JPH0339901A - Color filter - Google Patents

Abstract

PURPOSE:To obtain color filters having excellent surface smoothness by incorporating at least one kind of the compds. formed by the coupling reaction of a specific precursor compd. and the oxidant of a color developing agent into at least one color of picture elements and incorporating a high boiling solvent therein. CONSTITUTION:At least one kind of the substantially colorless compds. formed by the coupling reaction of the precursor compd. expressed by formula I and the oxidant of the color developing agent are incorporated into at least one color of the picture elements and the high boiling solvent is incorporated therein. In the formula I, R denotes an alkyl group (including a substd. alkyl group) (including a substd. aryl group) substd. to an active point; X denotes the atom group (the heterocyclic nucleus may further form a condensed ring with other rings and may have a substd. on the ring) necessary for forming 5- or 6-membered heterocyclic nuclei contg. at least one nitrogen atom, sulfur atom or oxygen atom. The excellent smoothness of the filter surface is exhibited and the fatigue of the developer is lessened in this way. The smaller times of the exchange of the developer are necessitated and the cost of production is reduced.

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a color filter, and more particularly to 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 gray. 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, if a difference in level occurs between the pixels of the color filter, the spectral characteristics of each pixel after IR for producing a color liquid crystal display will be different from desired ones, resulting in deterioration of image quality. Therefore, in order to solve the above problem, the inventors developed a coupler (hereinafter referred to as a vise coupler) that forms a substantially colorless compound by coupling reaction with an oxidized form of a color developing agent in an external color developer. proposed that the B (blue), G (green), and R (red) pixels of a color filter selectively contain the coupling product of the optical coupler (Patent Application No. 63). -241800). However, it has been found that the above-mentioned product precipitates and crystallizes on the surface of the color filter, creating convex portions on the surface and impairing its smoothness. Another disadvantage is that the product precipitates from the light-sensitive material layer into the external color developing solution, significantly accelerating fatigue of the developing solution. [Object of the Invention] An object of the present invention is to provide a color 7 and filter having excellent surface smoothness. Another objective is to provide a color filter that is low cost and has stable performance. [Structure of the Invention] The above-mentioned object of the present invention is to provide a color filter which is produced by color development using a silver halide photosensitive material in which a photosensitive agent layer is provided on a light-transmitting substrate, and which is divided from 3FJK colors of light. , (i) at least one color pixel contains at least one substantially colorless compound formed by a coupling reaction between a precursor compound represented by the following general formula [1] and an oxidized product of a color developing agent, and (2) Achieved by a color filter characterized by containing at least one kind of high boiling point solvent. General formula CI) In the formula, R represents an alkyl group (rI!, including substituted alkyl groups) or an aryl group (#, including substituted aryl groups) substituted at the active site, and X is at least one nitrogen atom, Atom group necessary to form a 5- to 6-membered heterocyclic nucleus containing a sulfur atom or an oxygen atom (the heterocyclic nucleus may further form a condensed ring with another ring, or a substituent on the ring) may have a group). The present invention will be explained in more detail below. The optical coupler represented by the general formula (1) has the compound dissolved in whole or in part in the treatment liquid on the ring or on the alkyl group represented by R, as necessary, and the compound has a substituent group having a molecular size and shape that renders it immobile in the emulsion layer after coupling with the oxidized form of the color developing agent. Examples of the substituent include organic groups having 6 to 24 carbon atoms. More preferable examples of the optical coupler represented by the general formula (1) according to the present invention include the following general formulas [2] to

[9]
It is a compound represented by the general formula [2] and [3]
Compounds represented by are preferred. -Soft formula (9) R1 O In the above -soft formula, R is the same as defined in general formula [l]. R4 represents a substituted or unsubstituted alkyl group or aryl group. R represents an R-substituted, unsubstituted alkyl group, aryl group, alkylamino group, arylamino group, acylamino group, ureido group, cyano group or carbamoyl group. R and R2 or R3 at adjacent positions may be combined to form a ring. R3 represents a substituted or unsubstituted alkyl group or aryl group. More preferable compounds are the following in soft formula [2].
It is a coupler represented by the soft type [lO]. -Soft formula (10) In the formula, R has the same meaning as R in general formula (1), and R6
represents a hydrogen atom, a halogen atom, and an alkyl, asacoxy, alkylamide, arylamide, alkylsulfonamide, arylsulfonamide, alkoxycarbonyl, carbamoyl, or sulfamoyl group, and R
1 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 0 to 5. These alkyl groups, alkoxy groups, aralkyl groups, and aryl groups may further have a substituent. Preferred examples of R5 include groups such as methyl, ethyl, benzyl, phenethyl, phenyl, and tolyl. Specific examples of the compound represented by the general formula (1) according to the present invention are shown below. E-1 WE-14 WE-23 WE 4 WE 5 WE 6 0 H3 WE-27 WE-28 WE-29 WE-30 WE-31 WE-32 The treatment liquid containing the optical coupler according to the present invention is It may be the same as or different from the formula developer or the black and white developer for SDR, but it is preferable to use the same in terms of simplifying the treatment process and reducing process costs. The amount used is preferably 10g or less per treatment liquid IQ, and 0.
．． A range of 0.01 to 2 g is more preferable. The high boiling point solvent (hereinafter abbreviated as HBS) according to the present invention can be used in the photosensitive agent layer or in the external developer, or both in the photosensitive agent layer and in the external developer. However, it is preferable to use it in the photosensitive agent layer. The amount of HBS used is 0.1 when used in the photosensitive layer.
~20mg/d+s'' is preferred, 0.2~5 sog/d
a” is more preferable. When used in an external developer, 0
．． 1-30g is preferable, more preferably 0.5-1O
It is g. Here, the high boiling point solvent refers to a compound having a boiling point of 200°C or higher. If a compound with a boiling point of less than 200°C is used, there is a risk that the compound will vaporize and disappear from the photosensitive material when a protective layer, usually made of polyimide, polyacrylamide, etc., as a main component, is provided after color filter production. There is. In addition, when providing a light-transmitting electrode or an alignment film on the sample after the protective layer has been created, it is treated at high temperature, so the boiling point is 200°C.
It is not preferred to use compounds with less than Examples of HBS include esters such as heptatarate and phosphate, phenolic compounds, organic acid amides, and ketones. Among these HBSs, phthalate esters, phosphoric esters, and phenol compounds are preferred. Note that the HBS used in the present invention may be a mixture of two or more. Examples of the phthalate esters used in the present invention include those represented by the following general formula CI). General Formula (I) In the formula, R1 and R8 each represent an alkyl group, an alkenyl group, or an aryl group. However, the total number of carbon atoms in the groups represented by %RI and R1 is 2 to 36. More preferably, the total number of carbon atoms is 6 to 24. The alkyl group represented by R and R3 may be linear or branched, such as butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, Examples include groups such as octadecyl and eicosyl. Examples of the alkenyl group represented by Rt and R2 include allyl, hexenyl, heptenyl, octenyl, and octadecenyl, and examples of the aryl group include phenyl and naphthyl groups. These alkyl groups, alkenyl groups and aryl groups may have single or multiple substituents. Examples of substituents for alkyl and alkenyl groups include halogen atoms and groups such as alkoxy, aryl, aryloxy, alkenyl, and alkoxycarbonyl; examples of substituents for aryl groups include halogen atoms and alkyl, alkoxy, aryl, Examples include groups such as aryloxy, alkenyl, and alkoxycarbonyl. Two or more of these flllllll groups may be introduced. Phosphoric esters advantageously used in the present invention include those represented by the following general formula (II). General Formula (If) In the formula, R8, R6 and R1 each represent an alkyl group, an alkenyl group or an aryl group. However, the total number of carbon atoms in the groups represented by R3, R4 and R6 is 3 to 54. The alkyl group represented by Rs%R1 and R6 may be linear or branched, and specifically, R and R of the soft formula (I) above
Examples of the alkyl group represented by 8 include the same groups as those listed above. As the alkenyl group represented by R3, R, and R,
Examples of the aryl group include a vinyl group, an allyl group, a butenyl group, and a phenyl group, a tolyl group, a xylyl group, and the like. These alkyl groups, alkenyl groups and aryl groups may have single or multiple substituents. Rs, R4 and R2 are preferably alkyl groups, such as butyl, 2-ethylhexyl, octyl, t
-octyl, 3.5.5-trimethylhexyl, nonyl, decyl, 5ec-decyl, 5aC-dodecyl and the like. Any conventionally known phenolic HBS can be used as the phenolic HBS used in the present invention, but in the present invention, it has a melting point of 50°C or less and is solid at normal temperature (25°C), or liquid at normal temperature and under normal pressure. (at 1 atm), the boiling point is 2
It is preferable that the 4-position of the phenol is substituted with a group that does not leave during coupling so that it cannot react with the oxidation product of the color developing agent at temperatures above 00°C. Furthermore, those having a diffusion-resistant group (hereinafter referred to as a ballast group) are preferred, and those represented by the following soft formula (III) are particularly preferred. - Soft formula (III) H - In the formula, R and R7 are each a hydrogen atom or a carbon number of 1 to 2
0 straight chain or branched alkyl group (e.g. methyl, ethyl, t-butyl, t-pentyl, (-octyl, dodecyl, pentadecyl, etc.), and R. represents a straight chain or branched alkyl group having 1 to 20 carbon atoms. group (the above R
6 and R7) or a cycloalkyl group (for example, cyclopentyl, cyclohexyl, etc.). However, the total number of carbon atoms in the groups represented by R1 and R is 6 to 24. Typical specific examples of the HBS according to the present invention are shown below, but the present invention is not limited thereto. B5-1 B5-3 HBS HBS-7 ■S-9 B5-2 R5-4 B5-6 B5-8 HBS 0 11BS-11 HBS 2 118s-14 B5-16 C11゜11BS-13 1 (BS 5 11BS- 17 HBS-18 HBS -20 HBS -22 1Bs 4 HBS -26 B5-19 C, H. Sauce CiH @ B5-21 HBS 3 [(BS 5 HBS 7 HBS -28 ) IBS -29 HBS -30 B5-31 HBS -32 HBS -33 I (BS) according to the present invention is preferably used as a dispersion of a hydrophilic colloid such as gelatin, a surfactant, water, etc. Regarding silver halide photosensitive materials, in the present invention, A silver halide photosensitive material is used which has a photosensitive layer (referred to as an emulsion layer) formed by coating a silver halide emulsion on the substrate. Furthermore, since color filters may be exposed to high temperatures during the vapor deposition process of transparent electrodes, the material for the light-transmitting substrate should have good heat resistance. Examples of materials constituting such a light-transmitting substrate include:
Examples include glasses such as polyethylene terephthalate, polybutylene terephthalate, polystyrene, polycarbonate, polyether sulfone soda glass, and borosilicate glass, and inorganic materials 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-transmitting substrate can be set appropriately depending on the purpose and material, but usually 0.5 μs = IOm.
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 mm. 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 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, It is preferable that the layer absorbs light of 500n layer or less. Furthermore, the backing layer may contain a UV absorber. As the ultraviolet absorber, for example, rUVINUL MS-
40J (manufactured by BASF), rTINIIVIN-PJ
(Chiz<・Kaikysha ml) is mentioned. Non-diffusible dyes or pigments and UV absorbers have known high boiling point a! After dissolving in a solvent and a low boiling point organic solvent such as methyl acetate, ethyl acetate, propyl acetate, butyl acetate, cyclohexane, tetrahydro7rane, carbon tetrachloride, chloroform, etc., it is dissolved in an aqueous gelatin solution containing a surfactant. The mixture is mixed and then emulsified and dispersed using a dispersing means such as a stirrer, homogenizer, colloid mill, 70-jet mixer, ultrasonic dispersion device, etc., and then added to a coating composition for a hydrophilic colloid backing layer for use. The amount of non-diffusible dye or pigment used is preferably 0.lff1 g or more, particularly preferably 1 yag or more per 100 cm of light-transmitting substrate. Although an emulsion layer can be coated, 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. Materials for forming this undercoat layer include, for example, gelatin, albumin, casein, cellulose derivatives, starch derivatives, Examples include sodium alginate, polyvinyl alcohol, polyvinylpyrrolidone, polyacrylic acid copolymer, polyvinylidene chloride copolymer, and polyacrylamide.The thickness of the undercoat layer is preferably thin considering the spectral characteristics of the color filter. , usually less than 1 μm, 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-based binder. , may further contain a dye having a pigment that exhibits a silver dye 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 ttta or less.If the average grain size of silver halide is large, the image quality mainly in 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 a silver halide emulsion in which a dye exhibiting a silver dye bleaching action is used. 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. The silver halide emulsion in the present invention contains silver halide, a water-soluble binder, and a dye at a weight ratio of (silver halide):(water-soluble binder) of 120 to 8:11. It is desirable that the weight ratio of the dye to the water-soluble binder is 1/10 to 50, and the weight ratio of the dye to the 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 usually in the range of 0.3 to lOμ- 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 μm, 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 photosensitive material by a combination of an external color development method and a silver dye bleaching method. When this method is adopted, it is preferable to carry out the treatment by the silver 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 dye bleaching method. (Processing step using external color development method) In this method, it is preferable that all colored parts to be formed on the light-transmissive substrate by external color development method are formed in advance before performing the silver 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 those used in normal pattern exposure such as contact exposure, -proximity exposure, and step exposure;
One example is the law. In 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 dye exhibiting a silver dye bleaching action and laminated on a light-transmissive substrate 11. This is done by applying light to the photomask 14 from above. By this operation, the portions 16 of the emulsion layer to be exposed corresponding to the openings 15 provided in the photomask 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 in the range of 340 to 420 nm, the width of the opening 15 is usually 340 nm or more, and further considering its use as a color filter, It is preferable to repeat the process 1μ times or more. In addition, 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 width of the aperture ff115 is preferably set to 1000 μm or less, particularly preferably. It is preferable to set it to 500jZa+ 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, CEE K Mies, Te(-
- H. James (C, E, Mees and
T. The Theory of the Photography (The Theory of Photography, 3rd Edition) by James H.
y of thePhotographic Proc
ess 3rd, Edition) J, 293-298
Specific examples include (1) 4-amino-3-methyl-N-(2-hydroxyethyl)aniline sulfate (2) N-ethyl-N- Methoxyethyl-3-methyl-
p-phenylenediamine/p-toluenesulfonate (3) 4-amino-3-methyl-N-ethyl-N-(
2-methylsulfonamidoethyl)aniline sulfate
Hydrate (4) N,N-diethyl-p-7/enylenediamine sulfate (5) N,N-diethyl-3-methyl-p-
Examples include phenylenediamine 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 IQ. 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 developer solution Iff in an amount of 0.5 to 7 g, and it is particularly preferable to use the developing agent in the range of 1 to 5 g. By setting the amount of the developing agent within this range, regardless of the type of color forming coupler used,
Development time at normal density is within an appropriate range (e.g. 1 to I
(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 type coupler) used in ordinary color photography, and is used in a state where it is added to the developer and at least a portion thereof is 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-
acylacetanilides such as carboxyphenoxy)-a-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, tonohyrazolones such as l-(2,4,6-1-lichlorophenyl)-3-(p-nitroanilino)-5-pyrazolone, 7-chloro-3 -phenyl6-isopropyl-I H-pyrazolo[5, l -c]-1,
2. pyrazoloazoles such as 4-triazole and dianoacetanilides), and furthermore, OLS No. 2,016,587, U.S. Pat.
No. 152,896, No. 3,615,502, Special Publication No. 4
4-133111 etc. can be used. Furthermore, examples of cyan color forming couplers include phenolic compounds (e.g.
-Methylphenol); 1-)-7i-- compound (e.g., N-(2-acetamidophenethyl)-
U.S. Pat. No. 3,002.836, U.S. Patent No. 3,54
2. 552, British Patent No. 1,062,1.90, etc. can be used. In addition to the above, rThe Th5ory of
the Ph. tographic Process 3rd Edi
tionJ (cited above), Chapter 17. 382-395 may also be used. In the developer, the total content of color forming couplers in the developer Iff is preferably set within a range of 0.1720 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 to be within 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 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 color-forming coupler and a magenta color-forming 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. Further, when a cyan color-forming coupler and a yellow color-forming coupler are combined, the weight ratio of both is usually in the range of 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 9:1-1:9,
Preferably it is within the range of 8:2 to 2:8. 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).
It is used after adjusting the pH value in C) 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, by performing development using a developer (blue developer) containing a cyan coupler and a magenta coupler as color couplers, the exposed areas are developed blue. Further, by using a developer (green developer) containing a cyan color-forming coupler and a yellow color-forming coupler, the exposed area is developed green. Further, by using a developer (red developer) containing a magenta color-forming coupler and a yellow color-forming coupler, the exposed area is developed in red. Also, a developer containing a cyan color forming coupler (cyan developer)
, by using a developer containing a magenta color-forming coupler (magenta developer) and a developer containing a yellow color-forming coupler (yellow developer), the exposed areas become cyan and cyan, respectively.
Developed to magenta and yellow colors. The first exposed area is 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 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, usually, a bleach solution is added. Alternatively, it can be immersed in a black and white developer to prevent color turbidity in the first development area during second and subsequent development processes, and then washed with water and dried.Thus, red, blue, green, cyan,
A first colored portion having either magenta or yellow pixels 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 of the following. 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 the first to third colored portions are formed as described above, a silver dye bleaching treatment described in detail below is performed. (Processing step using silver dye bleaching method) In this method, after forming all the colored parts by the external color development method, a silver dye bleaching process is performed to remove the silver dye bleaching effect contained in the silver halide photosensitive material. Decolorize the dye that shows. The processing steps by the silver dye bleaching method include at least black and white development, dye bleaching, and silver bleaching in this order. Next, processing steps using the silver dye bleaching method, black and white development processing,
Dye bleaching treatment and silver bleaching treatment will be explained separately 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, a developing agent (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, talolhydroquinone, 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 bromide and benzotriazole. 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. An example of the content of the various components in the black and white developer is as follows: developing agent (D): 1 to 20 g/Q, developing aid: 0
．． 05-8g/(2, preservative 1-120g#!, development antifoggant o, ooi~5g/L alkaline buffer 0.1
~50g, 1, and when using a developing crude drug and a developing aid solvent, the solvent is 1~20a+(2#!).Black and white development is usually carried out at 20~60°C and 10~200°C.
This is carried out by immersing the image-exposed photosensitive material in a black and white developer for a second. 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, 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 bleach accelerating catalysts include pyrazine, naphthazine, quinoline, quinoxalines, phenazines, anthraquinones, naphthoquinones, indo-7enazines, N
Examples include -substituted isoalloxazines, floquinoxalines, chenoquinoxalines, diphenyl derivatives, triphenylmethane derivatives, lumazines, alloxazines, cinnolines, orthophenylenediamine derivatives (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 as follows: 1 to 20 g of bleach/L of silver salt or 0.1 to 20 g of a compound forming a silver complex/(1), 0 of dye bleach accelerating catalyst
．． 001-10g #2. Dye bleaching treatment is usually carried out at 20-60°0 and 10-20°C.
This is done by immersion in a dye bleach solution for 0 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 described 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 18-60°C for 5-500 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, 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. 2, each exposure table shown in FIG. The colored part is yellow dye (YI or Y)
, contains two different dyes among magenta dye (Ml or Mli) and cyan dye (C+ or C3). Table A shows the method for forming each of these dyes. That is, this method After forming a dye image at the location indicated by GA in Table A using an external color development method,
A silver dye bleaching method is used to remove the color of the dye in areas other than those indicated by SDR, which exhibits a silver dye bleaching effect. 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, development is performed using an external 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. After the red light transmitting pixels are pattern-exposed in a third exposure/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 exposed in a pattern, the silver 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, especially if silver dye bleaching treatment is performed after all outer color development processes are completed, There are no 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, a light-transmissive colored region consisting of a red region (R), a blue region (B), and a green region (G) is formed on a light-transmissive substrate 31 as shown in FIG. 3, for example. 32 are formed with gaps between them, pattern exposure is applied to these gaps, and then development is performed using a developer containing a cyan coloring coupler, a magenta coloring coupler, and a yellow coloring coupler. A light-impermeable section (black stripe) 33 can also be formed in the gap between the red part (R), the blue part (B), and the green part (G). Also in this case, the silver 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 process 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 4 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 461).
3, 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. [Example] Next, the present invention will be explained in more detail with reference to Examples. Note that % in the examples represents weight % unless otherwise specified. Example 1 A silver iodobromide emulsion containing 4 mol% silver iodide (average grain size: 0 .05 μm 1 gelatin concentration 9%) was prepared. Addition conditions were regulated so as to obtain a Tubman emulsion having an average grain size of 0.05 microns. To the obtained silver iodobromide emulsion, 2L3mg per mole of silver was added.
Sodium thiosulfate pentahydrate was added to the mixture and chemically aged at 59.5°C for 45 minutes. Next, l-phenyl-5-mercaptotetrazole and l-carboxyethyl-3°4.
1 5-hydroxybenzene per mole of silver, respectively.
41.5 mg and 3.40 g were added, and 15.9 g of the following compound sc-i was added per mole of silver, and the following compounds H-1 and H-2 were added as hardeners to geladin Ig.
By adding 40 mg and 5 aag of each SC-1)1-1-2 ((C)I!-Cl2O,CI3CCH!SO□CH
zCHz]xNCHzCHxSOsK The obtained emulsion coating solution was applied to a transparent borosilicate glass substrate (30 cm
A silver halide light-sensitive material having an emulsion layer was prepared by coating the film on Peng X30cIB) to a dry film thickness of 3 pta. Bank clerk: 1.5g/m”, amount of pigment applied: 0.24g
/m''. The thus produced photosensitive material was designated as Photosensitive Material-1. In addition, in the production process of Photosensitive Material-1, Photosensitive Materials-2 to 9 in Table 1 were used.
A dispersion containing each of the compounds shown in is added to the emulsion coating solution,
Photosensitive materials-2 to 2 were prepared in the same manner, except that the amount of water added was adjusted so that the volume of the emulsion coating solution per mole of silver was the same as the volume of the emulsion coating solution in the manufacturing process of photosensitive material-1.
9 was produced. For bank clerks, 1.5g/m'', the amount of pigment applied is 0.2
The amount of HBS applied was 0.1 g/m''. As the dispersion liquid, each of HBS shown in Table 1 was 7.54%
A solution prepared by dissolving 75.7 g of ethyl acetate was added to an aqueous solution containing 15.19 g of gelatin, 94 g of a 5% aqueous solution of sodium triisopropyl-β-naphthalenesulfonate, 7 mQ, and 254.6 mff1 of water.
After ultrasonic dispersion at 0°C, ethyl acetate was removed, and water was added to make a total of 454.7t12. The silver halide photosensitive materials mentioned above all have a backing layer on the surface of the borosilicate glass substrate opposite to the surface having the emulsion layer. The formation of this backing layer will be explained next. A dispersion of the compound Y-l below was added to an aqueous gelatin solution, and hardeners H-l and H-2 were added for 40s+g15 each.
Added a gram. Here, the amount of gelatin added to the gelatin aqueous solution was adjusted in advance to be 5%. Also, the amount of Y-1 added to the gelatin aqueous solution was 1.3
It was 5%. -1 Thereafter, this aqueous gelatin solution was applied to the borosilicate glass substrate and dried to form a backing layer. Y-
The amount of 1Os + g/da'' was added.The above-mentioned dispersion was dissolved per 11g of Y-1 in 4.29g of tricresyl phosphate Igs ethyl acetate, then 0.83g of gelatin, 0.83g of reimprovir- 5% aqueous solution of sodium β-naphthalene sulfonate 2.63a
ff and 8.4 m (l) of water were added and mixed, subjected to ultrasonic dispersion at 50°C, ethyl acetate was removed, and water was further added to make 17.6 mff. Table 1 Halogen HBS in silver-sensitive materials: 3 (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
0μ5×15Qμ−. On each of the above silver halide photosensitive materials, one side is 150 μm.
A chromium mask for a color filter having a square opening of - was overlaid, 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 developer composition Magenta coupler... 0.26g5-
t-Butyl-7-chloro-3-(3-methylbutyl) I
H-pyrazolo[3,2-eli, 2.4-triazole coupler (WE-20)... ・0.
6g developing agent... 2.0g4
-Amino-3-methyl-N-ethyl-N-β methanesulfonamide ethylaniline 11/2 sulfate l hydrate;, Sodium trilotrimethylenephosphonate (40
% aqueous solution)... 3.00mQ anhydrous sodium sulfate...20.0g sodium bromide...1.0g sodium sulfite, lithium...・・10.00g ethylene glycol ・1O, Om (2 polyethylene glycol ・Add 2.0g water
14 Furthermore, by adding hydroxide to the above magenta color developer, the pH value at 25°C is 1.
I adjusted it to 260. Next, after washing with water for 1 minute, bleaching was performed by immersing it in a silver source white liquor having the following composition for 3 minutes, washing with water for 4 minutes, and then drying to form a blue part on the substrate (first treatment )
. Silver source White liquor composition Ethylenediaminetetraacetic acid iron (III) ammonium salt
200.0g ammonium bromide...IO, 0g glacial acetic acid, 10.01112 Add water to adjust to IQ, use ammonia water to pH-6.0
Adjust to. 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 following composition at 23°0 for 3 minutes.
The substrate was washed with water for a minute, then bleached, washed with water, and dried in the same manner as the first time to form a green portion on the substrate (second treatment). Yellow color developer composition Yellow coupler... 1.5gσ
-(4-carboxyphenoxy)-σpivaloyl2.
4-dichloroacetanilide developing agent/
2.0g 4-amino-3-methyl-N=ethyl-N-β methanesulfonamidoethylaniline/l
) / 2 sulfate l hydrate Sodium nitrilotrimethylenephosphonate (40% aqueous solution) 3.00 mQ anhydrous sodium sulfate 20.0 g sodium bromide 3.0 g sodium sulfite
・・・ 1O,00g ethylene glyfur・・
・・・・・・ io, omQ polyethylene glycol・
・Add 2.0g water
IO In addition, hydroxide 1 is added to the above yellow color developing solution.
-addition of lithium to achieve a phi value of 12 at 25°C
．． I adjusted it so that it was 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 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 washed, bleached, washed with water and dried in the same way as the second exposure, and then placed on a substrate. A black part is formed (third process). Red color developer composition Magenta coupler...0.28g6-
[-butyl-7-chloro-3-(3-methylbutyl)H
l-pyrazolo [3,2-cl-i, 2,4-triazole coupler (WE-20)
0.32g yellow coupler 1
．． 42gα-(4-carboxyphenoxy)-αpivaloyl-2,4-dichloroacetanilide developing agent.
・ 2.0 g 4-aminol 3-methyl-N-ethyl-N-β-methanesulfonamide ethylaniline 11/2 sulfate l hydrate sodium nitrilotrimethylenephosphonate (40% aqueous solution) ・ ・ 3.00 m (2 Anhydrous sodium sulfate, 20.0g sodium bromide, 3.0g sodium sulfite,
10.00g ethylene glycol
10.00m4 polyethylene glycol, add 2.0g water
112 Furthermore, by adding sodium hydroxide to the above red color developing solution, the pH value at 25°C was 12.
I adjusted it so that it was 0. Next, a chrome mask for a color filter is placed on the photosensitive material after the above processing so that the exposed area is the R area in FIG. 2, and a fourth exposure is 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 1 minute water wash 1 minute dye bleach 1 minute water wash 1 minute silver
Bleach 6 minutes in water Wash 1 minute fixing 1 minute in water
Wash and dry for 4 minutes
The bath used for each drying process had the following composition. Black and white developer composition Sodium sulfite 10g Hydroquinone 10g Potassium hydroxide (48
% aqueous solution) 5m12 diethylene glycol
20a+ff Jimaison
0.7g sodium carbonate 2
0゜Potassium bromide 2g Thiadiazole 0.05g Add water
Ha dye bleaching solution composition 96% sulfuric acid 40m potassium iodide 15g 2. Add 3.6-dolimethylquinoxaline 2g water
112 Silver bleaching solution composition Pure water 800p Sodium ferricyanide 206g Sodium bromide 15g Borax
Add 1g water 1
12 (Adjust the pH to 8.0 using an aqueous potassium hydroxide solution.) Fixer composition Ammonium thiosulfate 175.0g Sodium sulfite 8.5g Sodium metasulfite 2.3g Add water
112 (adjusted to pH=6.0 using acetic acid) Also, color filter production fl! After that, the backing layer was completely removed by impregnating the backing layer with a 3% aqueous sodium hypochlorite solution and wiping it with gauze. The color filters obtained in this way were sample No.
1 to 9. In the manufacturing process of samples No. 1 to 9, photosensitive material sample N
Sample L was prepared in the same manner except that the amount of color coupler in the magenta color developer and the red color developer and the type and amount of the coupler were changed as shown in Table 2.
0 to 17 were produced. However, sample No. 10.12.14 and 16 use photosensitive material sample No. 1, and sample No. 11.13.15
and 17 are Table 2 Amount of color coupler in magenta color developer and red color developer and type and amount of optical coupler Sample No. 1 to 9
Sample no.
In the same manner as 1 to 9, color 71 Luther sample No. 18
~26 Fabrication 3 Types and amounts of coupler and developing agent in each external developer Regarding the obtained color filter samples No. 1 to 26,
As a result of scanning the density of blue light transmitting pixels and red light transmitting pixels using blue light (B), green light (G), and red light (R) using a microdensitometer with an aperture scanning area of 250 μi, The difference in concentration between samples at each pixel is
The concentration distribution [(standard deviation)/(average concentration) x 100) was small within ±3%. Further, for each sample, the difference in level between each pixel and the state of the protrusion formed on the sample surface of each pixel were examined using a Tally Step manufactured by Rank Taylor Hobson Co., Ltd. The height difference between each pixel when the protrusions were ignored was within 0.05 .mu.- for all color filter samples. or,
The presence of protrusions is shown in Table 4. In each color filter sample, for each blue light transmitting pixel and red light transmitting pixel, each side of a 500-pixel square pixel and one line above the center of the pixel in the horizontal direction are shown. , measured by the above device, 0
．． The number of protrusions larger than 1μ and uglier than 0.3μ is shown as an average value for one pixel. Table 4: Number of protrusions in the 11i element From the results in Table 4, the number of protrusions on the sample surface after color filter fabrication is very small in the samples of the present invention. In addition, after preparing the sample of the color filter, the turbidity of the magenta color developing solution and the red color developing solution was measured using a turbidity meter 30 minutes after development. Compared to the developer used to create the sample, the level of turbidity in the developer was much lower, and it was almost transparent. When 10 copies of the same sample were made in the sample preparation process for each color filter, this tendency was further expanded. In addition, when the same measurements as shown in Table 4 were carried out on the 10th color filter sample, there was a tendency for the number of protrusions on each pixel to increase in each sample, but in the sample of the present invention,
It increased by 0 to 30% compared to the first sample, whereas it increased by 100 to 150% in the comparison sample. As described above, in the present invention, the color filter surface exhibits excellent smoothness, and the fatigue of the developer is small, and the number of times the developer needs to be replaced is small, thereby reducing manufacturing costs.

[Brief explanation of drawings]

FIG. 1 is a cross-sectional view showing an example of pattern exposure in the Jukuzo 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... Photomask 15... Opening 16... Area to be exposed 21.31
...Light-transparent substrate 22.32...Colored part 33...
・Black stripe 43...color filters 46a, 46b'' ・Polarizing plate

Claims (1)

[Scope of Claims] A color filter consisting of three primary colors of light produced by color development using a silver halide photosensitive material having a photosensitive layer provided on a light-transmissive substrate, (1) having the following general formula: [1]
(2) at least one color pixel contains at least one substantially colorless compound formed by a coupling reaction between a precursor compound represented by the formula and an oxidized product of a color developing agent; A color filter characterized by containing a boiling point solvent. General formula [1] ▲ Numerical formulas, chemical formulas, tables, etc. is 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 heterocyclic nucleus may further form a fused ring with another ring) , and may have a substituent on the ring). ]