JP3347934B2 - Coloring composition for black matrix, method for producing black matrix, and light-emitting flat panel display panel provided with light-shielding black matrix - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to office equipment such as televisions and television telephones for home and office use, personal computers, word processors and the like.
A black or dark colored composition used to form a light-shielding black matrix on the display panel of a full-color or mono-color light-emitting flat panel display used for display of factory automation equipment, store automatic control equipment, measuring equipment, etc. The present invention relates to a product, a method for producing the black matrix, and a light-emitting flat panel display panel provided with the light-shielding black matrix.

More specifically, the present invention relates to a light shielding property for forming a black matrix on a substrate of a display panel of a light emitting type flat panel display such as a plasma display, a fluorescent display, a light emitting diode display, and a cathode ray tube color display panel. In the pigment-containing coloring composition, as a light-shielding pigment, a complex oxide black pigment having excellent properties such as tinting power and light-shielding properties, and excellent fastness such as ultraviolet light resistance, light resistance, and heat resistance is optionally used. The BET specific surface area is about 40 m ² /
By making the primary particles finer on the basis of g or more, improvement in coloring power, blackness or optical density, improvement in light-shielding properties, improvement in dispersion stability, and the like can be achieved.

Further, if necessary, the surface of the coloring composition is treated with a coating material such as amorphous silica or low-melting glass to obtain characteristics such as dispersibility and dispersion stability of the coloring composition and low-melting glass binder. A coloring composition for a black matrix used by improving the adhesion to a glass substrate and the like by improving affinity for a glass substrate, a method for producing a light-shielding black matrix using the same, and a light-shielding black matrix produced by the method were attached. The present invention relates to a light emitting flat panel display panel.

[0004]

2. Description of the Related Art Conventionally, a display panel of a light emitting type flat panel display used for a display of a home or office image receiving device such as a television and a television telephone, a factory automation device, a store automatic control device, a measuring device and the like. Indicates a pixel pattern of a light-emitting element such as white or orange on a substrate such as a glass plate in the case of monocolor, and red (hereinafter referred to as R) and green (hereinafter referred to as G) in full-color display. And blue (hereinafter referred to as B)
A mosaic or stripe pixel pattern of the three primary colors composed of light-emitting elements is formed by printing or photolithography, etc., but the separability and sharpness of those light-emitting pixels, especially in the case of full color display R, G and B
There are difficulties in the separability and sharpness of the three colors of light emission.
Attempts have been made to solve the above problem by adding a black matrix to the three colors G and B.

[0005]

Generally, as a method of forming a black coating on a glass substrate used for a flat panel display, there are a method of depositing a metal such as chromium and a method of coating a black colorant. The former has the disadvantage that the cost is high, the process is complicated and the productivity is not improved, and the equipment and the like are large and expensive. What is usually used as a black pigment used for a black colorant is a black dye,
Black compound dyes, organic pigments, carbon black, etc. cannot be used for forming a black matrix of a display panel of a light-emitting flat panel display because of a high-temperature baking process. In addition, there are iron black and titanium black as inorganic black pigments, and iron black changes to brown or brown iron oxide by heating at a high temperature, and titanium black similarly changes to white titanium oxide. Change,
It cannot be used as a black matrix dye that requires heat resistance at high temperatures.

According to the present invention, a black colored composition having excellent dispersibility, dispersion stability, and coating suitability is produced by using a black pigment having high-temperature heat resistance that withstands a firing temperature and excellent light-shielding properties. An object of the present invention is to form a light-shielding black matrix on a display panel of a light-emitting flat panel display using the same, and to provide a light-emitting flat panel display panel provided with the light-shielding black matrix.

[0007]

Means for Solving the Problems The present inventors have studied the emission of R, G, and B primary color phosphors excited by ultraviolet light,
A pigment having a light-shielding property for use as a black matrix for improving pixel separation and sharpness for a display panel of a light-emitting flat panel display such as light emission of light-emitting diodes of three primary colors G and B or light emission by a discharge gas. As a result of various studies, the inventors have found that a specific inorganic pigment provides an effective means for solving the above-mentioned problems, and have completed the present invention.

That is, the present invention eliminates the organic binder.
Baking process to fix the light-shielding black pigment to the substrate
In a colored composition containing a light-shielding black pigment for forming a black matrix on a display panel substrate of a light-emitting flat panel display, the binder is an organic resin.
Light shielding properties used as an binder and inorganic binder
Composite oxidation of black pigment with copper and manganese as main metal components
Black pigment, composite containing copper, iron and manganese as main metal components
Oxide black pigment, and cobalt, chromium, iron, and manganese
From the group consisting of composite oxide black pigments containing
A coloring composition for a black matrix , which is a single or a mixture of a selected composite oxide black pigment having a spinel-type or reverse spinel-type crystal structure, and a method for producing a black matrix using the coloring composition And a light-shielding light-emitting type flat panel display panel provided with a black matrix obtained as a result.

According to the present invention, there is provided a flat panel display using a light-emitting display element as an information display method,
For example, plasma display, fluorescent display,
A light emitting diode display, a cathode ray tube color display panel and the like are collectively referred to as a light emitting type flat panel display, and a substrate on which a black matrix of these display panels is formed is generally referred to as a glass substrate.

[0010] Generally a black dye as a black dye used in the black colorant, black compounding dyes, organic pigments, there are carbon black, can not be used because of the high temperature baking process. Also, there are iron black and titanium black as inorganic black pigments, but iron black is also called magnetite and has magnetism, so pigment particles tend to aggregate due to magnetism, and when producing a coloring composition, tend dispersion immediately agglomerated be difficult and dispersion, even inferior dispersion stability over time, coloring power is low, disadvantage black pigment by heating changes to red iron oxide is iron oxide brown to brown And titanium black is similarly 300 ° C to 35 ° C.
It has the disadvantage that it is converted to white titanium oxide at 0 ° C., and cannot be used as a black matrix dye that requires heat resistance at high temperatures.

In contrast, the present invention uses
Composite oxide black pigmentAnd copper and manganese as main metal components
Composite oxide black pigment, copper, iron and manganese as main metal components
Composite oxide black pigment, and cobalt, chromium, and iron
Oxide black pigment containing iron and manganese as main metal components
Single or mixture of complex oxides selected from the group consisting of
so,Made by baking at high temperature, chemical resistant as pigment
Excellent properties such as heat resistance, heat resistance, light resistance, etc.
Has light-shielding properties and good dispersibility in varnish, preserved
Excellent stability, even when blended in photosensitive resin
Almost impedes its photocurability compared to carbon black pigments
It has the feature of not harming. Especially about heat resistance
Is superior to other black pigments,
Table of luminous flat panel display
Temperature baking of black matrix formation of display panel
It is stable to the process and is the most suitable pigment.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION Next, the present invention will be described in more detail with reference to preferred embodiments of the invention. In the present invention, the display panel forms a mosaic or stripe-like pixel pattern of three primary colors composed of red, green and blue light-emitting elements on a rear (rear) glass substrate in the case of full color display. In the case of mono color, a pixel pattern of a light emitting element such as white or orange is formed. However, in order to enhance the separability and clarity of these luminescent colors and to make them visually easy to see, the front (front) is used. 2.) Inserting a black matrix between pixels on a glass substrate corresponding to those pixels.

The coloring composition for a black matrix of the present invention is obtained by dispersing a composite oxide black pigment in a photosensitive or non-photosensitive resin varnish or the like as described below.
A desired black matrix can be formed by forming a pattern on a glass substrate or the like of a display panel of a light-emitting flat panel display according to a conventionally known method.

The composite oxide black pigment used in the black matrix coloring composition of the present invention will be described.
The composite oxide black pigment contains copper and manganese as main metal components.
Composite oxide black pigment, copper, iron and manganese as main metal components
Composite oxide black pigment, and cobalt, chromium, and iron
Oxide black pigment containing iron and manganese as main metal components
Comprising a composite oxide selected from the group, as the crystal structure is of the spinel or inverse spinel.

[0015] More specific composite oxide black pigments, composite oxide black pigments of copper and chromium as a main metal component, a composite oxide black pigments of copper and manganese as a main metal component, copper and iron and manganese A composite oxide black pigment whose main metal component is a composite oxide black pigment whose main metal component is cobalt, chromium and iron, a composite oxide black pigment whose main metal component is cobalt, chromium, iron and manganese, A single oxide or a mixture of a composite oxide black pigment containing nickel, chromium, and iron as main metal components may be used.

As the light-shielding pigment of the black matrix of the present invention, a composite oxide pigment having a chromatic color tone that is not black can be used alone or in color if it is a composite oxide capable of sufficiently shielding the visible light portion of a pixel. Used. Upon coloration, it is preferable to use these chromatic pigments in addition to the above black pigments. As the color of the color scheme, black, dark gray or dark chromatic color is desirable in order to make the absorption of visible light more complete.

The chromatic composite oxide pigments used herein include C.I. I. Pigment Blue 28 (cobalt-aluminum-based), 36 (cobalt-aluminum-chromium-based), and C.I. I. Pigment Green 26 (Cobalt-
Aluminum-chromium-based), 50 (titanium-nickel-
Cobalt-zinc), as a composite oxide brown pigment, C.I.
I. Pigment Brown 33 (iron-zinc-chromium),
34 (iron-nickel-aluminum-based). In the present invention, these pigments are also included in the expression of the composite oxide black pigment.

The dry synthesis method, the wet synthesis method, the wet oxidation method, which are the methods for producing the composite oxide black pigment, and the characteristics of the pigment by those methods will be described. The dry synthesis method is a synthesis method in which oxides and the like of the constituent metal components are mixed and sintered, and the oxides, hydroxides or carbonates of the constituent metal components are uniformly mixed,
This is a method of baking at a predetermined temperature of about 600 ° C. or higher, and then pulverizing the sintered coarse particles with a powerful pulverizer to form a pigment. The primary particles of the pigment have an average particle diameter of about 0.3 to 0.7.
In μm, the BET specific surface area of the pigment is about 5 m ² / g.

In the wet synthesis method, a salt of a constituent metal component is co-precipitated with an alkali agent by a heat treatment such as an oxide, a hydroxide or a carbonate to form a co-precipitated compound, which is calcined and pulverized. The primary particles of the pigment have an average particle size of about 0.1 to 0.4 μm and a BET specific surface area of about 25 m ² / g or less.

There is also a new synthetic method called wet oxidation method, in which two or more metal salts selected from copper, chromium, iron, manganese, cobalt, aluminum, nickel, zinc, antimony, titanium and barium are used. Dissolved in water,
Neutralize and precipitate by adding an alkali agent, oxidize the small valent metal hydroxide of the polyvalent metal contained in the liquid phase to a large valence at the same time as or after the precipitation, and then calcinate For example, the pigment is produced by baking at about 400 ° C. to 650 ° C. to obtain a pigment. The BET specific surface area of the obtained pigment is about 40 m ² / g or more, and the average particle diameter of the primary particles is about 0. 0.01 to 0.1 μm.

As described above, the pigments obtained by the synthesis method have different average particle diameters and BET specific surface areas. Pigments having a large particle size, such as pigments obtained by a dry method or a wet method, can have a higher pigment content when dispersed in a varnish to form a colored coating agent, and at almost the same pigment content, the viscosity of the colored coating agent can be increased. Can be reduced. or,
Since these composite oxide black pigments are inorganic pigments, their coloring power is absolutely inferior to organic pigments, and since the specific gravity is high, sedimentation of the pigment during storage cannot be avoided,
Its BET specific surface area is about 40 m ² /
pigment particles into approximately 0.01~0.1μm to become more than g average particle diameter of primary particles as a guide, the coloring power of the pigment, blackness or improved optical density, dispersion stability and stable sedimentation And the like.

[0022] To describe a preferred embodiment for the wet oxidation process described above, salts of the constituent elements of the complex oxide black pigment, manufactured sulfates, nitrates, carbonates, chlorides, acetates and the like conventional composite oxide pigment Anything that is used at the time can be used. The concentration of the mixed salt aqueous solution is about 5 to 5
It is appropriate that the concentration is about 0% by weight. The alkaline agent is preferably caustic such as caustic soda. In the case of the oxidation treatment, the lower the concentration of the mixed metal hydroxide precipitate, the higher the oxidation efficiency, which is effective in miniaturization.
5 to 0.5 mol / l is suitable. The pH during the reaction and the oxidation treatment is suitably in the range of 7 to 13. The synthesis temperature is preferably in the range of 20 to 40 ° C, and the ripening temperature is 70 to 40 ° C.
A range of 100 ° C. is preferred.

It is essential to oxidize a polyvalent metal ion from a low valence to a high valence so as to oxidize, for example, a divalent metal ion of a precipitated mixed metal hydroxide to a trivalent metal ion. As the oxidizing agent to be used, any oxidizing agent such as adding hydrogen peroxide, sodium peroxide, sodium chlorate, etc. and / or bubbling air or oxygen gas may be used. Preferred are no oxidizing agents , such as aqueous hydrogen peroxide, air and oxygen gas.
The dried product is fired in an oxidizing atmosphere at a temperature of 400 to 650 ° C. for 30 minutes to 1 hour to obtain a complete spinel structure.
The composite oxide black pigment thus obtained is a composite oxide having a BET specific surface area of about 40 m ² / g or more.

According to this method, primary particles having a single spinel structure can be made fine even at a relatively low firing temperature by oxidizing the precipitated mixed metal hydroxide in an aqueous phase, The pigment is a soft particle and also has a feature that it can be easily dry-milled and wet-milled.

Since the above composite oxide black pigment is a baked pigment, it has excellent properties such as heat resistance, light resistance, water resistance, chemical resistance, and solvent resistance, as well as high hiding power. . Further, if necessary, the surface of these composite oxide black pigments can be surface-treated with a coating material such as amorphous silica and / or low-melting glass. Thereby, properties such as chargeability can be imparted to the pigment, the dispersibility in the varnish becomes good even during the production and storage of the colored composition, and the redispersibility and dispersion stability after storage. Etc. were also improved. Further, the baking on the glass substrate is improved by improving the affinity for the low-melting glass binder.

The surface treatment with an inorganic surface-treating compound such as the above-mentioned amorphous silica, low-melting glass, or a mixture thereof is performed by a conventionally known method for forming a silica or glass coating. For example, the above-mentioned black composite oxide black pigment is finely dispersed in water, and an aqueous solution of sodium silicate, potassium silicate, or the like, a solution obtained by adding an aqueous solution of lead nitrate and a diluted aqueous solution of sulfuric acid to the aqueous solution are dropped or dropped at the same time. These pigments are finely dispersed in a solvent such as ethanol, and organic lead is added thereto, if necessary, for example, tetraethyl orthosilicate or tetramethyl orthosilicate. It is obtained by a method of reacting. In the resulting composite oxide black pigment, the surface of the black pigment is almost uniformly treated with amorphous silica, low-melting glass, or a mixture thereof. The resulting composite oxide black pigment is subjected to a treatment, washed sufficiently with water to remove soluble salts and water-soluble components, and dried and used.

The treatment amount of the amorphous silica, the low-melting glass, and the mixture thereof must be such that the surface of the black pigment is coated, and 1 to 100 parts by weight, preferably 3 to 100 parts by weight per 100 parts by weight of the black pigment. Processed at a rate of 50 parts by weight. Depending on the particle size and specific surface area of the pigment particles, it is desirable to carry out the treatment in an amount commensurate with that, and the oil absorption of the pigment may be used as a guide. In addition, these coatings may be applied multiple times to the same black pigment.

If the amount of the coated amorphous silica, low-melting glass or a mixture thereof is too small, the improvement of the dispersibility and dispersion stability is insufficient, and if the amount is too large, the content of the pigment decreases. In order to secure a desired degree of coloring, a large amount of surface-treated pigment is required. One of the features of the composite oxide black pigment is that it is composed of a composite metal oxide with a specific crystal structure formed by firing the pigment at a high temperature. Is to endure without changing much. Therefore, in the case of manufacturing by a firing method after patterning a black matrix, a low-melting glass frit component or the like as an inorganic binder of the above-described composite oxide black pigment, a material obtained by adding organic lead to organic silica such as ethoxy silica or the like. Etc. can be used.

The low-melting glass frit component is , for example, fine powder of lead borosilicate glass containing lead oxide, silicon oxide and boron oxide as main components. From the fired glass frit, there is a glass frit that is fired at a high temperature of about 700 ° C., to which sodium oxide, titanium oxide, zirconium oxide, lithium oxide, aluminum oxide, and the like are added as accessory components. The composition, varnish, and additives of the coloring composition for a black matrix are determined by the method of applying the composite oxide black pigment to a glass substrate and the method of forming a pattern.

As a method of forming a black matrix using the above coloring composition, there are various printing methods such as stencil screen printing, intaglio gravure printing, offset intaglio printing, offset lithographic printing, letterpress printing, electrodeposition coating method, and electronic printing. Method, electrostatic printing method, thermal transfer method and the like.

As a method for forming a black matrix by photolithography using a photosensitive coloring composition, the entire surface is coated by spin coating or roll coating and then coated by photolithography, printing or thermal transfer. A method of forming a precise pattern by photolithography after forming a pattern or the like is used. As the varnish for dispersing the composite oxide black pigment or the above-mentioned inorganic binder as the coloring composition, a conventionally known non-photosensitive and photosensitive varnish suitable for each of the above-described coating method and pattern forming method is used. Can be

Non-photosensitive varnishes include stencil screen ink, intaglio gravure ink, offset intaglio ink,
Varnish used for printing ink such as offset lithographic ink and letterpress ink, varnish used for electrodeposition coating, varnish used for developer of electronic printing and electrostatic printing, varnish used for thermal transfer ribbon, photosensitive varnish For example, a photosensitive resin varnish used for an ultraviolet curable ink, an electron beam curable ink, or the like, and a varnish more suitable for the above-described coating method and photolithography method can be used.

Examples of the resin binder of the non-photosensitive resin coating agent include cellulose acetate butyrate resin, nitrocellulose resin, styrene (co) polymer, polyvinyl butyrate resin, amino alkyd resin, polyester Resin, amino resin modified polyester resin, polyurethane resin, acrylic polyol urethane resin, soluble polyamide resin, soluble polyimide resin, etc., casein, hydroxyethyl cellulose, water-soluble salt of styrene-maleic acid ester copolymer, Water-soluble salts of a (meth) acrylic ester (co) polymer, a water-soluble amino alkyd resin, a water-soluble amino resin-modified polyester resin, a water-soluble polyamide resin, and the like are used alone or in combination. The colored composition of the present invention is obtained by mixing, dispersing and kneading the composite oxide black pigment and the binder by a conventionally known method.

Examples of the photosensitive resin varnish include ultraviolet curable inks, electron beam curable inks, and the like.
Particularly, it is a photosensitive resin varnish used in a pattern forming method by photolithography and etching.
For example, photosensitive cyclized rubber-based resin, photosensitive phenol-based resin, photosensitive (meth) acrylic resin, photosensitive styrene-
(Meth) acrylic resin, photosensitive polyamide resin, photosensitive polyimide resin, photosensitive unsaturated polyester resin, polyester acrylate resin, polyepoxy acrylate resin, polyurethane acrylate resin,
A varnish in which an organic solvent or an aqueous medium is added as a reactive diluent to a polyether-based acrylate resin, a polyol-based acrylate resin, or the like as a reactive diluent, if necessary, may be used.

A photopolymerization initiator such as benzoin ether or benzophenone is added to the composite oxide black pigment and the varnish, and the mixture is kneaded by a conventionally known method.
The coating agent type photosensitive coloring composition of the present invention can be obtained. When a black matrix is formed using the above photosensitive resin coating agent, the coating agent is uniformly applied on a transparent substrate by a coating method such as spin coating or roll coating, and after predrying, a photomask is adhered. Exposure is performed using an ultra-high pressure mercury lamp. Next, development and washing are performed, and post-baking is performed as necessary, whereby a black matrix can be formed. A thermopolymerizable colored composition can be obtained by using a thermopolymerization initiator instead of the photopolymerization initiator.

The composite oxide black pigment coloring composition described above
The ratio of the organic binder to the pigment is 100
weightParts, organic binder 5weightDepartment-300weight
Parts, preferably 10weightPart to about 200weightIn the range of parts
You. In addition, low melting glass free which is the inorganic binder described above.
In the method of firing using a sheet, the inorganic material for the pigment
The ratio of the binder is 100weightParts,
Indah 5weightDepartment-200weightParts, preferably 10weight
Part to about 100weightParts and the baking temperature
All organic binders burn off and
A condition in which the binder melts to fix the composite oxide black pigment
About 450-900 ° C is a desirable temperature condition.
You.

The black matrix formed as described above is also used as a monochrome display panel as a display panel of a light emitting type flat panel display, but it can be used as a color plasma display panel, a fluorescent display color display panel, or a light emitting diode color display. It is used as a means for avoiding color bleeding or color overlap of a color display such as a panel, a cathode ray tube color display panel, etc., and is particularly suitable for a color display which produces a clear and sharp image.

A display panel of a light emitting type flat panel display and a method of manufacturing the same according to the present invention are characterized by using the coloring composition containing a composite oxide black pigment for forming a black matrix as described above. is there.
For example, an example of manufacturing a display panel of a color plasma display will be described. Using a composite oxide black pigment-containing coloring composition to form a lattice pattern of a black matrix on the front glass substrate in the manner described above, then a transparent electrode, a metal electrode, a transparent dielectric layer, a stripe partition, a seal layer, A magnesium oxide layer is formed. A data electrode, a white dielectric layer, stripe barrier ribs, blue, green and red phosphor layers, and a seal layer are formed on the rear glass substrate. The processed front glass substrate and rear glass substrate are assembled, subjected to sealing, exhausting, and gas-filling steps, and connected to the assembled circuit portion to form a display panel.

The coloring composition and the forming method for forming the R, G and B pixels of the display panel of the light emitting type flat panel display may be conventionally known ones, for example, a phosphor pigment used for a color plasma display panel. As a preferable example of (A), for example, (Y,
Gd) BaAl ₁₂ O as a green phosphor such as BO ₃ : Eu
₁₉ : Mn, Zn ₂ SiO ₄ : Mn, etc.
aMgAl ₁₄ O ₂₃ : Eu ²⁺ , BaMg ₂ Al ₁₆ O ₂₇ : E
u and the like, and the light emitting diode is InGa
Examples include an N-based blue light emitting diode, a GaAlAs-based red light emitting diode, and a GaP-based green light emitting diode.

[0040]

Next, the present invention will be described more specifically with reference to examples. In the description, parts and% are based on weight unless otherwise specified. Example 1 A copper-iron-manganese composite oxide black pigment is synthesized by a wet synthesis method. 120 parts of copper sulfate, 104 parts of iron sulfate heptahydrate and 170 parts of manganese sulfate are measured and completely dissolved in about 800 parts of water to obtain a mixed salt aqueous solution. Next, 240 parts of caustic soda is measured and dissolved in about 800 parts of water as a precipitant to form an aqueous solution.

Separately, 800 parts of water are prepared, and the above mixed salt aqueous solution and caustic soda aqueous solution are simultaneously dropped with stirring at 26 ° C., and the precipitation reaction is completed in about 30 minutes to 1 hour. The solution is filtered and washed with water to sufficiently remove the soluble salts to obtain a filter cake, and dried at a temperature of 100 ° C to 120 ° C for 8 hours or more. The dried product is fired at 520 ° C. for one hour in an oxidizing atmosphere. C. comprising the obtained copper-iron-manganese composite oxide. I. Pigment Black 26 pigment has an average primary particle size of 0.1 μm and a BET surface area of 2 μm.
It was 5 m ² / g.

36 parts of the above-mentioned copper, iron and manganese composite oxide black pigment and 24 parts of low melting glass frit are mixed with 35 parts of a varnish for screen printing ink and 5 parts of an ink solvent, and kneaded using a three-roll mill. And sufficiently dispersed. The varnish for preparing a screen printing ink is mainly composed of ethyl hydroxyethyl cellulose, pentaerythritol ester of rosin, petroleum-based solvent, and cellosolve.

[0043] The above black ink in order to examine the performance as a black matrix for a display panel of a plasma display using a wire bar coater, was coated on the whole surface at a thickness before drying 3.mu. m on a glass substrate, to 200 ° C. And then fired in a firing furnace at 550 ° C. for 1 hour in air to burn out organic components. The optical density of the obtained black coating film was 3.2, indicating high light-shielding properties, excellent adhesion to a glass substrate, and excellent performance as a black matrix light-shielding material.

Next, a plasma display panel having a black matrix was produced. Using the above black ink, the screen printing machine front
A lattice pattern was printed on a glass substrate. 2
The resultant was dried at 00 ° C. and then fired in a firing furnace at 550 ° C. for 1 hour in air to burn organic components to form a black matrix. Next, a transparent electrode, a metal electrode, a transparent dielectric layer, a stripe partition, a seal layer, and a magnesium oxide layer were formed. On the rear (rear) glass substrate, a data electrode, a white dielectric layer, a stripe partition, blue, green and red phosphor layers, and a seal layer were formed. The processed front glass substrate and rear glass substrate obtained above were assembled, subjected to sealing, exhausting, and gas-filling steps, and connected to the assembled circuit portion to obtain a color plasma display panel.

In the obtained color plasma display panel, the emission colors of the blue, green and red phosphors are separated by a grid-like black matrix on the front glass substrate and illuminated, and the color purity and contrast are high. A clear image with excellent brightness can be formed.

Example 2 The black pigment of the copper-iron-manganese composite oxide used in Example 1 was subjected to a surface treatment with silica. 500 parts of the black pigment of Example 1, 3 parts of an aqueous solution of sodium silicate (29% as silicic acid anhydride) and 1000 parts of water are added and moistened, and a uniform and fluid slurry is formed with an attritor filled with steel balls. Disperse well. The resulting slurry was separated from steel balls through a net and diluted with water to 10,000 parts by volume.

Separately, 380 parts of an aqueous sodium silicate solution (29% as silicic anhydride) was diluted with water to 1700 parts by volume. Also, 1700 parts of a 3.30% sulfuric acid aqueous solution was prepared.
The pigment dispersion was heated to 90 ° C. and the pH was adjusted to 10.0 by adding a dilute aqueous sodium hydroxide solution. The diluted sodium silicate aqueous solution and dilute sulfuric acid aqueous solution were added dropwise thereto. The amount added was controlled so as to keep the reaction solution alkaline. Stirring is continued for 1 hour after the completion of the addition of both solutions, and the pH is adjusted to 6.5 to 7.0 by adding dilute sulfuric acid. Next, the slurry was filtered, washed until there was no soluble salt, and dried to obtain 600 parts of silica surface-treated black fine particle composite oxide pigment. The throughput of silica is about 20% based on the pigment. A plasma display panel having a black matrix was manufactured in the same manner as in Example 1.

Forty parts of the above silica surface-treated black fine particle composite oxide pigment and 10 parts of a low-melting glass frit were mixed with 20 parts of an alkali-developing methacrylic ester-methacrylic acid copolymer resin and pentaerythritol triacrylate 7
Parts, added to the photosensitive resin varnish consisting of 3 parts of di-ethylene glycol diacrylate and propylene glycol monomethyl ether acetate 18 parts, mixed using a ball mill and dispersed, further adding a photopolymerization initiator 2 parts, were mixed, A UV-curable ink was prepared.

The above UV curable black ink was applied to a thickness of 3 μm before drying on a front glass substrate using a roll coater. Next, preliminary drying was performed at 60 ° C. for 5 minutes. Thereafter, a photomask having a lattice-shaped pattern was brought into close contact with the photomask, and exposed to light at a light amount of 400 mJ / cm using an ultra-high pressure mercury lamp of 250 W to make it insoluble. Next, the unexposed portion is washed away with a developer mainly containing a dilute isopropyl alcohol aqueous solution containing sodium carbonate, and dried at 60 ° C.
A lattice pattern was obtained. Heat it at 200 ° C,
Next, the mixture was fired in a firing furnace at 550 ° C. for 1 hour in the air to burn the organic components to form a black matrix. An electrode, a dielectric layer, a partition, a seal layer, a magnesium oxide layer,
Blue, green and red phosphor layers were formed, the two substrates were assembled, sealed, evacuated, gas-sealed, and connected to a circuit section to obtain a color plasma display panel.

In the obtained color plasma display panel, the emission colors of the blue, green, and red phosphors are separated by a grid-like black matrix on the front glass substrate and shine, and the color purity and contrast are high. A clear image with excellent brightness can be formed.

Example 3 A fine particle type copper-iron-manganese composite oxide black pigment was synthesized, and a silica-based surface treatment was further performed. Copper sulfate 1
20 parts, iron sulfate heptahydrate 104 parts and manganese sulfate 170
A portion is weighed and completely dissolved in about 800 parts of water to obtain a mixed salt aqueous solution. Next, 240 parts of caustic soda is measured and dissolved in about 800 parts of water as a precipitant to form an aqueous solution. Separately water 8
The above mixed salt aqueous solution and caustic soda aqueous solution were simultaneously dropped while stirring at 26 ° C.
To perform a precipitation reaction. 35% while maintaining pH after dropping
Oxidation treatment is performed by dropping aqueous hydrogen peroxide. After completion of the oxidation treatment, the solution temperature is set to 70 ° C. and aging is performed for about 1 hour. Filter and wash with water to remove the soluble salts sufficiently to obtain a filter cake.
Dry at a temperature of 00C to 120C for 8 hours or more. The dried product is fired at 520 ° C. for one hour in an oxidizing atmosphere.

The pigment thus obtained has small primary particles, a particle diameter of about 0.01 to 0.06 μm, a BET specific surface area of 56 m ² / g, a blackness, a coloring power, and a dispersibility. Is a copper-iron-manganese-based fine particle composite oxide black pigment exhibiting a good bluish black color.

The fine particle composite oxide black pigment obtained above was subjected to a siliceous surface treatment in the same manner as in Example 2.
An aqueous solution of sodium silicate and water are added to wet the fine black pigment, and the pigment is sufficiently dispersed with an attritor filled with steel balls until a uniform and fluid slurry is obtained.
The resulting slurry was separated from the steel balls through a screen and diluted with water. Separately, a diluted sodium silicate aqueous solution and a dilute sulfuric acid aqueous solution were prepared. The pigment dispersion is heated to 90 ° C. and the pH is adjusted to 1 by adding a dilute aqueous sodium hydroxide solution.
Adjusted to 0.0. The diluted sodium silicate aqueous solution and dilute sulfuric acid aqueous solution were added dropwise thereto. After completion of the addition, stirring is continued for 1 hour, and the pH is adjusted to 6.5 to 7.0 with dilute sulfuric acid. Next, the slurry was filtered, washed and dried to obtain a silica surface-treated black fine particle composite oxide pigment. Silica throughput is about 30% based on pigment. A plasma display panel having a black matrix was manufactured in the same manner as in Example 1.

[0054] The silica surface treated black fine composite oxide pigment 35 parts of low melting point glass frit 10 parts of an alkali development type styrene - methacrylic ester - 15 parts of methacrylic acid copolymer resin, 7 parts of pentaerythritol triacrylate, di ethylene glycol Diacrylate 3
Parts and a photosensitive resin varnish consisting of 28 parts of propylene glycol monomethyl ether acetate, and mixed.
It was dispersed using a ball mill, and 2 parts of a photopolymerization initiator was further added and mixed to prepare a UV-curable black color.

The front glass substrate was set on a spin coater, and the above-mentioned UV-curable black color was treated at 200 rpm for 30 minutes.
After that, spin coating was performed at 500 rpm for 5 seconds, and applied before drying at a thickness of 3 μm. Then at 60 ° C 5
Pre-drying was performed for minutes. Thereafter, a photomask having a lattice-shaped pattern was brought into close contact with the photomask, and exposed to light with a light amount of 400 mJ / cm using an ultra-high pressure mercury lamp of 250 W to make it insoluble. Next, the unexposed portion was washed away with a developer mainly composed of a dilute isopropyl alcohol aqueous solution containing sodium carbonate, and dried at 60 ° C. to obtain a lattice pattern. It is heated at 200 ° C. and then fired in air in a firing furnace.
The mixture was fired at 0 ° C. for 1 hour to burn the organic components to form a black matrix. An electrode, a dielectric layer, a partition, a sealing layer, a magnesium oxide layer, blue, green and red phosphor layers are formed on the front and rear glass substrates in the same manner as in Example 1, and both substrates are assembled and sealed. Exhaust gas and gas were sealed, and connected to the circuit section to obtain a color plasma display panel.

The color plasma display panel thus obtained shines with the emission colors of the blue, green and red phosphors separated by a grid-like black matrix on the front glass substrate, and has high color purity and contrast. A clear image with excellent brightness can be formed.

Further, instead of the copper-iron-manganese composite oxide black pigment used in Examples 1, 2 and 3, the cobalt-chromium-iron composite oxide black pigment, cobalt-chromium-iron-manganese was used. -Based composite oxide black pigment, cobalt-nickel-chromium-iron-based composite oxide black pigment or iron-zinc-chromium-based composite oxide brown pigment / cobalt-aluminum-chromium-based composite oxide green pigment / cobalt-aluminum-based Using each of the composite oxide blue pigment (10: 7: 3) -containing black pigments, a color plasma display panel having an excellent black matrix was obtained in the same manner as described above.

[0058]

According to the present invention, a composite oxide black pigment having excellent fastness and hiding power as a light-shielding pigment or the surface thereof is made of amorphous silica, a low-melting glass, or a mixture thereof. The coloring composition containing the composite oxide black pigment treated with the coating material of the above is excellent in optical properties such as blackness and optical density, and also excellent in dispersion stability in a dispersion medium. By using this composite oxide black pigment-containing coloring composition to form a black matrix such as a display panel of a light-emitting flat panel display, the blackness and light-shielding property can be more easily and inexpensively compared with the conventional method. The present invention provides a black matrix which is excellent in heat resistance, ultraviolet light resistance, light resistance, chemical resistance, solvent resistance and the like.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI C01G 45/00 C01G 45/00 49/00 49/00 A 51/00 51/00 A 53/00 53/00 A C09C 3 / 04 C09C 3/04 G02B 5/00 G02B 5/00 B 5/20 5/20 G09F 9/00 315 G09F 9/00 315C H01J 1/74 H01J 1/74 9/227 9/227 DF 11/00 11 / 00 B 17/04 17/04 29/32 29/32 // C01F 7/16 C01F 7/16 C09K 11/64 CPP C09K 11/64 CPP 11/78 CPK 11/78 CPK 11/79 CPR 11/79 CPR (72) Inventor Kanako Sato 1-7-6 Nihombashi Bakurocho, Chuo-ku, Tokyo Inside Dainippon Seika Kogyo Co., Ltd. (72) Inventor Shigeru Sakamoto 1-7-6 Nihonbashi Bakurocho, Chuo-ku, Tokyo Dainichi Seika Kogyo (72) Inventor Hiromi Terada Chuo-ku, Tokyo Nihonbashi Bakurocho 1-7-6 Dainichi Seika Kogyo Co., Ltd. (72) Inventor Nakamura Michie 1-7-6 Nihonbashi Bakurocho 1-chome, Chuo-ku, Tokyo Dainichi Seika Kogyo Co., Ltd. (56) References JP-A-6-5202 (JP, A) JP-A-6-5204 (JP, A) JP-A-4-50119 (JP, A) JP-A-7-27912 (JP, A) A) JP-A-60-155533 (JP, A) JP-A-8-236036 (JP, A) JP-A-2000-235114 (JP, A) Patent 3048126 (JP, B2) (58) Fields investigated (Int. Cl ^7, DB name) C09C 1/00 -. 3/12

Claims (9)

(57) [Claims] 1. A light-shielding black by eliminating an organic binder.
In a light-shielding black pigment-containing coloring composition for forming a black matrix on a substrate of a display panel of a light-emitting flat panel display through a baking step of fixing a pigment to a substrate , a binder is an organic binder and a non-organic binder.
A machine binder, light-shielding black pigment, copper and manganese
Composite oxide black pigment containing copper as the main metal component, copper, iron and man
Composite oxide black pigment containing a gun as a main metal component;
Complex acid containing sodium, chromium, iron and manganese as main metal components
Single oxide black pigment having a spinel-type or reverse spinel-type crystal structure selected from the group consisting of oxide black pigments
Alternatively , a coloring composition for a black matrix , which is a mixture . 2. The composite oxide black pigment is a composite oxide obtained by dry-mixing a metal oxide, a hydroxide and / or a carbonate of a constituent metal component and then performing a calcination treatment. 2. The coloring composition for a black matrix according to 1. 3. A complex oxide black pigment dissolves a metal salt of a constituent metal component in water, forms a coprecipitate of a compound composed of a metal oxide, a hydroxide and / or a carbonate with an alkali agent, and then calcinates. The colored composition for a black matrix according to claim 1, which is a composite oxide obtained by performing the treatment. 4. The composite oxide black pigment is prepared by dissolving a metal salt of a constituent metal component in water, neutralizing and precipitating by adding an alkali agent, and oxidizing in a liquid phase simultaneously with or after the precipitation, ^{2. The} colored composition for a black matrix according to claim 1, which is a composite oxide having a BET specific surface area of about 40 m ² / g or more obtained by performing a baking treatment. 5. The colored composition for a black matrix according to claim 1, wherein the firing treatment in the production of the composite oxide black pigment is at about 400 ° C. or higher. 6. The black matrix coloring composition according to claim 1, wherein the surface of the composite oxide black pigment is surface-treated with a coating material composed of amorphous silica and / or low-melting glass. 7. The black matrix coloring composition according to claim 1, wherein a low-melting glass frit is mixed as a heat-fusible binder for the composite oxide black pigment. 8. An organic binder and an inorganic heat-fusible material on a display panel substrate of a light emitting type flat panel display .
Use a coloring composition containing a light-shielding pigment and a binder
The organic binder disappears, and the light-shielding pigment is fixed on the substrate.
In the manufacturing method of forming a black matrix through a baking step of wearing, the light-shielding pigment used is copper
Oxide black pigment with copper and manganese as main metal components, copper
Oxide black face containing iron and manganese as main metal components
Material and cobalt, chromium, iron and manganese as main metal components
A black matrix characterized by being a single or mixture of a composite oxide black pigment having a spinel-type or inverse spinel-type crystal structure selected from the group consisting of composite oxide black pigments Production method. 9. A low-melting glass frit is used as a heat-fusible binder for the composite oxide black pigment at a temperature of about 450 ° C. to 9 ° C.
The organic binder burns at 00 ° C., the glass frit is heat melted thereby removing method of the black matrix according to 請 Motomeko 8 you secure the composite oxide black pigments.