JP2000066381A - Photosensitive colored composition and color filter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a photosensitive colored compsn. excellent in shelf stability, suitability to coating and spectral characteristics and to make a color filter smooth without deteriorating its color separation effect, antireflection effect and display contrast by incorporating a transparent resin, a multifunctional acrylic monomer or oligomer, a photopolymn. initiator, a colorant and barium sulfate. SOLUTION: Barium sulfate is added to a compsn. contg. a transparent resin, a multifunctional acrylic monomer or oligomer, a photopolymn. initiator and a colorant. The barium sulfate is particles of <=0.1 μm average particle diameter, is preferably added by 1-200 wt.% of the amt. of the colorant and has satisfactory heat resistance. The transmittance of the barium sulfate is preferably >=80% in the wavelength range of 400-700 nm in the visible light region. Since the photosensitive colored compsn. is used in combination with the barium sulfate, the coloring material layer of a color filter can be made smooth without deteriorating the spectral characteristics of the color filter.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a color filter applied to a display device such as a field emission display, a plasma discharge display panel, a fluorescent display device and a color liquid crystal display and a solid-state image pickup device, and to the formation of the color filter. It relates to the photosensitive colorant composition used.

[0002]

2. Description of the Related Art Color filters have been used in various display devices. For example, in a color liquid crystal display, a color filter having a spectral characteristic of a desired color is indispensable for displaying a color image. M. Tan
i, et al: “LCD Color Filter
s: Characteristics and Fut
ure Issues ”SID 95 SEMINAR
As described in LECTURE (1995) and the like, a color filter used generally comprises a resin layer containing an organic pigment or an organic dye, and is formed by, for example, a dyeing method, a pigment dispersion method, or a printing method. I have.

In a cathode ray tube display (CRT) and a low-speed electron beam fluorescent display panel, for example, T.M. Ito, et al:
"MicrofilterTM" Color CR
T, SID 95 Digest, p. 25 (199
As described in 5) and the like, it has been proposed to use the above-described color filter in order to reduce the reflectance and improve the contrast of a display image. in this way,
The use of color filters for reducing the reflectance and controlling the spectral characteristics of a display device is regarded as a useful means for improving display image quality.

A plasma discharge display panel or a field emission display requires a high-temperature heating process of 400 ° C. or more for melting a low-melting glass and sealing two glass substrates during production. When color filters are used in plasma discharge display panels and field emission displays, the organic materials in the color filters can burn, decompose, etc. during the high-temperature heating process, improving display contrast, reducing reflectance, and controlling spectral characteristics. The characteristics of the filter cannot be exhibited. For this reason, good heat resistance is particularly required for the colorants constituting the color filter layers R1, G1, B1 and the black matrix 22.

[0005] Sakai et al. "Ultra-low reflectance color display discharge panel (3)" Technical Report of the Institute of Television Engineers of Japan, ED 993, I
As described in PD113-8 (1986-11), one method of imparting heat resistance to a color filter is to use a coloring agent in which an inorganic pigment is dispersed in a low-melting glass to produce a color filter at a high temperature. A color filter corresponding to a process has been proposed.

In this method, a paste made of 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 material is printed. About 6 pixel patterns
By baking at 00 ° C. to burn off organic components such as a resin binder and the like, a low-melting glass powder is melted and an inorganic pigment is coated and fixed on a transparent substrate to form a color pattern of each color as a color filter. . At this time, since the coloring pattern of each color is made of only the inorganic material, it has durability to a high-temperature heating process related to manufacturing.

However, when the screen printing method is used, the screen plate expands and contracts in accordance with conditions such as the ambient temperature of the printing press, humidity, squeegee pressure and squeegee moving speed, so that the printed pattern is easily distorted. There is a disadvantage that it is difficult to print a fine pattern due to the limit of the mesh opening of the plate.

Furthermore, the spectral characteristics of the color filter require that the thickness of the low-melting glass and the pigment constituting the color filter be about 10 μm. In order to improve the spectral characteristics of the color filter, of the coloring material layers of the plurality of colors used, the amount of the pigment having a high coloring power is reduced, and the Balanced. However, the difference in the amount of the pigment appears as a step in the thickness of the color material layer of each color. This step causes disconnection of a drive electrode and the like formed later. For this reason, not only the resolution and the dimensional accuracy of the colored pattern but also the image quality of the display are likely to cause problems.

That is, in a plasma discharge display panel, a field emission type display, or the like, since the electrodes and the dielectric are formed on the color filter, the step on the surface of the color filter exerts an influence and the dielectric pin is affected. This causes disconnection of holes and electrodes, and further causes display defects of the display. Therefore, it is necessary that the transparent substrate including the surface of the color filter and the step between the color material layers of each color be flat with as few irregularities as possible.

[0010] For example, Japanese Patent Application Laid-Open No. Hei 8-220341 discloses that a photosensitive coloring composition having an acrylic resin, a polyfunctional acrylic monomer, a photopolymerization initiator, and a coloring pigment as constituents is applied, pattern exposure is performed, and the required number of colors is adjusted. After repeating for minutes, baking and heating are performed to pattern only the pigment in a predetermined shape on the transparent substrate, and then the patterned pigment and its surroundings are provided with a light-transmitting overcoat layer for planarization. A way to do that has been proposed.

According to this method, the color filter is composed of a pigment exhibiting a desired color spectral characteristic and a light-transmitting overcoat material provided in the periphery thereof, and the color filter has a thickness difference for each color pattern. Is absorbed by the particle size of the pigment and the thickness of the transparent overcoat layer provided on the periphery thereof, so that the step on the transparent substrate can be reduced.
In addition, even in a display having a configuration in which an electrode is formed under a color filter, the dielectric layer formed on the color filter can be smoothed. Display quality can be improved.

However, even with this method, a difference in light absorption coefficient between color pigments of each color, that is, a difference between coloring material layers caused by a difference in coloring power remains, and is substantially the same as the thickness of the coloring material layer. Alternatively, in the case of a thin overcoat layer, for example, a layer obtained by a sol-gel method using an alkoxide compound such as silicon or titanium, the effect of reducing the step was hardly observed.

In the case of using an overcoat layer having a thickness several times or more than the thickness of the colored pattern and exceeding 10 μm, for example, a dielectric or the like whose main component is a low-melting glass, unevenness on the overcoat is required. Although light is reduced, the light absorption by the low melting point glass is not negligible, and there is a problem that the brightness of the display is reduced.

In addition, it has been difficult to increase the thickness of the overcoat layer by the sol-gel method and reduce the thickness of the overcoat layer by the low-melting glass due to the properties inherent to the material. On the other hand, acrylic resin or polyfunctional acrylic monomer,
A photosensitive coloring composition prepared by adding a photopolymerization initiator and a solvent is a photosensitive curable material, but basically has a property of starting a curing reaction when there is a trigger for starting a polymerization reaction. ing. For example, activation of molecular motion by heating and electron transfer on the surface of a substance having high surface activity tend to initiate a curing reaction. This is due to the fact that the viscosity of the photosensitive coloring composition deteriorates with the storage time due to the high temperature at the time of storage or the effect of the type of the coloring agent used, and in some cases, it hardens and becomes unusable. It is easy to appear as.

[0015] In order to reduce the deterioration of the storage stability of the photosensitive coloring composition described above, a polymerization inhibitor is generally added. It is difficult to select an appropriate polymerization inhibitor because it may reduce the viscosity, increase the viscosity and cause a decrease in coatability, or may cause adverse effects such as remaining when firing the color filter and causing unnecessary coloring. In some cases, an appropriate polymerization inhibitor cannot be selected.

In addition, when the activity of the color pigment surface is high, or when the affinity for the acrylic resin or polyfunctional acrylic monomer to be used is high, the dispersion of the color pigment in the production process of the photosensitive coloring composition is carried out by dissolving the solution. In many cases, it is difficult to obtain a photosensitive colored composition having good coating suitability and spectral characteristics.

[0017]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and has as its object to provide excellent storage stability, coating suitability, and spectral characteristics, as well as color separation, antireflection, Another object of the present invention is to provide a photosensitive coloring composition capable of smoothing a color filter without impairing display contrast.

Another object of the present invention is to provide a color separation property, an antireflection property, a contrast property, a sufficient smoothness, a dielectric pinhole, an electrode line, and a display defect. There is no color filter to offer.

[0019]

The photosensitive coloring composition of the present invention comprises a resin having transparency, a polyfunctional acrylic monomer or oligomer, a photopolymerization initiator, a coloring agent, and barium sulfate. I do.

The color filter of the present invention is a color filter comprising a transparent substrate and a color material layer formed on the transparent substrate, wherein at least a part of the color material layer is transparent. , A photosensitive coloring composition containing a polyfunctional acrylic monomer or oligomer, a photopolymerization initiator, a colorant, and barium sulfate.

[0021]

BEST MODE FOR CARRYING OUT THE INVENTION The photosensitive coloring composition of the present invention contains barium sulfate in a composition containing a resin having transparency, a polyfunctional acrylic monomer or oligomer, a photopolymerization initiator, and a coloring agent. Have been.

Further, at least a part of the color material layer constituting the color filter of the present invention is formed by using the above-mentioned photosensitive coloring composition. According to the present invention, by using barium sulfate in combination with the above-mentioned photosensitive coloring composition, the bulk of the color material layer can be increased without impairing the spectral characteristics of the color filter. For example, among the color material layers of a plurality of colors, when forming a color material layer having a high coloring power and a small amount of pigment,
By using the photosensitive coloring composition in combination with barium sulfate, it is possible to reduce the level difference between the other coloring material layers and to smooth the entire coloring material layer, and to reduce the disconnection of the driving electrode and the image quality. A decrease or the like can be prevented.

Further, the photosensitive coloring composition of the present invention has improved storage stability and coating suitability by blending a resin having transparency, a polyfunctional acrylic monomer or oligomer, a photopolymerization initiator and barium sulfate. Good.

Further, the use of this photosensitive coloring composition in the color filter of the present invention improves the spectral characteristics, color separation, antireflection, and display contrast.

The barium sulfate used in the present invention is particles having an average particle diameter of 0.1 μm or less, preferably 1 to 200% by weight, more preferably 5 to 200% by weight based on the weight of the colorant. 100% by weight.

This barium sulfate has sufficient heat resistance, and has a transmittance of preferably 80% or more, more preferably 95% or more in the entire wavelength region of 400 to 700 nm in the visible light region.

The average particle size of the barium sulfate particles is 0.1 μm
If it is larger, the transparency becomes insufficient and the spectral characteristics of the coloring pattern of the color filter tend to be adversely affected. If the amount of the barium sulfate particles exceeds 200% by weight based on the weight of the color pigment, the amount of transmitted light that is not absorbed on the pigment surface increases, and the spectral characteristics of the color filter become insufficient. Tend.

It is desirable that barium sulfate be selected and applied in such an amount that the spectral characteristics of the color filter and the reduction of the level difference between the color material layers are compatible. In addition, it is preferable to select and use a grade having a pH and an oil absorption amount at which the dispersibility in the photosensitive coloring composition becomes good.

Preferred examples of the transparent resin used in the present invention include alkali-soluble resins, for example, acrylic resins containing acrylic acid and methacrylic acid, rosin resins and maleic resins. Even in the case of alkali-insoluble resin, 10% by weight in the nonvolatile content of the photosensitive coloring composition
If the processing amount is limited to 5% by weight or less, the effect on developability is small.

Acrylic resin is a copolymer of monomers of acrylic acid, methacrylic acid and esters thereof or a mixture of monomers thereof, and is used as a copolymer with not more than 60 mol% of radically polymerizable monomers such as styrene, vinyl acetate and maleic anhydride. 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.

The maleic acid resin has an acid value of 40 to 16
0 is used, but in the case of alkali development, those having an acid value of 80 or more are preferred from the viewpoint of developability when a colored composition is used.

Examples of the polyfunctional acrylic monomer or oligomer include (meth) acrylic acid, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, (meth) acrylamide, vinyl acetate, −
Hydroxymethyl (meth) acrylamide, polyethylene glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, styrene, vinyl acetate, various acrylates, various methacrylates, acrylonitrile, dipentaerythritol hexa (meth) acrylate, tri Cyclodecanyl (meth) acrylate, hexa (meth) acrylate of caprolactone adduct of dipentaerythritol hexa (meth) acrylate, melamine (meth) acrylate, epoxy (meth) acrylate prepolymer, 1,6-hexadiol diacrylate, Ethylene glycol diacrylate, neopentyl glycol diacrylate, triethylene glycol diacrylate, trimethylolpropatone triacrylate Chromatography, tris (2-hydroxyethyl) isocyanate, ditrimethylolpropane tetraacrylate, dipentaerythritol pentaacrylate and the like.

Examples of the photopolymerization initiator include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropane-1one, 1-hydroxycyclohexyl phenyl ketone, 2-benzyl-2-dimethylamino-1-
An acetophenone-based photoinitiator such as (4-morpholinophenyl) -butan-1-one and the like, a benzoin-based and benzophenone-based photoinitiator such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzyldimethyl ketal. Benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-
Benzophenone photoinitiators such as 4'-methyldiphenyl sulfide, etc .; , 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-
(Piperonyl) -6-triazine, 2,4-trichloromethyl (4'-methoxystyryl) -6-triazine,
2,4,6-tris (trichloromethyl) -s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-chlorophenyl)-
4,6-bis (trichloromethyl) -s-triazine,
A triazine photoinitiator such as 2- (4'-methoxy-1'-naphthyl) -4,6-bis (trichloromethyl) -s-triazine and a carbazole photoinitiator;
(2,3-dichlorophenyl) -4,5-diphenyl-
Imidazole dimer, 2- (2,3-dichlorophenyl) -4,5-bis (3-methoxyphenyl) -imidazole dimer, 2- (2,3-dichlorophenyl)-
4,5-bis (4-methoxyphenyl) -imidazole dimer, 2- (2,3-dichlorophenyl) -4,5-
Bis (4-chlorophenyl) -imidazole dimer, 2
-(2,3-dichlorophenyl) -4,5-di (2-furyl) -imidazole, 2,2'-bis (2-chlorophenyl) -4,5,4 ', 5'-tetraferyl-1-
Compounds such as 2'-biimidazole and imidazole-based photoinitiators such as HB22 (manufactured by Hodogaya Chemical) can be used. Other photopolymerization initiators include Irgacure 907,651 (benzyl methyl ketal),
184 (manufactured by Ciba-Geigy Corporation; trade name), diethylthioxanthone (manufactured by Nippon Kayaku Co., Ltd.), benzophenone, and the like can be used, and a mixture of a plurality of these can be used. The addition amount of the photopolymerization initiator is not particularly limited, but 1 to 50% by weight, preferably 5 to 30% by weight of the total resin weight is used by adding one or two kinds.

As the colorant used in the present invention, red, green, and blue inorganic pigments are preferred. By using such an inorganic pigment, a color filter having good heat resistance can be obtained.

As a red inorganic pigment, for example, Fe ₂ O ₃ ,
Pb ₃ O ₄ , 2Sb ₂ S, Sb ₂ O ₃ , Sb ₂ S ₃ , S
Preferred are b ₂ O _{3 and the} like. Particularly preferably,
Fe ₂ O ₃ may be used.

Green inorganic pigments include, for example, Cr ₂ O
_{3, Cr 2 O (OH)} 4, Cu (CH 3 CO 2) 2 · 3
_{CuO (AsO 2) 2, CoO} -ZnO-MgO, and the like TiO ₂ -CoO-NiO-ZnO are preferably mentioned. Particularly preferably, TiO ₂ —CoO—NiO—
ZnO may be used.

As the blue inorganic pigment, for example, 3NaAl
· SiO ₄ · Na ₂ S ₂ , 2 (Na ₂ O · Al ₂ O ₃ ·
_{2SiO 2) · Na 2 S 2} , Fe 4 [Fe (CN) 6]
3nH ₂ O, CoO.nAl ₂ O ₃ , where n = 2
3), CoO.nSnO ₂ .mMgO (n = 1.5 to
3.5, m = 2~6), such as CoO-Al ₂ O ₃ is preferably mentioned. Particularly preferred may use CoO-Al ₂ O _3.

For spectral adjustment of the color filter,
Any number of pigments can be mixed and adjusted.
Further, as the inorganic pigment used in the black matrix,
Fe, C including FeCr ₂ O ₄ and CuMnO ₄
Composite oxides such as r and Mn can be applied, and other metal materials and inorganic pigments can be mixed and used.

The amount of the pigment added to the resin is 50 to 400.
% By weight is preferred. Preferably, a coating layer made of a transparent inorganic material can be provided on the surface of the pigment particles. The transparent covering layer is made of a transparent material such as silicon dioxide, magnesium oxide, aluminum oxide, and cesium oxide.

The coating amount is based on the weight of the coloring pigment.
A range of 5 to 100% by weight is preferred. The transparent coating layer
This has the effect of increasing the bulk of the color pigment and increasing the thickness of the formed color material layer. For example, by forming a transparent coating layer on a pigment having high coloring power and using it in combination with barium sulfate, the bulk of the color material layer can be easily adjusted to a high level without a significant change in spectral characteristics. In this way, it is possible to more effectively reduce the level difference between a color material layer using a large amount of a pigment having a low coloring power and a color material layer having a high coloring power and using only a small amount of a pigment.

If the coating amount of the transparent coating layer is less than 5% by weight, the thickness of the coating layer is too thin to cover the pigment surface sufficiently. Since the thickness of the layer is too large, the light scattering on the pigment surface increases and the amount of transmitted light not absorbed on the pigment surface increases, so that the spectral characteristics of the color filter tend to be insufficient.
Therefore, it is desirable that the amount of the transparent coating layer be determined within the above range in consideration of these characteristics.

As a method for forming a transparent coating layer on the surface of the color pigment, the color pigment is poured into water so as not to aggregate, and then uniformly dispersed by a disperser or an emulsifier.
A method of adding a metal salt solution while adding a pH adjuster while heating so that the liquid temperature is 60 ° C. or higher, and adjusting the pH to a pH range in which the metal salt hydrolyzes,
General.

When silicon dioxide is used, inorganic salts such as sodium silicate and organic silicates such as ethyl orthosilicate are preferably used as metal salts. When cesium oxide is used, a cerium inorganic salt such as CeO ₂ is used as an aqueous solution.

For example, the amount of the silicate solution to be added is determined so as to be in the range of 5 to 100% by weight based on the total weight of the coloring agent, taking into account the thickness of the transparent inert layer on the surface of the coloring pigment.
As the pH adjuster to be added, for example, HCl, H ₂ SO
₄ , acids such as HNO ₃ , NaOH, KOH, Na ₂ C
Bases such as O ₃ and K ₂ CO ₃ may be preferably used.

In producing the photosensitive coloring composition,
Various dispersing means such as a three-roll mill, a two-roll mill, a sand mill, and a kneader can be used as a means for dispersing the colorant and barium sulfate particles in the alkali-soluble resin and the polyfunctional acrylic monomer.

Various additives can be applied to the photosensitive coloring composition according to the present invention. Examples of such additives include a photopolymerization initiator, a sensitizer, a dispersant, an antioxidant, a heat stabilizer, and other solvents.

A photopolymerization initiation aid can be added to the photosensitive coloring composition in order to promote a photoreaction. Generally, amines are used as the photopolymerization initiation aid, such as tertiary amines such as triethanolamine and 4,4-amine.
Examples thereof include dimethylaminobenzophenone and ethyl 4-dimethylaminobenzoate.

Examples of the sensitizer include α-acyloxime ester, acylphosphine oxide, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethylanthraquinone,
4,4'-diethylisophthalophenone, 3,3 ',
4,4'-tetra (t-butylperoxycarbonyl)
Compounds such as benzophenone and 4,4'-diethylaminobenzophenone can also be used.

For example, cyclohexanone, toluene, xylene, ethyl, etc. may be used as a solvent for improving the dispersibility, adjusting the viscosity of the photosensitive colorant composition, and adjusting the coating thickness of the colorant layer on the transparent substrate. Cellsolve, 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 ketone , Diclime, cyclohexanone, ethyl carbitol, and other petroleum solvents, and the like, used alone or in combination.
Since it differs depending on the monomer composition of the resin, the photopolymerizable monomer, the photopolymerization initiator, and the like, a solvent having a single or plural solvent composition can be appropriately selected.

In addition, in order to improve the heat resistance of the resin, it is effective to add a small amount of an antioxidant or a heat stabilizer. For example, 2,6-di-t-butyl-p-cresol, n-octadecyl-3- (4'-hydroxy-
3 ', 5'-di-tert-butylphenol) propionate, tetrakis (methylene-3- (3,5-di-
tert-butyl-4-hydroxyphenyl) propionate) methane, thiobis (β-naphthol), tetramethylthiuram disulphide, distearylthiodipropionate, triphenylphosphite, tri (nonylphenyl) phosphite, trilauryltrithiophos Fight and the like are preferably used.

Further, a dispersant can be blended if necessary. As the dispersant, a wide range of dispersants such as surfactants and pigment intermediates are used. The proportion of the composition at the time of dispersion is not particularly limited, but the dispersant is about 1 to 10% by weight of the pigment. The dispersant 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 of the photosensitive coloring composition can be obtained. It is preferable to select one that does not hinder the characteristics.

Hereinafter, the present invention will be described in detail with reference to the drawings. FIG. 1 is a diagram illustrating a configuration of an example of a plasma display panel for color display using a color filter according to the present invention. As shown in the drawing, the plasma display panel for color display includes a front substrate 11, a rear substrate 12 disposed opposite to the front substrate 11, and a front substrate 11 and a rear substrate 12 which are connected to each other. A barrier 13 fixed at the periphery and the front substrate 1
The main part is composed of a mixed gas containing a rare gas as a main component, which is filled in a discharge space 14 surrounded by a backside substrate 12 and a barrier 13.

FIG. 2 is a view for explaining a screen display area of the plasma display panel for color display shown in FIG. As shown in the figure, the front substrate 11 includes a glass substrate 21 and a color material layer R1 of a color filter which is provided for each pixel in a pixel portion on the inner surface side of the glass substrate 21 and improves the color purity of transmitted light for each color. G1, B1 and the color material layer R
The main part is constituted by a black matrix 22 formed around 1, G1, and B1 and a first discharge electrode 23 disposed on these. Color material layers R1, G1, B
1 is formed by using a photosensitive coloring compound;
At least one of 1, B1 is formed using a photosensitive coloring composition containing a resin having transparency, a polyfunctional acrylic monomer or oligomer, a photopolymerization initiator, a coloring agent, and barium sulfate. The amount of barium sulfate with respect to the colorant is appropriately adjusted so that the entire thickness of the color material layers R1, G1, and B1 becomes smooth.

On the other hand, the rear substrate 12 is a glass substrate 25.
A second discharge electrode 26 provided for each pixel at a pixel portion on the inner surface side of the glass substrate 25, a barrier 28 separating the pixels, and a second discharge electrode 2 facing the first discharge electrode 23.
6. A phosphor layer 2 provided for each pixel around an intersection with
7 constitute the main part. Further, in the discharge cells surrounded by the first discharge electrode 23, the second discharge electrode 26, and the barrier 28, which are these discharge spaces, a mixed gas mainly composed of a rare gas that generates ultraviolet rays by discharge is not shown. Introduced from the priming path.

In this plasma display panel for color display, a discharge was generated between the first discharge electrode 23 and the second discharge electrode 26 of the pixel to be displayed, and was excited by the discharge of the mixed gas containing a rare gas as a main component. Utilizing ultraviolet rays generated from atoms and molecules, the phosphor layer 27 emits light and converts it into visible light. Here, the color material layers R1, G1, B
By using the color filter containing 1, the unnecessary color light component is removed from both the visible light generated from the phosphor layer 27 and the extraneous light reflected by the phosphor layer 27, and the color purity of the surface screen is increased. , The contrast can be improved. In addition, the black matrix 22 can shield portions other than the display pixels from light, thereby improving the contrast ratio between the pixels and the other portions.

Incidentally, the plasma display panel for color display can be manufactured through the following steps, for example. First, a color material layer R is formed on a glass substrate 21.
1, G1, B1, and a black matrix 22 are sequentially formed to form a color filter, and a first discharge electrode 23 is formed on the obtained color filter to form a front-side substrate 11
Is prepared.

Next, the second discharge electrode 2 is placed on the glass substrate 25.
6, the barrier 28 and the phosphor layer 27 are formed to manufacture the rear substrate 12. Then, the front substrate 11 and the rear substrate 12 are overlapped with each other via a glass paste containing low-melting glass, and the glass paste is heated to about 400 ° C.
The baking process is performed as described above, and the front substrate 11 and the rear substrate 12
And fix.

Finally, the front substrate 11 or the rear substrate 1
2, a mixed gas mainly composed of a rare gas that generates ultraviolet rays by discharge is introduced into the discharge space 14 through an introduction hole (not shown) provided in the plasma display panel 2 to obtain a plasma display panel for color display.

As a method of applying the photosensitive coloring composition on the transparent substrate 1, a method that matches the viscosity characteristics of the manufactured photosensitive coloring composition may be selected. In the case of low viscosity by silk screen printing or die coating, a method having good coating flatness may be selected from methods such as spin coating, spray coating, and roll coating. The nonvolatile components contained in the solution at the time of coating and the amount thereof may be appropriately selected depending on the desired film thickness and the type of coater, and the film thickness after drying is preferably 1 to 10 μm, particularly preferably 3 to 5 μm. .

The composition of the photosensitive coloring composition according to the present invention shown in FIG. 1 is, for example, 100 parts by weight of an acrylic resin (alkali-soluble photosensitive resin), 50 parts by weight or less of a photopolymerizable monomer, Polymerization initiator 0.1 to 30
Parts, 10 to 200 parts by weight of a pigment, 10 to 100 parts by weight of a transparent pigment, and small amounts of other components. Further, the above composition is appropriately added to and dispersed in a solvent in combination with the coating method. The alkali-soluble photosensitive resin is desirably contained in an amount of 20% by weight or more.

The transparent substrate to which the photosensitive coloring composition is applied preferably has good dimensional stability, can withstand heat when forming a colored layer or a light-shielding layer, and has excellent surface flatness. It is. Usually, a glass substrate is used.

At the time of forming the color filter, an overcoat layer may be provided on the color material layer for firing and fixing the color material layer. The overcoat layer can be formed using light-transmitting low-melting glass or metal alkoxide.

As the transparent material used for the overcoat layer, a low-melting glass such as lead borosilicate glass or a metal alkoxide such as silicate can be used. Also,
For example, a composite oxide of SiO ₂ and TiO ₂ which is a transparent inorganic oxide can be used.

The overcoat layer made of low-melting glass was
When the thickness is less than 1 μm, the step between the respective color material layers is 1 μm.
Even if it is sufficiently small, it is easy for pinholes to be generated in bubbles contained in the low-melting glass or in a step between the colored pattern and the transparent substrate 1, which tends to be an obstacle during electrode formation.

If the overcoat layer has a thickness of more than 10 μm, the transparency tends to be insufficient, and there is a tendency that sufficient characteristics cannot be obtained as a color filter used for a display.

When the overcoat layer of the metal oxide film formed by firing from the metal alkoxide is formed to have a thickness of 2 μm or more, cracks are apt to be formed in the overcoat layer, which is likely to be an obstacle to the formation of the electrodes. Conversely, if the thickness is too small, such as 0.1 μm, a step between the colored pattern and the transparent substrate 1 and a portion at which the colored pattern is not sufficiently covered at the edge of the colored pattern are likely to occur, and pinholes are easily generated. It can be a time defect.

The above-mentioned overcoat layer has a function of fixing the coloring material layer substantially composed of a coloring agent to the transparent substrate after firing and improving the adhesion between the coloring material layer and the transparent substrate. By selecting an appropriate material and film thickness,
This has the function of reducing the unevenness of the transparent substrate 1.

[0068]

The present invention will be described below in detail with reference to examples. Example 1 A transparent pigment composed of precipitated barium sulfate used in the present invention was "Barifine" B manufactured by Sakai Chemical Industry Co., Ltd.
F-1, BF-10 and BF-20. When the transparent pigment is 60 parts by weight of a pigment, 84 parts by weight of an acrylic resin, and 30 parts by weight of xylene, the transmittance (%) of incident light of light passing through a coating film of 50 μm is as follows.

BF-1 95.3% BF-10 94.4% BF-20 98.6% (resin alone 99.5%) First, 40.00 parts by weight of n-butyl methacrylate and 20.00 parts by weight of ethyl methacrylate Part, methacrylic acid 3
0.00 parts by weight, 50.00 parts by weight of ethyl methacrylate and 10.00 parts by weight of 2-hydroxyethyl methacrylate are copolymerized using cyclohexanone as a solvent so that the ratio of the acrylic resin is 50 parts by weight and the ratio of cyclohexanone is 50 parts by weight. Prepared. Then, a photosensitive coloring composition was prepared using the acrylic resin and a transparent pigment at the following compounding ratio.

Red photosensitive coloring composition Acrylic resin 10.17 parts by weight Acrylic monomer Dipentaerythritol pentaacrylate 6.06 parts by weight Photopolymerization initiator Triazine 1.22 parts by weight Diluent solvent Cyclohexanone 30.01 parts by weight Red pigment BASF "Sico Trans Red L-2817" manufactured by Co., Ltd. 25.21 parts by weight Transparent pigment (barium sulfate) "Barifine" BF-1 6.31 parts by weight (weight ratio of barium sulfate to red pigment: 25%) This red photosensitive coloring composition After the product 1 was applied with a spinner, the coating was dried in a hot air oven at 70 ° C. for 20 minutes to form a 20 μm-thick red photosensitive coloring composition coating layer.

A red photosensitive coloring composition was prepared in the same manner as the red photosensitive coloring composition except that barium sulfate was 12.6 parts by weight and the weight ratio to the red pigment was 50%. After coating and drying with
A red photosensitive coloring composition coating layer 2 having a thickness of 0 μm was formed.

Further, the red photosensitive coloring composition coating layers 1 and 2 formed as described above are heated at a heating rate of 4 ° C./min, and baked at a temperature of 420 ° C. for 60 minutes.
The substrate was further heated to 0 ° C., baked at a temperature of 580 ° C. for 10 minutes, and then cooled at a rate of 4 ° C./min.
By firing treatment under these conditions, the acrylic resin in the colored composition layer, the photopolymerizable monomer is burned, burned off,
A red color material layer containing only a pigment was formed. Further, by changing the film thickness, red color material layers having various film thicknesses were formed.

For comparison, red color material layers of various thicknesses were obtained in the same manner except that barium sulfate was not mixed. The absorbance at 610 nm of each of the obtained red color material layers was measured. FIG. 3 is a graph showing the relationship between the thickness of each color material layer and the absorbance.

In the figure, a graph 301 shows that when the weight ratio of the transparent pigment (barium sulfate) to the color pigment is 50% by weight,
Graph 302 shows that the weight ratio of the transparent pigment to the color pigment is 2
In the case of 5% by weight, the graph 302 shows the case where no transparent pigment is added.

As shown in the figure, even if barium sulfate is mixed in the photosensitive coloring composition, the absorbance is slightly reduced, and there is no significant effect. Example 2 Next, a process of manufacturing a color filter will be described with reference to the drawings.

FIGS. 4 to 8 are schematic views showing an example of a process for manufacturing a color filter according to the present invention. 9.07 parts by weight of the same acrylic resin as in Example 1, 5.38 parts by weight of a photopolymerizable monomer, 1.03 parts by weight of a photopolymerization initiator, 25.45 parts by weight of a diluting solvent, and 4.59 parts by weight of barium sulfate And 15.56 parts by weight of “Cobalt Blue X” (manufactured by Toyo Pigment Co., Ltd.) (CoO—Al ₂ O ₃ ) as a coloring pigment, to prepare a blue photosensitive coloring composition.

As shown in FIG. 4, the obtained blue photosensitive coloring composition was applied on a glass substrate 5 by a spinner and dried to form a blue photosensitive coloring composition coating layer 1 having a thickness of 3 μm. .

Next, a mask 4 in which a stripe pattern having a width of 150 μm is repeatedly formed is brought into close contact with the above-mentioned blue photosensitive coloring composition coating layer 1, and an exposure amount of 1 is applied by an ultra-high pressure mercury lamp.
Contact exposure was performed under the condition of 00 mJ / cm ² .

Following exposure, alkali development was performed with a 5% sodium carbonate solution to remove the unexposed portions of the blue photosensitive coloring composition coating layer 1 as shown in FIG. Filter 1 'was formed. In addition, 230 ° C
The blue filter 1 'was completely cured by post-baking for -60 minutes.

Further, 9.07 parts by weight of the same acrylic resin as in Example 1, 5.38 parts by weight of a photopolymerizable monomer, 1.03 parts by weight of a photopolymerization initiator, 25.45 parts by weight of a diluting solvent, and coloring "ND-801" as the pigment (Nippon Denko Co., _{Ltd.) (CoO 2 -Al 2 O 3} -CrO 2 -TiO 2) 2
A 0.15 part by weight of a green photosensitive coloring composition was applied on a glass substrate 5 with a spinner and dried to form a film having a thickness of 3 μm.
After forming the green composition coating layer, the blue composition coating layer 1
In the same procedure as shown in FIG. 6, as shown in FIG.
Was formed.

Further, 9.07 parts by weight of the same acrylic resin as in Example 1, 5.38 parts by weight of a photopolymerizable monomer, 1.03 parts by weight of a photopolymerization initiator, 25.45 parts by weight of a diluting solvent, and 7. 94 parts by weight, 7.94 parts by weight of a transparent pigment, and "Sicotrans Red L-281" as a coloring pigment.
7 "(manufactured by BASF) (Fe ₂ O ₃ ) (12.21 parts by weight) to prepare a red photosensitive coloring composition. The obtained red photosensitive coloring composition is applied on a glass substrate 5 by a spinner and dried to form a red photosensitive coloring composition coating layer having a thickness of 3 μm, and then the same procedure as in the blue coloring material layer 1 ′ is performed. At
As shown in FIG. 7, a red color material layer 3 'was formed.

Further, by baking under the same conditions as in Example 1, the acrylic resin and the photopolymerizable monomer in the patterned colored layer were burned and burned off, and only the inorganic colored pigment and the transparent pigment were used. A color material layer of a color was formed on the glass substrate 5. At this time, the thickness of each of the red, green, and blue color material layers was 2.3 μm, and a color filter having a uniform thickness was formed for each color.

Further, the three color material layers 1 ', 2', 3
A transparent overcoat material made of low-melting glass or the like was applied on the glass substrate 5 on which the 'was formed using a 300-mesh screen printing plate. The overcoat material used here is a low-melting glass paste ("ELD-350" manufactured by Okuno Pharmaceutical Co., Ltd.).

By firing this glass substrate 5 under the same conditions as in the first embodiment, as shown in FIG. 8, an overcoat layer 6 made of low-melting glass is formed on the glass substrate 5, thereby forming a color material. The layers 1 ', 2', 3 'are fixed to the glass substrate. The solvent, resin component, and the like contained in the overcoat material were evaporated or burned in this step and completely removed.

Example 3 Next, an example in which a transparent coating layer is provided on the surface of a color pigment will be described. The coloring agents used are as follows.

Red pigment: manufactured by Dainichi Seika Kogyo Co., Ltd .: TR
ANS Oxide Red (Fe ₂ O ₃ ) Blue pigment: Asahi Kasei Co., Ltd .: “Asahi Super Blue CR” (CoO ₂ —Al ₂ O ₃ ) Green pigment: Dainichi Seika Kogyo Co., Ltd .: “TM Green 33”
20 "(TiO ₂ —NiO ₂ —CoO ₂ —ZnO) 10 parts by weight of each of the above-mentioned pigments were put into 150 parts by weight of pure water, and after being sufficiently stirred and dispersed, ultrasonic waves were applied. It heated to 80 degreeC, performing dispersion and stirring.

Next, a 5% NaOH solution was added to adjust the pH to 9
After that, 5 parts by weight of an aqueous solution of sodium silicate (27 parts by weight of sodium silicate in 73 parts by weight of pure water) was added dropwise over time. At this time, 5% HC was added to maintain the solution at pH 9.
1 solution was appropriately added dropwise and reacted for 1 hour.

Thereafter, a 5% HCl solution was added until the pH reached 6, and the mixture was kept for another 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 Transparent Resin 30 parts by weight of butyl methacrylate, 25 parts by weight of acrylic acid, 20 parts by weight of methyl methacrylate, 15 parts by weight of 2-hydroxyethyl methacrylate, 10 parts by weight of methyl acrylate
A part by weight was copolymerized using 2- (2-ethoxyethoxy) ethanol as a solvent to prepare an acrylic resin in a ratio of 40 parts by weight and a solvent in a ratio of 60 parts by weight.

A photosensitive coloring composition was prepared using the above-mentioned pigment having a transparent coating layer and an acrylic resin at the following compounding ratio. Red photosensitive coloring composition Acrylic resin 8.2% by weight Polyfunctional oligoester acrylate Dipentaerythritol hexaacrylate 4.9% by weight Photopolymerization initiator Piperonyl trichloromethyl S-triazine 1.0% by weight Diluent solvent 2- ( 2-ethoxyethoxy) ethanol 56.4% by weight Color pigment Red pigment 29.5% by weight Transparent barium sulfate fine powder Barifine BF-1 (manufactured by Sakai Chemical Industry Co., Ltd.) 29.5% by weight A Cr film as a black matrix having an opening of 200 mm long × 150 μm wide and a line width of 1;
On a transparent substrate 1 formed as a 0 μm light-shielding film, 300
Screen printing was performed using a stainless steel screen plate having a mesh and a plate thickness of 80 μm. After left at room temperature for 5 minutes to dry the film surface, it was dried at 70 ° C. for 20 minutes to form a red photosensitive coloring composition coating layer. The thickness of the obtained red photosensitive coloring composition coating layer was 3.5 μm, the entire surface had a uniform thickness, and the surface state 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 was repeatedly formed at a pitch of 480 μm was brought into close contact with the photosensitive coloring composition layer, and an exposure amount of 400 mJ / was applied by an ultra-high pressure mercury lamp.
Contact exposure was performed under the condition of cm ² .

After exposure, an alkali developing solution at a temperature of 20 ° C. was spray-developed for 50 seconds at a jetting pressure of 1 kg / cm ² to remove an unexposed portion of the red photosensitive coloring composition coating layer. After drying the substrate after the development processing, a heat hardening treatment was performed at 230 ° C. for 1 hour. The thickness of the coating layer after curing is 3.3 μm
Met.

Next, on the transparent substrate 1 on which the coloring pattern 2 (before firing) is formed, the following green photosensitive coloring composition, green photosensitive coloring composition, acrylic resin 8.2% by weight polyfunctional oligoester acrylate dipentane Erythritol hexaacrylate 4.9% by weight Photopolymerization initiator Piperonyl trichloromethyl S-triazine 1.0% by weight Diluent solvent 2- (2-ethoxyethoxy) ethanol 56.4% by weight Color pigment Green pigment 29.5% by weight Was applied under the same conditions as above, and a photomask similar to that described above was adhered to the green photosensitive coloring composition layer, and exposed to light with an ultra-high pressure mercury lamp at an exposure amount of 300 mJ / cm ² .

After exposure, an alkali developing solution at a temperature of 20 ° C. is spray-developed for 60 seconds at a jetting pressure of 1 kg / cm ² to remove the green photosensitive coloring composition layer in the unexposed area, thereby exposing the glass substrate 8. Was. After drying the developed substrate,
The film was heated at 230 ° C. for 1 hour to perform a hardening treatment. The thickness of the coating layer after hardening was 3.8 μm.

A blue coloring material layer was obtained in the same manner using the following blue photosensitive coloring composition. Blue photosensitive colorant composition Acrylic resin 8.2% by weight Polyfunctional oligoester acrylate Dipentaerythritol hexaacrylate 4.9% by weight Photopolymerization initiator Piperonyl trichloromethyl S-triazine 1.0% by weight Diluent solvent 2- (2-ethoxyethoxy) ethanol 56.0% by weight Colored pigment Blue pigment 29.5% by weight The glass substrate on which these color material layers were formed was heated at 4 ° C. /
After heating at 420 ° C. for 60 minutes in the atmosphere, heating continuously at 420 ° C. for 60 minutes, further heating to 580 ° C. continuously, firing at 580 ° C. for 30 minutes, and then heating at 4 ° C./min. The substrate is cooled to remove the organic resin component of the color material layer by burning, and a 2.8 μm-thick red color material layer composed of a surface-coated red pigment and transparent barium sulfate fine powder, and a surface-coated green color A green color material layer composed of a pigment and a blue color material layer composed of a surface-coated blue pigment (both have a thickness of 2.7 μm)
A color filter with a Cr matrix black matrix on which was formed was obtained.

On this color filter, a low melting glass paste (LF made by NEC Glass Co., Ltd.) was used by using a 325 mesh plate and a stainless steel screen plate having a thickness of 80 μm.
-01) was screen-printed and left at room temperature for 10 minutes to dry the film surface.
After drying at 90 ° C. for 15 minutes, a low-melting glass paste layer was formed.

Next, similarly to the above, heating was performed in an air atmosphere at a heating rate of 4 ° C./min, and calcination was performed at a temperature of 420 ° C. for 60 minutes. After baking for 30 minutes, the substrate was cooled at a temperature lowering rate of 4 ° C./min. By baking under these conditions, the low-melting-point glass became an overcoat layer having light transmittance, and the color-patterned pattern pigment components became color filters coated with the molten low-melting-point glass.

The pattern shape and formation position of this color filter both accurately reflect the light-shielding film pattern of the photomask. The spectral transmittance of the color filter shows a desired value, and the film thickness difference between the colors is It was as good as 0.3 μm.

Example 4 Example 3 was repeated except that the amount of the aqueous solution of sodium silicate (27 parts of sodium silicate in 73 parts by weight of pure water) was changed to 30 parts by weight.
The red pigment surface was coated with a transparent substance in the same manner as described above.

Using the above surface-coated red pigment and the same acrylic resin as in Example 3, a photosensitive coloring composition was prepared at the following compounding ratio. Red photosensitive coloring composition Acrylic resin 8.2% by weight Polyfunctional oligoester acrylate Dipentaerythritol hexaacrylate 4.9% by weight Photopolymerization initiator Piperonyl trichloromethyl S-triazine 1.0% by weight Diluent solvent 2- ( 2-ethoxyethoxy) ethanol 56.4% by weight Color pigment Red pigment 29.5% by weight Transparent barium sulfate fine powder Barifine BF-1 (manufactured by Sakai Chemical Industry Co., Ltd.) 14.8% by weight Screen printing and drying were performed on a transparent substrate using the same apparatus as in Example 3, and the thickness was 3.
A 7 μm colored photosensitive composition coating layer was obtained. The entire surface had a uniform film thickness, and the surface state was smooth.

After the same green and blue photosensitive coloring compositions as in Example 3 were patterned by the same method, a baking treatment was performed in the same manner as in Example 3 to obtain a surface-coated red pigment and transparency. 2.6 μm thick barium sulfate fine powder
A color filter with a black matrix of a Cr film on which a red color material layer, a green color material layer made of a surface-coated green pigment, and a blue color material layer made of a surface-coated blue pigment were formed.

On this color filter, using a 325 mesh plate 80 μm thick stainless steel screen plate,
In order to fix each color material layer, a metal alkoxide material (manufactured by Nippon Soda Co., Ltd .: Atron NSi-500) is screen-printed, and left at room temperature for 10 minutes to dry the film surface. Then, a sol film of a metal alkoxide material was formed.

Next, in the same manner as above, heating was performed in an air atmosphere at a heating rate of 4 ° C./min, and calcination was performed at 420 ° C. for 60 minutes. After firing for 30 minutes, the substrate was cooled at a rate of 4 ° C./min. By performing the baking treatment under these conditions, the dehydration reaction and the condensation polymerization reaction by the dealcoholization reaction of the metal alkoxide sol film were promoted, and a gelled metal oxide film was formed. The color material layer composed of a pigment was baked and fixed on the transparent substrate 1 by the overcoat layer of the gelled metal oxide film, thereby forming a coated color filter.

Both the pattern shape and the formation position of this color filter accurately reflect the light-shielding film pattern of the photomask. The spectral transmittance of the color filter shows a desired value, and the film thickness difference between the colors is It was as good as 0.2 μm.

Comparative Example 1 A color filter was manufactured in the same manner as in Example 3 except that the surface-inactive treatment was not performed, using the same color pigment as in Example 3.

Photosensitive coloring composition Acrylic resin 8.2% by weight Polyfunctional oligoester acrylate dipentaerythritol hexaacrylate 4.9% by weight Photopolymerization initiator Piperonyl trichloromethyl S-triazine 1.0% by weight Diluent solvent 2 -(2-ethoxyethoxy) ethanol 56.4% by weight Color pigment 29.5% by weight of each color pigment The color filter having the overcoat layer shows almost the same optical characteristics, but the thickness of the red color material layer Is 1.3
μm, the level difference between the color material layer of another color and the colored pattern is 1 μm
It became a nearby color filter.

The red photosensitive coloring composition of Example 3 did not show a large change in viscosity even after storage at room temperature for one month, but the red photosensitive coloring composition of Comparative Example gelled. It became difficult to form a flat and uniform coating film by screen printing.

[0108]

According to the present invention, storage stability, coating suitability, and spectral characteristics are excellent, and color separation, antireflection,
In addition, a photosensitive colored composition capable of smoothing a color filter without impairing display contrast can be obtained.

Also, by using the photosensitive coloring composition of the present invention, it is excellent in spectral characteristics and contrast characteristics, has sufficient smoothness, and has dielectric pinholes, electrode step lines,
In addition, a color filter free from display defects can be obtained.

[Brief description of the drawings]

FIG. 1 is a diagram illustrating a configuration of an example of a plasma display panel for color display using a color filter according to the present invention.

FIG. 2 is a view for explaining a screen display area of the plasma display panel for color display shown in FIG. 1;

FIG. 3 is a graph showing the relationship between the thickness of each color material layer and the absorbance.

FIG. 4 is a schematic diagram illustrating an example of a process for manufacturing a color filter according to the present invention.

FIG. 5 is a schematic diagram illustrating an example of a process for manufacturing a color filter according to the present invention.

FIG. 6 is a schematic diagram illustrating an example of a process of manufacturing a color filter according to the present invention.

FIG. 7 is a schematic diagram illustrating an example of a process of manufacturing a color filter according to the present invention.

FIG. 8 is a schematic diagram illustrating an example of a process of manufacturing a color filter according to the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 11 ... Front side substrate 12 ... Back side substrate 13, 28 ... Barrier 14 ... Discharge space 21, 25 ... Glass substrate 22 ... Black matrix 23 ... First discharge electrode 26 ... Second discharge electrode 27 ... Phosphor layer

 ────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Koichi Kumai 1-5-1, Taito, Taito-ku, Tokyo Toppan Printing Co., Ltd. (72) Inventor Kazushige Kitazawa 1-1-5-1 Taito, Taito-ku, Tokyo Letterpress Inside Printing Co., Ltd. (72) Ikuo Hirota 1-5-1, Taito, Taito-ku, Tokyo Toppan Printing Co., Ltd. (72) Kenichi Fujita 2-3-13-1 Kyobashi, Chuo-ku, Tokyo Toyo Inki F term in the manufacturing company (reference) 2H025 AA00 AA18 AB13 AC01 AD01 BC13 BC31 BC51 CB42 CB51 CC11 CC12 CC20 DA17 2H048 BA20 BA28 BA48

Claims (5)

[Claims] 1. A photosensitive coloring composition comprising a transparent resin, a polyfunctional acrylic monomer or oligomer, a photopolymerization initiator, a coloring agent, and barium sulfate. 2. The barium sulfate comprises particles having an average particle diameter of 0.1 μm or less, and the content thereof is 1 to 200% by weight based on the total weight of the colorant. 2. The photosensitive coloring composition according to item 1. 3. The photosensitive coloring composition according to claim 1, wherein the coloring agent includes pigment particles whose surface is covered with a transparent inert layer. 4. The inactive layer is substantially composed of a material selected from the group consisting of silicon dioxide, magnesium oxide, aluminum oxide, and cesium oxide, the content of which is based on the total weight of the colorant. The photosensitive coloring composition according to claim 3, wherein the content is 2 to 100% by weight. 5. A color filter comprising a transparent substrate and a color material layer formed on the transparent substrate, wherein the color material layer has at least a part thereof according to any one of claims 1 to 5. A color filter formed using the photosensitive coloring composition described in any one of the above.