JPH08236020A - Manufacture of filter pattern - Google Patents

Abstract

PURPOSE: To easily manufacture a filter pattern by applying rinse treatment to remove the second pigment layer formed on the first pigment layer obtained by means of exposure-hardening-treatment, by using a pigment solution containing an adhesion controlling agent at least in one part. CONSTITUTION: A silica or aluminosilane film is formed in a whole surface of a glass substrate 1. A photoabsorptive layer 2 of prescribed pattern of graphite particle is formed on this substrate 1. Next on this layer, after applying a blue pigment dispersed solution dried, exposure hardening and rinsing is performed through a color select filter, to form a blue color pigment layer 3. Then, by using a green color pigment dispersed solution, a green color pigment layer 5 is formed by means of exposure hardening and rinse treatment. A red color pigment dispersed solution is applied to be dried to form a red color pigment layer 6 on this substrate 1. Here, in each pigment dispersed solution, an adhesion controlling agent of silica, Li-silicate, alumina, etc., of 0.1μm or less grain size is contained. Next, by rinse treatment, each color pigment layer 3, 5, 6 of prescribed pattern is obtained. Thereafter, each color fluorescent material layer 7 to 9 is provided.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a filter pattern in a phosphor layer with a filter having a two-layer structure, for example.

[0002]

2. Description of the Related Art A red, blue, green dot-shaped or stripe-shaped phosphor layer is formed on the inner surface of a face plate of a cathode ray tube or a color image receiver. When the electron beam collides with the phosphor layer, the phosphor layer emits light to display an image. In order to improve image display characteristics such as contrast and color purity, the phosphor layer has been conventionally improved. For example, there is a phosphor layer with a filter in which a pigment layer having a body color similar to the emission color of the phosphor layer is provided between the face plate and the phosphor layer. The filter-attached phosphor layer selectively selects the green or blue component light for the red pigment, the green or red component light for the blue pigment, and the blue or red component light for the green pigment among the incident external light. Since they are absorbed respectively, the contrast and color purity are improved.

A method for manufacturing the phosphor layer with a filter is disclosed in, for example, Japanese Patent Application Laid-Open No. 5-275008. In this conventional example, a resist is applied and a pattern other than a predetermined position is exposed to form a resist pattern, and then a pigment liquid is applied thereon, and then the resist and the pigment layer on the resist are peeled off by acid decomposition to remove the pigment pattern at a predetermined position. Is used to obtain the pigment layer of each color.

[0004]

However, in this conventional example, it is necessary to form a resist pattern each time a pigment layer of each color is obtained, and the number of steps is large, and a filter pattern can be manufactured more easily. desired.

Further, as a method of forming a pigment layer, as disclosed in, for example, Japanese Patent Laid-Open No. 275007/1993,
A pigment dispersion prepared by mixing a water-soluble polymer such as polyvinyl alcohol (PVA) or polyvinylpyrrolidone (PVP) with a crosslinking agent such as ammonium dichromate (ADC) or a diazonium salt is applied, and exposure and development with warm water are performed. It is also conceivable that a pigment layer having a predetermined pattern is obtained.

However, this method also has the same problem as the above-mentioned conventional example because the exposure and development with a predetermined pattern are repeated each time a pigment layer of each color is obtained. The present invention has been made to address such a problem, and an object thereof is to provide a method for manufacturing a filter pattern by simpler steps.

[0007]

According to the present invention, a solution containing first pigment particles is applied and dried on a substrate, exposed to a predetermined pattern, cured, and then developed to develop a pattern of the first pigment layer. And a second step of coating and drying a solution containing second pigment particles on a substrate and a pattern, the first pigment particles At least one of the solution containing and the solution containing the second pigment particles contains an adhesiveness adjusting agent, and rinsed after the second step to remove the second pigment layer on the pattern, The method includes a step of forming first and second pigment layers.

The pigment according to the present invention may be either an inorganic pigment or an organic pigment. Particularly preferred is a pigment that can be uniformly dispersed in the filter layer and can have sufficient transparency in the filter layer without causing light scattering.

The following pigments can be given as specific examples. In the inorganic type, as red pigments, ferric oxide type trade name Sicotrans Red L-2817 (particle diameter 0.01 to 0.02 μm, manufactured by BASF), anthraquinone type trade name Chromophartal Red A2B
(Particle diameter 0.01 μm, manufactured by Ciba Geigy), and as a blue pigment, cobalt aluminate (Al ₂ O ₃ —CoO) -based cobalt cobalt X (particle diameter 0.01 to 0.
02 μm, manufactured by Toyo Pigment Co., Ltd.)
o. 8000 (particle size 0.3 μm, manufactured by Daiichi Kasei Co., Ltd.), phthalocyanine blue-based product name Rionol Blue F
G-7370 (particle diameter 0.01 μm, manufactured by Toyo Ink Co., Ltd.), as a green pigment, TiO ₂ —NiO—CoO—Z
Product name of nO type Dipiroxide TM-Green #
3320 (particle size 0.01 to 0.02 μm, manufactured by Dainichiseika Co., Ltd.), CoO—Al ₂ O ₃ —Cr ₂ O ₃ —TiO ₂ system, trade name Dipyroxide TM-Green # 3340.
(Particle diameter 0.01 to 0.02 μm, manufactured by Dainichiseika Co., Ltd.), C
oO-Al ₂ O ₃ is a -Cr ₂ O ₃ system product name die Piroki side TM- Green # 3420 (particle diameter: 0.01
0.02 μm, manufactured by Dainichiseika Co., Ltd., Cr ₂ O ₃ type trade name ND-801 (particle size 0.35 μm, manufactured by Nippon Denko KK), chlorinated phthalocyanine green type trade name First Gen Green S ( Particle diameter 0.01 μm, manufactured by Dainippon Ink and Chemicals, Inc., brominated phthalocyanine green type trade name Fastgen Green 2YK (particle diameter 0.01)
μm, manufactured by Dainippon Ink and Chemicals, Inc.).

Among the organic pigments, the red pigment is the azo lake type trade name Lake Red C (manufactured by Dainichiseika Co., Ltd.), and the blue pigment is the copper phthalocyanine type trade name Fast Genpur GNPS (Dainippon Ink and Chemicals Co., Ltd.). As a green pigment, there can be exemplified a chlorine-brominated copper phthalocyanine-based product name, Rionol Green 2Y-301 (manufactured by Toyo Ink Co., Ltd.).

By mixing and stirring this pigment with a dispersant for dispersing the pigment, an adhesion control agent, a photoresist and pure water, a dispersion liquid for forming a pigment layer can be obtained. If the pure water is 5% by weight or less, a water-soluble organic solvent such as alcohol can be included.

Examples of dispersants include anionic sodium salt dispersants, anionic ammonium salt dispersants, and nonionic dispersants. Examples of the anionic sodium salt dispersant include acrylic type, acrylic-styrene type, acrylic copolymer, polycarboxylic acid type, and naphthalenesulfonic acid formalin condensate. As a specific example, as an acrylic type, Despec N-40 (manufactured by Allied Colloid Co., Ltd.), and as a polymer polycarboxylic acid type, Demol EP
(Manufactured by Kao), Poise 520 (manufactured by Kao), Naphthalenesulfonic acid formalin condensate, Demol N (manufactured by Kao), Special aromatic sulfonic acid formalin condensate, Demol MS (manufactured by Kao), Octylphos As Fate Monoethanol amino salt, Elenone No. 19
M is mentioned. Examples of the anionic ammonium salt dispersant include acrylic type, acrylic-styrene type, acrylic copolymer, polycarboxylic acid type, and polyoxyethylene alkyl ether sulfate. As a specific example, as the acrylic type, Despec A-40 (manufactured by Allied Colloid), as the high-molecular polycarboxylic acid type, DISCOTE N-14 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), polyoxyethylene alkyl ether sulfate. Examples of the ammonium salt include Hitenol 08 (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.), and condensed naphthalene sulfonic acid includes Lomer PWA (manufactured by San Nobuco). Examples of nonionic dispersants include polyoxyethylene lauryl ether, polyoxyethylene derivatives, polyoxyalkylene alkyl ethers, polyoxyethylene nonylphenyl ethers, and polyoxyethylene sorbitan monolaurate. Specific examples thereof include Neugen EA-140 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), Emulgen 106 (manufactured by Kao Corporation), and Leodol TW.
-L120 (manufactured by Kao Corporation) is available.

As an example of the adhesion control agent, fine particle silica,
There are Li-silicate, fine particle alumina, and the like, and the solid content may be added in an amount of 10 to 60% by weight. Further, it is desirable that the particle diameter of the fine particle silica and the fine particle alumina be 0.1 μm or less.

As the photoresist, ammonium dichromate (ADC) / polyvinyl alcohol (PV
A), various types of water-soluble photoresists such as sodium dichromate (SDC) / PVA, diazonium salts, etc./PVA, stizobal, ADC / casein, etc. can be used.

The concentration of the pigment dispersed in the dispersant is in the range of 0.1% by weight to 50% by weight, preferably 1% by weight to 50% by weight. If the pigment concentration is less than 0.1% by weight, coloring of the pigment layer will not be recognized. If it exceeds 1% by weight,
Coloring is more clearly seen. On the other hand, if it exceeds 50% by weight, the viscosity of the dispersion liquid increases sharply, making it impossible to apply a uniform film.

Next, the developer used in the step of developing the pigment layer and the solution used for rinsing will be described. Warm water or an aqueous alkali solution can be preferably used as the developer and the rinse solution.

The present invention is carried out in the following procedure when forming a filter on a color cathode ray tube panel, for example. First, the pigment dispersion liquid of the first pigment layer is applied to the inner surface of the face plate and dried. As a coating method, the inner surface of the face plate is coated upward, sideways, downward, or the like. The parameters such as solid content, viscosity and coating method of the pigment dispersion can be controlled and selected so that uniform coating can be performed. As a coating method, a dipping method, a flow coating method or the like can be used other than the spin coating method. The spin coating method is particularly preferable in order to obtain a uniform and predetermined film thickness. Examples of the drying method include drying by shaking off, drying by a heater, drying by hot air, drying by dry air, and drying at room temperature for a long time. With this, a pigment layer can be formed. It is also possible to form a patterned light absorbing layer on the inner surface of the face plate before forming the pigment layer. Subsequently, a desired pattern is exposed through the shadow mask using, for example, a high pressure mercury lamp. After that, the developing solution is immersed in the inner surface of the face plate for a few seconds to perform development. Next, the pigment dispersion liquid of the second pigment layer is applied to the inner surface of the face plate and dried, and then, for example, water is sprayed and rinsed to finally complete the first and second pigment layers.

According to the present invention, after the solution containing the second pigment particles is applied and dried on the substrate, it is possible to perform a simple rinsing treatment without particularly exposing the applied film to a predetermined pattern. It becomes possible to form the second pigment layer. For this purpose, it is important to provide sufficient differences in adhesion between the coating film of the second pigment layer and the substrate and between the coating film of the second pigment layer and the first pigment layer. . Therefore, the inventors repeated various experiments and noticed the following points.

When the substrate is an inorganic material such as glass,
It has been found that the coating film of the second pigment layer can be patterned by a simple rinsing treatment by including the adhesiveness adjusting agent in at least one of the coating films of the first and second pigment layers. The function of the adhesion control agent is considered as follows. That is, by including an adhesion control agent in the pigment layer, the pigment layer can be charged to a predetermined charge (for example, negative charge for fine particle silica and positive charge for Li-silicate and fine particle alumina). On the other hand, by forming silica or aminosilane before forming the pigment layer, the substrate can be charged to a predetermined charge (for example, silica has a negative charge and aminosilane has a positive charge). Therefore, by the action of the adhesion control agent, the charge amount charged in the first and second pigment layers is set to a predetermined value, so that the space between the second pigment layer and the substrate and between the second pigment layer and It becomes possible to make a sufficient difference in the adhesiveness with the first pigment layer.

[0020]

BEST MODE FOR CARRYING OUT THE INVENTION The details of the present invention will be described below with reference to the drawings in which the first pigment layer is a blue pigment layer and a green pigment layer and the second pigment layer is a red pigment layer.
1 to 3 are process drawings showing an embodiment of the present invention. First, as shown in FIG. 1A, a film (not shown) made of aminosilane is formed on the entire surface of a substrate 1 made of, for example, glass, and then a light absorption layer 2 having a predetermined pattern made of, for example, graphite fine particles is formed. To do.

Next, a pigment dispersion having the following composition was prepared as a pigment dispersion for forming blue, green and red filters. <Blue pigment dispersion> Blue pigment particles: Cobalt aluminate 30% by weight (trade name: Cobalt Blue X (particle size 0.01 to 0.02 µm, manufactured by Toyo Pigment Co., Ltd.) Dispersant: ammonium salt of polyacrylic acid copolymer 0.7% by weight (Despec GA-40 (manufactured by Allied Colloid)) Adhesion control agent: Fine particle silica (particle size 0.08 μm) 3% by weight (Snowtex (manufactured by Nissan Chemical Industries)) Photoresist: heavy ammonium chromate (ADC) + polyvinyl alcohol (PVA) 0.5 wt% respectively dispersed in pure water <green pigment dispersion> green pigment _{particles: TiO 2 -NiO-CoO-ZnO} 30 wt% (trade name die Piroki side TM-Green # 3320 (particle diameter 0.01 to 0.02 μm, manufactured by Dainichiseika Co., Ltd.) Dispersant: sodium salt of acrylic acid 0.7% by weight Adhesion control agent: Fine particle silica (particle diameter 0.08 μm) 3% by weight (Snowtex (manufactured by Nissan Kagaku)) Photoresist: ADC + PVA 0.5% by weight Dispersed in pure water <Red Pigment dispersion> Red pigment particles: Fine particles of Fe ₂ O ₃ 20% by weight (particle diameter 0.01 to 0.02 μm) Dispersant: ammonium salt of polyoxyethylene alkyl ether sulfate (Hitenol 08 (Daiichi Kogyo Seiyaku Co., Ltd. 0.7% by weight Adhesion control agent: Fine particle silica (particle diameter 0.08 μm) 3% by weight (Snowtex (manufactured by Nissan Kagaku)) Photoresist: ADC + PVA 0.5% by weight Dispersed in pure water Next, the substrate 1 was kept at a temperature of 30 ° C. and the pigment dispersion liquid of the blue pigment layer 3 was applied as shown in FIG. Then, the excess pigment dispersion was shaken off and dried for 3 to 4 minutes at a heater temperature of 120 ° C. Then, for example, as shown in FIG. Then, the liquid was exposed to a predetermined pattern.
By spraying at 10 kg / cm ² and rinsing, a blue pigment layer 3 having a predetermined pattern was formed as shown in FIG.

Next, the substrate 1 was kept at a temperature of 30 ° C., and as shown in FIG. 2A, the pigment dispersion liquid of the green pigment layer 5 was applied. The substrate 1 was rotated at 100 to 300 rpm to shake off excess pigment dispersion. It was dried at a heater temperature of 120 ° C. for 3 to 4 minutes. Then, as shown in FIG. 2B, for example, using a high pressure mercury lamp through the color selection electrode 4,
It was exposed to a predetermined pattern. Subsequently, atomized water, for example, was sprayed at a liquid pressure of ² to 10 kg / cm ² and rinsed to form a green pigment layer 5 having a predetermined pattern as shown in FIG. 2C.

Next, the substrate 1 was kept at a temperature of 30 ° C., and the pigment dispersion liquid of the red pigment layer 6 was applied as shown in FIG. The substrate 1 was rotated at 100 to 300 rpm to shake off excess pigment dispersion. It was dried at a heater temperature of 120 ° C. for 3 to 4 minutes. Then, for example, atomized water was sprayed at a liquid pressure of ² to 10 kg / cm ² and rinsed to form a red pigment layer 6 having a predetermined pattern as shown in FIG. 3B.

Thus, a pigment layer consisting of the blue pigment layer 3, the green pigment layer 5 and the red pigment layer 6 was obtained on the substrate 1. In this example, by forming a film made of aminosilane on the entire surface of the substrate 1 and incorporating fine particle silica into the blue pigment layer 3, the green pigment layer 5 and the red pigment layer 6, the substrate 1 is
Charge, blue pigment layer 3, green pigment layer 5 and red pigment layer 6
Charges to the negative charge. As a result, the adhesive force between the red pigment layer 6 and the substrate 1 becomes sufficiently larger than the adhesive force between the red pigment layer 6, the blue pigment layer 3 and the green pigment layer 5, and the blue color is obtained by the rinsing process. Pigment layer 3 and green pigment layer 5
The upper red pigment layer 6 is completely rinsed, and is covered with the red pigment layer 6 except the portions where the blue pigment layer 3 and the green pigment layer 5 are located on the substrate 1, as shown in FIG. Therefore, the exposure process for forming the red pigment layer 6 which has been conventionally required is not necessary, and the filter manufacturing process can be simplified.

Next, as shown in FIG. 3C, the blue phosphor layer 7, the green phosphor layer 8 and the red phosphor layer 9 are respectively replaced by a conventional method with the blue pigment layer 3, the green pigment layer 5 and the red pigment layer 5, respectively. It was formed so as to correspond to the pigment layer 6.

In this way, a desired phosphor layer with a filter having a pigment layer and a phosphor layer on the substrate 1 is obtained, and a color cathode ray tube using this is excellent in contrast and color purity. Further, the filter pattern forms a blue filter corresponding to a predetermined position, for example, a position where the blue phosphor layer is to be formed, and the pigment of the blue filter does not remain as a residue at the position of another color, resulting in a mixed color. The filter has excellent color purity characteristics.

Other examples in which the effects of the present invention can be obtained are as follows: (a) When a film made of aminosilane is formed on the substrate 1 The blue pigment dispersion liquid and the green pigment dispersion liquid contain an adhesion control agent. Of course, the fine particle silica is included only in the red pigment dispersion (b) When a film made of silica is formed on the substrate 1. The blue pigment dispersion, the green pigment dispersion, and the red pigment dispersion have Li
-Incorporating silicate or fine particle alumina Blue pigment dispersion liquid and green pigment dispersion liquid do not contain an adhesion control agent, and only the red pigment dispersion liquid contains Li-silicate or fine particle alumina. In the above, the first pigment layer in the pigment layer is the blue pigment layer and the green pigment layer, and the second pigment layer is the red pigment layer. However, the present invention is not limited to this, and the second pigment layer may be a blue pigment layer or a green pigment layer. It goes without saying that either of them may be used. Further, the present invention can be applied to a color filter for a liquid crystal display device and the like. Furthermore, when patterning each pigment layer, the unnecessary portion of each pigment layer can be more surely peeled off by immersing the substrate in, for example, an alkali developing solution before spraying atomized water.

[0028]

According to the present invention, the adhesiveness modifier is contained in at least one of the solution containing the first pigment particles and the solution containing the second pigment particles, and the rinse treatment is performed on the first pigment layer. Since the step of forming the first and second pigment layers by removing the second pigment layer is provided, it is possible to reliably obtain the predetermined pattern of the pigment layer by a simpler step than in the past.

[Brief description of drawings]

FIG. 1 is a cross-sectional view showing a process of forming a blue pigment layer in an example of the present invention.

FIG. 2 is a cross-sectional view showing a step of forming a green pigment layer in an example of the present invention.

FIG. 3 is a cross-sectional view showing a step of forming a red pigment layer in one example of the present invention.

FIG. 4 is a plan view showing the structure after formation of a pigment layer in one embodiment of the present invention.

[Explanation of symbols]

 1 ... Substrate 3 ... Blue pigment layer 5 ... Green pigment layer 6 ... Red pigment layer

Claims (3)

[Claims] 1. A first step of forming a pattern of a first pigment layer by applying a solution containing a first pigment particle on a substrate, drying it, exposing it to a predetermined pattern to cure it, and then developing it. And a second step of applying and drying a solution containing second pigment particles on the substrate and the pattern, wherein the solution containing the first pigment particles and the second pigment At least one of the solutions containing particles contains an adhesion modifier, which is rinsed after the second step to remove the second pigment layer on the pattern to remove the first and the second pigment layers. 2. A method of manufacturing a filter pattern, comprising the step of forming the pigment layer of 2. 2. The method of manufacturing a filter pattern according to claim 1, wherein silica or aminosilane is formed on the entire surface of the substrate. 3. The method for producing a filter pattern according to claim 1, wherein the adhesion control agent has a particle diameter of 0.1 μm.
The following fine particle silica, Li-silicate, particle size 0.1
A method for producing a filter pattern, which is one of fine particle alumina having a particle size of not more than μm.