JPS594820B2 - Manufacturing method of color separation filter - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for manufacturing a color separation filter section for use in a Galaju image pickup tube, in which an optical Filleau element and a transparent conductive film are provided on a transparent substrate 15. A method for manufacturing a color separation filter part used in a glass picture tube characterized by forming a transparent conductive film directly on the surface of an optical filter (stripe filter) element using a highly heat-resistant coloring agent. It is.

Conventionally, various color separation filters have been developed and proposed for use in single-tube type or two-tube type Gala H image tubes. It is known to form an organic dyed filter by forming an organic polymer substance film and dyeing the organic polymer substance film in a striped, lattice, monochromatic or multicolored manner with a suitable dye.

These color separation filters function as a 30-color image tube by combining a transparent conductor and a photoconductor on the dyed surface of the above-mentioned 30 organic dyed filter. It is.

However, conventional methods for combining a transparent conductor and a photoconductor on the dyed surface of an organic dyed filter generally do not involve directly forming the transparent conductor and photoconductor on the dyed surface of the organic dyed filter. Instead, a transparent conductive film and a photoelectric film are formed on separate substrates, and these are brought into contact with the dyed surface so that the surface of the transparent conductive film overlaps with the dyed surface, and the two are adhesively bonded to each other via an adhesive or the like.

To explain in more detail about the color separation filter used in the above color image pickup tube, as shown in FIG. The basic structure is to form a film layer 2 dyed in the order of blue B, further provide a transparent conductive film 3 and a photoconductive film 4, and fix these to a tube body 5 with a target 6.

In such a structure, there is no problem in principle in providing the transparent conductive film directly on the filter layer, but since the filter layer is the chromosome of the organic polymer material film, it is extremely difficult to directly attach the transparent conductive film. Have difficulty. That is,
The old conductive film is generally formed using methods such as vapor deposition, sputtering, or hot spraying of tin oxide SnO2 or indium oxide 11203, but the manufacturing process requires temperatures of about 200 to 500°C. It requires temperature conditions. However, such temperature conditions exceed the heat resistance limit of the filter layer, which is made of an organic polymer film dyed in the order of red, green, and blue, and it is impossible to directly form a transparent conductive film on one layer of pool water. It is possible.

For example, if the organic polymer material film is a gelatin layer or the like, if a transparent conductive layer is directly attached, the film may crack and become a crack-like surface or a mat-like surface, resulting in a significant decrease in transparency. Many of them are undesirable.

For this reason, as shown in FIG. 2, in the case of a color separation filter used in a glass/image tube, a transparent conductive film 3 is deposited on a transparent plate 7 such as a glass plate as a support by a vapor deposition method or the like. It is common practice to form a transparent conductor, and to adhere the transparent conductor to the filter layer 2 with an adhesive 8 or the like.

According to such a configuration, it is possible to eliminate the effects on the filter layer caused by heat and the like when forming the transparent conductive film.

However, regarding the color separation filter used in the glass/image pickup tube with the above configuration, the thinner the Q transparent plate, such as the glass plate, is, the better the image pickup tube characteristics will be in order to receive color separation information with good resolution. , which is usually required to be on the order of several microns to 20 microns.However, when manufacturing transparent conductors using such thin transparent plates, major problems such as breakage and other problems occur, which is undesirable. It is something.

In addition to the above, the optically dyed filter is formed by the following method.

That is, first, a solution of a water-soluble organic polymer material such as a gelatin solution or a polyvinyl alcohol solution is applied to a transparent glass substrate and dried to form an organic polymer material film.

Next, a hydrophobic photoresist such as Kodatsu Photoresist or KPR (manufactured by Kodatsu Co., Ltd.) is coated on the organic polymer material film, dried to impart photosensitivity, and then a suitable striped or grid pattern is applied. A photographic original plate is placed in close contact with the original and printed using near-ultraviolet light, etc., and the phenomenon is developed according to a conventional method.

As a result, the exposed portions of the photoresist remain, and the non-exposed portions are dissolved and removed by the developer.

Next, the glass substrate is placed in a dyeing solution containing an organic dye and a dyeing operation is performed to dye only the exposed organic polymer film on the glass substrate where the photoresist has been removed. The remaining portion of the organic polymer material film is blocked by the resist and is dyed, resulting in the formation of a dyed image on the photographic original plate.

After dyeing as described above, it is thoroughly washed with water, dried, and then the remaining photoresist is dissolved and removed with a solvent or the like to obtain an optically dyed filter.

Furthermore, if necessary, a photoresist plate is applied in the same manner as above on the organic polymer material film after staining in Figure 1 shown in ±.
It can be dyed with a dye different from the dye shown in the figure to make a multicolored fillo. Generally, the colors of a filter are red, green, and blue dyed into a single filter.

In order to improve the above-mentioned problems with color separation filters used in glass image pickup tubes, the inventors of the present invention have conducted various researches and found that a transparent conductor can be easily and easily formed directly on one layer of the filter. The present invention was completed by discovering a method that enables this.

That is, by using the manufacturing method of the color separation filter section of a glass picture tube, which is made by providing an optical filter element and a transparent conductive film on a transparent substrate, a heat-resistant coloring agent is vacuum-deposited or sputtered onto a transparent substrate. Then, a resist pannone is formed on the colored thin film layer by a photolithography method, and then areas of the colored thin film layer not covered with the resist pannone are subjected to plasma etching or reverse sputtering. Dry etching with a ring to remove the colored thin film layer in the colored thin film layer area and simultaneously remove the above resist pane, or remove the colored thin film layer area not covered with the resist pattern with a solvent that dissolves the colorant. The resist pattern is further removed using a solvent that dissolves and removes the resist of the resist pattern to form an optical pool element, and if necessary, heat-resistant,
V) Coat a resin with high chemical resistance to a thickness of about 5,000 to 20,000 A using a spin coating method or a coating method in a vacuum device, dry it, fully cure it to form an intermediate protective film, and then use the same method as above. By repeating the process of forming an optical pool element with
Next, an intermediate protective film is formed on the surface of the optical filter element by a method similar to that described above, and then a transparent conductive film is formed on the intermediate protective film by a vacuum evaporation method. It is the law. The above-mentioned present invention will be explained in more detail below.

First, in connection with the above-mentioned present invention, a method of forming an optical pool element using a highly heat-resistant colorant on a transparent substrate substrate will be described. Examples of such a method include the following methods. First, in the VC of the present invention, it is necessary to use a material that is a water-insoluble colorant, has heat resistance that can withstand temperatures of about 200° C. or higher, and can be evaporated or sublimed by appropriate means. Materials compatible with this can be selected from pigments and water-insoluble dyes (oil-soluble or vat dyes, etc.). Colorants that meet the above conditions are:
Generally, a thin film is deposited on a transparent substrate (e.g. glass) in a vacuum apparatus. For this purpose, vacuum evaporation or sputtering is used; however, the former is generally better.

Further, in order to strengthen the adhesion between the colored thin film layer and the transparent substrate such as glass, the surface of the transparent substrate such as glass may be treated with an adhesive strengthening agent in advance. The thickness of the colored thin film layer is determined depending on the desired spectral characteristics, but is usually 2,000 to 10,000
It is about 000A. This thickness is much smaller than in the case of organic polymer layer dyeing.

The colored thin film layer is then coated with a suitable photoresist (e.g. KPR).
．． After applying a photosensitive solution (KTFR, polyvinyl alcohol monoammonium chromate photosensitive solution, etc.) and drying, the image of the photographic original plate having a desired pattern is transferred by printing, developed and dried in a conventional manner to form a resist pannon.

This plate-making plate is installed in a dry etching apparatus such as a plasma etching apparatus or a sputter etching apparatus using a reverse sputtering method to perform dry etching. Since the colored thin film layer and the resist layer are etched at the same time, the resist film thickness must be adjusted so that the colored thin film layer is completely etched before the resist etching is completed. According to the present invention, as described above, an optical pool element can be formed on a transparent substrate using a colorant having high heat resistance.

If the colored thin film layer contains certain chemicals (e.g. alcohol 6
benzene, etc.), care must be taken to determine whether the solvent used in coating the photoresist dissolves the colored layer, and to use a photoresist that is combined with a solvent that does not dissolve the colored layer. The optical pool Shioichi element can also be formed by a resist dissolution/removal method or the like. In this case as well, the above-mentioned dry etching may be performed after forming the resist image, or the non-resist portions may be removed by dissolving with a suitable soluble solvent. In the present invention, as shown in FIG. 3, a monochromatic optical filter element 22 made of, for example, red R, green G1, or blue B is formed on the transparent substrate 21 by the above-described operation. In addition, according to the present invention, as an optical film element formed on a transparent substrate, for example, Red R, Green G. There are various methods for forming a multicolored optical filter element consisting of hexagram, blue B, etc., but for example, although not shown, after forming a monochromatic optical filter element on a transparent substrate as described above, , an intermediate protective film to be described later is formed on the surface of the optical filter element, and then a coloring agent of a different color from the coloring agent constituting the first optical filter element is applied on the intermediate protective film in the same manner as described above. An optical filter element is formed using the same method as described above, an intermediate protective film is formed on the surface of the optical filter element again, and by repeating such operations, an optical filter element is formed on the transparent substrate. A polychromatic optical film element can be formed. Alternatively, in the VC of the present invention, when forming an optical filter element on the transparent substrate described above, multicolor optical It is possible to form a target pool Shioichi. Next, in accordance with the present invention, a method of providing a colorless and transparent intermediate protective film made of a resin with high heat resistance and chemical resistance on the optical filter element surface will be explained. , it must be able to withstand various processing conditions for forming a transparent conductive film in the next step.

That is, although the intermediate protective film itself must have heat resistance as described above, it is desirable to further protect the surface of the optical filter element and at the same time improve its heat resistance.

Of course, it must be colorless and transparent, and the pretreatment for forming the transparent conductive film, such as washing for surface cleaning, must not affect the optical filter element itself or the internal optical filter element. That is, it is desirable to have sufficient resistance to aqueous solutions such as alkaline cleaning agents, acid cleaning agents, neutral cleaning agents, and general-purpose aliphatic or aromatic solvents during immersion and ultrasonic cleaning. An intermediate protective film having such characteristics can be applied to an optical filter element by coating it to a thickness of about 5,000 to 20,000 to A by a spin coating method or a coating method in a vacuum device, drying it, and curing it to form a sufficient film. An intermediate protective layer can be formed on the surface.

Next, in accordance with the present invention, a method for forming a transparent conductive film on the above-mentioned intermediate protective film will be explained. After thoroughly cleaning the surface of the intermediate protective film, a transparent conductive film having a thickness of several 100 Ω/Criil to several KΩ/.d is laminated. Transparent conductive films are generally made of SnO2, In2O3, T
Although iO2 and the like are used, In2O3 is often used due to temperature conditions and the like.

As is well known, this is usually deposited on the intermediate protective film by vacuum deposition. In some cases, a finished product is a product on which the transparent conductive film has been formed, but in other cases, it is necessary to pattern the transparent conductive film to correspond to the patterned optical film element. Conventional photoetching methods are used for this patterning. That is, a photoresist is coated on a transparent conductive film, a photographic original plate with a desired pattern is aligned with the pattern of an optical filter element using a mask alignment device, and the transparent conductive film is etched in the areas where the photoresist has been removed. Remove.

Finally, the remaining photoresist is removed to create a finished product.

In the case of a color separation film having a plurality of colored balloons, after forming the intermediate protective film layer, another coloring material is deposited again to form a second intermediate protective film after panonization. .

This operation may be repeated any number of times. A transparent conductive film is formed on the final intermediate protective film. The product obtained by the force method of the present invention has a thin intermediate protective film, so that it can be almost ignored optically, resulting in a product with good properties.

The color separation filter section used in the glass image pickup tube obtained by the method of the present invention as described above is as shown in FIG.
An optical filter element 22 made of a colorant with high heat resistance is formed on a transparent substrate 21, and then a colorless and transparent intermediate protective film 23 made of a resin with high heat resistance and chemical resistance is provided on the surface of the optical filter element 22. Then, a transparent conductive film 24 is formed on the intermediate protective film 23.

Examples of various materials used in the method of the present invention described above are shown below, but the present invention is not limited thereto. First, as the colorant constituting the colored thin film layer which becomes the optical filter element of the present invention, the following can be used.

(4) Dispersed dye Kayase Tobunoshi-318 Kayase Noise Blue J Mo V6, etc. (5) Oil-soluble dye Diamond Resin Red H Diamond Resin Brown A Diamond Resin Blue N (002), etc., (6) Indance Len-based dye Mikesuretsu Yellow IGCN (CJ.NO.673OO)
Mikeslen Yellow (C.I.NO.6842)
O) Mikethren Orange R (CJLNO.733
35) Mikethlen Scarlet G Mikethlen Brilliant Pink R (C.I.NO.7336O) Mikethlen Brilliant Biot RR (C.I.NO.6OOlO) Mikethlen Blue 3G (C.I.NO.6984O) Competition ( 7) Phthalocyanine pigment-free metal phthalocyanine, copper phthalocyanine, lead phthalocyanine, zinc phthalocyanine, chrome phthalocyanine, iron phthalocyanine, other gold phthalocyanine, etc. Next, in addition to the present invention, an intermediate protective film can be used. As the forming material, for example, resins such as polyurethane resin, polycarbonate resin, silicone resin, glass resin, polyparaxylene resin, and polyfluoroethylene propylene, which are rich in heat resistance, chemical resistance, etc., can be used.

Next, in addition to the above-mentioned present invention, if it is necessary to increase the adhesion between a transparent substrate such as a glass substrate and a colored thin film layer, polyurethane resin, polycarbonate resin, cinnamate ester resin, etc. It is effective to thinly apply a photosensitive resin such as silane coupling agent, etc. and then form a colored thin film layer.

This effect can be achieved by selecting an appropriate adhesive layer to form an intermediate adhesion-enhancing film even in combinations where the adhesion between the intermediate protective film and the colored thin film layer is inappropriate for the second or higher layer. can be increased. As is clear from the above explanation, the method of the present invention enables the formation of a transparent conductive film directly on the surface of an optical filter element through an intermediate protective film that protects it, and therefore has excellent workability and is extremely simple. It is something that can be done.

Further, according to the present invention, since the intermediate protective film can be made extremely thin, its thickness can be almost ignored, and color separation information can be received with good resolution as a filter.

Therefore, the VC of the present invention, in which a transparent conductive film is provided on the surface of an optical filter element by the method of the present invention, can be used in color image pickup tubes, etc. by providing a yellow conductive layer on the transparent conductive film. It is something that can be done. Next, the present invention will be described in more detail with reference to Examples. [Example 1] A glass plate with a cleaned surface was installed in the evaporation machine, and a Sumirra Fast Yellow IG (C.I.NO.
．． 1168O, manufactured by Dainippon Ink & Chemicals KK), vacuum suction was applied, and the degree of vacuum was set to 10-3 to 10-4 T0rr, and the coloring material was heated to evaporate and adhered to the glass plate to a thickness of ~3000 to 4000A.

The transmittance of the yellow glass plate obtained was 8 on a scale of 530 mμ.
It was 5% to 90%. Next, yellow thin film layered soil VCKTF
R (Kodatsushin ~ Film Resist) 5000~6
After spin coating to a thickness of 000A, drying and baking according to the processing method, striped pannon was transferred from the photographic original plate by baking, developed and dried.

This plate-making plate is processed into an ashing device (Trape) using plasma.
(manufactured by IO Corporation) and plasma etching was performed.

The gas used is argon, and etching is completed in about 15 minutes.
At that point there was some residual layer of KTFR on the yellow layer. Next, a polyurethane resin solution (viscosity of 10 to 15 centipoise) is applied onto the etched surface by spin coating to give a 0.5 to 2 centipoise viscosity.
It was coated to a thickness of 0μ and cured at 100-150℃ for 2 hours or more, then left to cool to form a yellow monochrome filter with an intermediate thin film layer.Then it was placed in the evaporation equipment again, and the evaporation source boat was filled with oxidation. Indium (In2O3) is added, the temperature of the yellow monochrome film is set to 200-230℃, and the degree of vacuum is approximately 1.
0-("Indium oxide was deposited at 5T0rr.

The electrical resistance of the indium oxide transparent conductive layer after vapor deposition is generally V
It was heated at C7OO~3500Ω/,d. In this example, it was possible to obtain a product in which a transparent conductive layer was integrated on a yellow striped filter made of glass plate clay.

[Example 2] In the same manner as in Example 1, a yellow thin film layer was formed on a glass plate by vacuum evaporation, and then a striped plate was made and plasma etched.

Then, a glass resin (Howa Denki KI5) was spin-coated to a film thickness of about 1 μm.

Curing of the glass resin required 12 to 24 hours at 100 to 150°C. Then, it was placed in the vapor deposition apparatus again and 10-3 to 10-
It was deposited and laminated at 4T0rr. Next, a diazo type photosensitive resin based on polyvinyl alcohol was applied and dried, and a cyan stripe photographic original plate was printed and transferred. This printing was performed so that the yellow and cyan stripes intersected. After baking, the film was developed with water according to a conventional method, dried, and then plasma etched in the same manner as the yellow stripes to produce cyan stripes. Next, in the same manner as the first intermediate thin film layer, a glass resin was applied and cured to produce a color separation pool 11 in the form of an intersection of yellow and cyan stripes (the intersection is green).

Furthermore, as in Example 1, this was placed in a vapor deposition apparatus, and indium oxide (In2O3) containing 5% tin oxide (SnO3) was deposited.
) was vapor-deposited to form a transparent conductive layer with an electrical resistance of 100 to 500 Ω/(71).The substrate temperature during vapor deposition was approximately 250°C.By the above method, yellow stripes and first Intermediate thin film layer, cyan stripe (crossing), second
A color separation filter section having a structure in which an intermediate thin film layer and a transparent conductive layer were laminated was obtained.

[Example 3] Instead of the transparent glass plate of Example 1, a cyan stripe filter in which a cyan multilayer interference film was already processed into stripes on the glass plate was used as a starting material, and cyan was coated on top of it by the method of Example 1. Yellow stripes were formed so as to intersect with the stripes, and an intermediate thin film layer and a transparent conductive layer were further laminated.

This was a part of a color separation pool consisting of a glass plate, cyan multilayer interference film stripes, crossed yellow thin film stripes, an intermediate thin film layer, and a transparent conductive layer, and had the same effect as that obtained in Example 2. . In addition, the one in which one intermediate thin film layer is introduced between the cyan multilayer interference film stripe and the yellow thin film has the effect of filling up the irregularities of approximately 1μ between the glass plate surface and the stripe surface that occur during the cyan multilayer interference film stripe processing. A part of a high quality color separation filter was obtained. [Example 4] In the same manner as in the previous example, indanthrene yellow-GCN was evaporated onto a glass plate, and after photoresist plate making, yellow stripes were created by plasma etching.Then, the evaporation was performed again, and a red thin film layer was directly formed on the yellow stripes. (Smirror Forest 4081 Dainippon Ink) was vapor-deposited, and then a red stripe plate was made so that it was juxtaposed to the yellow stripe.For this plate making, water-soluble polyvinyl alcohol monobichromate ammonium research solution was applied. Using.

After the plate making was completed, the red thin film in the areas where no resist was dried was dissolved and removed with xylene to juxtapose the yellow and red colors, while the adjacent areas were left as colorless stripes. Next, as in the previous example, a glass resin was spin-coated and cured, and then an indium oxide transparent conductive layer was deposited. This example is a color separation filter section consisting of yellow stripes, red stripes, and colorless stripes arranged side by side on a glass plate, and further laminated with an intermediate thin film layer and a transparent conductive layer.

[Example 5] Color separation filter Q with transparent conductive layer obtained in Example 4
This image, which was image-engraved using KTFR on a transparent conductive layer, is a pattern for separately extracting the color separation signals obtained from each stripe of yellow, red, and colorless, so the position of the image was precisely aligned with each stripe. It is something.

After completing KTFR plate making, immerse it in a solution of 1 part concentrated hydrochloric acid and 2 to 5 parts water to etch away the indium oxide and transparent conductive layer in the non-resist area, wash with water and dry, then remove the remaining resist using KTFR's special stripping solution. did.

As described above, a color separation filter part was obtained by etching the transparent conductive layer part of the product obtained in Example 4 into a desired image.

[Brief explanation of the drawing]

Figures 1 and 2 are enlarged sectional views of main parts of a color separation filter used in a conventional image tube, and Figures 3 and 4 are
The figure is an enlarged sectional view showing the configuration of each step in the method of the present invention. 21... Transparent substrate, 22... Optical filter element, 23... Intermediate protective film, 24...
-Transparent conductive film.

Claims (1)

[Claims] 1. In a method for manufacturing a color separation filter section of a color image pickup tube in which an optical filter element and a transparent conductive film are provided on a transparent substrate, a colored thin film layer is formed by vacuum evaporation or sputtering of a heat-resistant colorant on the transparent substrate. Then, a resist pattern is formed on the colored thin film layer by a photolithographic method, and then the colored thin film layer area not covered with the resist pattern is dry etched by plasma etching or reverse sputtering to remove the colored thin film layer. Either the colored thin film layer in the area is removed and the above resist pattern is removed at the same time, or the colored thin film layer area not covered with the resist pattern is dissolved and removed using a solvent that dissolves the colorant, and then the resist pattern is removed from the resist pattern. forming an optical filter element by removing the resist with a solvent that dissolves and removes the resist;
Furthermore, a resin with high heat resistance and chemical resistance is applied to the surface of the filter element using a spin coating method or an in-vacuum coating method.
After coating and drying to a thickness of about 0 to 20,000 Å and sufficiently curing to form an intermediate protective film, a polychromatic optical filter element is formed by repeating the process of forming an optical filter element in the same manner as above. and then forming an intermediate protective film on the optical filter element surface in the same manner as above,
A method for manufacturing a color separation filter section, which comprises: next forming a transparent conductive film on the intermediate protective film by vacuum evaporation.