JPH02191903A - Production of color filter - Google Patents

Abstract

PURPOSE:To improve a relief property by incorporating at least one kind of couplers which form colorless compds. by making coupling reaction with the oxidant of a color developing agent and processing the same with a processing liquid having >=9pH at 25 deg.C. CONSTITUTION:The couplers which form the colorless compds. by making coupling reaction with the oxidant of the color developing agent are preferably the couplers substd. by an alkyl group (including a substd. alkyl group) at the active point of the couplers or an aryl group (including a substd. aryl group) and particularly an alkyl group. A methyl group, ethyl group, etc., are particular ly preferably used as the more specific examples of the alkyl group. A phenyl group, etc., are used as the aryl group. The couplers expressed by the formula I are preferably as the compd. as the oxidant of the color developing agent. In the formula, R: the alkyl group (including the substd. alkyl group) substd. at the active point or aryl group (including the substd. aryl group); X: the atom group necessary for forming 5- to 6-membered heterocyclic nuclei including at least one nitrogen atom or sulfur atom or oxygen atom.

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a method for manufacturing a color filter, and more particularly, to a method for manufacturing a color filter suitable for use in a color liquid crystal display. [Background of the Invention] As a method for manufacturing color filters, Japanese Patent Application Laid-open No. 55-63
As disclosed in No. 42, there is an external color development method using a color silver salt photographic material. However, in the method described in the above-mentioned patent, relief occurs between pixels having different spectral characteristics, which is a major cause of deterioration in image quality, especially after producing a color liquid crystal display. That is, in a color liquid crystal display, the spectral characteristics based on the orientation 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. Therefore, there is a demand for the development of a color filter in which relief between pixels having different spectral characteristics is reduced. [Object of the Invention] An object of the present invention is to provide a method for manufacturing a color filter with improved relief properties on the surface of the color filter, and a method for manufacturing a color filter that provides good image quality after producing a color liquid crystal display. Our goal is to provide the following. [Structure of the Invention] An object of the present invention is to expose a light-sensitive material having a silver halide emulsion layer on a light-transmitting substrate in a pattern, and then use a developer containing a coupler and a color developing agent to develop the pattern. A method for producing a color filter comprising a step of forming a dye image containing at least one coupler that forms a substantially colorless compound by a coupling reaction with an oxidized form of the color developing agent, and at 25°C.
This is achieved by a method for manufacturing a color filter, which is characterized in that the color filter is treated with a treatment liquid having a pH of 9 or more. The present invention will be explained in more detail below. A processing solution containing a coupler (hereinafter abbreviated as the compound according to the present invention) that forms a substantially colorless compound by a coupling reaction with the oxidized form of the color developing agent of the present invention is:
It may be the same as or different from the external developer or the black-and-white developer for silver salt dye bleaching, but from the viewpoint of simplifying the treatment process and reducing manufacturing costs, the external developer or the above-mentioned Preferably, it is the same as the black and white developer. In the case of using an external developer, the compound of the present invention is used in a form in which the whole or a part of the compound of the present invention is dissolved in a conventional external developer. If it is the same as the black and white developer, it must necessarily contain a color developing agent. Further, when the processing solution containing the compound according to the present invention is different from the external developer or the black and white developer, it may contain additives used in ordinary color developers. However, a color developing agent must be included. In this case, the treatment with the treatment liquid may be performed before or after immersion in the external developer. The compound according to the present invention, that is, the coupler that forms a substantially colorless compound by coupling reaction with the oxidized product of a color developing agent, includes an alkyl group (including substituted alkyl) or an aryl group at the active site of the coupler. Group (
Couplers substituted with alkyl groups (including substituted aryl) are preferred. Specific examples of the alkyl group mentioned above include groups such as methyl group, ethyl group, propyl group, butyl group, octyl group, dodecanyl group, and octadecanyl group, with methyl group and ethyl group being particularly preferred. A specific example of the aryl group is a phenyl group. Substituents on the alkyl group and aryl group are not particularly limited, and may be, for example, an aryl group, an alkoxy group, a hydroxyl group, a sulfamoyl group, a carbamoyl group, or the like. Particularly preferred compounds according to the present invention are couplers represented by the following general formula. General formula (1) The ring nucleus may further form a condensed ring with another ring, and may have a substituent on the ring. Furthermore, the coupler represented by the general formula (I) is such that the compound is dissolved in whole or in part in the processing liquid on the ring or on the alkyl group represented by R, and the compound develops color. It has a substituent having a molecular size and shape that makes it immobile in the emulsion layer after coupling with the oxidized form of the developing agent. Examples of the substituent include organic groups having 6 to 24 carbon atoms. More preferable examples of couplers represented by general formula (1) according to the present invention include the following general formulas [2] to

Couplers represented by [9], and compounds represented by general formulas [2] and [3] are particularly preferred. In the formula, R is an alkyl group (including substituted alkyl groups) or an aryl group (including substituted aryl groups) substituted at the active site.
, X represents a group of atoms necessary to form a 5- to 6-membered heterocyclic nucleus containing at least one nitrogen atom, sulfur atom, or oxygen atom (the heterogeneous general formula [2] general formula (3) general formula [8] General formula [4] General formula

[9] General formula [6] General formula [7] In the above general formula, R is the same as defined in general formula (1). R1 represents a substituted or unsubstituted alkyl group or aryl group. R8 represents a substituted or unsubstituted alkyl group, aryl group, alkylamino group, arylamino group, acylamino group, ureido group, cyano group or carbamoyl group. R and R8 or R3 at adjacent positions may be combined to form a ring. R8 represents a substituted or unsubstituted alkyl group or aryl group. A more preferred compound is a coupler represented by the following general formula [1O] in general formula [2]. General formula [lO] Hereinafter, specific examples of the metal compound represented by the general formula CI) according to the present invention will be shown. E-1 In the formula, R has the same meaning as R in general formula (1), and R4
represents a hydrogen atom, a halogen atom, and six groups: alkyl, asakoxy, alkylamido, arylamide, alkylsulfonamide, arylsulfonamide, alkoxycarbonyl, and carbamoylsulfamoyl, R,
represents an alkyl group having 8 or less carbon atoms, an aralkyl group having 10 or less carbon atoms, or an aryl group, and n represents an integer of θ to 5. These alkyl groups, alkoxy groups, aralkyl groups, and aryl groups may further have a substituent. Preferably, R5 is a group such as methyl, ethyl, benzyl, phenethyl, phenyl, tolyl or the like. E-2 E-3 Q E- E- E- E- E-12 E E-14 E-15 1E- E- E-10 E-11 E-16 E-17 E-18 WE-19 WE-20 WE-21 WE-25 oc, t+. WE WE-23 WE-24 WE-28 WE-29 WE-30 WE-31 WE-32 The amount of the compound according to the present invention ranges from 0.01 g to 20 g per IQ of the treatment liquid of the present invention. Preferably, 0.1
A range of ˜log is more preferable. Silver halide photosensitive material In the present invention, a silver halide photosensitive material having an emulsion layer formed by coating a light-transmitting substrate with a silver halide emulsion is used. The light transmitting substrate used may be transparent or semitransparent as long as it has light transmittance. Furthermore, since the color filter is sometimes exposed to high temperatures during the vapor deposition process of transparent electrodes, it is preferable that the material of 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, sheet, film, or the like using the above-mentioned materials. The thickness of the light-transmissive substrate can be set appropriately depending on the purpose and material, but it is usually 0.5μ■ to 10m.
It is within the range of m. In particular, when glass is used as a light-transmissive substrate for a liquid crystal color display, the thickness is preferably within the range of 0.3 to 2 cm. The surface of the light-transmitting substrate forming the emulsion layer is not particularly limited as long as it has the same level of surface precision as the light-transmitting substrate conventionally used for color filters; In order to achieve image quality, it is desirable that the surface precision of the light-transmitting substrate be ±0.1 μm. In the present invention, it is preferable to provide a backing layer for antihalation coating on the surface of the light-transmissive substrate opposite to the surface on which the emulsion layer is formed. In this case, the dye or pigment contained in the backing layer is preferably a non-diffusible dye or pigment. Specifically, a carbon black dispersion can be suitably used. The carbon black dispersion may be produced by either the furnace method or the channel method, and for example, "Diablack" (manufactured by Mitsubishi Kasei Corporation) can be suitably used. The non-diffusible dye or pigment is contained in the backing layer in a state dispersed in a hydrophilic colloid, but it must not be eluted into each processing solution even after development. The light absorption properties of the dye or pigment used vary depending on the spectral absorption properties 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, 500na+
It is preferable that it absorbs the following light. Furthermore,
The backing layer may contain a UV absorber. UV absorbers, such as rUVINUL, MS
-40J (manufactured by BASF), rTINUVIN-PJ
(manufactured by F-Ba Geigy). Non-diffusible dyes or pigments and ultraviolet absorbers are known high-boiling organic solvents and low-boiling organic solvents such as methyl acetate, ethyl acetate, propyl acetate, butyl acetate, cyclohexane, tetrahydrofuran, carbon tetrachloride, chloroform, etc. After dissolving in a solvent, it is mixed with an aqueous gelatin solution containing a surfactant, and then a stirrer and a homogenizer are used.
After emulsifying and dispersing it using a dispersing means such as a colloid mill, 70-jet mixer, or ultrasonic dispersion device, it is used by adding it to a coating composition that requires a hydrophilic colloid backing. The amount of the non-diffusible dye or pigment used is preferably 0.1 g or more, particularly preferably 1 mg or more per 100 cm of the light-transparent substrate. Although the emulsion layer can be applied directly, 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. At the same time, if the surface of the light-transmitting substrate is rough, the rough surface is made smooth. Materials for forming this subbing layer include, for example, gelatin, albumin, casein, cellulose derivatives, and starch. Examples include derivatives, sodium alginate, polyvinyl alcohol, polyvinylpyrrolidone, polyacrylic acid copolymer, polyvinylidene chloride copolymer, and polyacrylamide.The thickness of the undercoat layer should be thin considering the spectral characteristics of the color filter. is preferably 1 μl or less, preferably within the range of 0.05 to 0.5 μm. The silver halide emulsion layer used contains at least silver halide and a water-soluble binder, but Furthermore, it may contain a dye having a silver salt dye having a bleaching action. Examples of silver halides include silver chloride, silver iodide, silver bromide, silver chloroiodide, silver chlorobromide, and iodobromide. Examples include silver. These may be used alone or in combination of two or more. It is desirable to use silver halide with a small average particle size, and in particular, it is desirable to use one with a small average particle size. It is preferable to use a so-called Lippmann emulsion having a grain size of 0.1 .mu.m or less.If the average grain size of silver halide is large, the image quality, mainly the graininess, of the resulting color filter may deteriorate. Examples of the water-soluble binder include gelatin, albumin, casein, cellulose derivatives, starch derivatives, sodium alginate, polyvinyl alcohol, polyvinylpyrrolidone, polyacrylic acid copolymers, polyacrylamide, etc. These may be used alone. gelatin may be used, or two or more types may be used in combination. Among these, gelatin is preferred. One of the preferred embodiments of the present invention is to use silver salt dyes that exhibit a bleaching action as silver halide dyes. be contained in the emulsion layer. 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. Compound R′ a 2-No. b 2-NO3 c2-C(1 H e2-C(1 f 2-So, NH. g 2 5OICH3 R2R3 H'-0CR3 5NO30CH3 H-OC!(3 H-0CH3 H-OCH, CH!OH H-0CH3 H-0CH3 R' J -OCH3-CO- -OCH, -CO- 1α:n, -co- -OCH, -CO- H-SO, - H-5O2- -OCR, -CO- 12-No, H0CHICHZOHH-Sow
Hj 2-α) CHs HOCRs
OCHs -COH (at and n each represent 1 or 2) The silver halide emulsion in the present invention contains silver halide, a water-soluble binder, and a dye in the formula (silver halide) = (water-soluble binder). It is preferable that the weight ratio is 1=6 to 8:1, 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 thus formed is usually in the range of 0.3 to 10 μm in terms of dry thickness. Thickness is 0.
If it is less than 3 μm, sufficient color development may not be achieved, while if it exceeds 10 μl, the light transmittance may decrease and the brightness of the color filter may become insufficient. In particular, in the present invention, the thickness of the emulsion layer is set to 0.5 to 3 μm.
By keeping it within this range, the spectral characteristics of the resulting color filter can be improved. One of the preferred embodiments of the present invention is a method in which the emulsion layer detailed above is processed using a silver halide light-sensitive material by a combination of an external color development method and a silver salt dye bleaching method. When this method is adopted, it is preferable to carry out the treatment by the silver salt dye bleaching method after all the processing steps by the external color development method are completed. Next, a preferred embodiment of the production method of the present invention will be explained in this order by dividing it into a processing step using an external color development method and a processing step using a silver salt dye bleaching method. (Processing step using external color development method) In this method, it is preferable that all colored parts formed on the light-transmitting substrate by external color development method be formed in advance before applying the silver salt dye bleaching treatment. . 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. Exposure Processing Exposure methods that can be employed in the present invention include, for example, methods used in normal pattern exposure such as contact exposure, proximity exposure, and step exposure. In the pattern exposure, for example, as shown in FIG. 1, a photomask 14 is placed on a silver halide photosensitive material 13 having an emulsion layer 12 containing the silver salt dye exhibiting a bleaching action and laminated on a light-transmitting substrate 11. This is done by placing the photomask 14 on the photomask 14 and applying light from above. With this operation, 7
Portions 16 of the emulsion layer to be exposed corresponding to openings 15 provided in the otomask 14 can be selectively exposed. The size of the portion 16 to be exposed, that is, 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 nI11, the width of the aperture s15 is usually 340 nm or more, and furthermore, considering its use as a color filter, the width of the aperture s15 is 1 μm. It is preferable to do the above. In the case of a color filter for a liquid crystal display, in order to effectively reproduce colors by additively mixing red, blue, and green colored parts, the convergence of the aperture 15 should preferably be 100 μm or less. It is preferable to set it to 500μ or less. Other conditions such as exposure time and light source can follow normal conditions. In the external color development method, development is performed using a developer containing one or more color couplers.
This is a method of dyeing or precipitating a dye into an emulsion layer. The developer used contains at least a color forming coupler and a developing agent. As a developing agent, C.E.K. Mees, T.K./C.
ndT. “The Theory of the Photography 4”) by H. Jamas)
y of thePhotographic Proc
ess 3rd, Edition) J, 293-29
The compounds described on page 8 can be mentioned, and specific examples include (1) 4-amino-3-methyl-N-(2-hydroxyethyl)aniline sulfate (2) N-ethyl-N -Methoxyethyl-3-methyl-p~7 22-diamine p-)luenesulfonate (3) 4-amino-3-methyl-N~ethyl-N-
(2-Methylsulfonamidoethyl)aniline sulfate hydrate (4) N,N-diethyl-p-phenyl diamine sulfate (5) N,N-diethyl-3-methyl-p-ph Examples include 22 diamine hydrochloride. In the developer, it is preferable to select and use one type of developing agent from among the developing agents listed above. The selection of the developing agent is usually made in consideration of the type and combination of color forming couplers. The developing agent in the developer is usually used in a content within the range of 0.1 to 10 g in the developer la. If the content of the developing agent is less than 0.1 g, effective development may not be possible, and even if more than 10 g is used, not only will no significant improvement in developability be observed, but depending on the type of developing agent. may not dissolve sufficiently. In particular, it is preferable to use the developing agent in the range of 0.5 to 7 g in the developer 1 (2), and it is particularly preferable to use the developing agent in the range of 1 to 5 g. By setting the blending amount of the developing agent, regardless of the type of color forming coupler used,
Development time at normal density is within an appropriate range (e.g. 1-1
(within a range of 0 minutes), resulting in very good workability. Furthermore, by keeping it within this range, the coloring property becomes particularly good. The color-forming coupler is different from the internal coupler (ballast coupler) used in normal color photography, and is used in a state where it is added to the developer and is at least partially dissolved in the developer. It is an external coupler, and any known external coupler 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 coloring couplers include active methylene compounds (for example, pyrazolones such as l-(2,4,6-dolichlorophenyl)-3-(p-nitroanilino)-5-pyrazolone, 7-chloro-3 pyrazoloazoles such as -phenyl-6-itubrobyl-IH-pyrazolo[5,1-c]-1,2.4-triazole and cyanoacetanilides), and furthermore, , No. 016,587, U.S. Pat. No. 3.
No. 152.896, No. 3,615,502, Special Publication No. 4
4-133111 etc. can be used. Further, as an example of a cyan coloring coupler, a phenol compound (for example, 2-acetamido-4,6-dichloro-
5-methylphenol) or naphthol compounds (for example, N-(2-acetamido7enethyl)-1-hydroxy-2-naphthamide);
U.S. Pat. No. 3,002.836, 3,542. 552, British Patent No. 1,062,190, etc. can be used. In addition to the above, rThe Theory of
the Ph. tographic Process 3rd Edi
tionJ (cited above), Chapter 17. It is also possible to use those described on pages 382-395. In the developer, the total content of color forming couplers in the developer Iff is preferably set within the range of 0.1 to 20 g. If it is less than 0.1 g, sufficient color development may not be achieved, while if it is used in excess of 20 g, so-called fogging may occur. In particular, in the present invention, by controlling the total content of color-forming couplers in the developer la within the range of 0.2 to log, a color filter with less color turbidity and good spectral characteristics can be obtained. The blending ratio of color-forming couplers exhibiting different color development in this developer can be appropriately set in consideration of the color-forming properties of the color-forming couplers used. For example, when combining a cyan coupler and a magenta coupler, the weight ratio of both is usually 1:9 to 7:3.
Preferably it is within the range of 1:9 to 4:6. When a cyan color-forming coupler and a yellow color-forming coupler are combined, the weight ratio of the two is usually 1:9 to 7:3, preferably 1:9 to 4:6. Furthermore, when combining a magenta coloring coupler and a yellow coloring coupler, the weight ratio of both is usually 9:l to 2:8,
Preferably it is within the range of 8:2 to 6:4. When a coloring coupler, a magenta coloring coupler, and a yellow coloring coupler are combined, it is preferable to mix approximately the same amount of each of the three. 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 depends on the type and content of the color couplers and the developing agent, etc. The weight ratio of the color forming coupler and the developing agent can be set appropriately in consideration of the above, but usually the weight ratio of the color forming coupler and the developing agent is within the range of 1:9 to 9:1. Additionally, the developer may contain preservatives (e.g., sodium sulfite,
(diethylhydroxylamine), accelerators (e.g. alkaline agents such as sodium hydroxide), control agents (e.g. potassium bromide, potassium iodide), auxiliary agents (e.g. water conditioners such as polyethylene glycol, citrazic acid, imidazole) It may also contain additives contained in ordinary external developers, such as color toning agents such as derivatives. A developer can be prepared by dissolving the above components in water. Note that the developer should be used at a normal operating temperature (for example, 10 to 40°C).
) is used after adjusting the pH value using sodium hydroxide or the like so that the pH value falls within the range of 9.0 to 13.0. In the method of the present invention, pixels can be formed by external color development using the developer as described below, for example. First, the silver halide photosensitive material is pattern-exposed by a conventional method (first exposure). After performing the first pattern exposure, a first development of the exposed portion is performed using a developer containing the color forming coupler. For example, as a color coupler, a developer containing a cyan coupler and a magenta coupler (blue developer) is used to develop the first exposed area using a cyan developer, magenta developer, or yellow developer depending on the purpose. , a blue developer, a green developer, and a red developer. After the first exposed area is developed in this way, the photosensitive material is usually immersed in a stop solution containing an acid such as acetic acid to stop the reaction accompanying the development, then washed with water, and then washed with a bleach solution or a stop solution containing an acid such as acetic acid. By dipping it in a black and white developer to prevent color turbidity in the first developing area during the second and subsequent development processes, and then washing it with water and drying it, it is possible to remove any of red, blue, green, cyan, magenta and yellow. A first colored portion having any pixel is formed. Next, the unexposed area adjacent to the first exposed area is pattern-exposed using a 7-oto mask in the same manner as the first exposure, and then a developer other than that used in the first step is used. Develop using one type. Further, if desired, a second colored portion can be formed by performing steps such as immersion in a bleach solution or a black and white developer, washing with water, and drying. Similarly, 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. Further, if desired, a third colored portion can be formed by performing steps such as dipping in a bleach solution or a black and white developer, washing with water, and drying. In one example of 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. (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 steps by the silver salt dye bleaching method include at least black and white development, dye bleaching, and silver bleaching in this order. Next, the processing steps by the silver salt dye bleaching method will be divided into black and white development processing, dye bleaching processing, and silver bleaching processing, and will be explained in this order. Black-and-white development processing In this method, the photosensitive material is subjected to image exposure in the same pattern as the desired colored part pattern among the patterns of each colored part formed by the above-mentioned external color development method.
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 is, for example, developing agent E (hereinafter referred to as developing agent (D)). ], a developing aid, a preservative, a so-called developing antifoggant, an alkaline buffer, and, if necessary, a solvent for the developing agent (D) and the developing aid. 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, pbenzotriazole, 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 evaporated ethylene glycol, triethanol, and jetanol. An example of the contents of the various components in the black and white developer is as follows: 1 to 20 g IQ of developing agent (D) and 0 g of developing aid.
．． 05 to 8 g/(1, preservative 1'' 120 g/L development antifoggant o, ooi to 5 gIQ, alkaline buffer 0.1 to 50 gIQ, and when using a developing agent and a developing aid solvent) The amount of the solvent is 1 to 20 ml.The black-and-white development process is usually carried out by immersing the image-exposed photosensitive material in a black-and-white developer at 20 to 60°C for 10 to 200 seconds. Photosensitive material image-exposed through processing (A)
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, which will be described in detail below, is performed. Dye Bleaching Process 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 a positive image of the dye is formed by bleaching the dye in the dye contained in the image-exposed light-sensitive material in the portion containing a large amount of image silver. The dye bleach solution used contains, for example, a bleaching agent, a silver salt or a compound forming a silver complex, and a dye bleach accelerating catalyst. Examples of bleaching agents include mineral acids such as hydrochloric acid, sulfuric acid, and nitric acid; organic acids such as sulfamic acid, succinic acid, and acetic acid. Examples of compounds that form silver salts or silver complexes include potassium bromide, potassium iodide, urea, thiourea, semicarbazide, thiosemicarbazide, and the like. Examples of dye bleaching accelerating catalysts include pyrazine, naphthazine, quinoline, quinoxalines, phenazines, anthraquinones, naphthoquinones, indophenazines, N
-Substituted isoalloxazines, floquinoxalines, chietukizalines, diphenyl derivatives, triphenylmethane derivatives, simazines, alloxazines, cinnolines, orthophenylenediamine derivatives, etc. (U.S. Pat. No. 2,270,118, 2,410,02
No. 5, No. 2,541.884, No. 2,627,461
No. 2,669,517, British Patent No. 657.374
No. 711.247, Japanese Patent Publication No. 45-22195, etc. ). An example of the content of the various components in the dye bleaching solution is: 1 to 20 g of bleach IQ, 0.1 to 20 g/12 of a compound that forms a silver salt or complex, and 0.001 to 10 g of a dye bleach accelerating catalyst. /12. Dye bleaching treatment is usually carried out at 20-60°C and 10-200°C.
This is done by immersion in a dye bleaching solution for 2 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. Silver bleaching process Silver bleaching process is a process in which all black silver remaining in the image-exposed light-sensitive material that has been subjected to the dye bleaching process is rehalogenated. A silver source white liquor is used for this silver bleaching treatment. The silver source white liquor may be a conventionally known one, and for example, a bleaching liquor containing a ferric chelate of ethylenediaminetetraacetic acid can be suitably used. Silver bleaching is usually carried out at 18 to 60°C for 5 to 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. (Regarding Exposure/Treatment Process) Next, a preferred exposure/treatment process in the present invention will be described. For example, Table A shows the pattern of the exposure and processing process when forming a color filter having B (pixel for transmitting blue light), G (pixel for transmitting green light), and R (pixel for transmitting red light) shown in FIG. Shown below. Table A Each colored part shown in Figure 2 is yellow pigment (M+ or M2)
, magenta dye (y+ or Y, ) and cyan dye (C1
or C2), containing two different color pigments. Table A shows the method for forming each of these dyes. 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,
A silver salt dye bleaching method is used to erase the color of the dye in areas other than the areas indicated by SDR, which exhibits a silver salt dye bleaching action. For example, in the pixel forming pattern shown in Pattern Example 1 in Table A, first, the blue light transmitting pixels are pattern-exposed in the manner described above in the first exposure/processing process. Thereafter, a development process is performed using an external group developer containing a magenta color-forming coupler. Next, after the green light transmitting pixels are pattern-exposed in a second exposure/processing process, a development process is performed using an external developer containing a yellow color-forming coupler and a cyan color-forming coupler. Subsequently, the red light transmitting pixels are pattern-exposed in a third exposure/processing process, and then developed using an external developer containing a yellow color-forming coupler and a magenta color-forming coupler. lastly,
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. Ba,
There are no particular restrictions. Further, the arrangement of the blue light transmitting pixels, the green light transmitting pixels, and the red light transmitting pixels is not defined as shown in FIG. 2. (Others) In the method of the present invention, for example, a light-transmissive colored part 32 consisting of a red part (R), a colored part CB) and a green part (G) is provided on a light-transmissive substrate 31 as shown in FIG. are formed with gaps between them, pattern exposure is performed in these gaps, and development processing is performed using a developer containing a cyan coloring coupler, a magenta coloring coupler, and a yellow coloring coupler. A light-transmitting section (
A black stripe) 33 can also be formed. Also in this case, the silver salt dye bleaching process is preferably carried out after all external development processes have been completed. Further, in the method of the present invention, it is also possible to perform an 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 a mosaic pattern or a stripe pattern. 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, 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.
If placed, it can be used as a filter for liquid crystal color displays. Furthermore, it can also be suitably used in place of other conventionally used color filters for image pickup tubes. EXAMPLES Next, examples will be shown to further specifically explain the present invention. Note that % in the examples represents weight % unless otherwise specified. (Example 1) Silver halide sensitivity Preparation of material An iodine containing 4 mol% silver iodide was prepared by simultaneously adding a silver nitrate aqueous solution and an aqueous solution containing potassium bromide and potassium iodide to a 10% aqueous solution of gelatin. A silver oxide emulsion (average particle size: 0.05 ua + 1 gelatin concentration: 9%) was prepared. Addition conditions were regulated to obtain a Lippmann emulsion with an average grain size of 0.05 μI. The resulting silver iodobromide emulsion contained 28.3a+ per mole of silver.
g of sodium thiosulfate pentahydrate was added and chemically ripened at 59.5°C for 45 minutes. Then, 1-phenyl-5-mercaptotetrazole and 1-carboxyethyl-3°4.5-hydroxybenzene were added to the emulsion at 141.0% per mole of silver, respectively.
At the same time, add 15.9 g of the following compound SC-1 per mole of silver, and further add 40 mg of the following compounds H-1 and H-2 as hardeners, 5 rtrg per Ig gelatin. An emulsion coating solution was prepared. A backing layer is provided on the surface of the margin C-1 below. The formation of this backing layer will be explained next. A dispersion of compound Y-1 below was added to an aqueous gelatin solution, and 40+ags each of hardeners H-1 and H-2 were added.
Here, the amount of gelatin added to the aqueous gelatin solution was adjusted in advance so that it was 5%. Also, the amount of Y-1 added to the aqueous gelatin solution 100I1112 was 1.35%. Compound Y-1 ((CH, -CHSO□CHx)sccHzsOzcH
zcHJ zNcHzcHzsOsK The obtained emulsion coating solution was applied to a transparent borosilicate glass substrate (3
A silver halide photosensitive material having an emulsion layer was prepared by coating the film on a surface of 0 cm x 30 cm so that the dry film thickness was 3 μm. Silver coating amount is L5g/m", pigment coating amount is 0.24g
/m''. This silver halide photosensitive material was coated on the opposite side of the borosilicate glass substrate from the side having the emulsion layer and then dried to form a backing layer.Y-1 The amount applied was 10 mg/d+++''. The above-mentioned dispersion liquid was prepared by dissolving 11 g of Y-1 in tricresyl phosphate Igx ethyl acetate 4.29+aQ, followed by 0.83 g gelatin and triisopropyl-β.
- 5% aqueous solution of sodium naphthalene sulfonate 2.6
The mixture was added and mixed into an aqueous solution containing 3 cc and 8.4 raQ of water, subjected to ultrasonic dispersion at 50° C., ethyl acetate was removed, and water was added to make a total volume of 17.6 μa. Preparation of color filters As shown in Figure 2, three colors (blue), G (green), and R (red) are prepared.
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 0μ×150μm. A color filter chromium mask having a square opening with a layer of 150 μm on each side is placed on top of the photosensitive material, and a tungsten lamp is used to conduct the first [[! I@ exposure was performed. Exposure was carried out at positions corresponding to 8 portions 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 developer composition Magenta coupler・0.8g1-(
2,4,6-)dichlorophenyl)-3-(p-nitroanilino)-pyrazolone-5-, t-ton developing agent.
2.0g 4-amino-3-methyl-N-ethyl-N-(2-hydroxyethyl)anilino sulfate Sodium nitrilotrimethylene sulfonate (40% aqueous solution) 3.00m (2-anhydrous sodium sulfate・・・・・・ ・20.0g Sodium bromide・・・・・・・・・・ 1.0g Sodium sulfite・・
... ・10.0g ethylene glycol...
...1G, 0mff1 polyethylene glycol
... 2.0 g of water was added, and sodium hydroxide was added to the above magenta color developer to adjust the pH value at 25° C. to 12.0. Next, after immersing in a stop solution (3% acetic acid aqueous solution) for 1 minute and washing with water, bleaching was performed by immersing in a silver source white liquor of the following composition for 1 minute, and then washed with water for 1 minute and then dried. , a blue portion was formed on the substrate (first treatment). Silver source White liquor composition Ethylenediaminetetraacetic acid iron(II[) ammonium salt.
・200.0g ammonium bromide・IO, 0g glacial acetic acid... Add IO, 0mg water to make ta, and adjust to pH=6.0 using aqueous ammonia. Next, another chrome mask for a color filter was placed on the photosensitive material after the above processing so that the exposed area was part G in FIG. 2, and a second exposure was performed. 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 immersed in the stop solution for 1 minute, washed with water, and bleached in the same manner as the first exposure. , washed with water, and dried to form a green portion on the substrate (second treatment). Yellow color developer composition Yellow coupler・1.5gσ-
(4-carboxyphenoxy)-α-pivaloyl-2,
4-dichloroacetanilide developing agent...
2.0g 4-amino-3-methyl-N-ethyl-N-(2-hydroxyethyl)aniline sulfate Sodium nitrilotrimethylenesulfonate (40% aqueous solution) 3.00t12 Anhydrous sodium sulfate 20.0g Sodium bromide・・3.0g Sodium sulfite・
・・・・・・ IO, 00g ethylene glycol・
Add 1000% polyethylene glycol and 2.0g water
IO Note that by adding sodium hydroxide to the above yellow color developer, the pH value at 25°C is 12.0.
It was prepared so that 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 material subjected to this third exposure was immersed in a red color developer having the composition shown below at 23°C for 3 minutes, then stopped, washed with water, bleached, washed with water, dried, and placed on a substrate in the same manner as the second time. A black part was formed on the surface (third process). Color developer composition Magenta coupler・2.00g1-
(2,4,6-Dolichlorophenyl)-3-(p-nitroanilino)-5-pyrazolone 5-...
......0.82ga-(4-carboxyphenoxy)-a-bivaloyl-2,4-dichloroacetanilide developing agent...2.0g4
-Amino-3-methyl-N-ethyl-N-(2-hydroxyethyl)aniline sulfate sodium nitrilotrimethylene sulfonate (40%)
・・・・・・ ・・・ 3.00m! 1 Anhydrous sodium sulfate... 20.0g sodium bromide 3.0g sodium sulfite
10.0g ethylene glycol
・・to,oo■a polyethylene glycol・
Add 2.0g water...
... lIl In addition, sodium hydroxide was added to the above red color developer to adjust the pH value at 25° C. to 12.0. Next, a 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 fourth exposure was performed. The photosensitive material that has been exposed for the fourth time is processed at 33°C as follows to form red areas (fourth process), resulting in B (blue), G (green), R (red ) A color filter having a three-color mosaic pattern was obtained. Black and white development Stop for 1 minute Wash with water for 1 minute Dye bleach for 1 minute Wash with water for 1 minute Silver Bleach for 1 minute with water
Wash for 1 minute
Arrival 1 minute water
Washing: Drying for 4 minutes The bath used for each treatment had the following composition. ``Ryoichiji'' Taka 1 Higashi Gnu Sodium sulfite 10g Hydroquinone 10g Potassium hydroxide (48
% aqueous solution) 5tQ diethylene glycol
201a Jimaison
0.7g Sodium carbonate 20g
Potassium bromide 2g Thiadiazole 0.05g Add water
11 Dye bleaching solution composition 96% sulfuric acid 40w, Q potassium iodide 15g2.3.6-
Add 2g of trimethylquinoxaline water
11 Silver Bleaching Solution Composition The same silver source white solution composition as described above was used. Fixer composition Ammonium thiosulfate 175.0g Sodium sulfite 8.5g Sodium metasulfite 2.3g Add water
In (adjusted to pH=6.0 using acetic acid) Also, after making the color filter, 3% In was added to the backing layer.
The backing layer was safely removed by soaking it with an aqueous sodium hypochlorite solution and wiping it with gauze. The color filters obtained in this way were sample No.
Let it be l. In the manufacturing process of sample No. 1, the magenta color developer and the red color developer were added to Nos. 002 to 11 in Table 1 and Table 2.
Samples Nos. 092 to 11 were prepared by changing the developing solutions shown in Nos. 2 to 11, respectively. For each sample obtained, blue light (B), green light (G)
, the density of each color transmission source pixel is determined by scanning with a microdensitometer (aperture scanning area 250 μm), and the level difference between each color transmitted light pixel is determined using a rank-Taylor Hobson Co., Ltd. Talystep. It was determined by The results obtained are shown in Table 3. In addition, the concentration was shown as a relative value with the value of sample No. 1 being 1. In addition, the difference in level between pixels was determined by the fact that the dry film thickness of the green light transmitting pixel layer was the largest in all samples. As is clear from the results, the color filter produced using the treatment liquid of the present invention exhibited good relief properties with small steps between each pixel.

[Brief explanation of the drawing]

FIG. 1 is a cross-sectional view showing an example of pattern exposure in the manufacturing method of the present invention, and FIG. 2 is a cross-sectional view showing an example of a color filter obtained by the manufacturing method of the present invention.
FIG. 3 is a cross-sectional view showing another example, and FIG. 4 is a cross-sectional explanatory view showing an example of a liquid crystal color display using a color filter obtained by the manufacturing method of the present invention. 11. - Light-transmitting substrate 12. - Emulsion layer 13...
Silver halide photosensitive material 14. 7 otomask 15... opening 16. .Exposure planned area 21.3
1. Light-transmitting substrate 22.32. Colored part 43.
・Color filters 46a, 46b・・Polarizing plate 47・・Liquid crystal 48a
, 48b...electrode

Claims (1)

[Claims] A color filter comprising the step of exposing a photosensitive material having a silver halide emulsion layer on a light-transmitting substrate in a pattern, and then forming a dye image corresponding to the pattern using a developer containing a coupler and a color developing agent. The manufacturing method includes at least one coupler that forms a substantially colorless compound by a coupling reaction with the oxidized form of the color developing agent, and has a pH of 9 at 25°C.
A method for producing a color filter, characterized by processing with the above processing liquid.