JPS5944601B2 - Polychromatic optical filter and its manufacturing method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a polychromatic optical filter and a method of manufacturing the same, and more particularly to a polychromatic optical filter used in a color image pickup tube and a method of manufacturing the same.

Single-tube or dual-tube color image pickup tubes use polychromatic optical filters in the form of multicolor stripes or multicolor mosaics.

Usually, a polychromatic optical filter is one in which the three colors red, green, and blue, or the three colors cyan, magenta, and yellow are regularly arranged in a stripe or mosaic pattern.
The color composition is not necessarily limited to these three colors, and may consist of two colors, four colors, or more. Conventionally known polychromatic optical filters include, for example, Japanese Patent Publication No. 40-8590 and Japanese Patent Application Laid-Open No. 52-344.
Those using a dichroic film as described in Japanese Patent Application No. 47-37237, etc.
JP-A-48-63739, JP-A-48-6685
There are products in which a polymeric material layer is dyed with a dye, as described in Japanese Patent Publication No. 3 and Japanese Patent Publication No. 53-248, etc., but the manufacturing process for these involves coating each color with a photoresist, Furthermore, pattern formation processes such as image exposure, development, coloring or decolorization, and resist removal, which involve precise placement of masks, are required, and these steps are repeated many times (usually 3 times).
It was extremely complicated and troublesome because it had to be repeated (more than once).

Furthermore, various additional steps are actually required to obtain an excellent polychromatic optical filter. For example, when a multicolor optical filter is manufactured by repeating the steps of coating a photoresist such as dichromate gelatin, image exposure, development to form a relief pattern, and coloring many times, It is necessary to take measures to prevent the colored pattern from being colored in a color different from the previous color in the subsequent coloring process and causing color mixing. The drawback is that a non-staining protective layer must be applied to the screen between each coloring process, which ultimately complicates the manufacturing process and makes the resulting multicolor optical filter extremely expensive. It was hot. Furthermore, a pattern with high optical density called optical black must be formed on the polychromatic optical filter for the image pickup tube in order to detect the absolute zero value of the optical input signal. Chromium thin film patterns formed by one method have been used.

The reason is optical black (hereinafter referred to as 0.R).
This is because an optical density of 4.0 or more is required, and an optical density of 4.0 or more can be easily obtained by using a chromium vapor deposited film or a sputtered film.

A specific example of the manufacturing process of a multicolor optical filter 1 according to the conventional method will be described below with reference to the drawings.

FIG. 1 shows a specific example of the manufacturing process of a polychromatic optical filter having 0B by a conventional method, and FIGS. B. The process to form
1e to 1h are 0. B. The steps of forming one color of a multicolor optical filter on a support having a structure formed thereon are shown. In FIG. 1a, a thin chromium film 11 is deposited on a glass support 10 by vacuum evaporation or sputtering to achieve an optical density of 4.
Indicates that the value is set to 0 or more.

FIG. 1b shows a state in which a photoresist film 12 is further applied thereon. In FIG. 1c, after exposing the photoresist film to a 0B pattern, the photoresist film is developed to form openings 14 and non-openings 13 that function as etch resists.
This shows the state in which it has been formed. FIG. 1b J shows the state in which the chromium film exposed in the opening 14 is removed, for example, by chemical etching, and the glass support surface in that area is exposed (15). FIG. 1e shows the photoresist removed and 0. B. 1
6 is formed. In this way, 0.000. B. After 16 is formed, a multicolor optical filter 1 is formed.This method will be explained using an example in which this method is carried out by dyeing dichromate gelatin.

Figure q and Figure 1f show a state in which a photosensitive/hydrophilic polymer layer 17 such as dichromate gelatin is provided over the entire surface.

FIG. 1g shows the layer 17 exposed to light in a stripe pattern and then developed to form a stripe relief pattern 18 of hydrophilic polymer. FIG. 1h shows a state in which the relief thus obtained is dyed with a dye to form a striped filter 19. In this way, a first color stripe filter having 0B is obtained. After the first color stripe filter is formed in this way,
Efforts are made to prevent color mixing by applying a non-dying protective layer, and the steps shown in FIGS. 1f to 1h are repeated to form a multicolor optical filter. Therefore, in manufacturing conventional multicolor optical filters for image pickup tubes, in addition to the above-mentioned complex coloring pattern, the ring graphing method is used to create a chromium thin film with a 0.0-. B. This method has the disadvantage that it requires a considerable amount of time to form a film, making it even more expensive.

The present inventors first used a photographic material having a known black-and-white fine-grain silver halide emulsion layer, and by combining this with an external color development method, the manufacturing process was much easier than that of conventional multicolor optical filters. We have found a method for obtaining an easy and inexpensive polychromatic optical filter and proposed this method.

(Japanese Patent Application No. 78313/1983) The present invention further develops this method to obtain 0. B. An object of the present invention is to provide an optical filter that can be obtained very easily and is also inexpensive, and a method for manufacturing the same. That is, the object of the present invention is to provide (1) a photographic material having at least one black and white silver halide emulsion layer provided on a support, in which dye patterns of at least two colors are formed in the emulsion layer; A photographic material comprising a multicolor optical filter characterized in that an optical black composed of silver or silver and a dye is formed, and (2) at least one black and white silver halide emulsion layer provided on a support. The emulsion layer is subjected to pattern exposure for the first color, and then a pattern containing the first color dye and silver is formed by outside mold color development, and then the silver in the pattern portion is eluted by bleaching or a silver compound is formed. and then, if necessary, a second color pattern exposure to form a pattern containing the second color dye and silver, and the silver in the pattern is eluted by bleaching or converted to a silver compound; Furthermore, if necessary, a pattern containing a third or subsequent color dye and silver is formed.By repeating the same process, a pattern of at least two colors is formed.Finally, pattern exposure corresponding to optical black is performed, and black and white development is performed. Alternatively, this can be achieved by a method for manufacturing a multicolor optical filter in which external color development is performed and then fixed to form an optical black made of silver or silver and a dye.

First, an example of a method for manufacturing the polychromatic optical filter of the present invention will be briefly described with reference to FIG.

FIG. 2a shows a photographic material used in the present invention, in which a black and white silver halide emulsion layer 21 is provided on a support 20. After the emulsion layer of this photographic material is exposed in a striped pattern as shown in FIG. 2b, a first color outer color development and silver bleaching are performed to form a first color stripe filter 22. Ru. Further, similar processing is performed for the second and subsequent colors to form a multicolor stripe filter. Reference numeral 23 indicates an unexposed emulsion layer in which silver halide remains.

Next, the unexposed area 23 of this photographic material is subjected to pattern exposure of 0B as shown in FIG. A filter is formed. As described above, according to the present invention, 0. B. It becomes possible to obtain a polychromatic optical filter having the following properties. Hereinafter, the method of the present invention will be explained in more detail with reference to FIG.

In the photographic material used in the present invention, as shown in FIG. 2a, an undercoat layer is optionally provided on a support 20, and a fine grain black and white emulsion layer 21 is provided thereon. When the support 20 itself serves as a support for an optical filter, it needs to be transparent, but a layer of color filter is formed on the support and this is layered on another transparent support. In the case of transferring onto a temporary support, the support is not only transparent but also may be translucent or opaque. The support may also be in the form of a plate, a sheet, or a film. Examples of materials for the support include polyethylene terephthalate, polystyrene, polycarbonate,
Plastics such as cellulose acetate, glass, quartz, sapphire, etc. are used as supports. Further, the support itself may have other uses, such as a face plate for an image pickup tube, and a layer plate on which a large number of solid-state image pickup devices are formed. The undercoat layer optionally used in the present invention is a layer of a substance that exhibits strong adhesion to both the support 20 and the silver halide emulsion layer 21.

Examples of substances used in the undercoat layer include gelatin, albumin, casein, cellulose derivatives, starch derivatives, sodium alginate, polyvinyl alcohol, polyvinylpyrrolidone, polyacrylic acid copolymers, polyacrylamide, and the like. The thickness of the undercoat layer is preferably as small as possible, 0.01 to 1 μm, preferably 0.05 μm.
It is in the range of ~0.5 μm. As the silver halide emulsion coated directly onto the support or via an undercoat layer, a known silver halide emulsion obtained by dispersing silver halide in a water-soluble binder is used. In this case, fine-grain emulsions are particularly preferred, such as so-called Lippmann emulsions in which the average grain size of silver halide is 0.1 μm or less. The weight ratio of silver halide to water-soluble binder ranges from about 1:6 to about 8:1. Examples of the silver halide include silver chloride, silver bromide, silver iodide, silver chlorobromide, silver iodobromide, silver chloroiodide, silver chloroiodobromide, and the like. Examples of water-soluble binders include gelatin, albumin, casein, cellulose derivatives, agar, sodium alginate, sugar derivatives, polyvinyl alcohol, polyvinylpyrrolidone, polyacrylamide, and others. Compatible mixtures of two or more of these binders may be used if desired. The thickness of the silver halide emulsion layer after drying is about 0.8 to about 10 μm
A range of is preferred. If necessary, a back layer for antihalation may be provided on the back side of the support of the photographic material thus formed. This photographic material is subjected to image exposure through a photomask, for example, into a pattern corresponding to the first color of a multicolor optical filter, such as a cyan stripe or mosaic pattern.

Any known photomask can be used, but for example, chromium is provided as a light-opaque part on a glass plate, and an image-shaped transparent pattern corresponding to the first color pattern is formed. A formed chrome mask is used. The light source used in this exposure may be any light source that emits light at a wavelength to which the silver halide emulsion layer is sensitive; for example, a light source that emits white light is used. Here, this exposure method may be a so-called contact exposure method in which a photomask is overlaid on the emulsion layer and irradiated with uniform light, but it may also be a projection exposure method in which the image is exposed through a lens system. Good too. The exposed photographic material is then subjected to a first outer mold color development.

For example, when such a photographic material is developed with an external color developing solution containing a cyan coupler, a pattern consisting of cyan dye and silver particles is formed in the exposed areas. After the first development is completed, the photographic material is bleached of the silver particles of the pattern. To bleach the silver particles, use an aqueous solution of an alkali metal dichromate or ammonium salt and sulfuric acid, or an aqueous solution of a ferrician compound and potassium bromide, in what is known in the photographic industry as a reducing solution or a bleaching solution. In particular, a latent image destroying liquid is used that satisfies the conditions of destroying the latent image, not dissolving the silver halide in the unexposed area, and not destroying the dye. As a result, the latent image of the pattern of the first color is destroyed by, for example, silver particles and undeveloped silver nuclei generated by color development being dissolved and removed, or these silvers are re-halogenated, and the latent image of the pattern of the first color is destroyed. Since silver, which serves as a development nucleus, is no longer present in the pattern, the dye produced in the second and third colors in the subsequent process will not be present in the pattern of the first color, unless the pattern is subjected to imagewise exposure again. These dyes are not produced. Therefore, color mixture does not occur in the pattern of the first color. When a second color or a pattern of two or more colors is to be formed, the same steps are repeated after the second and subsequent colors are developed, so that the resulting pattern has no color mixture. In the present invention, for example, when creating a so-called crossed multicolor optical filter in which cyan and yellow stripe patterns are crossed with each other to form cyan, yellow, green, and transparent patterns, the dye pattern of the first color is In the bleaching step performed after forming the pattern, it is desirable to use a bleaching solution that re-halogenates the silver particles contained in the pattern.

Next, a pattern corresponding to the second color, for example, a magenta color pattern, is imagewise exposed using a second photomask in the same manner. This image-exposed area may be an unexposed area next to the cyan pattern 22 in FIG. 2b,
It may also be a portion including a cyan pattern 22 like the above-mentioned crossed-type multicolor optical filter 1. After exposure, the photographic material is then subjected to a second outer mold color development. For example, when such a photographic material is developed with an external color developing solution containing a magenta coupler, a pattern 22 containing the cyan dye already formed and a pattern consisting of the magenta dye and silver particles are formed. After the second development is completed, the photographic material is bleached of the silver particles in the same manner as described above. Then, in the same manner, a pattern corresponding to a third color, for example, a single yellow pattern, is imagewise exposed and developed with a third outer mold color developer, for example, an outer mold color developer containing a yellow coupler, to produce a single yellow pattern. A pattern consisting of dye and silver particles is formed,
Furthermore, the silver particles are bleached in the same manner as above.

The external color developer used in the present invention is a compound whose oxidation product reacts with a color former (color coupler) to form a color product, that is, a developing agent such as N,N-diethyl-
p-phenylenediamine sulfate, N,N-diethyl-3
It is an alkaline aqueous solution of p-phenylenediamines such as -methyl-p-phenylenediamine hydrochloride (PH 8 or higher, preferably PH 9 to 12), and contains couplers of each color described below in this aqueous solution.

This aqueous solution usually contains salts such as sodium sulfite,
PH adjusting agents and buffering agents such as sodium hydroxide, sodium carbonate, and sodium phosphate, and ordinary antifoggants such as alkali halides such as potassium bromide are added. The most preferred embodiment of the present invention is to add the above-mentioned development inhibitor to the color developing solution. Examples of couplers contained in each color developer include U.S. Pat.
Yellow couplers described in Japanese Patent Publication No. 510,306, No. 3,619,189, Japanese Patent Publication No. 40-33775, Japanese Patent Publication No. 44-3664, etc., German Patent Publication (0LS) No. 2
,016,587, U.S. Patent No. 3,152,896, U.S. Pat.
Magenta coupler described in U.S. Patent No. 3,00, etc.
Examples include cyan couplers described in British Patent No. 2,836, British Patent No. 3,542,552, and British Patent No. 1,062,190.

Although the above has described known couplers for developing cyan, magenta, and yellow colors, it is of course possible to use color developing solutions using couplers of other colors from the perspective of the purpose of the present invention. , and the color development may be carried out in any order.

The processing solution that precedes the color development process is usually a pre-hardening process, for example an aqueous solution containing aldehydes that have the effect of reacting with and hardening gelatin, which is a constituent factor in photographic emulsions. It will be done.

In this way, the pattern containing cyan dye, the pattern containing magenta dye, and the pattern containing yellow dye are regularly arranged to form a multicolor pattern, and then the second c.
0 as shown in the figure. B. is formed.

In the present invention, 0. B. The unexposed area 23 (shown in FIG. 2b) of the photographic material on which the multicolor pattern has been formed is exposed to 0.000. B. After pattern exposure is performed, black-and-white development or external color development is performed.

The black and white developer used in the present invention is generally well known in the art, and includes, for example, hydroquinone, pyrogallol, 1-phenyl-3-pyrazolidone, p-aminophenol, ascorbic acid, and the like. The developer contains an alkaline agent (e.g., sodium hydroxide, sodium carbonate), PU powder, or a buffer agent (e.g., acetic acid, boric acid) as necessary.
Known compounds and compositions such as , antifoggants (eg, potassium bromide), and preservatives (eg, sodium sulfite) can be added. Also, 0. B. For example, all of the above-mentioned couplers can be used alone or in combination as the outer mold color developing solution used for the outer mold color development to form.

0. B. The functions required of the outer mold color developing solution used for forming the outer mold color developing solution are that the dye image produced by the outer mold color development should be highly concentrated, and that the density of the silver particles should also be high. For example, it can be obtained by appropriately selecting the type of coupler, color developer, auxiliary developer, etc.

In this way, 0. B. If black and white development is used as a method to obtain 2c, it is difficult to achieve an optical density of 4.0 or higher for visible light since it is made of silver, but if external color development is performed, it is easy to An optical density of .0 or more can be obtained.

Therefore, forming 0B by external color development is a particularly advantageous embodiment of the present invention. When black-and-white development is performed, the optical density may be slightly lower than 4.0, but the optical density may be used as it is, or the optical density may be increased to 4.0 or higher by known intensification. 0. B. The photographic material in which the color is formed is then fixed to remove the silver halide grains contained in the unexposed areas and/or the coloring pattern, resulting in the 0.0. B. A polychromatic optical filter is completed.

The fixing agent used in this process can be any commonly known silver halide solvent (e.g., sodium thiosulfate, sodium thiocyanate), and the solution containing the fixing agent may be added with a preservative (e.g., sulfite) if necessary. sodium), PH buffering agents (eg, boric acid), PH adjusting agents (eg, acetic acid), chelating agents, and the like. The polychromatic optical filter obtained by the method of the present invention can be used as it is in an image pickup tube if the support is, for example, a glass disk for the face plate of an image pickup tube.

Further, the support may be a film or a thin glass plate (for example, 0.1
~0.2 mm thick), it can be used by bonding it to a glass disk using, for example, an epoxy adhesive. Further, as an aspect of the present invention, for example, Japanese Patent Application Laid-Open No. 491329
A silver halide emulsion layer of a photographic material is prepared by providing a silver halide emulsion layer on a support whose surface has been subjected to mold release treatment as described in Japanese Patent No. 30, and the emulsion layer is coated with a 0.0. B. It is also possible to form a polychromatic optical filter pattern having the following emulsion layer and then transfer the emulsion layer to a glass disk for the face plate of the image pickup tube.

As explained above, according to the method of the present invention, a photographic material having a known black and white fine-grain silver halide emulsion layer is used, and this is subjected to image exposure, external color development processing, and bleaching a plurality of times to form the same emulsion layer. A multicolor optical filter is formed by forming patterns of each color, and furthermore, a pattern of each color is formed in the same emulsion layer. B. is formed by a photographic method, so each emulsion layer of the outer or inner color film is provided with a plurality of emulsion layers with different spectral sensitivities, and each emulsion layer develops a different color to create a multicolor optical filter. This is completely different from the usual color photographic technology that obtains the same results.

The polychromatic optical filter formed according to the present invention has a very high precision in which a line width of 1 .mu.m can be easily obtained. According to the present invention, it is not only possible to obtain patterns in various colors much more easily than in the conventionally known methods, such as those using a dichroic film or those in which a polymer material layer is dyed with a dye. 0.0 which was formed using one method. B. Since they can be formed in the same emulsion layer by a simple method, an extremely inexpensive multicolor optical filter can be obtained.

[Brief explanation of the drawing]

FIG. 1 shows a specific example of the manufacturing process of a multicolor optical filter by a conventional method, FIGS. 1a to 1d show a process for forming an optical black on a support, and FIG. Figures 1h to 1h each show the steps of forming one color of a multicolor optical filter. FIG. 2 shows an embodiment of the process for manufacturing the polychromatic optical filter of the present invention. FIG. 2a shows the photographic material used in the present invention, and FIG. FIG. 2c shows the steps for forming one color, and FIG. 2c shows the steps for forming optical black. 20: Support, 21: Silver halide emulsion layer, 22: Coloring pattern,
24: Optical black.

Claims (1)

[Scope of Claims] 1. A photographic material having at least one black and white silver halide emulsion layer provided on a support, in which dye patterns of at least two colors are formed in the emulsion layer, and the emulsion layer contains silver or silver and silver. A polychromatic optical filter characterized by an optical black formed from pigment. 2. A photographic material having at least one black and white silver halide emulsion layer provided on a support is exposed to a first color pattern on the emulsion layer, and then subjected to external color development to contain the first color dye and silver. After forming the pattern, the silver in the pattern area is eluted by bleaching or converted into a silver compound, and then, if necessary, a second color pattern is exposed,
Forming a pattern containing a second color pigment and silver,
After the silver of the pattern is eluted by bleaching or converted into a silver compound, a pattern of at least two colors is formed by repeating the same process to form a pattern containing a third color and subsequent colors and silver, if necessary. A method for manufacturing a multicolor optical filter, which comprises forming a multicolor optical filter, and finally performing pattern exposure corresponding to optical black, performing black-and-white development or external color development, and then fixing to form optical black consisting of silver or silver and a pigment.