JPS6151285B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method of manufacturing a color stripe filter used in a color television image pickup tube or a color solid-state image pickup device.

Color stripe filters used in image pickup tubes for color televisions, etc., have their color filter parts made of an inorganic interference film or dyed organic dye layers, but the latter is considered to be more advantageous in terms of manufacturing. .

Color stripe filters generally have a structure in which several striped filter layers of different colors are arranged in series, so the boundaries between adjacent ones become unclear, and especially in the case of dyed filters, the colors may overlap near the boundaries. There were problems such as the colors mixing with each other, and the stripe elements that were previously dyed during the manufacturing process causing significant color mixing due to different colors. In order to prevent this color mixture, conventionally, as shown in FIG. 1, there is a method of coating a transparent substrate 1 with an intermediate protective film 2 each time a colored stripe 3 is formed by dyeing one color, or a method of applying heat treatment every time one color is dyed. A method was considered to make it dye-resistant.

However, in the former method, the process is complicated because an intermediate protective film is coated for each color, and the resulting striped filter is coated with an intermediate protective film of several thousand Å to several micrometers at least once, so the entire filter is coated with an intermediate protective film. The surface irregularities become larger and the overall film thickness also increases to 4.
There was a problem that the thickness was considerably thick at ~8μ, which adversely affected the imaging characteristics. In addition, the latter method has the problem that the effect of preventing color mixture by heat treatment alone is extremely small, making it unsuitable for practical use.

The present invention was discovered as a result of intensive research to correct the above-mentioned drawbacks, and its characteristics are as follows: After dyeing a striped resin film with a dye having predetermined spectral characteristics, Before forming colored stripes, the colored resin film is treated with a metal compound having the ability to form a chelate compound with the colored resin film to modify the surface of the colored resin film and make it stain resistant. Therefore, according to the method of the present invention, there is no color mixing, and since no intermediate protective film is used, it is possible to easily produce a high-quality color stripe filter with a smooth surface and an extremely thin overall film thickness of 1 to 3 μm. And it can be manufactured at low cost.

The present invention will be explained in detail below.

FIG. 2 shows an example of the structure of a color stripe filter obtained by the method of the present invention, and the color stripe filter has a colored stripe layer 4 on a transparent substrate 1. Figure 3A
-K are diagrams showing a method of manufacturing a filter having the structure shown in FIG. 2. To explain the method of the present invention based on FIG. 3 according to an example, first, as shown in FIG. Forms around ~1500Å. Next, a mask having a predetermined striped pattern is placed on the photosensitive resin film 5 and selectively exposed to ultraviolet light. Thereafter, by developing, the unexposed portions of the photosensitive resin film are dissolved and removed, leaving only the exposed portions in the form of stripes as shown in FIG. 3B, forming a striped dyed resin film 6. That is, about 30 to 30 μm in stripes with a width of about 10 to 30 μm.
Form a pattern arranged at a pitch of 90μ.
Next, this part of the striped resin film 6 to be dyed is dyed with, for example, a red dye as a first color, and the excess dye is removed by washing thoroughly with water.
A colored stripe resin film 7 of the first color is formed as shown in FIG. Next, immerse or spray in a solution or dispersion containing one or more metal compounds capable of reacting with the colored resin film to generate a chelate compound, pour over, apply with a spinner, and then wash with water if necessary. By drying preferably at a temperature of 100°C to 160°C, the colored resin film and the metal compound are sufficiently chelated, and the colored resin film is surface-modified as shown in Figure 3D. Then, a surface-modified colored stripe 8 of the first color with extremely strong stain resistance is formed.

Next, as shown in FIG. 3E, a photosensitive resin film 9 for dyeing is formed again in the same manner as for the first color, and then selectively exposed using a mask having a striped pattern and developed. As shown in FIG. 3F, a striped resin film 10 to be dyed is formed adjacent to the surface-modified first colored stripe 8, and this is dyed with a dye, for example, a green dye. As shown in FIG. 3G, a colored stripe resin film 11 of a second color is formed. At this time, the surface-modified colored stripe resin film 8 of the first color is surface-modified by a chelation reaction with a metal compound and has strong dyeing resistance, so color mixing will not occur due to the dye of the second color. do not have. Next, by treating again with a solution containing a metal compound, a colored striped resin film 12 of the second color whose surface has been modified to have stain resistance is formed as shown in FIG. 3H. Next, in the same manner as the first and second colors, a colored stripe resin film 15 of a third color is formed by coloring with, for example, a blue dye as shown in FIGS. 3I to 3K. A striped filter is formed in which green and blue colored stripes are arranged at a constant pitch on a flat surface without color mixture, with a smooth surface and an extremely thin overall film thickness of around 2 μm.

Note that the colored stripe resin film 15 colored in the final step above may be subjected to surface modification treatment as described above. Furthermore, in the present invention, a protective film can be provided on the surface of the color stripe filter by a conventional method. If the surface is modified in the final stage, even if the manufactured color stripe filter is attached to a thin glass plate using an adhesive during the manufacture of a color image pickup tube, the uppermost layer will be damaged due to the influence of the adhesive. Effects such as being able to prevent discoloration of the final colored stripe resin film, which may occur even if a protective film is provided on the film, can be obtained.

In the present invention, the photosensitive resin that can be used is one obtained by adding dichromate or chromate to gelatin, casein, fiberglass, polypinyl alcohol, etc., and in particular, it can be used to form a chelate ring with a metal compound. Those having easily active groups, such as amino groups, carboxyl groups, carbonyl groups, hydroxyl groups, and azo groups, are preferably used.

Furthermore, in the above, examples of the dye used to color the striped dyed resin film include acid dyes, direct dyes, and reactive dyes. More specifically, examples of acidic dyes include Suminol Fastred G (CIAcid Red118,
(Manufactured by Sumitomo Chemical Industries, Ltd.), Kayanol Milling
Red RS (CIAcid Red114, manufactured by Nippon Kayaku Co., Ltd.),
Diamond Fast Red 3BL (CI
Acid Red158, manufactured by Mitsubishi Chemical Industries, Ltd.), Kayanol Yellow NGS (CIAcid Yellow110, manufactured by Nippon Kayaku Co., Ltd.), Suminol First Yellow G
(CIAcid Yellow61, manufactured by Sumitomo Chemical Co., Ltd.), Alizarin Green (CIAcid Green9, manufactured by Tokyo Chemical Industry Co., Ltd.), Brilliant India Blue 5G (C.
I.Acid Blue103, Hoechst), Kayanor
Cyanine 6B (CIAcid Blue83, manufactured by Nippon Kayaku Co., Ltd.), acid cyanine 7BFH (CIAcid Blue83, manufactured by Nippon Kayaku Co., Ltd.)
Blue100, manufactured by Hodogaya Chemical Industry Co., Ltd.), as a reactive dye, Prosyn Brilliant Yellow H-
5G (CIReactive Yellow2, manufactured by Nippon Kayaku Co., Ltd.), Diamira Brilliant Red GD (CI
Reactive Red63, manufactured by Mitsubishi Chemical Industries, Ltd.), Mikasion Green 2BS (CIReactive Green7, manufactured by Nippon Kayaku Co., Ltd.), Sumifix Navy Blue R (C.
I.Reactive Blue20, manufactured by Sumitomo Chemical Co., Ltd.), Direct First Yellow as a direct dye
GN (CIDirect Yellow85, manufactured by Nippon Kayaku Co., Ltd.), Sumilite Red 4B (CIDirect Red81, manufactured by Sumitomo Chemical Industries, Ltd.), Kayarasu Splat Blue BWL
(CIDirect Blue237, manufactured by Nippon Kayaku Co., Ltd.), Eisen Green GX (CIDirect Green8, manufactured by Sumitomo Chemical Industries, Ltd.), etc. One or more types can be applied.
In particular, those having the above-mentioned active groups in their structure are preferably used.

Further, as the metal compound used in the above, any compound having a colored resin film and a chelate-forming ability can be applied. It is desirable that the metal compound be dissolved or dispersed in a solvent or dispersant in an amount of 1 to 20% by weight, preferably 5 to 10% by weight. Examples of solvents or dispersants include water; alcohols such as methanol and ethanol; ketones such as acetone and methyl ethyl ketone; esters such as ethyl acetate and butyl acetate; aromatic hydrocarbons such as benzene and toluene; carbon tetrachloride; Chlorinated solvents such as trichlorethylene and chlorobenzene are used alone or in combination.

Next, the above metal compounds include, for example, zinc compounds such as zinc chloride and zinc carbonate (basic); aluminum compounds such as aluminum tartrate and aluminum acetate; chromic acetate, chromic chloride, chromic chloride, Chromium compounds such as dichromic sulfate and chromium formate; cobalt chloride, cobaltous ammonium sulfate, and cobaltous oxalate compounds;
Tin compounds such as tin acetate, stannic chloride, stannous chloride, stannous sulfate; ferric chloride, ferric nitrate, ferric oxalate, potassium iron oxalate, ferrous chloride, ferrous sulfate Iron compounds such as cuprous chloride, cupric chloride, copper oxalate,
Copper compounds such as copper formate, copper acetate, copper acetate (basic), cupric carbonate; nickel compounds such as nickel chloride, nickel formate, nickel acetate, nickel carbonate, nickel nitrate, nickel oxalate; barium acetate , barium compounds such as barium carbonate and barium chloride; sodium compounds such as sodium molybdate and sodium phosphomolybdate; and particularly preferred one selected from organometallic compounds such as metal alkoxides, metal carboxylates, and metal chelates. Alternatively, a mixture of two or more types is used.

As the organometallic compound, those which are active and are preferably used as ester catalysts, aldol catalysts, polymerization catalysts, resin crosslinking agents, adhesion improvers, high purity metal oxide raw materials, etc. are used. The specific types of metals constituting the organometallic compound are preferably vanadium, titanium, silicon, aluminum, chromium, iron, cobalt, copper, magnesium, zirconium, nickel, etc., and the groups that bond to metals include: Alkoxides include acyl groups corresponding to aliphatic alcohols and aromatic alcohols, chelates include ligands consisting of β-diketones such as acetylacetone and its derivatives, and metal carboxylates include aliphatic carboxylic acids and aromatic carboxylates. Acids, especially carboxy groups of fatty acid carboxylic acids, are preferably used. The organometallic compound of the present invention preferably includes one containing two or more of the above-mentioned bonding groups, such as one in which both an acyl group and a chelate-forming ligand are bonded to the metal.

Furthermore, specific examples of such organometallic compounds include the following: vanadium compounds such as n-propoxyvanadium, isopropoxyvanadium, n-butoxyvanadium, and vanadium n-butyrate; propoxyzirconium, n-butoxy Zirconium compounds such as zirconium, butoxyzirconium ethylacetoacetate; methoxytitanium, ethoxytitanium, n-propoxytitanium, isopropoxytitanium, n-butoxytitanium, n-
Titanium compounds such as butoxytitanium polymer, stearyl titanate, 2-ethylhexyl titanate, nonyl titanate, cetyl titanate, triethanolamine titanate, isopropylhexyl glycol titanate, tributyloleyl orthotitanate, titanium lactate, titanium octylene glycolate; methyl silicate, ethyl Silicon compounds such as silicates; aluminum ethyl acetoacetonate, n-butoxyaluminum, isopropoxyaluminum, 2-ethylhexoxyaluminum, 2-
Aluminum compounds such as ethylhexaoxyaluminum isopropyropoxide; aluminum acetylacetonate, vanadium acetylacetonate, n-butoxyzirconium acetylacetonate, titanium acetylacetonate, chromium ()acetylacetonate, iron ()acetylacetonate, cobalt Metal acetylacetonates such as () acetylacetonate, copper () acetylacetonate, magnesium acetylacetonate, manganese () acetylacetonate, nickel () acetylacetonate, nickel acetylacetonate.

The present invention is characterized in that the colored resin film undergoes a chelate reaction with a metal compound, thereby becoming dye resistant. This is because the metal compound modifies the surface of the colored resin film by forming a chelate ring with the resin and/or dye that forms the colored resin film, and the dye for the next coloring is physically adsorbed onto the surface. It is thought that this is due to some form of interference.

Hereinafter, the present invention will be explained in more detail with reference to Examples.

Example 1 After applying an aqueous solution consisting of ammonium casein monochromate on a transparent glass substrate and drying it, a mask having a striped pattern was aligned and contact exposure was carried out, and the solution was developed and dried to form a 15 μm film on a glass substrate. Stripes of the layer to be dyed with a width of 45 μm were formed at a pitch of 45 μm. Next, it was immersed in a red dye bath Kayanol Milling Red RS (CIAcid Red114, manufactured by Nippon Kayaku Co., Ltd.) at 70℃ for 2 minutes, washed with water, and dried.
It was immersed in a 10% ethanol solution of tetrabutyl titanate at 20°C for 5 seconds and then dried at 150°C for 30 minutes to obtain a red colored stripe.

Repeat the same operation and dye the green dye bath Brilliant India Blue 5G (CIAcid Blue103 manufactured by Hoechst) and Suminol Milling Yellow at 65℃.
MR (CIAcid Yellow42, manufactured by Sumitomo Chemical Co., Ltd.)
After immersing in a mixed solution of for 3 minutes, washing with water, and drying, 10
Processed for seconds and dried to obtain green colored stripes.
Next, in the same manner, after dyeing for 2 minutes in a blue dye bath Kayanol Cyanine 6B (CIAcid Blue83, manufactured by Nippon Kayaku Co., Ltd.) at 60°C, it was washed with water and dried to finally form stripes as shown in Figure 3K. Width 15μ, pitch 45
A μ color stripe filter was obtained.

According to this method, red colored stripes are surface-modified by chelation reaction by treatment with organometallic compound tetrabutyl titanate and become dye-resistant, and even when immersed in the next green dyeing bath, no color mixing occurs and the same is true. The green colored stripes also become dye resistant, and furthermore, no color mixing occurs during the next blue dyeing. The color stripe filter produced by this method had a smooth surface, an extremely thin overall film thickness of 2 μm, and high quality.

Example 2 An aqueous solution consisting of gelatin-ammonium dichromate was applied onto a transparent glass substrate, and stripes with a width of 25μ were formed at a pitch of 50μ, and then cyan dyed at 70°C with Sumifix Starkis Blue GS.
(manufactured by Sumitomo Chemical Industries, Ltd.) for 2 minutes, washed with water,
Next, an organic silicon compound (manufactured by Shin-Etsu Chemical Co., Ltd.)
KR216) 10% methanol-acetone mixed solution (20
℃) for 10 seconds, washed with water, and dried at 130℃ for 30 minutes to obtain cyan colored stripes.

Repeat the same operation to form a stripe that intersects the cyan colored stripe at an angle of 45°, and dye it in a yellow dye bath Suminol Milling Yellow 4G (CIAcid Yellow141, manufactured by Sumitomo Chemical Industries, Ltd.) at 70°C for 3 minutes. Yellow colored stripes were formed by dipping, washing with water, and drying to produce a color stripe filter.

[Brief explanation of the drawing]

FIG. 1 is a schematic sectional view showing an example of a conventional color stripe filter, FIG. 2 is a schematic sectional view showing an example of a color stripe filter obtained by the method of the present invention, and FIGS. FIG. 3 is a cross-sectional view showing an example of the method in order of steps. DESCRIPTION OF SYMBOLS 1... Transparent substrate, 2... Intermediate protective film, 3... Colored stripe layer, 4... Colored stripe layer, 5...
...Photosensitive resin film, 6...Striped colored resin film, 7...First color colored striped resin film, 8
...Surface-modified colored striped resin film of the first color, 9... Photosensitive resin film, 10... Striped dyed resin film, 11... Colored striped resin film of the second color, 12... Surface Modified second colored striped resin film, 13...photosensitive resin film,
14... Striped colored resin film, 15... Colored striped resin film of third color.

Claims (1)

[Claims] 1. After forming a striped resin film to be dyed on a substrate, the striped resin film to be dyed is colored with a dye having predetermined spectral characteristics to form colored stripes of a first color, and then by the same method, In a method for manufacturing a color stripe filter in which colored stripes of a plurality of colors are sequentially formed adjacent to each other such that a colored stripe of a second color is formed adjacent to a colored stripe of a first color, a striped colored resin film is formed in a predetermined manner. After dyeing with a dye that has spectral characteristics, and before forming the next colored stripe, the colored resin film is treated with a metal compound that has the ability to form a chelate compound with the film to modify its surface and improve its stain resistance. A method for manufacturing a color stripe filter characterized by: