JPH03209405A - Manufacture of color filter - Google Patents

Abstract

PURPOSE:To improve smoothness between picture elements and processing stability at the time of a continuous processing by executing a coloring development processing by external coloring development so that developing silver can be more than 30% to the amount of exposed silver, and executing a processing not to practically include a whitening process after the coloring development process excepting for the final coloring development process. CONSTITUTION:The coloring development processing is executed so that the developing silver can be more than 30% to the amount of exposed silver, and the coloring development processing is executed by the external coloring development. After one coloring development process at least excepting for the final coloring development process, the processing not to practically include the whitening process is executed. For pattern exposure, a photomask 14 is arranged on a silver halide photosensitive material 13 equipped with an emulsion layer 12 exerting silver salt coloring matter whitening operation laminated on a light transmissive substrate 11 and the pattern exposure is executed by irradiating the photomask 14 with light from the upper side. Thus, a satisfactory picture can be obtained so that the smoothness between picture elements can be satisfactory, the processing stability in continuous processing can be improved and colors can not be muddy.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for manufacturing a color filter. The color filter obtained by the manufacturing method of the present invention can be used for various purposes, for example, it can be suitably used as a color liquid crystal display.

[Background of the invention]

As a method for manufacturing color filters, Japanese Patent Application Laid-Open No. 55634
As disclosed in Publication No. 2, there is a method using an external color development method using a color silver salt photographic material.

However, with the method described in the above publication, smoothness may be insufficient between pixels having different spectral characteristics. Pixels of one color and pixels of another color may have different thicknesses on the substrate, resulting in a step difference. Insufficient smoothness as described above is a major cause of deterioration in image quality after producing a color liquid crystal display. That is, in a color liquid crystal display, the spectral characteristics based on the arrangement of liquid crystal molecules are determined by the voltage applied to the liquid crystal layer, and the voltage is influenced by the thickness of the liquid crystal layer. Therefore, when a difference in level occurs between pixels of a color filter, the spectral characteristics of each pixel after producing a color liquid crystal display are different from desired ones, resulting in deterioration of image quality.

Further, in the conventional technology, when a large number of color filters are subjected to external color development processing in succession, the processing stability is insufficient, leading to deterioration of image quality.

Therefore, there is a demand for the development of a color filter that has excellent smoothness between pixels with different spectral characteristics and excellent processing stability during continuous processing.

[Purpose of the invention]

An object of the present invention is to provide a method for manufacturing a color filter that improves the smoothness between pixels on the color filter surface and also improves processing stability during continuous processing.

[Structure of the invention]

The purpose of the present invention is to produce a color filter, which includes a process of exposing a light-sensitive material having a silver halide emulsion layer on a light-transmitting substrate in a pattern, and then forming a dye image according to the pattern using a color development process. In the method, a color development process is performed in which developed silver is 30% or more based on the amount of exposed silver, and the color development process is performed by external color development, and at least one color development process other than the final color development process is performed. This can be achieved by a method for producing a color filter, which is characterized in that the process is followed by a process that does not substantially include a bleaching step.

By employing the above configuration, although the effect is not necessarily clear, it is possible to improve smoothness between pixels and improve processing stability after image processing.

Further, the effects of the present invention become even more remarkable by performing an external color development process in which the amount of developed silver is 50% or more relative to the amount of exposed silver. Furthermore, after all colored parts are formed by an external color development process, the dye that exhibits a silver salt dye bleaching action and contained in the silver halide emulsion layer of the light-sensitive material is decolorized by a silver salt dye bleaching process. This effect can be made even more pronounced. Furthermore, the effects of the present invention can be more significantly achieved by controlling the average grain size of silver halide in the silver halide emulsion layer to 0.1 μm or less.

The present invention will be explained in more detail below.

In the method for manufacturing a color filter of the present invention, the color development treatment is performed by external color development.

Here, "external color development" refers to development in which dye is applied to the material to be developed from a developer (developer, etc.), and the dye is provided from an external developer to the color filter, which is the material to be developed. It is called Gaishiki in the sense that it is

In the present invention, external color development is such that the amount of developed silver is 30% or more relative to the amount of exposed silver.

In the case of normal color development processing, the amount of developed silver relative to the amount of exposed silver is about 10 to 20%, and as in the present invention, the amount of developed silver is <30%.
As described above, when preferably 50% or more of developed silver was produced, surprisingly, the effects of the present invention were manifested.

A more preferred ratio of developed silver is 60% or more, and the most preferred ratio is 70% or more. These are findings discovered by the present inventors.

Any means can be used to increase the amount of developed silver to 30% or more of the exposed silver amount, but one preferred method is the addition of a color developing agent contained in the external color development solution. There are ways to adjust the amount.

Regarding the amount of the color developing agent added, it is preferable that the content of the developing agent in the developer is within the range of 0.1 g to 10 g per liter of the developer. As for the amount to minimize development fog, it is more preferable to use the developing agent in the range of 1 g to 8 g in 1, and it is particularly preferable to use the developing agent in the range of 2 g to 5 g in If. . Furthermore, it is also effective to use two or more of these color developing agents in combination.

Various kinds of developing agents can be used, but
For example, C. E. K. Mees, T. H. James (C, E., Mees and T. H.).

James) The Theory of the Photographic Process, 3rd Edition
f thePhotographic Process
3rd, Edition) J, 293-298
Mention may be made of the compounds described on page.

Specific examples include (1) 4-amino-3-methyl-N-(2-hydroxyethyl)aniline sulfate (2) N-ethyl-N-methoxyethyl-3-methyl-
p-phenylenediamine-p-)luenesulfonate (3) 4-amino-3-methyl-N-ethyl-N=(2
-methylsulfonamidoethyl) aniline sulfate hydrate (4) N,N-diethyl-P-phenylenediamine sulfate (5) N,N-diethyl-3-methyl-p-phenylenediamine hydrochloride, etc. can be mentioned.

In addition, increasing the amount of buffering agent is also effective as a means to increase the amount of developed silver to 30% or more of the amount of exposed silver. Examples of buffering agents include alkali metal phosphates,
There are carbonates, sulfates, and borates, and the amount added is preferably 20 g or more per 12 color developing solutions.

In addition, reducing agents such as hydroxylamine, diethylhydroxylamine, sulfites, hydrazines, and phenyl semicarbazides, as well as reducing agents such as hydroquinone, metol, pyrogallol, 1-phenyl-3-pyrazolidone, p-aminophenol, and ascorbic acid, are used in the industry. Needless to say, it is an effective method to use a combination of one or more additives such as generally well-known black and white developing agents, as well as development accelerators such as benzyl alcohol, polyethylene glycol, quaternary ammonium salts, and amines. be.

Furthermore, it is also effective to adjust the pH value of the developer to 10.0 or higher, preferably 11.00 or higher, and most preferably 11.50 or higher using sodium hydroxide, potassium hydroxide, or the like.

Regarding external color development processing conditions, it is generally effective to set the processing temperature to a range of 10°C to 40°C, more preferably a range of 20°C to 33°C, Further, it is effective from the viewpoint of processing stability that the processing time is in the range of 1 minute to 10 minutes, preferably in the range of 2 minutes to 6 minutes.

Further, in the present invention, the ratio of developed silver to the exposed silver amount is calculated by converting the exposed silver amount into a solution equal to the silver amount added to the light-sensitive material, and then converting the developed silver into a solution and measuring it by atomic absorption.

In the external color development process in the method for producing a color filter of the present invention, a process that does not substantially include a bleaching process is performed after at least one color development process other than the final color development process.

Formation of pixels by external color development can be performed, for example, as follows.

First, a silver halide photosensitive material is pattern-exposed by a conventional method (first exposure).

After performing the first pattern exposure, a developer containing a color forming coupler is used to apply a first pattern to the first exposed portion.
Develop. For example, a developer containing a magenta color coupler as a color coupler (magenta developer) is used for development.

The first exposed area is thus developed using any one of a cyan developer, a magenta developer, a yellow developer, a blue developer, a green developer, and a red developer depending on the purpose. .

After the first exposed area is developed in this way, the photosensitive material is immersed in a stop solution containing an acid such as acetic acid to stop the reaction associated with development, washed with water, and then dried, if necessary. A first colored portion having any one of red, blue, green, cyan, magenta, and yellow pixels (for example, magenta pixels) is formed.

Next, using a photomask, the unexposed area adjacent to the first exposed area is pattern-exposed in the same manner as the first exposure, and then a color-forming coupler other than that used in the first step is exposed. Develop using one of the developing solutions.

Furthermore, a second colored portion can be formed by performing the same steps as above, such as washing with water and drying.

Further, in the same manner, the unexposed portion adjacent to the second colored portion is exposed in a pattern, and then developed using a developer other than that used in the first and second steps.

Furthermore, in the same manner as above, a third colored portion can be formed by performing steps such as washing with water and drying.

A process according to the present invention that does not substantially include a step of dipping in a bleaching solution after the first development or after the second development (substantially does not include a dipping step that excludes short-time dipping such as rinsing). ), it became possible to obtain extremely good results for the purpose of the present invention by developing 0.30% or more of the exposed silver.

In the present invention, the color coupler used as the color forming coupler is different from the internal coupler (ballast type coupler) used in ordinary color photography, and is added to the developer so that at least a part of it remains in the developer. It is an external coupler that is used in a dissolved state. As such an external coupler, in the present invention, any various external couplers, such as various known external couplers, can be used.

Among the above-mentioned color couplers, examples of yellow couplers include ketomethylene compounds (e.g. α-(4-
(carboxyphenoxy)-α-pivaloyl-2,4-dichloroacetanilide);
No. 3,619.189, Special Publication No. 1977-33775
No. 44-3664 and the like can be used.

Examples of magenta color-forming couplers include active methylene compounds (for example, pyrazolones such as 1-(2,4,6-dolichlorophenyl)-3-(p-nitroani'J/)-5-pyrazolone, 7- Chloro-3-phenyl-6-ituprobyl-IH-pyrazolo(5,1-c)-
pyrazoloazoles such as 1,2,4-) lyazole and cyanoacetanilides), and furthermore, OLS 2,016.587;
U.S. Patent No. 3.152.896, U.S. Patent No. 3,615.502
Those described in Japanese Patent Publication No. 44-133111 can be used.

Furthermore, examples of cyan color-forming couplers include phenolic compounds (for example, 2-acetamido-4°6-dichloro-
5-methylphenol) or naphthol compounds (for example, N-(2-acetamidophenethyl)-1-hydroxy-2-naphthamide); 55
No. 2, British Patent No. 1,062,190, etc. can be used.

In addition to the above, rThe Theory of
thePhotographic Process 3
rd Edition” (cited above), Chapter 17, 382-3
The one described on page 95 can also be used.

In the developer, the total content of color-forming couplers in 1/1 of the developer is preferably set within the range of 0.1 to 20 g. Sufficient color development can be achieved by setting the content to 0.1 g or more. . By using 20 g or less, so-called fogging can be reliably prevented. In particular, in the present invention, the developer 11. By controlling the total content of color-forming couplers in the range of 0.2 to 10 g, a color filter with less color turbidity and good spectral characteristics can be obtained.

The blending ratio of color-forming couplers showing different color formation in this developer can be set appropriately taking into consideration the color-forming properties of the color-forming couplers used. For example, when combining a cyan color-forming coupler and a magenta color-forming coupler, The weight ratio of both is usually preferably 1:9 to 1:9.
7:3, more preferably within the range of 1:9 to 4:6. Further, when a cyan color-forming coupler and a yellow color-forming coupler are combined, the weight ratio of both is usually preferably within the range of 1:9 to 7:3, more preferably 1:9 to 4:6. Furthermore, when combining a magenta color-forming coupler and a yellow color-forming coupler, the weight ratio of both is usually preferably 9:1 to 2:8, more preferably 8.
: within the range of 2 to 6:4. When combining a color-forming coupler, a magenta color-forming coupler, and a yellow color-forming coupler, it is preferable to blend the three in substantially equal amounts.

In addition, the blending weight ratio of the total amount of color couplers and the developing agent in the developer that can be suitably used in the external color development method of the present invention is determined by the types and content of the color couplers and the developing agent, etc. Although it can be set appropriately in consideration of the above, it is usually preferable that the blending weight ratio of the color forming coupler and the developing agent be within the range of 1:9 to 9:1.

In a preferred embodiment of the present invention, after forming the first to third colored portions as described above, a silver salt dye bleaching treatment described in detail below is performed, thereby achieving the object of the present invention more effectively. can be achieved. In particular, the effect on smoothness was remarkable.

This will be discussed below.

(Processing step by silver salt dye bleaching method) In this method, after forming all the colored parts by the external color development method, a silver salt dye bleaching process is performed to remove the silver salts contained in the silver halide photosensitive material. Decolorizes pigments that exhibit a pigment bleaching effect.

The processing step using the silver salt dye bleaching method is one in which at least black and white development processing, dye bleaching processing and silver bleaching processing are performed in this order.

The processing steps by the silver salt dye bleaching method are divided into black and white development processing, dye bleaching processing and silver bleaching processing and will be explained in this order.

In this process, among the patterns of each colored part formed by the above-mentioned external color development method, the photosensitive material is subjected to image exposure in the same pattern as the desired colored part pattern,
A black-and-white development process using a black-and-white developer is performed to form a reduced silver image on the light-sensitive material.

The black and white developer used includes, for example, a developing agent [hereinafter referred to as developing agent (D)], a developing aid, a preservative, a so-called development fog preventive agent, an alkaline buffer, and, if necessary, the aforementioned developing agent. (D) and a developing aid solvent.

Examples of the developing agent (D) include hydroquinone, chlorohydroquinone, and catechol.

Examples of the development aid include pyrazolone, pyrazolone derivatives, metol, and the like.

Preservatives include sulfites, ascorbic acid, and the like.

Examples of the development antifogging agent include bromides, benzotriazole, and the like.

Examples of alkaline buffers include carbonates, hydroxides, phosphates, borates, and metaborates.

Examples of the solvent for the developing agent (D) and the developing aid include ethylene glycol, triethanol, and jetanol.

Examples of the contents of the various components in the black and white developer include: developing agent (D) 1 to 20 g/l, developing aid 0.05 to 8 g/2, preservative 1 to 120 g/f, Development fog prevention agent 0.001-5g/l, alkaline buffer 0.1-50g/j! In addition, when a solvent for a developing agent and a developing aid is used, the amount of the solvent is 1 to 20 d/l.

The black and white development process is usually preferably carried out at 20 to 60°C for 10
This is carried out by immersing the image-exposed photosensitive material in a black and white developer for 200 seconds.

Photosensitive material (A) image-exposed by this black-and-white development process
A reduced silver image (silver negative image) is generated inside.

After the black and white development process, a washing process is usually performed, and then a dye bleaching process described below is performed.

In the dye bleaching process, a dye bleaching solution is used to bleach the pigment of the dye contained in the light-sensitive material.

That is, this dye bleaching process is a process in which, among the dyes contained in the image-exposed light-sensitive material, the dyes in the areas containing a large amount of image silver are bleached to form a positive image of the dyes.

The dye bleach solution used contains, for example, a bleaching agent, a silver salt or a compound forming a silver complex, and a dye cleanliness promoting catalyst.

Examples of bleaching agents that can be used include mineral acids such as hydrochloric acid, sulfuric acid, and nitric acid; organic acids such as sulfamic acid, succinic acid, and acetic acid.

As the compound that forms a silver salt or a silver complex, for example, potassium bromide, potassium iodide, urea, 1,000 urea, semicarbazide, thiosemicarbazide, etc. can be used.

Examples of dye bleach accelerating catalysts that can be used include pyrazines, naphthazines, quinolines, quinoxalines, phenazines, anthraquinones, naphthoquinones, indophenazines, N-substituted isoalloxazines, floquinoxalines, chietoxalins, and diphenyl derivatives. , triphenylmethane derivatives, lumazines, alloxazines,
Examples include cinnolines, orthophenylenediamine derivatives (US Pat. No. 2,270.118,
2.410.025, 2+54L884, 2
, No. 627,461, No. 2.669.517, British Patent No. 657.374, No. 711.247, Special Publication No. 1973
-22195 etc.).

Examples of the contents of the various components in the dye bleaching solution include: 1.-20 g/l of bleach, 0.1-20 g/f of a compound forming a silver salt or silver complex, and 0.0 g/f of a dye bleach accelerating catalyst. 001-10 g/1.

The dye bleaching treatment is usually carried out by immersion in a dye bleaching solution at a temperature of 20 to 60°C for 10 to 200 seconds.

By this dye bleaching treatment, the silver-rich portions of the image-exposed photosensitive material are bleached to form a positive dye image. Black silver that is not used to bleach the dye may remain as it is.

After the dye bleaching treatment, a washing treatment with water is usually performed, and then a silver bleaching treatment, which will be described in detail below, can be performed.

The silver bleaching process is a process for rehalogenating all the black silver remaining in the image-exposed photosensitive material that has been subjected to the dye bleaching process.

A silver source white liquor is used for this silver bleaching treatment.

The silver source white liquor may be one that is conventionally known (for example, a bleaching liquor containing a ferric chelate of ethylenediaminetetraacetic acid can be suitably used).

The silver bleaching treatment is usually preferably carried out at 18 to 60°C and 50°C.
Perform for ~500 seconds.

After performing the above processing, washing with water, fixing processing to remove silver halide in the photosensitive material, and further washing with water.
dry.

Next, a preferred exposure/processing process in the method for producing a color filter of the present invention will be described.

For example, as shown in FIG. 2, Table A shows a pattern of exposure and processing processes when forming a color filter having blue light transmitting pixels B, green light transmitting pixels G, and red light transmitting pixels R.

Each colored part shown in Table 2 is a yellow pigment (Mu or M
z), a magenta dye (Y or Yz), and a cyan dye (C+ or Cz).

Table A shows how each of these dyes are formed.

That is, in this method, after forming a dye image at the location indicated by GA in Table A by employing an external color development method, SD
A silver salt dye bleaching method is used to remove the color of the dye in areas other than the areas indicated by B, which exhibits a silver salt dye bleaching action.

For example, in the pixel formation pattern shown in Pattern Example 1 in Table A, first, blue light transmitting pixels are pattern-exposed in the manner described above in the first exposure/processing process. After that, a development process is performed using an external developer containing a magenta color coupler.Next, in a second exposure/processing process, the green light-transmitting two-way pixels are exposed in a pattern, and then a yellow color coupler and a cyan color coupler are applied. Development processing is performed using an external developer containing the material, followed by a third exposure and
After the red light transmitting pixels are exposed in a pattern through a processing process, a development process is performed using an external developer containing a yellow color-forming coupler and a magenta color-forming coupler. Finally, after the green light transmitting pixels and the red light transmitting pixels are pattern-exposed, the silver salt dye bleaching treatment is performed. Here, regarding the order of exposure and processing of blue light transmitting pixels, green light transmitting pixels, and red light transmitting pixels, silver salt dye bleaching treatment is performed after all external color development treatments are completed. For example, there is no particular restriction, and the arrangement of the blue light transmitting pixels, the green light transmitting pixels, and the red light transmitting pixels is not limited to that shown in FIG. 2.

In the method of the present invention, for example, on a light-transmissive substrate 31 as shown in FIG. After the formation, pattern exposure is applied to this gap, and then a development process is performed using a developer containing a cyan coloring coupler, a magenta coloring coupler, and a yellow coloring coupler. A light-transmissive section (black stripe) 33 can also be formed in the gap between the green part B and the green part G. In this case, it is the most preferable embodiment to carry out the silver salt dye bleaching process after all the external development processes are completed in order to achieve the effects of the present invention.

Furthermore, in the method of the present invention, it is also possible to perform etching treatment on the color filter layer to remove unnecessary portions of the color filter layer, depending on the use of the color filter.

Furthermore, the pixel formation mode may be either mosaic or striped.

The color filter thus obtained can be suitably used, for example, as a filter for a liquid crystal color display as shown in FIG. That is, as shown in FIG. 4, if the color filter 43 is arranged so that the color filter 43 and the liquid crystal 47 controlled by the electrodes 48a and 48b are sandwiched between the polarizing plates 46a and 46b, a liquid crystal color display can be obtained. It can be used as a filter for

Furthermore, it can also be suitably used in place of other conventionally used color filters for image pickup tubes.

(About Silver Halide Photosensitive Material) Next, in the present invention, a photosensitive material in which a silver halide emulsion layer is provided on a light-transmitting substrate is used, and this photosensitive material will be described below.

The light transmitting substrate that can be used may be transparent or semitransparent as long as it has light transmittance.Furthermore, the color filter may be exposed to high temperatures during the vapor deposition process of the transparent electrode, etc. Therefore, it is preferable that the material for the light-transmitting substrate has good heat resistance.

Examples of materials that make up such a light-transmissive substrate include:
Examples include polymer compounds such as polyethylene terephthalate, polybutylene terephthalate, polystyrene, polycarbonate, polyether sulfone, polyvinyl alcohol and cellulose acetate, glasses such as soda glass and borosilicate glass, and inorganic substances such as quartz and sapphire.

The light-transmitting substrate can be used in the form of a plate, a sort, a film, or the like using the above-mentioned materials.

The thickness of the light-transmitting substrate can be set appropriately depending on the purpose and material, but it is usually preferably 0.5 μm.
~10+og. In particular, when glass is used as the light-transmissive substrate for the liquid crystal display, the thickness is preferably within the range of 0.3-2 ms.

Also, the surface of the light-transmissive substrate on which the emulsion layer is formed is 4°.

There is no particular restriction as long as the surface precision is on the same IS level as the light-transmitting substrates conventionally used for color filters, but in order to achieve even higher image quality, it is necessary to It is desirable that the surface precision of the substrate is 0.1 μm.

In the present invention, it is preferable to provide a backing layer exhibiting an antihalation effect on the surface of the light-transmitting substrate opposite to the surface on which the emulsion layer is formed. The dye or pigment contained in is preferably a non-diffusible dye or pigment,
Specifically, a carbon black dispersion can be suitably used. The carbon black dispersion may be produced using either the furnace method or the channel method (for example, Diablack 1 (manufactured by Mitsubishi Kasei) can be suitably used.

The non-diffusible dye or pigment is contained in the backing layer in a state of being dispersed in a hydrophilic fluid, but it must not dissolve into each processing solution even after development. The light absorption characteristics of the dye or feed used vary depending on the spectral absorption characteristics of the silver halide emulsion used in the present invention, but for example, when using a silver halide emulsion that has not been spectral sensitized with a sensitizing dye, 5001
It is preferable that it absorbs the following light. Furthermore,
The backing layer may contain a UV absorber. As an ultraviolet absorber, for example, rUVINUL? lS-4
0J (manufactured by BASF), rTINUVIN-PJ (
When using a non-diffusible dye or pigment and an ultraviolet absorber, a known high-boiling organic solvent such as methyl acetate, ethyl acetate, propyl acetate, butyl acetate, cyclohexane,
After dissolving in a low-boiling organic solvent such as tetrahydrofuran, carbon tetrachloride, chloroform, etc., it is mixed with an aqueous gelatin solution containing a surfactant, and then heated using a stirrer, homogenizer, colloid mill, flow jet mixer, and ultrasonic wave for 9 hours. After emulsifying and dispersing using a fractional means such as a device,
It is generally used by adding it to a coating composition that requires a hydrophilic colloid backing.

Note that the amount of non-diffusible dye or pigment used is preferably 0.1 or more per light-transmitting substrate 1004,
Particularly preferably, it is 1111 g or more.

Although the emulsion layer can be directly coated on the surface of the light-transmitting substrate, a subbing layer can also be provided between the emulsion layer and the light-transmitting substrate. The subbing layer strengthens the adhesion between the emulsion layer and the light-transmitting substrate, and if the surface of the light-transmitting substrate is rough, the rough surface is made smooth.

Examples of materials forming this undercoat layer include gelatin, albumin, casein, cellulose derivatives, starch derivatives, sodium alginate, polyvinyl alcohol, polyvinylpyrrolidone, polyacrylic acid copolymer, polyvinylidene chloride copolymer, and polyacrylamide. can be mentioned.

The thickness of the undercoat layer is preferably thin considering the spectral characteristics of the color filter.
The silver halide emulsion layer used contains at least a silver halide and generally a water-soluble binder, but may also contain a dye having a silver salt dye bleaching action. .

Examples of the silver halide include silver chloride, silver iodide, silver bromide, silver chloroiodide, silver chlorobromide, and silver iodobromide. These may be used alone or in combination of two or more.

It is preferable to use a silver halide having a small average grain size, and it is particularly preferable to use a so-called Lippmann emulsion having an average grain size of 0.1 μm or less. By using particles with such a small average particle size,
The purpose of the present invention is to improve the image quality of the obtained color filter mainly in terms of graininess. Further, development silver can be easily produced.

Examples of the water-soluble binder include gelatin, albumin, casein, cellulose derivatives, starch derivatives, sodium alginate, polyvinyl alcohol, polyvinylpyrrolidone, polyacrylic acid copolymers, and polyacrylamide. These may be used alone or in combination of two or more,
Among these, gelatin is preferred.

One of the preferred embodiments of the present invention is to use a light-sensitive material containing a silver halide emulsion layer containing a dye exhibiting a silver salt dye bleaching action.

Examples of such dyes include phthalocyanine dyes,
Examples include azo dyes. Among azo dyes, bisazo dyes are particularly preferred, and specific examples include the following compounds.

(m (n each represents 1 or 2) 1 Not 2-No.

-cI -c1 2.5OtNHs 2 5ofcH3 3 1■1゜ 1■1゜ 1■1゜ 10CR.

=OCR1CIItOH CHs −■1゜ 4 -OCI+.

1■1゜1α1゜1α1゜■ 1α1゜1■- 1ω- 1■- Itsuya 1ichihamari- -SO,- 1■- 2-Now H-0CR*CB*OHH! ;
IJx-2-α)Ca1. 11 OCRw -α1. -ω- The silver halide emulsion of the photosensitive material contains silver halide, a water-soluble binder, and a dye in a weight ratio of (silver halide) = (water-soluble binder) of 1.
=6 to 8:1, /% It is desirable that the weight ratio of dye to silver halide is 1/10 to 50, and the weight ratio of dye to water-soluble binder is 1/100 to 2.

The emulsion layer can be formed by applying the emulsion onto the light-transmitting substrate using a conventionally known coating method such as a spinner coating method or a spray coating method.

The thickness of the emulsion layer formed in this way is preferably within the range of 0.3 to 10 μm in terms of dry thickness. If the thickness is 0.3 μm or more, sufficient color development cannot be achieved. When the thickness is 10 μm or less, the light transmittance is good and the color filter has sufficient brightness. In particular, in the present invention, by setting the thickness of the emulsion layer within the range of 0.5 to 3 μm, the spectral characteristics of the resulting color filter can be improved.

Specifically, the silver halide photosensitive material is subjected to mask exposure for forming pixels, and then developed with a developer containing a color-forming coupler to form a colored portion.

In the present invention, examples of exposure methods that can be employed when exposing the photosensitive material include methods used in normal pattern exposure such as contact exposure, proximity exposure, and step exposure.

The pattern exposure is carried out, for example, by using a silver halide photosensitive material 13 having an emulsion layer 12 containing the dye exhibiting a silver salt dye bleaching action and laminated on a light-transmitting substrate 11 as shown in FIG.
This can be done by placing a photomask 14 above and applying light from above the photomask 14. The opening 1 provided in the photomask 14 by this operation
The exposure constant portion 16 of the emulsion layer corresponding to 5 can be selectively exposed.

The size of the exposure element fixed portion 16, ie, the size of the opening 15, can be appropriately set depending on the use of the color filter to be manufactured. However, if the width of the opening 15 is narrower than the wavelength of the light source used for exposure, effective exposure cannot be performed, so the width of the opening 15 is made wider than the wavelength. Since silver halide has effective photosensitivity to light within the range of 340 to 420 nm, the preferred width of the opening 15 is usually 340 nm or more, and furthermore, considering its use as a color filter. In this case, it is preferable to set the thickness to 1 μm or more.

In addition, in the case of the color filter σ for the liquid crystal display 1/-, in order to effectively reproduce colors by adding the red, blue, and green colored parts, the width of the m opening 15 must be set to 1.
It is preferable to set it to 00011 m or less, particularly preferably 50 μm or less.

Other conditions such as light path time and light source can follow normal conditions.

〔Example〕

Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited thereto.

Note that % in the examples represents weight % unless otherwise specified.

Example 1 Preparation of optical material using silver halide 5 By adding an aqueous solution of silver nitrate and an aqueous solution containing potassium chloride and potassium iodide to a 10% aqueous solution of gelatin, 4 mol% of silver iodide was added. A silver iodobromide emulsion (average grain size: 0.05 μm, gelalan concentration: 9%) was prepared.Addition conditions were as follows: parent control 7 to obtain a Lippmann emulsion with an average grain size of 0.05 μm. .

To the obtained silver iodobromide emulsion was added 28.3 μm of sodium thiosulfate pentahydrate per mole of silver, and the mixture was heated at 59.5°C.
Chemically aged for 5 minutes.

1-phenyl-5-mercaptotetrazole and 1-carboxyethyl-3,4,5-hydroxybenzene were then added to the emulsion at 141.0% per mole of silver, respectively.
5M, 3.40 g, and the following compound 5C-
An emulsion coating solution was prepared by adding 15.9 g of 1 per mole of silver, and further adding 40 m and 5 g+g of the following compounds H-1 and H2 as hardeners per 1 g of gelatin, respectively.

C-1 -1 -2 ((Ctb = CH30zCHz) zcc) IzS
OzCI (zcHzl zNcHzcHzsOJ) The obtained emulsion coating solution was placed on a transparent borosilicate glass substrate (30C11X 30C1+) with a thickness of 1.1- to a dry film thickness of 3 μm.
A silver halide photosensitive material having an emulsion layer was prepared by coating the material so as to have the following properties. The silver device was 1.5 g/bo, the dye (
The loading of the compound 5C-1) was 0.24 g/i.

This silver halide photosensitive material has a backing layer on the surface of the borosilicate glass substrate opposite to the surface having the emulsion layer.

Formation of this backing layer will be explained next.

Add the following dispersion of compound Y-1 to an aqueous gelatin solution, and add 40 g and 5+ g of hardeners H-1 and H-2, respectively.
Added. Here, the amount of gelatin added in advance was adjusted so that the gelatin aqueous solution was 5%. In addition, the amount of Y-1 added to 100 Jd of gelatin aqueous solution was 1.3
It was 5%.

Compound Y-1 Thereafter, this aqueous gelatin solution was applied to the borosilicate glass substrate and dried to form a backing layer. Y-
The attachment of 1 was 10■/drrf.

The above-mentioned dispersion was prepared by dissolving 1 M of Y-1 in L g of tricresyl phosphate and 4.29 af of ethyl acetate, followed by 0.83 g of gelatin and 4.29 g of ethyl acetate.
5% aqueous solution of sodium β-naphthalene sulfonate2.
The mixture was added and mixed into an aqueous solution containing 63 cc and 8.4 d of water, subjected to ultrasonic dispersion at 50° C., ethyl acetate was removed, and water was further added to make a total volume of 17.6 d.

Color filters (blue), G (green), and R (red) as shown in Figure 2
A method for producing a color filter having a color mosaic pattern will be described below. The size of each pixel is 15
The size is 08m x 150μm. In Fig. 2, 21 is the substrate, 2
2 is a color layer composed of each pixel.

A chromium mask for a color filter having a square opening having a side of 150 μm was placed on top of the photosensitive material described above, and a first exposure was performed using a tungsten lamp. Exposure was carried out at a position corresponding to part B in FIG.

The exposed photosensitive material is heated to the following magenta color developer at 23°C.
immersed in water for 3 minutes.

Magenta Color Image set Magenta coupler 1-(2,4,6-drichlorophenyl)-3-(p-nitroanilino)-pyrazolone-5-one 0.8gDeveloping agent 4-amino-3-methyl-N-ethyl -N-(2-Hydroxyethyl)anilino sulfate 2.0g Sodium nitrilotrimethylenesulfonate (40% aqueous solution > 3.(ld) Benzyl alcohol 9.0m Anhydrous sodium sulfate 20.0g Tripotassium phosphate
30.0 g sodium bromide
1.0g sodium sulfite
10.0g diethylhydroxylamine (85%)1.
0g ethylene glycol 10. Add 2.0g of Od polyethylene glycol water and lI! ,
shall be.

However, sodium hydroxide was added to the above magenta color developer to adjust the pH value at 25° C. to 12.0.

Next, after washing with water for 4 minutes, a blue portion was formed on the substrate by drying (first treatment).

Next, a second exposure was performed on the photosensitive material after the above processing using another chrome mask for a color filter so that the exposed area was part G in FIG.

The photosensitive material subjected to the second exposure was immersed in a yellow color developer having the composition shown below at 23° C. for 3 minutes, then washed with water and dried in the same manner as the first exposure to form a green area on the substrate (
2nd process).

Yellow Color Imager composition Yellow coupler α-(4-carboxyphenoxy)-α-pivaloyl-2,4-1 dichloroacetanilide 1.5g Developing agent 4-amino-3-methyl-N-ethyl-N-(2-hydroxyethyl ) Aniline sulfate 2.0g Sodium nitrilotrimethylene sulfonate (40% solution) 9.0+d
Benzyl alcohol 9.0 m Anhydrous sodium sulfate 20.0 g Potassium phosphate 30.0 g Sodium bromide
3.0g sodium sulfite
10.0g diethylhydroxylamine 1.
0g ethylene glycol 10.0m polyethylene glycol 2.0g Add water to 11
shall be.

However, sodium hydroxide was added to the above yellow color developer to adjust the pH value at 25° C. to 12.0.

Next, another chrome mask for a color filter was placed on the photosensitive material after the above processing so that the exposed area was the R area in FIG. 2, and a third exposure was performed.

The photographic light-sensitive material subjected to this third exposure was immersed in a red color developer having the composition shown below at 23°C for 3 minutes, and then immersed in a silver source white liquor having the composition shown below for 1 minute to perform bleaching. Ta. Thereafter, by washing with water for 4 minutes and dry-smoking, a black part was formed on the substrate, and at the same time, the parts formed in the first treatment and the second treatment were bleached.

Toki 1ヱ1''lI area- magenta cobra 1-(2,4,6-dolichloro phenyl)-3-(p-nitro anilino)-5-pyrazolone yellow coupler α-(4-carboxyphenoxylate) c)-α-pivaloyl-2,4 dichloroacetanilide developing herbal medicine 4-amino-3-methyl-N Ethyl-N-(2-hydroxy ethyl) aniline sulfate Nitrilotrimethylene sulfone Sodium acid (40%) 2.00g 0.82g 2.0 3.00m benzyl alcohol anhydrous sodium sulfate tripotassium phosphate sodium bromide sodium sulfite ethylene glycol polyethylene glycol Add water and 1f! , and so on.

However, sodium hydroxide was added to the above red color developer to adjust the pH value at 25° C. to 12.00.

Village! n Foot I - Ethylenediaminetetraacetic acid iron (I .

Next, a color filter 9.0〆20.0g 30.0g 3.0g 10゜0g 10.0m 2.0g is placed on the photosensitive material after the above processing so that the exposed area becomes the R area in FIG. A chrome mask was placed and a fourth exposure was performed. The photosensitive material that had been exposed for the fourth time was processed at 33°C as follows to form a red part ( Fourth
A color filter having a mosaic pattern of three colors, B (blue), G (green), and R (red) was obtained.

Black and white development Stop for 1 minute Wash with water for 1 minute
1 minute dye bleach 1 minute water wash 1 minute silver bleach
Wash with water for 1 minute Fix for 1 minute
Washing with water for 1 minute Drying for 4 minutes Here, the bath used for each treatment had the following composition.

Black and white developer composition> Sodium sulfite 10g Hydroquinone 10g Potassium hydroxide (48% aqueous solution) 5all diethylene glycol 20m Dimezone
0.7g sodium carbonate
20g potassium bromide
2g Thiadiazole
Add 0゜05g water
1! <Dye bleaching solution composition> 96% sulfuric acid 40M1 potassium iodide 15g2.3.
Add 2g of 6-drimethylquinoxaline water
1! <Silver source white liquor composition> The same silver source white liquor composition as described above was used.

<Fixer composition> Ammonium thiosulfate 175.0 g Sodium sulfite 8.5 g Sodium metasulfite 2.3 g Add water 1j! (p using acetic acid
Adjust to H=6.0. ) After the color filter was prepared, the backing layer was safely removed by impregnating the backing layer with a 3% aqueous sodium hypochlorite solution and wiping it off with gauze.

The color filter obtained in this way was used as sample Nα1.
shall be.

In the manufacturing process of sample kl, magenta color developer, yellow color developer, red color developer
Samples Nα2 to 6 were prepared by changing to the developer shown in
It was created.

For each sample obtained, the ratio of developed silver (developed silver of each pixel of B, G, and R) produced by each development was determined by atomic absorption, and the results are shown in Table 2.

In addition, for each sample obtained, blue light (B), green light (
Using a microdensitometer (aperture scanning area 250u
nf) was scanned, and the level difference between the transmitted light pixels of each color was determined using Talystep manufactured by Rank Taylor Hopson ■.

The results obtained are shown in Table-2.

In addition, the concentration is shown as a relative value with the value of sample concentration 1 being 1.

In addition, the difference in level between pixels was expressed as the difference with respect to the green light transmitting pixels, since the dry film thickness between the green light transmitting pixels was the largest in all samples.

Samples N+lL1 to 4, which are color filters obtained by the manufacturing method of the present invention, have improved smoothness as shown in Table 2. Also, satisfactory results were obtained regarding color turbidity as well as smoothness.

On the other hand, the comparative sample 5.6 in which the amount of developed silver was less than 30% of the amount of exposed silver had problems in smoothness.

Table shown by content in Table 1 Example 2 Using the same silver halide photosensitive material as in Example 1, the same processing steps as those for obtaining color filter sample Nα1 in Example 1 were carried out, except that in the processing step: After the first treatment and the second treatment, a sample was prepared by immersing it in a bleaching solution for 1 minute to bleach it, washing it with water for 4 minutes, and then drying it, and performing the other treatment steps in the same manner as Sample Floor 1. This is designated as sample Na7.

As in Example 1, the difference in level between the transmission source pixels of each color was measured for the obtained sample size 7. The results are shown in Table 3, and the changes in density of each pixel when processed continuously are shown in FIG.

Table 3 As shown in Table 3, Sample Ni'L1, which is a color filter obtained by the manufacturing method of the present invention, was more effective than Comparative Sample 7 in which a bleaching step was provided between each external color development process. , the smoothness was improved, and as shown in FIG. 5, the processing stability in the continuous processing special program was excellent.

Example 3 Sample floor 1 obtained by subjecting the silver halide photosensitive material of Example 1 to the same processing steps as in Example 1.
12, processing 1-2 using the photosensitive material and processing steps described in Example-1 of JP-A No. 55-6342, current @ζ-
Therefore, each type of color developing treatment solution was prepared so that the ratio of developed silver produced was the same as that of Sample No. 1, and the obtained sample was designated as No. 8.

Table A shows the difference in level between the transmission source pixels of each color for a given sample, as in Example 1.

Table 4 As shown in Table 4, sample 1, which is a color filter obtained by the manufacturing method of the present invention, has a smoothness compared to sample 8 obtained in a treatment process without a silver dye bleaching process. has been improved. Further, when continuous processing similar to that in Example 2 was performed, the processing stability during such continuous processing was also excellent.

Example 4 The silver halide bad light material of Example 1 was the same, except that the average grain size of the silver iodobromide emulsion containing 4 mol% silver iodide used therein was changed as shown in Table 5. Prepare the photosensitive material,
Using this, the same treatment steps as in Example 1 were performed to obtain samples 9 to 13. In this case, the sample
Sample No. 13 was obtained by preparing each external processing solution so that the same ratio of developed silver was obtained by performing the same development as Samples NQ and 1.

For the given sample, the level difference between the transmission source pixels of each color was measured in the same manner as in Example 1. The results are shown in Table 6.

As shown in Table 6, Samples N11l and 9.10, in which the average grain size of the silver halide used in the table is 0.1 μm or less, have improved smoothness compared to other samples Nos. 11 and 12. . Moreover, the processing stability during continuous processing was also better.

〔Effect of the invention〕

As described above, the color filter obtained by the manufacturing method of the present invention has the advantage of having good smoothness between pixels on the color filter surface and excellent processing stability during continuous processing.

Further, it can be configured to obtain an excellent image without color turbidity.

[Brief explanation of drawings]

FIG. 1 is an explanatory diagram showing an example of pattern exposure, which is one of the exposure methods that can be employed in the present invention. FIG. 2 is a schematic cross-sectional view showing an example of the configuration of a color filter obtained in the example. FIG. 3 is a schematic cross-sectional view showing an example of the configuration of a color filter having black stripes;
FIG. 4 is a schematic cross-sectional view showing an example of the configuration of a filter for a liquid crystal color display. Figure 5 (a) (b) (C
) is a graph showing the relationship between the number of continuously processed sheets and the density for the color filter samples obtained in Examples. Patent applicant Konica Corporation

Claims (1)

[Scope of Claims] 1. A color filter comprising the step of exposing a light-sensitive material having a silver halide emulsion layer on a light-transmitting substrate in a pattern, and then forming a dye image according to the pattern using a color development process. In the manufacturing method, a color development process is performed in which the amount of developed silver is 30% or more based on the amount of exposed silver, and the color development process is performed by external color development, and at least one color development process other than the final color development step is performed. After the development process,
A method for producing a color filter, characterized by performing a process that does not substantially include a bleaching step. 2. The method for manufacturing a color filter according to claim 1, wherein the color development treatment is a color development treatment in which the amount of developed silver relative to the amount of silver exposed is 50% or more. 3. The method for producing a color filter according to claim 1 or 2, wherein the light-sensitive material contains a dye whose color is erased by a silver salt dye bleaching action. 4. The color filter manufacturing method according to claim 4, wherein after forming all the colored parts by the color development process, a silver salt dye bleaching process is performed. 5. The method for producing a color filter according to claim 1 or 2, wherein the average grain size of the silver halide in the emulsion layer of the light-sensitive material is 0.1 μm or less.