JPH03174101A - Color filter - Google Patents

Abstract

PURPOSE:To obtain the color filter having excellent surface smoothness by incorporating the colorless compds. formed by the coupling reaction of specific precursor compds. and the oxidant of color developing agents into a picture element. CONSTITUTION:At least one kind of the substantially colorless compds. formed by the coupling reaction of the precursor compds. expressed by formula I and the oxidant of the color developing agent are incorporated into at least one color of the picture elements to constitute the color filter. In the formula I, R1 denotes 1 to 3C alkyl group; R2 denotes an electron donative group; m denotes 1 to 5 integer; R3 denotes a monovalent group; n denotes 0 to 5 integer. Plural R2 and R3 may respectively denote different groups when m, n are >=2. Thus, the excellent smoothness of the surface is exhibited and the fatigue of a developing soln. is lessened. The smaller number of developing soln. exchanges is necessitated and the cost of production is reduced.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] 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, JP-A-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. In order to eliminate these steps, for example, Japanese Patent Laid-Open No. 194257/1983 discloses a method using a Wise coupler.

In addition, in order to solve the above problem, the inventors also added a compound that forms a substantially colorless compound through a coupling reaction with the oxidized form of a color developing agent to an external color developer. Filter B (blue), G (green), R (
(red) It was proposed to selectively contain the coupling product of the coupler in the pixel (Japanese Patent Application No. 63-2418).
No. 00).

However, developing solutions containing these Weis couplers have the disadvantage that their performance deteriorates significantly over time, and that insoluble matter precipitates in the external color developing solution, significantly accelerating fatigue of the developer.

[Purpose of the invention]

An object of the present invention is to provide a color filter with excellent surface smoothness.

Another objective is to provide a color filter with stable performance at low cost, and to provide a stable manufacturing process.

[Structure of the invention]

The above-mentioned object of the present invention is to provide a color filter formed from three primary colors of light using a silver halide photosensitive material having a photosensitive layer provided on a light-transmissive substrate and developed by color development. By a color filter characterized in that at least one color pixel contains at least one substantially colorless compound formed by the coupling reaction between the precursor compound shown in I) and the oxidized product of a color developing agent. achieved.

General formula (I) In the formula, R represents an alkyl group having 1 to 3 carbon atoms, R2 represents an electron donating group (a substituent having a Hammett's σp value of less than O), and m is 1 to 3. represents an integer of 5, R1 represents a monovalent group, and n represents an integer of 0 to 5.

Furthermore, when m and n are 2 or more, each of the plurality of R, , R, may represent different groups.

The present invention will be explained in more detail below.

The coupling reaction product of the precursor compound of general formula CI) and the color developable oxidant of the present invention is substantially colorless.

Substantially colorless means that when the reaction product is included in the pixel, the increase in spectral density due to the reaction product is 0.2 or less (preferably 0.1 or less) over the entire visible region. say something.

To explain in more detail the substituents of the compound represented by the general formula [I], %R1 is methyl, ethyl, propyl, l
-propyl and the like, but methyl is most preferred.

R2 is a group whose σp value, which is Hammett's substituent constant, is less than 0, preferably -0.05 or less, more preferably -0.1 or less.

Therefore, it is a so-called electron-donating group, specifically a hydroxyl group, an amino group, an alkylamido group, an arylamido group, an alkyl group, an alkoxy group, an alkoxycarbonylamino group, an alkylureido group, an arylureido group. , alkylamino group, anilino group and the like are preferred.

As the alkylamide group, unsubstituted alkylamide groups such as butanamide and 2-ethylhexanamide are preferred.

Examples of the arylamide group include benzamide, p-methoxybenzamide, pt-butylbenzamide, 2.4.
Substituted benzamide groups such as 6-trimethylbenzamide and m-pivaloylamide benzamide are preferred, and those substituted with an electron-donating group are particularly preferred.

As the alkyl group, unsubstituted linear or branched alkyl groups having 1 to 16 carbon atoms such as methyl, ethyl, t-butyl, and dodecyl are preferred.

As the alkoxy group, unsubstituted linear or branched alkoxy groups such as methoxy, ethoxy, i-propoxy, t-butoxy, and octyloxy are preferred, and substituted alkoxy groups such as methoxyethoxy and 2-ethoxyethoxy are also preferred.

The alkoxycarbonylamino group is preferably a straight-chain or branched unsubstituted alkoxycarbonylamino group having 1 to 15 carbon atoms, such as ethoxycarbonylamino, 5ec-butoxycarbonylamino, and dodecylox7carponylamino.

As the arylureido group, phenylureido, p-
Substituted or unsubstituted ureido groups such as chlorophenylureido, m-nitrophenylureido, 3-noano-4-chlorophenylureido, and p-methquinphenylureido are preferred, and arylureido groups having an electron-donating group are particularly preferred.

As the alkylureido group, unsubstituted alkylureido groups having 15 or less carbon atoms are preferred, such as ethylureido and butylureido.

The alkylamino group is preferably an unsubstituted mono- or dialkylamino group having 1 to 15 carbon atoms such as ethylamino, dimethylamino, butylamino, etc., and the anilino group is preferably anilino, p-nitroanilino, p-chloroanilino, 0- Methoxyanilino, p-ethoxyanilino, 2-
Substituted or unsubstituted anilino groups such as methoxy-5-isobutyric acid amide anilino and 2-methoxy-5-octyloxycarbonylanilino are preferred.

The group represented by R1 may be any monovalent group, such as a halogen atom, an ano group, a nitro group, an alkyl group, an alkoxy group, an alkylamide group, an alkylsulfonamide group, an arylamide group, an arylsulfonamide group, A carbamoyl group, a sulfamoyl group, etc. are preferred.

Examples of the halogen represented by R1 include fluorine, chlorine, and bromine atoms.

Examples of the alkyl group represented by R1 include methyl, ethyl, and the same groups as those for R2 described above, preferably an unsubstituted alkyl group having 1 to 4 carbon atoms, and methyl, ethyl, and the like are particularly preferred.

As the alkyl part of the alkoxy group represented by R1,
It is the same as the above-mentioned alkyl group, and is preferably an unsubstituted alkoxy group having 1 to 4 carbon atoms, and methoxy, nidoxy, impropoxy groups, etc. are preferable.

The alkyl moiety of the alkylamido group represented by R1 is an unsubstituted alkyl group having 1 to 18 carbon atoms, such as acetamide, propionamide, butanamide, pivaloylamide, 2-ethylhexanamide, dodecanamide, etc., or cyclohexanecarboxylic acid. Cycloalkane carbonamide groups such as amide and adamantyl carbonamide,
Examples of the substituted alkylamide group include groups such as nitrogen-substituted alkanamide groups, such as chloroacetamide, trichloroacetamide, trifluoroacetamide, pentafluoropropionamide, heptafluorobutanamide, phenylacetamide, and hydrocinnamic acid amide. , aralkylamides such as γ-phenylbutanamide, phenoxyacetamide, and the like.

Aryl moiety of alkylsulfonamide group represented by R31. Preferred are straight chain or branched unsubstituted alkylsulfonamide groups, such as methanesulfonamide, butanesulfonamide, octanesulfonamide, etc., as shown in Tables 1 to 18.

The aryl moiety of the arylamide group and arylsulfonamide group represented by R8 includes, in addition to unsubstituted aryl groups such as phenyl and naphthyl, tolyl, 0-chlorophenyl, pt-butylphenyl, and suzu-nitrophenyl. ,
m-pentanamidophenyl, p-t-butylamidophenylmidophenyl, p-cyanophenylureidophenyl,
Examples include substituted aryl groups such as 0-octyloxyphenyl and 0-butoxyphenyl.

Examples of the carbamoyl group and sulfamoyl group represented by R include an alkylcarbamoyl group, an arylcarbamoyl group, an arylcarbamoyl group, and an arylsulfamoyl group. Typical examples include carbamoyl,
Dimethylcarbamoyl, diethylcarbamoyl, sulfamoyl, dimethylsulfamoyl, diethylsulfamoyl, phenylcarbamoyl, 3-nitrophenylcarbamoyl, 4-methoxyphenylcarbamoyl, and the like.

Typical specific examples of compounds used in the present invention are shown below, but the present invention is not limited thereto.

C.F.

The compounds of the present invention can be synthesized according to methods known in the literature, and representative examples are shown below, but the present invention is not limited thereto.

Synthesis example (synthetic leather of compound example 2) CH.

α-p-methoxybenzoylacetic acid ethyl ester 70.
Add 150 LIla of methanol to 3 g, and make 61.1 ml of 28 wt% methanol solution of sodium methoxide.
After adding mff and stirring for 5 minutes, 89.8 g of methyl iodide was gradually added, and the mixture was refluxed for 3 hours. Thereafter, 300 ml of ethyl acetate and 300 ml of water were added to extract the target product into ethyl acetate. After extraction, the yield after distilling off the solvent was 7
It was 1.1g.

a Mix 7.08 g of σ-p-methoxybenzoyl-α-l ethyl acetate synthesized above and 6.35 g of 2.4.6-trichlorophenylhydrazine,
The reaction was allowed to proceed for 9 hours at °C. The entire reaction solution was washed and filtered with n-hexane, and the filtration residue was recrystallized using methanol. The yield of the obtained compound (2) was 3.23 g, and the melting point was 205-207'C! Met.

The compound of the present invention may be contained in a photographic light-sensitive material or processed into a metal, but it is preferably contained in a processing solution, particularly an external developer or a black-and-white developer for silver dye bleaching, which will be described later. In the case of a white-black developer, it is necessary to include a color developing agent.

When the compound according to the present invention is contained in a processing solution different from the external developer or the black-and-white developer, the processing solution 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 amount of the compound of the present invention used is 10 g per 112 of the treatment liquid.
The following is preferable, and the range of 0.01 to 2 g is more preferable.

The silver halide photosensitive material according to the present invention contains a high boiling point solvent (
(hereinafter abbreviated as HBS) may be contained in the photosensitive agent layer, or two or more thereof may be used in combination.

The amount of HBS used is preferably 0.1 to 20 B/dm'', more preferably 0.2 to 510 g/di''.

Examples of HBS include esters such as phthalic esters and phosphoric esters, phenolic compounds, organic acid amides, and ketones. Among these HBSs, phthalate esters, phosphoric esters, and phenol compounds are preferred.

Regarding the silver halide photosensitive material In the present invention, a silver halide photosensitive material having a photosensitive layer (referred to as an emulsion layer) formed by coating a silver halide emulsion on a light-transmitting substrate 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, polyhinyl alcohol and cellulose acetate, glasses such as soda glass and borosilicate glass, and inorganic substances such as quartz and sapphire. can.

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 application and material, but it is usually 0.5μX+-10
It is within the range of 11111. 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 dispersed in a hydrophilic colloid and contained in the backing layer, but it must not dissolve 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, 500nm
It is preferable that it absorbs the following light. Furthermore,
The backing layer may contain a UV absorber.

As the ultraviolet absorber, for example, rUVINUL MS-
40J (manufactured by BASF), rTINUVIN-PJ (
(manufactured by Ciba 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, a flow jet mixer, or an ultrasonic dispersion device, it is used by adding it to a coating composition for a hydrophilic colloid backing layer.

The amount of non-diffusible dye or pigment used is preferably 0.1 mg or more, particularly preferably 1 mg or more per 100 cm'' of the light-transmitting substrate.

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

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

The thickness of the undercoat layer is preferably thin considering the spectral characteristics of the color filter, and is usually 1 μm 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 may further contain a dye having a silver dye bleaching action.

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

It is preferable to use a silver halide having a small average grain size, and it is particularly preferable to use a so-called Lippmann emulsion having an average grain size of 0.1 μm or less. If the average particle size of silver halide is large, the image quality, mainly in terms of 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, and polyacrylamide.

These may be used alone or in combination of two or more. Among these, gelatin is preferred.

One of the preferred embodiments of the present invention is that a silver halide emulsion layer contains a dye exhibiting a silver salt dye bleaching action.

Examples of such dyes include 7-lycyanine dyes,
Examples include azo dyes. Among azo dyes, bisazo dyes are particularly preferred, and specific examples include the following compounds.

(m 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 a weight ratio of (silver halide): (water-soluble binder). 1=6 to 8:11 The weight ratio of dye to silver halide is preferably 1/10 to 50 degrees, and the weight ratio of dye to water-soluble binder is preferably 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 within 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, by setting the thickness of the emulsion layer within the range of 0.5 to 3 μm, the spectral characteristics of the resulting color filter can be improved.

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 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 M12 containing the dye exhibiting a silver salt 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 an effective photosensitivity to light within the range of 340 to 420 no+, the width of the opening 15 is usually 340 nm or more, and considering its use as a color filter, The thickness is preferably 1 μm or more. Further, 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, it is particularly desirable that the width of the opening 15 be 1000 μm or less. is preferably set to 500 μm 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 developing agents, C.E.K. Mees, T.H. James (C, E, Ni, Mees and
T.

The Theory of the Photographic Process, 3rd Edition, by James H.
of the Photographic Process
ss 3rd, Edition) J, pages 293-298, and specific examples include: (1) 4-amino-3-methyl-N-(2-hydroxyethyl)aniline sulfate Salt (2) N-ethyl-N-methoxyethyl-3-methyl-
p-phinyl diamine@p-) J renin sulfonate (3) 4-amino-3-methyl-N-ethyl-N-(2
-Methylsulfonamidoethyl) aniline sulfate hydrate (4) N,N-diethyl-p-7 22-diamine sulfate (5) N,N-diethyl-3-methyl-p-722 Examples include 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 developing solution is normally used so that it is contained in the developing solution 112 in an amount within the range of 0.1 to 10 g. 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 ta within a range 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. 1-1
(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 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. a-(4-
(carboxyphenoxy)-σ-pivaloyl-2,4-dichloroacetanilide);
No. 3,619,189, Special Publication No. 1977-33775
No. 44-3664 and the like can be used.

Examples of magenta color-forming couplers include active methylene compounds (for example, 1-(2,4,6-trichlorophene=
pyrazolones with 7-chloro-3-phenyl-6-
Ituprovir-IH-pyrazolo[5,1-c]-1,2
, pyrazoloazoles such as 4-triazole and cyanoacetanilides), and furthermore, OLS No. 2,016,587, U.S. Pat.
, No. 152,896, No. 3.615.502, Japanese Patent Publication No. 133111/1973, etc. can be used.

Nor compounds (e.g., 2-acetamido-4,6-dichloro-5-methylphenol) or heptadol compounds (e.g., N-(2-acetamidophenethyl)-
1-hydroxy-2-naphthamide), and U.S. Pat. Nos. 3,002.836 and 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 3r4 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 IQ 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. Particularly in the present invention, color turbidity can be reduced by controlling the total content of color-forming couplers in the developing solution la within the range of 0.2 to 10 g.

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 coloring coupler and a magenta coloring 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 color-forming coupler and a yellow color-forming coupler, the weight ratio of both is usually 9:
The ratio is within the range of 1 to 1:9, preferably 8:2 to 2:8. When combining a coloring coupler, a magenta coloring coupler, and a yellow coloring coupler, 3
It is preferable to mix approximately the same amount of each.

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.

Furthermore, the developer may contain preservatives (for example, sodium sulfite,
diethylhydroxylamine), accelerators (e.g. alkaline agents such as sodium hydroxide), control agents (e.g. potassium bromide, potassium iodide), auxiliary agents (e.g. polyethylene glycol nanowater conditioner, 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 area is 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 coloring 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, by dipping in a black and white developer to prevent color turbidity in the first development area during the second and subsequent development processes, and then washing with water and drying, red, blue, green, cyan, magenta, and yellow colors can be created. The first one having any pixel of
Forms colored parts.

Next, using a photomask, the unexposed area adjacent to the first exposed area is pattern-exposed in the same manner as the first exposure, and then a 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 by 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 bleach the silver dye contained in the silver halide photosensitive material. Decolorizes the active pigment.

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)). 1. Contains 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, etc.

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) 1-20 g/Q, developing aid 0.05-8 g/72% preservative 1-12 Q g/12.
The developer fog preventive agent is o, ooi to 5 g/Q, the alkaline buffer is 0.1 to 50 g/Q, and when a solvent for a developing agent and a developing aid is used, the solvent is 1 to 20 IIIQ/Q.

Black and white development processing is usually done at 20-60°C and 10-200°C.
The image exposure described above is carried out for 2 seconds by immersing the photosensitive material in a black and white developer.

Through this black and white development process, the image-exposed photosensitive material U(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 bleach accelerating catalysts include pyrazine, naphthazine, quinoline, quinoxalines, phenazines, anthraquinones, naphthoquinones, indo-7enazines, N
Examples include -substituted in-alloxazines, 70-quinoxalines, chietukizalines, diphenyl derivatives, triphenylmethane derivatives, lumazines, alloxazines, cinnolines, and orthophenylenediamine derivatives (U.S. Pat. No. 2,270,118). No. 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 IQ of bleach, 0.1 to 20 g IQ of a compound forming a silver salt or silver complex, and dye bleach accelerating catalyst o.
, ooi~Log/(2.

Dye bleaching treatment is usually carried out at 20-60°C and at l0-200°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 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 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, the pattern of the exposure/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. 2 is shown. Shown in A.

Table A Each colored part shown in Figure 2 is yellow pigment (Yl or Y2).
, 'magenta dye (M l or Mi) and cyan dye (
C, 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 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, the green light transmitting pixels are pattern-exposed in a second exposure/processing process, and then developed 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.

Finally, the pixels for transmitting green light and the pixels for transmitting red light are exposed to pattern 1. After that, the #4 ring whitening 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, if silver dye bleaching treatment is performed after all external color development treatments are completed, then , 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 red part (R), a blue part (B) and a green part (
After forming the light-transmissive colored portions 32 with gaps between them, pattern exposure was applied to the gaps, and then a developer containing a cyan coloring coupler, a magenta coloring coupler, and a yellow coloring coupler was used. By performing the development process, the red part (R) and the blue part (
A light-impermeable section (black stripe) 33 can also be formed in the gap between the green 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 mosaic or striped.

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

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

〔Example〕

EXAMPLES 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 Preparation of silver halide photosensitive material Silver iodobromide 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. An emulsion (average particle size: 0.05 μm, gelatin concentration: 9%) was prepared.

The addition conditions were regulated so that a Lippmann emulsion having an average grain size of 0.05 μm was obtained.

The resulting silver iodobromide emulsion contained 28.3 mg per mole of silver.
of sodium thiosulfate pentahydrate at 59.5°C.
Chemically ripened the bottom skin for 5 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.
5 mg, 3.40 g, and the following compound 5C
An emulsion coating solution was prepared by adding 15-9 g of H-1 per mole of silver, and further adding 40 mg and 5 mg of the following compounds H-1 and 1 (-2) per 1 g of gelatin as hardeners.

-1 -2 ((CH2-CHSOICI(2)3CCH2SO2C
H2CH2) 2NCH2 (&S03) The emulsion coating solution obtained in S03 was coated on a transparent borosilicate glass substrate (30
cmX 30C! II) A silver halide photosensitive material having an emulsion layer was prepared by coating the film to a dry film thickness of 3 μm. Bank amount is 1.5g/m'', pigmentation amount is 0-2
4g/+a''.

A photosensitive material was thus produced.

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

Next, the formation of the conobacking layer will be explained.

A dispersion of the following compound Y-1 was added to an aqueous gelatin solution, and 40II1 g of each of hardeners H-1 and H-2 were added.
5 mg was added. Here, the gelatin aqueous solution is 5%
The amount of gelatin added in advance was adjusted so that or,
The amount of Y-1 added to the gelatin aqueous solution 100o+ff was 1.35%.

-t Thereafter, this aqueous gelatin solution was applied to the borosilicate glass substrate and dried to form a backing layer. Y-
The applied amount of No. 1 was 10 mg/da2.

The above-mentioned dispersion was prepared by dissolving 1 g of Y-1 in 1 g of tricresyl phosphate and 4.29 ml of ethyl acetate, followed by 0.83 g of gelatin,
5% aqueous solution of sodium β-naphthalene sulfonate2.
The mixture was added to an aqueous solution containing 63aff and water 8-8-4r, subjected to ultrasonic dispersion at 50°C, ethyl acetate was removed, and water was added to make 17.6 mff.

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
0/jm×150 μm.

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 (2) was placed on top of the mask, 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 coupler... 0.26g5-
t-Butyl-7-chloro-5-(3-methylbutyl)1
)]-pyrazolo[3,2-c]-1,2,4-triazole Weis coupler WE-1・・Amount shown in Table 1 Developing agent... 2・0 g 4-amino-3-methyl-N-ethyl -N-β-methanesulfonamidoethylaniline 1 1/2 sulfate l Ice salt Sodium nitrilotrimethylenephosphonate (40% aqueous solution) ・3.00 aff Anhydrous sodium sulfate ・ 20.0 g Sodium bromide ・ ・ 1.0 g Sodium vitrite・・10.00g ethylene glycol・・1O. Add 0m4 polyethylene glycol and 2.0g water
If, sodium hydroxide was added to the above magenta color developer to adjust the pH value at 25° C. to 12.0.

Next (after washing with water for 1 minute, bleaching by immersing in a silver source white solution with the following composition for 3 minutes, washing with water for 4 minutes and drying, a blue part was formed on the substrate (first process).

Silver source White liquor composition Ethylenediaminetetraacetic acid iron(II[) ammonium salt.
200.0g ammonium bromide...・10.0g glacial acetic acid・・lo. Add omQ water to make up to 1 volume, and adjust the pH to -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 6 in FIG. 2, and a second exposure was performed.

The photosensitive material that had been exposed for the second time was immersed in a yellow color developing solution having the following composition for 3 minutes at 23°C.
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 coupler・1.5g α-
(4-carboxyphenoxy)-a-pivaloyl-2,
4-dichloroacetanilide developing agent/
2.0g4-amino-3-methyl-N-ethyl-N-β-methanesulfonamidoethylaniline.
11/2 Sulfate hydrate Sodium nitrilotrimethylenephosphonate (40% aqueous solution) ・3.00m12 Anhydrous sodium sulfate・20.0g sodium bromide・・3.0g sodium sulfite・・10.00g ethylene glycol・・10. 0+aff polyethylene glycol・・Add 2.0g water
Incidentally, sodium hydroxide was added to the above yellow color developer to adjust the pH value at 25°C to 12.0.

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

The photographic 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 was formed (third process).

Red color developer composition Magenta coupler... 0.28g6-
t-Butyl-7-chloro-5-(3-methylbutyl)-
11-pyrazolo[3,2-cl-1,2,4-) lyazole Weis coupler WE-1...Amount shown in Table 1 Yellow coupler 1.42g α-(
4-carboxyphenoxy)-σ-pivaloyl 2.4
-Dichloroacetanilide developing agent・
2.0゜4-amino-3-methyl-N-ethyl-N-β methanesulfonamidoethylaniline・11
/2 sulfate l hydrate Sodium nitrilotrimethylenephosphonate (40% aqueous solution) ・3.00 mff anhydrous sodium sulfate ・ 20.0 g sodium bromide ・ 3.0 g sodium sulfite ・ ・ ・ 10.00 g ethylene glycol 10. 00m12 polyethylene glycol◆ Add 2.0g water
IQAdditionally, sodium hydroxide was added to the above red color developing solution to adjust the pH at 25°C.
The value was adjusted 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 1 minute water wash 1 minute dye bleach 1 minute water wash 1 minute silver
Bleach 6 minutes in water
Wash and fix for 1 minute
Rinse with water for 1 minute
Drying for 4 minutes The bath used for each treatment had the following composition.

Black and white developer composition Sodium sulfite 10g Hydroquinone 10g Potassium hydroxide (48
% aqueous solution) 5m0゜diethylene glycol
20112 Jimaison
0.7g sodium carbonate 2
Add 0g potassium bromide 2g thiadiazole 0.05g water
1Q96% sulfuric acid
40IIIQ potassium iodide
15g2.3.6-drimethylquinoxaline
Add 2g water and add 1a Silver Silver White Liquid Bo Pure Water 80hM Sodium Ferricyanide 206g Sodium Bromide
15g borax
Add 1g water 11
2 (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
Flood (p with acetic acid) I = 6.0
Adjust to. ) Also, after creating the color filter, infiltrate the backing layer with a 3% aqueous solution of hypochlorous acid,
The backing layer was completely removed by wiping with gauze.

The color filters obtained in this way were sample No.
Set to 1.

In the manufacturing process of Sample No. 1, Sample No. , 2 to 14 were prepared.

Table 1 Regarding the amount of Weis coupler in magenta color developer and red color developer, as a result of preliminary experiments, the step difference was 0.05.
The amount that satisfies μ-white was experimentally determined (comparative Weis coupler) WE-WE WE- WE-4 WE- WF,- Regarding the obtained color filter sample No. 1”14, Rank Co., Ltd. The level difference between each pixel was investigated using a Taylor Hobson Tali Step.The level difference between each pixel was
As shown in Table 2, all the color and filter samples were within <0.05 μm.

From this result, it can be seen that the level difference on the sample surface after color filter fabrication is very small in all samples.

Furthermore, after preparing the color filter sample, the turbidity of the magenta color developer and the red color developer was checked 30 minutes after development, and it was found that each developer used to prepare the sample of the present invention was different from that used in the preparation of the comparison sample. The level of turbidity of the developer was very low compared to that of the developer, and it was almost transparent. Table 3 shows the visual results of the turbidity level.

Further, another sample was prepared in the same manner except that each developer was left at room temperature for 3 hours before use, and for this sample,
When we similarly measured the level difference between each pixel, we found that the sample of the present invention had the same level difference between each pixel as the sample created the first time, whereas the comparative sample showed that the level difference between each pixel was the same as that of the first sample. As shown in Table 2, the height difference between the

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 reduced, thereby reducing manufacturing costs.

Table-3 Turbidity of developer solution 30 minutes after development Visual judgment criteria are as follows.

■...Almost transparent with no change ○...Slightly cloudy but almost transparent △...
Slightly cloudy×... Considerably cloudy×X... Large degree of cloudiness Comparison compound WE-1 (compound described in Jikai No. 63-194257) and WE-2 to WE -7 (both are 4-methylpyrazolone compounds substituted with a phenyl group at the 3-position, but unlike the compounds of the present invention, the 3-position is phenylated) +1-
Yi L, Z + parable 2 G 2] Pillar 小屡萩
It can be seen that in the treatment using the compound of the present invention, the stability of the treatment solution is greatly improved.

[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 ... Photomask 15 ... Opening 16 ... Portion to be exposed 21.31 ... Light-transmissive substrate 22.32 ...
Colored portion 33...Black stripe 43...Color filters 45a, 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 with a photosensitive layer provided on a light-transmitting substrate, which has the following general formula [I] A color filter characterized in that at least one color pixel contains at least one substantially colorless compound formed by a coupling reaction between a precursor compound represented by the above formula and an oxidized product of a color developing agent. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R_1 represents an alkyl group having 1 to 3 carbon atoms, and R
_2 represents an electron-donating group (a substituent having a Hammett's σp value of less than 0), m represents an integer from 1 to 5, and R_3
represents a monovalent group, and n represents an integer of 0 to 5. Further, when m and n are 2 or more, the plurality of R_2 and R_3 may each represent different groups. ]