color filters for color liquid crystal displays, and it is difficult to realize sufficient spectral contrast. In addition, since the types of pigments that can be applied are limited, various phosphors used in image display devices such as plasma discharge display panels and field emission displays can exhibit good color tone reproducibility for each color of RGB. However, there is a problem that the degree of correction can be limited.

That is, even if a heat-resistant color filter is applied to a plasma discharge display panel, a field emission type display, or the like, if the heat-resistant color filter has a low spectral contrast of each color of RGB, it is difficult to observe a bright room where external light enters. The effect of improving the display contrast is low. Further, unless pigments having different spectral characteristics can be obtained so that the hue of each color of RGB can be controlled to some extent, it is difficult to appropriately correct the color development of the phosphors of each color of RGB and expand the color reproduction range.

This is because the spectral characteristics, which is the relationship between the wavelength of light transmission / light absorption and the wavelength of the inorganic pigment, are almost fixed by the usable inorganic pigment. Even if a selected bright phosphor emits much light other than its main wavelength, that is, if it is a so-called phosphor having low color purity, it can be said that it is difficult to correct to a preferable color reproduction characteristic. It is.

[0016]

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems, and a heat-resistant color filter used for a plasma discharge display panel, a field emission type display, or the like, has a pattern. Fine,
The surface is flat, and as described above, the color correction of the phosphor is not limited by the inorganic pigment used, and has a remarkable effect as a color filter such as color separation and color correction, antireflection and display contrast improvement, that is, An object of the present invention is to provide a heat-resistant color filter capable of obtaining a display having excellent display quality.

[0017]

According to the present invention, there is provided a photosensitive coloring composition comprising, as constituents, an alkali-soluble resin, a photopolymerizable compound having an ethylenically unsaturated group, a photopolymerization initiator, and a coloring pigment on a transparent substrate. In the heat-resistant color filter provided with a plurality of colored patterns of a certain interval and shape using a material, and baked to form a pattern of only the colored pigments, a colored pigment is formed on the colored pigment formed as a pattern. A heat-resistant color filter comprising a single layer or a plurality of layers of colored or colloid-dyed glass for assisting the spectral characteristics of a colored pigment as an overcoat layer to be fixed.

The present invention also relates to the heat-resistant color filter according to the present invention, wherein the colored or colloid-dyed glass comprises at least one hydrolyzable silane or an oligomer derived therefrom, and at least one organosilane. At least one of a metal or nonmetal oxide, a colorable metal ion, a colloid of a metal or metal compound, and a metal ion capable of forming a metal colloid when reacted under reducing conditions with silane or an oligomer derived therefrom; A heat-resistant color filter formed by baking a composition containing a heat-resistant carrier as a main component.

The present invention also provides the heat-resistant color filter according to the present invention, wherein the composition comprises a composition obtained by hydrolysis and polycondensation of at least one compound containing a glass-forming element. It is a heat-resistant color filter characterized by the following.

The present invention also relates to the heat-resistant color filter according to the present invention, wherein the colored or colloid-dyed glass has a spectral characteristic obtained by integrating respective spectral characteristics that assist each spectral characteristic of a plurality of color pigments. It is a heat resistant color filter characterized by having.

According to the present invention, there is provided the heat-resistant color filter according to the above-mentioned invention, wherein the colored or colloid-dyed glass has a spectral characteristic having absorption near 500 nm or 620 nm. It is.

[0022]

Embodiments of the present invention will be described below. FIG. 1 is a sectional view showing one embodiment of a heat-resistant color filter according to the present invention. As shown in FIG. 1, the heat-resistant color filter includes a colored pattern (red) (2), a colored pattern (green) (3), a colored pattern (blue) (4), a colored pattern (red) on a transparent substrate (1). Black) (black matrix) (5) and an overcoat layer (6). FIG. 2 is an explanatory diagram showing an enlarged portion of the cross-sectional view shown in FIG. As shown in FIG. 2, the coloring pattern (red) (2) of the heat-resistant color filter is a red coloring pigment (12), the coloring pattern (green) (3) is a green coloring pigment (13), and the coloring pattern (blue) ( 4) Blue coloring pigment (14), colored pattern (black) (black matrix)
(5) is composed of a black colored pigment (15).

The present invention relates to a heat-resistant color filter formed by photolithography from a colored photosensitive composition, wherein a colored photosensitive composition having a required number of colors is coated on a transparent substrate, exposed to light, developed, and After baking to form a pattern of only a colored pigment, colored or colloidally stained glass is provided on the pattern as an overcoat layer. This glass overcoat layer has spectral characteristics such as assisting the emission characteristics of the phosphor used in the display and assisting the spectral characteristics of the pattern of the color pigment alone, such as improving the antireflection effect. Display quality can be improved.

The glass is a glass formed by a sol-gel method or the like and contains a metal colloid, and the necessary spectral characteristics are exhibited by selecting and using each of the materials having heat resistance. It is possible. In addition, the thickness of the glass layer, the fixation of the coloring pigment,
Determined in consideration of mechanical strength, uniformity, and required spectral characteristics.

Further, the glass layer has a spectral characteristic obtained by integrating the respective auxiliary spectral characteristics for assisting the respective spectral characteristics of the color pigments of a plurality of colors. Are laminated and used in some cases. Therefore, it is possible to correct the spectral characteristics of the phosphor used for the display to desired characteristics and sufficiently improve the display contrast in a bright room.

The glass layer having a spectral characteristic having absorption near 500 nm can correct the emission characteristics of the blue phosphor, and the glass layer having a spectral characteristic having absorption near 620 nm can be corrected. In order to eliminate unnecessary light emission, which is emitted by the plasma generated by the plasma display, it is necessary to correct the spectral characteristics, improve the color purity of the image displayed on the display, and expand the color reproduction range. Is made possible.

This glass has the function of assisting the spectral characteristics of the display as an overcoat layer.
The color pigment pattern is sufficiently covered and fixed, and has a durability adapted to washing and chemical treatment performed in an electrode formation and a dielectric layer formation step in forming a panel as a display. In addition, colored glass such as metal colloid formed by thermally densifying metal alkoxide or the like known as a sol-gel method at a high temperature may cause cracks when formed as an overcoat layer of about 3 μm or more. And it is likely to become an obstacle during electrode formation. Conversely, 0.
If the thickness is too thin, 1 μm or less, a step between the colored pattern and the transparent substrate and a portion where the edge of the colored pattern cannot be sufficiently covered are easily generated and pinholes are easily generated. There is.

As the coloring pigment in the present invention, red,
Use green, blue and black inorganic color pigments as appropriate.
You. As red, Fe_TwoO_Three, Pb_ThreeO_Four, 2Sb_Two
S ・ Sb_TwoO_Three, Sb_TwoS _Three・ Sb_TwoO_ThreeEtc. are green
As Cr_TwoO_Three, Cr_TwoO (OH)_Four, Cu (C
H_ThreeCO_Two)_Two・ 3CuO (AsO_Two)_Two, CoO ・ Z
nO.MgO is 3NaAl.Si as blue
O_Four・ Na_TwoS_Two, 2 (Na_TwoO ・ Al_TwoO _Three・ 2Si
O_Two) ・ Na_TwoS, Fe_Four[Fe (CN)₆] 3nH_Two
O, CoO ・ nAl_TwoO_Three, (More than n = 2-3), Co
O ・ nSnO_Two-MMgO (n = 1.5-3.5, m =
2-6), etc., but black as CuO.Cr_TwoO_Three,
CuO ・ Cr_TwoO_Three・ MnO_Two, CuO.Fe_TwoO_Three・
Cr_TwoO_Three, Etc. are listed as usable color pigments
It is.

Of these color pigments, each of the color pigments except black has appropriate transparency and coloring power within the spectral characteristics required for a color filter pigment and also has durability such as heat resistance. Desirably, the photosensitive coloring composition is also selected in consideration of compatibility with a resin component or the like so that appropriate viscosity characteristics and coating suitability are exhibited. Further, the coloring pigment to be used may be coated with a transparent material such as silicon dioxide, magnesium oxide, aluminum oxide, cesium oxide or the like so that the weight of the coloring pigment is in the range of 5 to 100% by weight.

The alkali-soluble resins usable in the present invention include (meth) acrylic resins containing (meth) acrylic acid, rosin resins and maleic acid resins. Even if the alkali-insoluble resin is used, if the processing amount is limited so as to be 10% by weight or less, preferably 5% by weight or less in the nonvolatile content of the photosensitive coloring composition, the effect on the developability is small. (Meth) acrylic resin is a copolymer of monomers of acrylic acid and methacrylic acid and their esters, or a mixture of monomers thereof. Copolymers are also included. However, a three-dimensionally crosslinked polymer such as a copolymer with a polyfunctional monomer has poor solubility and is not suitable for the present invention. As the maleic acid resin, those having an acid value of 40 to 160 are used.
The above are preferred from the viewpoint of suitability for alkali development when the photosensitive coloring composition is used.

The photopolymerizable compound used in the present invention is a compound having an ethylenically unsaturated group capable of undergoing free-radical addition polymerization or crosslinkable, and has at least one ethylenically unsaturated group, for example, vinyl. A monomer or oligomer having a group or an allyl group, or a polymer having an ethylenically unsaturated group at a terminal or a side chain. Examples thereof include acrylic acid and its salts, acrylic esters, acrylamides, methacrylic acid and its salts, methacrylic esters, methacrylamides, maleic anhydride,
Maleic esters, itaconic esters, styrenes, vinyl ethers, vinyl esters, N-vinyl heterocycles, allyl ethers, allyl esters and derivatives thereof.

Preferably, polyfunctional acrylic monomers and oligomers include (meth) acrylic acid, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, (meth) acrylamide, vinyl acetate,
N-hydroxymethyl (meth) acrylamide, polyethylene glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, styrene, vinyl acetate, various acrylic vinyl esters, various methacrylic esters, acrylonitrile, dipentaerythritol hexa (meth) Examples include acrylate, tricyclodecanyl (meth) acrylate, hexa (meth) acrylate of a caprolactone adduct of dipentaerythritol hexa (meth) acrylate, melamine (meth) acrylate, and epoxy (meth) acrylate prepolymer.

The photopolymerization initiator used in the present invention includes 4-phenoxydichloroacetophenone, 4-t-
Butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1one, 1-hydroxycyclohexylphenyl ketone, 2-benzyl-2-dimethylamino-1- (4 Benzophenone photoinitiators such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzyl dimethyl ketal; benzophenone, benzoyl benzoic acid; Methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-
Benzophenone-based photoinitiators such as 4'-methyldiphenyl sulfide; thioxanthone-based photoinitiators such as thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, and 2,4-diisopropylthioxanthone; 2,4,6-trichloro-
s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p- Tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-pipenyl-4,6
-Bis (trichloromethyl) -s-triazine, 2,4
--- bis (trichloromethyl) -6-styryl s-triazine, 2- (naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxy-naphth-1- Yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl-
Triazine photoinitiators such as (piperonyl) -6-triazine and 2,4-trichloromethyl (4′-methoxystyryl) -6-triazine, and compounds such as carbazole photoinitiators and imidazole photoinitiators Can be used.

The above photoinitiators may be used alone or in combination of two or more. As sensitizers, α-acyloxime esters, acylphosphine oxides, methylphenylglyoxylate, benzyl, 9,10-phenanthrene Quinone, camphorquinone, ethylanthraquinone,
4,4′-diethylisophthalophenone, 3,3 ′,
4,4'-tetra (t-butylperoxycarbonyl)
Compounds such as benzophenone and 4,4'-diethylaminobenzophenone can also be used.

In producing a photosensitive coloring composition, a coloring pigment coated with a transparent inert layer is treated with an alkali-soluble resin,
Various dispersing means such as a three-roll mill, a two-roll mill, a sand mill, and a kneader can be used for dispersing the polyfunctional acrylic monomer. Further, in order to improve the dispersion, a dispersion aid such as various surfactants and pigment derivatives may be appropriately added. The dispersing agent is excellent in dispersing the pigment and has a large effect of preventing re-aggregation of the pigment after the dispersion, so that a color filter having excellent transparency can be obtained, but the spectral characteristics after firing and the storage characteristics of the photosensitive coloring composition are obtained. Select and use ones that do not interfere with

As a method of applying the photosensitive coloring composition on the transparent substrate, a method that matches the viscosity characteristics of the manufactured photosensitive coloring composition may be selected. In the case of a high viscosity, screen printing or die coating is used. In the case of low viscosity by a method such as a spin coating method, a spray coating method and a roll coating method, a method having good coating flatness may be selected and used.

In order to improve the dispersibility of the coloring pigment in the photosensitive coloring composition and to adjust the coating thickness on the transparent substrate, the viscosity may be adjusted by adding a solvent. . As the solvent, for example, cyclohexanone, ethyl cellosolve acetate, butyl cellosolve acetate,
1-methoxy-2-propyl acetate, diethylene glycol dimethyl ether, ethylbenzene, ethylene glycol diethyl ether, xylene, ethyl cellosolve, methyl-n amyl ketone, propylene glycol monomethyl ether toluene, methyl ethyl ketone, ethyl acetate, methanol, ethanol, isopropyl alcohol, butanol, isobutyl Ketones, petroleum solvents and the like can be mentioned, and they are used alone or in combination.

The hydrolyzable silane used for colored or colloid-dyed glass is represented by the following general formula (1). SiX ₄ (1) [wherein the radicals X are the same or different and each is a hydroxy group or a hydrolyzable group]

Examples of the hydrolyzable group include hydrogen or halogen (F, Cl, Br or I), alkoxy (for example,
C1-6 alkoxy such as methoxy, ethoxy, n-propoxy, i-propoxy and butoxy), aryloxy (C6-10 aryloxy such as phenoxy), acyloxy (CC1-6 acyloxy such as acetoxy or propionyloxy) Alkylcarbonyl (C2-7 alkylcarbonyl such as acetyl), amino, monoalkylamino or dialkylamino having 1 to 12, especially 1 to 6 carbon atoms.

Particularly preferred hydrolyzable silanes are tetraalkoxysilanes, for example, tetraethoxysilane (TEOS). Particularly preferred organosilanes are epoxysilanes, such as 3-glycidyloxypropyl-trimethoxysilane (GPTS), and aminosilanes, such as 3-aminopropyl-triethoxysilane and 3- (aminoethylamino) -propyl-. Triethoxysilane (DIAMO) is an example.

The organosilane used for colored or colloid-dyed glass is represented by the following general formula (2). R1aR2bSix (4-ab) (2) wherein R1 is a non-hydrolyzable radical;
2 represents a radical having a functional group; X represents the same or different and represents a hydroxy group or a hydrolyzable group;
And b are 0, 1, 2 or 3 and the sum of (a + b) is 1, 2 or 3]

Examples of radicals R1 that cannot be hydrolyzed are
Alkyl (preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, s-butyl, and t-
C1-6 alkyl such as butyl, pentyl, hexyl or cyclohexyl), alkenyl (preferably C2-6 alkenyl such as vinyl, 1-propenyl, 2-propenyl and butenyl), alkynyl (preferably acetylenyl and propargyl) C2-6 alkynyl), and aryl (preferably C6-10 aryl such as phenyl and naphthyl). The radicals R1 and X may optionally have one or more commonly used substituents such as, for example, halogen or alkoxy.

Specific examples of the functional group of the radical R2 include epoxy, hydroxy, ether, amino, monoalkylamino, dialkylamino, amide, carboxy, mercapto, thioether, vinyl, acryloxy, methacryloxy, cyano, halogen, Aldehyde, alkylcarbonyl, sulfonic and phosphoric acid groups. The functional group is bonded to the silicon atom via an alkylene, alkenylene or arylene bridging group, and the bridging group may have an oxygen or sulfur atom or -NH- group interposed. The bridging group is derived from an alkyl, alkenyl or aryl radical as described above. The radical R2 preferably contains 1 to 18, particularly preferably 1 to 8, carbon atoms. The weight ratio of hydrolyzable silane to organosilane is from 5 to 50:50 to 95, preferably from 15 to 25:75 to 85.

The composition obtained by hydrolysis and polycondensation of one or more compounds containing a glass-forming element used in colored or colloid-dyed glass must be soluble or dispersible in the reaction medium. Examples of usable compounds (halides, alkoxides, carboxylates, chelate compounds and the like) include lithium,
Sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, boron, aluminum, titanium, zirconium, tin, zinc or vanadium.

The hydrolysis and polycondensation of a composition obtained by the hydrolysis of silane, organosilane, or one or more compounds containing silane, organosilane, or a glass-forming element and the polycondensation are carried out in the absence of a solvent. Below or
Preferably, in an aqueous or aqueous / organic reaction medium, optionally an acidic or basic condensation catalyst such as HC
1, performed in the presence of HNO ₃ or NH ₃ . If a liquid reaction medium is used, the starting components are soluble in the reaction medium. Suitable organic solvents include, in particular,
Water-miscible solvents such as mono- or polyhydric aliphatic alcohols, ethers, esters, ketones, amides, sulfoxides, and sulfones.

Preferably, the hydrolysis and polycondensation are sol-
It takes place under the conditions of a gel process, in which a reaction mixture in the form of a viscous sol is used to coat the support.
Hydrolysis and polycondensation, if desired, can be carried out with complexing agents such as nitrates, β-dicarbonyl compounds (eg, acetylacetonates or acetoacetates), carboxylic acids (eg, methacrylic acid), or The reaction is performed in the presence of carboxylate (eg, acetate, citrate, glycolate), betaine, diol, diamine (eg, DIAMO), or crown ether.

The sol obtained as described above includes a metal or nonmetal oxide as a coloring substance, a coloring metal ion, a colloid of a metal or a metal compound, and a metal which can react under reducing conditions to form a metal colloid. It is mixed with at least one molecularly dispersible or nanoscale carrier from the group of ions and becomes a raw material for colored or colloidally stained glass after its viscosity has been adjusted by adding or removing solvents as needed. .

Suitable metal or non-metal oxides include, for example, SiO ₂ , TiO ₂ , ZrO ₂ , Al ₂ O
₃ , Fe ₂ O ₃ , Cr ₂ O ₃ , CuO, Cu ₂ O, Zn
O, Mn ₂ O ₃ , SnO ₂ , PdO, and In ₂ O ₃ , preferably those having a particle diameter of 1 to 100 nm.

Coloring metal ions include, for example, Mn ²⁺ , C
It is preferably in the form of a water-soluble salt such as nitrates or halides of o ²⁺ , Fe ³⁺ or Cr ³⁺ . As metal colloids, Ag, Cu, Au, Pd,
Metal colloids of Pt and Pt are particularly preferred; ordinary metal colloids have a particle size of 1 to 100 nm, but when used in colored or colloidally stained glass, can be formed as a transparent glass layer. The particles having a particle diameter of 1 to 20 nm are preferred.

Examples of suitable metal compounds in colloidal form are
AgCl, AgBr, AgCl _x Br _1-x , and CuC
1, metal carbides such as TiC and B ₄ C, metal nitrides such as BN and TiN, Cd ₃ As ₂
Arsenic such as Cd ₃ P ₂ , metal phosphide such as Cd ₃ P ₂ , Ag
S, CdS, HgS, PbS, and ZnS; CdSe,
(Sulfide, selenide, telluride) chalcogenides such as ZnSe and CdTe, and ZnSe / P of mixed phase
bS ₂ or CdS / PbS ₂ .

The metal compound is preferably 1 to 100 n
m, more preferably 2 to 30 nm. The metal or metal compound colloid can be used in a pre-complexed form as required.
The type and amount of these coloring substances are determined in consideration of the spectral characteristics desired as colored or colloid-dyed glass, for example, the absorption main wavelength, transparency, and absorbance.

The overcoat layer using colored or colloid-stained glass is formed by patterning the above material whose viscosity is adjusted according to the coating method to be applied by using a spin coating method, a roll coater method, a screen printing method or the like. After being coated on the colored pigment formed in the above, it is dried and then densified by heat to be formed. Densification is performed at a temperature of 250 ° C. or higher, preferably 400 ° C. or higher, particularly preferably 50 ° C. or higher.
Heat using a known heating means so as to be 0 ℃ or more,
It is performed within the range of softening, distortion temperature, or decomposition temperature of the support. Densification by heating may be performed in air or, if necessary, in an inert gas such as nitrogen or argon gas.

The glass layer containing the heat-resistant coloring substance according to the present invention is coated with the coloring substance having a very small particle size in a very uniform state, and causes cracking due to densification by heating. Since they are not available, they have very good optical properties, especially transparency. In addition, by being formed into a strong vitreous material, it acts as a strong overcoat layer on a colored pigment formed in a pattern on a transparent substrate, and forms electrodes and a dielectric layer when forming a panel as a display. Sufficient durability can be imparted to the cleaning or chemical treatment performed in the process.

[0054]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments of the present invention will be described below in detail.

(Surface passivation treatment of coloring pigment) Black pigment (manufactured by Dainichi Seika Kogyo Co., Ltd .: TM Black 35
10 ") Red pigment (manufactured by Dainichi Seika Kogyo Co., Ltd .:" TRANS OX "
IDE RED ”) Blue pigment (manufactured by Dainichi Seika Kogyo Co., Ltd .:“ TM Blue 345 ”)
0 ") Green pigment (manufactured by Dainichi Seika Kogyo Co., Ltd .: TM Green 33
20)) Of the above pigments, 10 parts by weight of each of a black pigment and a red pigment were put into 150 parts by weight of pure water and subjected to sufficient stirring and dispersion treatment, followed by ultrasonic dispersion and stirring. Heated to 80 ° C. while performing. Next, a 5% NaOH solution was added to adjust the pH to 9, and then a sodium silicate aqueous solution (pure water 7) was added.
5 parts by weight of sodium silicate in 3 parts by weight) were added dropwise over time. At this time, in order to maintain the solution at pH 9, a 5% HCl solution was appropriately added dropwise and reacted for 1 hour. Next, a 5% HCl solution was added until the pH became 6, and the mixture was further kept for 15 minutes. The obtained precipitate was subjected to centrifugal filtration, washing with pure water, and sufficient heating and drying to produce each color pigment having a silicate layer formed on the surface.

(Preparation of Alkali-Soluble Acrylic Resin) 55 parts by weight of butyl methacrylate, 20 parts of methyl methacrylate
Parts by weight, 15 parts by weight of 2-hydroxyethyl methacrylate, and 10 parts by weight of methyl acrylate are copolymerized using 2- (2-ethoxyethoxy) ethanol as a solvent, to give a ratio of 40 parts by weight of acrylic resin and 60 parts by weight of solvent. It was prepared as follows.

<Example 1> A photosensitive coloring composition was prepared using the above-mentioned coloring pigment and acrylic resin at the following compounding ratio, and a coloring pattern comprising the coloring pigment was formed on a transparent substrate.

(Photosensitive black composition) Acrylic resin 8.2 parts by weight Polyfunctional oligoester acrylate dipentaerythritol hexaacrylate 4.9 parts by weight Photopolymerization initiator trichloromethyl S-triazine 1.0 part by weight Diluent solvent 2- (2-ethoxyethoxy) ethanol 56.4 parts by weight Color pigment Black pigment (the above-mentioned treated “TM black 3510”) 29.5 parts by weight This colored photosensitive composition was placed on a transparent substrate at 350 mesh and 80 μm in plate thickness. Screen printing was performed using a stainless steel screen plate, and the film surface was dried by standing at room temperature for 5 minutes, and then dried at 70 ° C. for 20 minutes to form a photosensitive coloring composition layer. The thickness of the obtained photosensitive coloring composition layer was about 2 μm, the entire surface had a uniform thickness, and the surface state was smooth.

Next, an opening having a length of 200 mm and a width of 150 μm is used.
And the repetition pattern of the frame part with a line width of 10 μm
Photomask formed on the light-shielding film to form a matrix
To the above-mentioned photosensitive coloring composition layer to form an ultra-high pressure mercury lamp.
More exposure amount 400mJ / cm ^TwoExposure was performed under the following conditions.
After exposure, an alkaline developer at a temperature of 20 ° C is ejected at a pressure of 1 kg.
/ Cm^TwoSpray development for 50 seconds,
The light colored composition layer was removed. Dry the developed substrate
After that, the film was heated and hardened at 230 ° C. for 1 hour. After dura
Has a thickness of about 1.
It was 8 μm.

(Photosensitive red composition) Acrylic resin 8.2 parts by weight Polyfunctional oligoester acrylate dipentaerythritol hexaacrylate 4.9 parts by weight Photopolymerization initiator Piperonyl trichloromethyl S-triazine 1.0 part by weight Dilution Solvent 2- (2-ethoxyethoxy) ethanol 56.4 parts by weight Color pigment Red pigment 29.5 parts by weight (The above-mentioned treated “TRANS OXIDE RED”) The colored photosensitive composition was mixed with the black matrix (before firing). On the formed transparent substrate, screen printing was performed using a stainless steel screen printing plate of 330 mesh, plate thickness of 80 μm, and the film surface was dried at room temperature for 5 minutes. A red composition layer was formed. The thickness of the obtained photosensitive red composition layer is about 3 μm.
Had a uniform film thickness over the entire surface, and the surface condition was smooth.

Next, a photomask having a light-shielding film in which a stripe pattern having a length of 200 mm and a width of 150 μm is repeatedly formed at a pitch of 480 μm is brought into close contact with the photosensitive red composition layer so as to match the opening of the black matrix 11. Exposure amount of 350 mJ / cm ² by ultra-high pressure mercury lamp
Exposure was performed under the following conditions. After exposure, an alkali developing solution at a temperature of 20 ° C. was spray-developed at a pressure of 1 kg / cm ² for 50 minutes.
Then, the photosensitive colored composition layer at the unexposed portion was removed.
After drying the developed substrate, the substrate was heated and hardened at 230 ° C. for 1 hour. The thickness of the patterned photosensitive coloring composition layer after hardening was about 2.8 μm.

(Photosensitive green composition) Acrylic resin 8.2 parts by weight Polyfunctional oligoester acrylate dipentaerythritol hexaacrylate 4.9 parts by weight Photopolymerization initiator piperonyl trichloromethyl S-triazine 1.0 part by weight Dilution Solvent 2- (2-ethoxyethoxy) ethanol 56.4 parts by weight Color pigment Green pigment ("TM Green 3320" above) 29.5 parts by weight

Next, the photosensitive green composition was applied to the transparent substrate on which the black matrix and the colored pattern (before firing) had been formed under the same conditions as above by a thickness of 3.5 μm, and the same photomask as described above was applied. Was brought into close contact with the photosensitive coloring composition layer, and exposed to light with an ultrahigh pressure mercury lamp under the conditions of an exposure amount of 300 mJ / cm ² . After the exposure, an alkali developing solution at a temperature of 20 ° C. was spray-developed for 60 seconds at a jetting pressure of 1 kg / cm ² to remove the unexposed colored photosensitive composition layer to expose the glass substrate. After drying the developed substrate, 2
The layer was heated at 30 ° C. for 1 hour to perform a hardening treatment. The thickness of the patterned photosensitive coloring composition layer after the hardening was 3.3 μm.

(Photosensitive Blue Composition) Acrylic resin 8.2 parts by weight Polyfunctional oligoester acrylate dipentaerythritol hexaacrylate 4.9 parts by weight Photopolymerization initiator Piperonyl trichloromethyl S-triazine 1.0 part by weight Dilution Solvent 2- (2-ethoxyethoxy) ethanol 56.4 parts by weight Color pigment Green pigment ("TM Blue 3450") 29.5 parts by weight The same process is repeated for the above-described photosensitive blue composition to form a transparent substrate. Black matrix and colored pattern (striped pattern) whose register matches the opening
(Before firing).

Then, the transparent substrate was heated in an air atmosphere at a heating rate of 4 ° C./min, baked at a temperature of 430 ° C. for 60 minutes, and further continuously heated to 580 ° C.
After baking at a temperature of 30 minutes, the substrate is cooled to room temperature at a temperature lowering rate of 4 ° C./min, whereby the organic resin component of the photosensitive coloring composition layer is burned off, and a film made of a surface-treated black pigment is removed. A 1.3 μm-thick black matrix, a 2 μm-thick colored pattern made of a surface-treated red pigment, a 2.3 μm-thick colored pattern made of a green pigment, and a 2.3 μm-thick colored pattern made of a blue pigment The formed color filter was obtained. At this time, the optical density of the black matrix at 500 nm was 1.5.

Next, a glass layer was formed on the transparent substrate on which the colored pattern was formed, and a heat-resistant color filter was manufactured.

(Preparation of Glass Raw Material Liquid) 160 parts by weight of 3-glycidyloxypropyltrimethoxysilane (GPTS) 40 parts by weight of tetraethoxysilane (TEOS) 120 parts by weight of ethanol were mixed and heated to 60 ° C. with stirring. 28.5 parts by weight of water and 0.5 parts by weight of concentrated HNO ₃ were added, and the mixture was stirred at 60 ° C. for 15 hours and diluted with 150 parts by weight of ethanol. The liquid thus obtained is referred to as a glass raw material liquid (A).

Next, 3- (aminoethylamino) -propyl-triethoxysilane (DIAMO) 0.18 was added to a solution of 0.4 parts by weight of H [AuCl ₄ ] -2H ₂ O and 4 parts by weight of ethanol. A solution prepared by mixing 1 part by weight of ethanol with 1 part by weight was dropped to prepare a glass raw material liquid (B).

Further, DIAMO was added to the glass raw material liquid (A).
After mixing 1.58 parts by weight, the glass raw material liquid (B) was added dropwise. After stirring the obtained solution for 30 minutes, it was filtered through a 0.8 μm filter to obtain a glass raw material liquid.

(Formation of Glass Layer) The above-mentioned glass raw material liquid is coated on the black matrix formed on the transparent substrate and the above-mentioned color filter composed of red, green and blue coloring patterns by spin coating, and then 150 ° C. After heating at 4 ° C./min in air atmosphere and baking at 420 ° C. for 60 minutes,
After further heating to 0 ° C. and firing at a temperature of 580 ° C. for 30 minutes, the substrate was cooled to room temperature at a rate of 4 ° C./min. By the firing treatment under these conditions, the functional low-melting glass became an overcoat layer having light transmittance, and a color filter covered with a strong film was produced.

Both the pattern shape and the formation position of the color filter produced as described above accurately reflect the light-shielding film pattern of the photomask. In addition, the spectral characteristics of the color filter are determined by the appropriate spectral characteristics of the inorganic pigment used. In addition to this, an absorption around 620 nm was given by the glass layer, and unnecessary light emission due to the plasma of the plasma display was excluded, and better color reproducibility than the color filter alone could be achieved.

Example 2 On a color filter produced in the same manner as in Example 1, an overcoat layer made of the following glass was provided. In 20 parts by weight of the glass material liquid (A) previously hydrolyzed, 0.51 part by weight of AgNO ₃ was dissolved in 3.3 parts by weight of DIAMO and 3 parts by weight of ethanol while stirring, and the mixture was stirred for 30 minutes. Filtration was performed to obtain a glass raw material liquid.

(Formation of Glass Layer) The functional glass raw material liquid was applied on the black matrix formed on the transparent substrate and the color filter composed of red, green and blue colored patterns in the same manner as in Example 1. Was coated, dried and fired to form an overcoat layer of low-melting glass having optical transparency, and a color filter covered with a strong film was produced.

Both the pattern shape and the formation position of the color filter produced as described above accurately reflect the light-shielding film pattern of the photomask. In addition, the spectral characteristics of the color filter depend on the appropriateness of the inorganic pigment used. In addition to the excellent spectral characteristics, the glass layer was provided with absorption near 500 nm, and exhibited good color reproduction characteristics excluding unnecessary light emission accompanying the blue phosphor.

[0075]

According to the present invention, an alkali-soluble resin, a photopolymerizable compound having an ethylenically unsaturated group on a transparent substrate,
A heat-resistant color filter using a photosensitive coloring composition containing a photopolymerization initiator and a coloring pigment as constituents, providing a coloring pattern of a plurality of colors at a certain interval and shape, and firing to form a pattern of only the coloring pigments of a plurality of colors. In the above, a single layer or a plurality of layers of colored or colloid-stained glass for assisting the spectral characteristics of the color pigment as an overcoat layer for fixing the color pigment was provided on the color pigment formed as a pattern. Therefore, when used in a plasma discharge display panel, a field emission display, or the like, the pattern is fine, the surface is flat, and, without being limited by the inorganic pigment used for color correction of the phosphor, color separation and Heat resistant to obtain a display with excellent display quality that has remarkable effects as a color filter such as color correction, anti-reflection, and improvement of display contrast It is possible to provide a color filter. Further, it is possible to provide a heat-resistant color filter capable of obtaining durability adapted to processing in a display manufacturing process.

[Brief description of the drawings]

FIG. 1 is a sectional view showing one embodiment of a heat-resistant color filter according to the present invention.

FIG. 2 is an explanatory diagram showing an enlarged portion of the cross-sectional view shown in FIG. 1;

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 ... Transparent substrate 2 ... Coloring pattern (red) 3 ... Coloring pattern (green) 4 ... Coloring pattern (blue) 5 ... Coloring pattern (black) (black matrix) 6 ... Overcoat layer 12. Red color pigment 13. Green color pigment 14. Blue color pigment 15. Black color pigment

 ────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Yoshiko Matsumoto 1-5-1, Taito, Taito-ku, Tokyo Toppan Printing Co., Ltd. F-term (reference) 2H048 BA45 BA48 BB02 BB37 BB46

Claims (5)

[Claims] 1. A transparent substrate, comprising a photosensitive coloring composition comprising an alkali-soluble resin, a photopolymerizable compound having an ethylenically unsaturated group, a photopolymerization initiator, and a coloring pigment, at a predetermined interval. Provide a colored pattern of multiple colors of the shape,
In a heat-resistant color filter having a pattern of only a plurality of color pigments by baking, coloring for assisting the spectral characteristics of the color pigment as an overcoat layer for fixing the color pigment on the color pigment formed as a pattern. A heat-resistant color filter comprising a single layer or a plurality of layers of colloid-stained glass. 2. The colored or colloidally stained glass comprises at least one hydrolyzable silane or an oligomer derived therefrom, at least one organosilane or an oligomer derived therefrom, and a metal or nonmetal. Composition comprising at least one heat-resistant carrier among oxides, colorable metal ions, colloids of metals or metal compounds, and metal ions capable of forming metal colloids under the reducing conditions The heat-resistant color filter according to claim 1, wherein the color filter is formed by baking. 3. The heat-resistant color filter according to claim 2, wherein the composition comprises a composition obtained by hydrolysis and polycondensation of at least one compound containing a glass-forming element. . 4. The color- or colloid-stained glass has a spectral characteristic obtained by integrating respective auxiliary spectral characteristics for assisting each spectral characteristic of a plurality of color pigments. The heat-resistant color filter according to claim 2, or 3. 5. The glass according to claim 1, wherein said colored or colloidally stained glass has a spectral characteristic having an absorption near 500 nm or around 620 nm. Heat resistant color filter.