JPH03144402A - Color filter - Google Patents

Abstract

PURPOSE:To improve surface smoothness and to improve heat resistance by incorporating at least one kind of compds. which are the coupling reaction product of a specific precursor compd. and the oxidant of a color developing agent and are substantially colorless into picture elements of at least one color. CONSTITUTION:At least one kind of the compds. which are the coupling reaction product of the specific precursor compd. expressed by formula I and the oxidant of the color developing agent and are substantially colorless are incorporated into the picture elements of at least one color. In the formula I, R0 denotes <=4C alkyl group; R1 denotes >=4C alkyl group or cycloalkyl group; R2 denotes a halogen atom, cyano group, sulfamoyl group, etc.; n denotes 0 to 5 integer; plural R2 may be same or different when n is >=2. The precursor compd. expressed by the formula I is preferably incorporated into a coupler-in-developer type developing soln. or a black and white developing soln. for silver dye bleach processing. A color developing agent is incorporated therein in the case of the black and white developing soln. The surface smoothness is improved in this way and the color reproducibility is upgraded.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a color filter, and 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. 55-6
As disclosed in No. 342, there is a method using an external color development method using a color silver salt photographic material.

However, in the above-described method, the color reproducibility between pixels having different spectral characteristics was insufficient, and especially the image quality after producing a color liquid crystal display was not satisfactory. That is, a coupler (for example, a yellow
It is difficult to combine magenta and cyan couplers, and the color reproduction balance between the pixels of the color filter is disturbed, leading to deterioration of image quality after producing a color liquid crystal display.

According to studies conducted by the present inventors, the above color reproducibility can be considerably improved by using a pyrazoloazole compound as a magenta coupler, but it was still not sufficient.

In addition, relief generation based on pixels with different spectral characteristics is also possible.
This causes deterioration in the image quality of color LCD displays.

Therefore, there is a demand for the development of color filters with improved color reproducibility and excellent surface smoothness.

[Purpose of the invention]

An object of the present invention is to provide a color filter that has excellent surface smoothness and improved color reproducibility, and furthermore, to provide a color filter that provides good image quality after producing a color liquid crystal display.

[The bottom of the invention]

The above object of the present invention is to provide a color filter consisting of 3WL colors of light on a light-transmitting substrate, in which at least one color pixel is coupled with a precursor compound represented by the following general formula (1) and an oxidized product of a color developing agent. This is achieved by a color filter containing at least one substantially colorless compound which is a reaction product.

General Formula [1] In the formula, Ro represents an alkyl group having 4 or less carbon atoms, and R represents an alkyl group or cycloalkyl group having 4 or more carbon atoms. R2 represents a halogen atom, a cyano group, a nitro group, an alkyl group, an alkokene group, an alkylamide group, an arylamide group, a carbamoyl group, an alkylsulfonamide group, an arylsulfonamide group, or a sulfamoyl group. n
represents an integer of 0 to 5, and when n is 2 or more, a plurality of R2s may be the same or different.

The present invention will be explained in detail below.

In the above general formula [■], the alkyl group having 4 or less carbon atoms represented by Ro is preferably methyl, ethyl, etc., and most preferably a methyl group.

The alkyl group having 4 or more carbon atoms represented by R1 may be linear or branched, and preferably has 4 to 18 carbon atoms.
is an alkyl group. Specific examples thereof include butyl, 5ec-butyl, t-butyl, 2-ethylpentyl, l-pentyl, hexyl, nonyl, dodecyl, and the like.

The cycloalkyl group having 4 or more carbon atoms represented by R3 is more preferably 4 to 18 carbon atoms, and examples thereof include groups such as cyclopentyl, cyclohexyl, cyclooctyl, and adamantyl.

Examples of the halogen atom represented by R2 include fluorine, chlorine, and bromine.

Examples of the alkyl group represented by R2 include the same alkyl groups listed above for R1, preferably those having 4 carbon atoms.
Among the following unsubstituted alkyl groups, methyl and ethyl groups are particularly preferred.

The alkyl part of the alkoxy group represented by R2 is the above R2
Examples include the same alkyl groups listed above, preferably unsubstituted alkoxy groups having 1 to 4 carbon atoms, and methoxy, ethoxy, i-propoxy and the like are preferred.

Examples of the alkylamide group represented by R2 include unsubstituted alkylamide groups having 1 to 18 carbon atoms such as acetamide, propionamide, butanamide, pivaloylamide, 2-ethylhexanamide, dodecanamide, cyclohexanecarbonamide, adamantylcarbonamide, etc. alicyclic alkylamide groups, halogen-substituted alkylamide groups such as chloroacetamide, trichloroacetamide, trifluoroacetamide, heptafluorobutanamide,
Examples include aryl-substituted alkylamide groups such as phenylacetamide, hydrocinnamic acid amide, γ-phenylbutanamide, and phenoxyacetamide.

The alkylsulfonamide group represented by R2 is preferably a group having a straight chain or branched unsubstituted alkyl moiety having 1 to 18 carbon atoms, such as methanesulfonamide, butanesulfonamide, and octanesulfonamide.

The aryl moiety of the arylamide group and arylsulfonamide group represented by R2 includes unsubstituted aryl groups such as phenyl and naphthyl, 0-chlorophenyl, p.1
-butylphenyl, m-nitrophenyl, m-pentanamidophenyl, pt-butylamidophenyl, 0-
Examples include substituted aryl groups such as butanesulfonamidophenyl and p-cyanophenylureidophenyl.

The carbamoyl group and sulfamoyl group represented by R2 include alkylcarbamoyl groups (e.g. carbamoyl,
dimethylcarbamoyl, diethylcarbamoyl, etc.), arylcarbamoyl groups (e.g. phenylcarbamoyl,
m-nitrophenylcarbamoyl, p-methquinphenylcarbamoylalkylsulfamoyl group (e.g. sulfamoyl, methylsulfamoyl, butylsulfamoyl, etc.), arylsulfamoyl group (e.g. phenylsulfamoyl, 0-chlorophenylsulfamoyl) Moyle,
l)-L-butylphenylsulfamoyl) and the like.

The general formula used in the present invention is shown below. Typical specific examples of compounds that can be used are listed below, but are not limited to these. It is not determined.

-3 -4 -5 -6- -10 ShiU -12 -9 -11 -13 -14 -18 -15 JiU -19 W-22 6 to 3 -23 -26 -27 2HI Shimizu Below are some typical examples of synthetic leather.

Synthetic leather methyl-3-t-butyl-3-oxopropionate 5 of Compound Example W-1
0 g was dissolved in 150 mα of dimethylformamide, 12.66 g of sodium hydride (60% by weight) was added thereto, and after stirring for 5 minutes, 89.8 g of methyl iodide was gradually added, and the mixture was refluxed at 60° C. for 4 hours. The reaction mixture was extracted with ethyl acetate and ice, and distilled under reduced pressure at 92°C and 17 mmHg to obtain 51 g of methyl-3-t-butyl-2-ethyl-3-oxopropionate. 10.32g of this compound and 6.49g of phenylhydrazine were mixed and heated neat to 100°C.
After reacting for 3 hours at 140°C, the mixture was further reacted for 4 hours.

The reaction solution was subjected to column separation using a mixed solvent of hexane and ethyl acetate (9:l volume ratio), extracted, and recrystallized from dilute methanol to obtain 12.01 g of a giant product W-12.0.

Melting point 103-105°C0 Synthetic leather methyl-3-t-butyl-2-ethyl-3-year-old xoprobionate of Compound Example W-4 5.16 g and a, a, a-2,3,
5,6-heptafluoro-p-tolylhydrazine 7.4
After reacting 4 g neat for 100'02 hours, 16
The reaction was carried out at 0°C for 6 hours, and hexane:ethyl acetate (9:
After column separation using a mixed solvent (1 volume ratio), the mixture was extracted and washed with hexane to obtain 8 g of W-43. Melting point 124-126
℃.

Other compounds can also be synthesized according to the above synthesis method.

The coupling reaction product of the precursor compound represented by the general formula [■] and the oxidized color developing agent 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.

The precursor compound of general formula CI) (hereinafter also referred to as vacuoler) may be contained in the photographic light-sensitive material or in the processing solution, but it may be contained in the processing solution, especially the external developer or the silver dye described below. It is preferably included in a black and white developer for bleaching. In the case of a black and white 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 according to the present invention used is preferably 10 g or less per treatment liquid IQ of the present invention, and more preferably in the range of 0.01 to 2 g.

Silver halide photosensitive material In the present invention, a silver halide photosensitive material having 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, polyvinyl alcohol and cellulose acetate, glasses such as soda glass and borosilicate glass, and inorganic substances such as quartz and sapphire.

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

The thickness of the light-transmitting substrate can be set appropriately depending on the purpose and material, but it is usually 0.5 μm to 10 m.
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 anti-nolation 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 bra 7-li dispersion may be produced by either the furnace method or the channel method, and for example, "Dia Blank" (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 material absorbs light of 500 nm or less. Furthermore, the backing layer may contain a UV absorber.

The UV absorber and shite are, 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 70-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 2 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 adhesive force 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 polyvinylidene chloride copolymer. The thickness of the undercoat layer, which may be made of acrylamide, 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 silver halides include silver chloride, silver iodide, silver bromide,
Examples include silver chloroiodide, silver chlorobromide, silver iodobromide, and the like. These may be used alone or in combination of two or more.

It is desirable to use a silver halide with a small average particle size, and in particular, silver halide with an average particle size of 0, I JLws
It is preferable to use the following so-called Lippmann emulsions. 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 silver dye bleaching action.

Examples of such dyes include phthalonanine dyes,
Examples include azo dyes. Among azo dyes, bisazo dyes are particularly preferred, and the compound RI R2 -No2H 2Noz 5 Now 2-CQ H [(f( 2-CCH 2-5o, NH, H 2-5o2CH, H 3 -OCH.

OCH.

0CFI3 0CH3 -OCI(, CH201( -QC)I.

-OCR.

4 -OCR.

10CR.

-OC+(3 -OC+(.

OCH3 C.O. CO- O- CO- 5O2- -SO,- C0- 2-NO□ 10CR2CH,OH O2- 2-COCH3H -OCR.

10CR.

100 The silver halide emulsion of the present invention contains silver halide, a water-soluble binder, and a dye in a weight ratio of (silver halide):(water-soluble binder) of 1:6 to 8:11. It is desirable that the weight ratio of dye to silver halogenide is 1/10 to 50, and the weight ratio of dye to water-soluble binder is 1/100 to 2.

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

The thickness of the emulsion layer thus formed is usually within the range of 0.3 to 10 μm in terms of dry thickness. Thickness is 0.
If it is less than 3 μm, sufficient color development may not be achieved, while if it exceeds 10 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.

There is a method of processing the emulsion layer using a silver halide photosensitive material by a combination of external color development method and silver dye bleaching method. After completion of all processing steps, it is preferable to carry out processing by silver dye bleaching method.

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, for example, methods used in normal pattern exposure such as contact exposure, proximity exposure, and step exposure.

In pattern exposure, for example, as shown in FIG. 1, a photomask i4 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 I6 of the emulsion layer to be exposed corresponding to the openings 15 provided in the 7-oto mask 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, The thickness is preferably 1 μm 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 opening 15 should be set to 10 mm.
It is preferable to set the thickness to 00 μm or less, particularly preferably 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, 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-phenyl diamine sulfate ( 5) N, N-'; Examples include ethyl-3-methyl-p-7 22-diamine hydrochloride.

In the developer, it is preferable to select and use one type of developing agent from among the developing agents listed above. The selection of the developing agent is usually made in consideration of the type and combination of color forming couplers.

The developing agent in the developing solution is usually used so that it is contained in the developing solution Iff 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 Log is used, not only will there be no significant improvement in developability, 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 112 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 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-forming couplers, a preferable example of a yellow-color-forming coupler is an acylacetanilide coupler represented by the following general formula (II) as described in Japanese Patent Publication No. 55-9697.

In the formula, R represents a branched alkyl group having 3 to 6 carbon atoms, and xl
and x2 each represent a chlorine atom or a bromine atom, and X represents a hydrogen atom, a chlorine atom, a bromine atom, or an alkyl group having 1 to 8 carbon atoms.

R is preferably a t-butyl group, X and X2 are preferably a chlorine atom, X is preferably a hydrogen atom,
A chlorine atom is mentioned and substituted at the active site of the coupler I;
The carboxyl group of the phenoxy group is preferably located at the meta or para position relative to the oxygen atom to which it is bonded.

Representative compounds are illustrated below.

Compound RXl Xs Xs C0
0HY-1(CHs)sCcaCff(3)
H4 position Y-2(CH3)3CCQ Cl2(4)
H3 position Y 3 (CH3)3CCQ CQ(4
) H4 position y-4 (CH,), CcQcQ (4)
cQ(5) 4th position y-5(CH3)ICcQcQ(
4) cI2 (5) 3rd position Y 6 CCHs)
3CBr Br(4) CHs d-position A particularly preferred compound among the above yellow coloring couplers is Y-4
This is a compound represented by

Magenta coloring couplers include active methylene compounds,
For example 1-(2,4,6-trichlorophenyl)-3-
Examples include pyrazolones such as troanilino-5-pyrazolone and cyanoacetanilides;
U.S. Patent No. 3.152.896, U.S. Patent No. 3,615.502
Although those described in Japanese Patent Publication No. 44-133111 can be used, it is preferable to use pyrazoloazoles. Representative examples of preferable pyrazoloazole magenta color-forming couplers are shown below, and further, U.S. Pat. No. 3,510,306 and U.S. Pat.
No. 9, Special Publication No. 40-33775 and No. 44-3664
You can use those listed in the No.

Furthermore, examples of cyan color-forming couplers include phenolic compounds (e.g., 2-acetamido-4,6-dichloro-
5-methylphenol) or naphthol compounds (for example, N-(2-acetamidophenethyl)-1-hydroxy-2-su7tamide);
U.S. Patent No. 3,002,836, 3,542°552
and British Patent No. 1,062,190, etc. can be used.

In addition to the above, rThe Theory of
the Ph.

tographic Process 3rd Edi
tionJ (cited above), Chapter 17.

It is also possible to use those described on pages 382-395.

In the developer, the total content of color forming couplers in the developer iff is 0. It is preferable to set it within the range of 1 to 20 g. If it is less than 0.1 g, sufficient color development may not be achieved, while if it is used in excess of 20 g, so-called fogging may occur. In particular, in the present invention, by controlling the total content of color forming couplers in the developer 1Q to 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 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.

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), auxiliaries (e.g. water conditioners such as polyethylene glycol, citrazic acid, imidazole) It may also contain additives that are included 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 coupler, a yellow color coupler, and a yellow color coupler, the exposed area is developed into green color. Furthermore, by using a developer (red developer) containing a magenta color-forming coupler and a yellow color-forming coupler,
The exposed areas are developed red, and a developer containing a cyan coloring coupler (cyan developer), a developer containing a magenta coloring coupler (magenta developer), and a developer containing a yellow coloring coupler (yellow developer) is used. As a result, the exposed areas are developed into cyan, magenta and yellow colors, respectively.

The first exposed portion 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 washed with a bleach solution or a stop solution containing an acid such as acetic acid. By dipping it in a black and white developer to prevent color turbidity in the first developing area during the second and subsequent development processes, and then washing it with water and drying it, it is possible to remove any of red, blue, green, cyan, magenta and yellow. A first colored portion having any pixel is formed.

Next, 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 type.

Further, if desired, a second colored portion can be formed by performing steps such as immersion in a bleaching 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. Furthermore.

If desired, the third 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.

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 includes, for example, a developing agent (hereinafter referred to as developing agent (D)), a developing aid, a preservative, a so-called development capri-inhibitor, an alkaline buffer, and, if necessary, the aforementioned developing agent. (D) and a developing aid solvent.

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

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

Preservatives include sulfites, ascorbic acid, and the like.

Examples of the development antifogging agent include 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 1 to 20 g IQ of developing agent (D).

Development aid 0.05-8 g/Q, preservative 1-120 g/
L Developing antifoggant 0.001-5 g/L Alkaline buffer 0.1-50 g/(2, and when using a solvent for the developing agent and development aid, the solvent 1-20 mff/(
It is 2.

Black and white development processing is usually done 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 nisuramic acid, succinic acid, and acetic acid.

Examples of compounds that form silver salts or silver complexes include potassium bromide, potassium iodide, urea, thiourea, semicarbazide, thiosemicarbazide, and the like.

Examples of dye bleaching accelerating catalysts include pyrazine, naphthazine, quinoline, quinoxalines, phenazines, anthraquinones, naphthoquinones, indo-7enazines,
N-1! isoalloxazines, floquinoxalines,
Examples include woodpeckers, diphenyl derivatives, triphenylmethane derivatives, lumazines, alloxazines, cinnolines, and orthophenylenediamine derivatives (U.S. Pat. No. 2,270.118, U.S. Pat. No. 2,410,
No. 025, No. 2,541,884, No. 2,627,4
No. 61, No. 2,669.517, British Patent No. 657.3
No. 74, No. 711.247, Special Publication No. 45-22195
(See No., etc.)

Examples of the contents of the various components in the dye bleaching solution include: 1 to 20 g/Q of bleaching agent, 1 to 20 g/Q of compound O1 that forms a silver salt or silver complex, and 0 g/Q of dye bleaching accelerating catalyst.
．． 001-10gIQ.

Dye bleaching treatment is usually carried out at 20-60°C for 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, which will be described in detail below, can be performed.

Silver bleaching process Silver bleaching process is a process in which all black silver remaining in the image-exposed light-sensitive material that has been subjected to the dye bleaching process is rehalogenated.

A silver bleaching solution is used for this silver bleaching process.

The silver bleaching solution may be one conventionally known, and for example, a bleaching solution containing a ferric chelate of ethylenediaminetetraacetic acid can be suitably used.

Silver bleaching is usually carried out at 18-60'C! So, 5-500
Do it for 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 fEt light/treatment process) Next, a preferred exposure/treatment process in the present invention will be described.

For example, Table A shows the pattern of the exposure and processing process when forming a color filter having B (pixel for transmitting blue light), G (pixel for transmitting green light), and R (pixel for transmitting red light) shown in FIG. Shown below.

Each colored part shown in Figure 2 is a yellow dye (Y or Y2)
, magenta dye (Mr or M2) and cyan dye (C,
or CZ) 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 SDB, 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, a development process is performed using an external group developer containing a magenta color-forming coupler. Next, after the green light transmitting pixels are pattern-exposed in a second exposure/processing process, a development process is performed using an external developer containing a yellow color-forming coupler and a cyan color-forming coupler. Subsequently, the red light transmitting pixels are pattern-exposed in a third exposure/processing process, and then developed using an external developer containing a yellow color-forming coupler and a magenta color-forming coupler. lastly,
After the green light transmitting pixels and the red light transmitting pixels are pattern-exposed, the silver 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, 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, 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-transmissive section (
A black stripe) 33 can also be formed. 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, if the color filter 43 is arranged so that the color filter 43 and the liquid crystal 47 controlled by the electrodes 48a and 48b are sandwiched between the polarizing plates 46a and 46b, a liquid crystal color display can be obtained. It can be used as a filter for

Furthermore, it is also possible to suitably use it 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 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 iodine containing 4 mol% silver iodide was prepared. A silveride emulsion (average particle size: 0.051 ml, 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 contains 28.311 mol of silver per mole of silver.
Add 1 g of sodium thiosulfate pentahydrate and heat to 59.5°C.
Chemically aged for 45 minutes.

Next, 1-phenyl-5-mercaptotetrazole and 1-carboxyethyl-3,4,5-hydroxybenzene were added to the emulsion at 141.0% per mole of silver, respectively.
In addition to adding 5mg53.40g, the following compound 5C-
An emulsion coating solution was prepared by adding 15.9 g of Ig gelatin per mole of silver, and further adding 40 mg and 5 mg of the following compounds H-1 and H-2 as hardeners per Ig gelatin.

C-1-2 C(CHz = CH5O2CHx) ICCH2SO
ZCH2CH2]2MCI (2CHx SOs K) The obtained emulsion coating solution was coated onto a 1.1 mm thick transparent borosilicate glass substrate (3 (lc+r+X 30 cm) to a dry film thickness of 3 μm to form an emulsion layer. A silver halide photosensitive material having the following was prepared.The amount of silver deposited was 1.5 g/m2, and the amount of dye deposited was 0.24 g/m''.

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

Formation of this backing layer will be explained next.

A dispersion of Compound Y-1 was added to the gelatin aqueous solution, and 40 mg 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,
100 ml of gelatin aqueous solution (1 added in 2; the amount of Y-1 added was 35%.

Compound Y-1 Thereafter, this gelatin aqueous solution was applied to the borosilicate glass substrate and dried to form a bar-noking layer. Y
The amount applied of -1 was 10 mg/dm2.

The above dispersion was prepared by dissolving 1 g of Y-1 in 1 g of tricresyl phosphate and 4.29 mff of ethyl acetate, followed by 0.83 g of gelatin and 0.83 g of triisopropyl-β.
- 5% aqueous solution of sodium naphthalene sulfonate 2.6
The mixture was added to an aqueous solution containing 3 cc and 8.4 ml of water, and subjected to ultrasonic dispersion at 50° C., the ethyl acetate was removed, and water was further added to make 17.6 ml (2).

Production of B (blue) pixels and G (green) pixels The production method of B (blue) pixels and G (green) pixels will be described below.

The photosensitive material was cut into a rectangular size of 33 mm x 100 mm using a glass cutter, and the entire surface of the sample was exposed using a tungsten lamp.

The exposed photosensitive materials were added to the following magenta color developer (Sample No. 1) and the following yellow color developer (Sample No.
O, 11) Soaked at 23°C for 3 minutes.

Magenta color developer composition Magenta coupler ・ ・・・0.24g6−
[-butyl-7-chloro-3-(3-methylbutyl)L
H-pyrazolo[3,2-c-1.2.4-)riazole W-1・・・
・ ・ ・ 1.21g developing agent ・ ・ ・ ・
・1.0g4-amino-3-methyl-N,N
-Diethyl-aniline hydrochloride Sodium nitrilotrimethylenephosphonate (40% aqueous solution) 3,00m (anhydrous sodium sulfate 20.0g Sodium bromide 1 .0g sodium sulfite... 10.0g ethylene glycol...
・ ・ ・ 10.0 mQ polyethylene glycol ・ ・ Add 2.0 g water ・ ・ ・
...If, by adding sodium hydroxide to the above magenta color developer, the pH value at 25°C becomes 12.
．． It was adjusted so that it was 0.

Yellow color developer composition Yellow coupler... 1.2gσ
-(4-carboxyphenoquine)-α-pivaloyl-2
, 4-dichloroacetanilide W-1・ ・ ・
・ ・ ・ 0.2g developing agent... 2.0g 4-amino-
3-Methyl-N~ethyl-N-β-methanesulfonamide ethylaniline 1 1/2 sulfate l hydrate Sodium nitrilotrimethylenephosphonate (40% aqueous solution)...3.00mQ Anhydrous sodium sulfate...20.0g Sodium bromide... 3.0g Sodium sulfite... 10.00g ethylene glycol... io. Omc polyethylene glycol・・Add 2.0g water・
... IQ In addition, sodium hydroxide was added to the above yellow color developing solution to adjust the pH value at 25° C. to 12.0.

Next, wash with water for 4 minutes, immerse in a silver source white liquor with the following composition for 6 minutes to bleach, wash with water for 1 minute, immerse in a fixer with the following composition for 1 minute, wash with water for 4 minutes, and then dry. By doing so, a blue portion and a black portion were formed on the substrate.

Silver source white liquor (1) Composition Pure water... 800mff sodium ferricyanide 206g sodium bromide 15g borax...
・Add 1g water...
・・25 using IQ potassium hydroxide aqueous solution
The pH value at °C was adjusted to 8.0.

Fixer composition Ammonium thiosulfate... 175.0g Sodium sulfite... 8.5g Sodium metasulfite 2.3g Add water... 12 (pH using acetic acid)
- Adjusted to 6.0. ) After each pixel was created, the backing layer was completely removed by impregnating the backing layer with a 3% aqueous sodium hypochlorite solution and wiping it off with gauze.

Each pixel obtained in this way is sample No. 1 and No.
．． 11.

Sample No. In the manufacturing process of No. 1 in Table 1, magenta color developing solution was used as No. 1 in Table 1. Sample No. 2 to No. 2 to 10, and sample no. ll
In the manufacturing process, the yellow color developing solution was
．． Sample No. 12 to 20 were created.

For each sample obtained, blue light (B), green light (G)
The spectral absorption density of each pixel was determined using a spectral absorption densitometer.

The measured results are shown in Table 3.

In addition, in Table 3, sample No. of the B pixel formation of the half width of the spectral absorption spectrum of each sample is shown. For 1 = 10, the short wavelength end (hs) is shown, and for the sample with G pixel formation, the value is shown at the long wavelength end (hL) of the B concentration part.

In addition, sample No. for B pixel formation. Regarding 1-10, see B.
The ratio B/G of the G concentration (values at 435nffi and 545nm, respectively) was determined using sample No. 1 for G pixel formation. 11-20
For G and B concentrations (545 nm and 4
Table 1: Amount of magenta coupler in magenta color developer and type and amount of Veye coupler W' - W' Table 2 Amount of yellow coupler and type and amount of Veye coupler in yellow color developer 3 s, hL and B/G of each sample.

G/B As is clear from Table 3, the sample based on the present invention has a low B light density in the B pixel, the short wavelength end of the spectral absorption spectrum is also in the long wavelength range, and exhibits good color reproducibility as a B pixel. .

Furthermore, the G density of the G pixel is low, and the long wavelength end of the B density portion of the spectral absorption spectrum is also in the short wavelength range, indicating good color reproducibility as a G pixel.

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
It is 0 μm×150 μm.

A chromium mask for a color filter having a square opening having a side of 150 μm was placed on top of the photosensitive material, 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 was placed in the magenta color developer at 23°.
C for 3 minutes.

Next, the substrate was washed with water for 1 minute, immersed in silver source white liquor (2) with the following composition for 3 minutes to perform bleaching, washed with water for 1 minute, and then dried to form a blue area on the substrate. process)
.

Ethylenediaminetetraacetic acid iron(III) ammonium salt 2
00.0g Ammonium Bromide・I (1.0g
Glacial acetic acid... IO, 0mff
Add water to make IQ, use ammonia water to pH-6,
Adjust to 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 part G in FIG. 2, and a second exposure was performed.

The light-sensitive material subjected to the second exposure was immersed in a developer obtained by removing W-1 from the yellow color developing solution at 23°C for 3 minutes, washed with water for 1 minute, and bleached in the same manner as the first exposure. A green portion was formed on the substrate by washing with water and drying (second treatment).

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-3-(3-methylbutyl) I
H-Virazo O[3,2,-c]-1,2,4-h Riazole Yellow Coupler ・ ・ ・ 0.82g
α-(4-carboxyphenoquine)-σpivaloyru2
, 4-dichloroacetanizod developing agent...
... ・ 1.2g 4-amino-3-methyl-N,
N-diethylaniline hydrochloride sodium nitrilotrimethylenephosphonate (40%)...3.00m4
Anhydrous sodium sulfate 20.0g Sodium bromide 3.0g sodium sulfite io, 0g ethylene glycol 10. OOm polyethylene glycol・・・・・・ Add 2.0g water・
II2 Note that by adding sodium hydroxide to the above red color developing solution, the pH value at 25°C is 1.
Adjusted to 2.0.

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 (1! Wash with water for 1 minute, bleach for 1 minute
Washing with water for 1 minute Silver bleaching for 1 minute Washing with water for 1 minute Fixing for 1 minute Washing with water for 1 minute Drying for 4 minutes Here, the baths used for each treatment had the following compositions.

Black and white developer composition Sodium sulfite... 10g Hydroquinone... 10g Potassium hydroxide (48% aqueous solution) 5IIlff Diethylene glycol... 20m (1 Dimezone...
・ ・・・・ 0.7g sodium carbonate ・ ・
... ... 20g potassium bromide
2g Thiadiazole・・・・・・・・・・ 0
．． Add 05g water...IQ dye bleaching solution 96% sulfuric acid...40mQ Potassium iodide...15g2.3.6-
Add trimethylquinoxaline and 2g water...
IQ silver bleaching solution composition The same composition as the silver source white solution (1) above was used.

Fixer composition The same fixer composition as above was used.

After the color filter was prepared, the backing layer was completely removed by impregnating the backing layer with a 3% aqueous solution of sodium hypochlorite and wiping it off with gauze.

The color filters obtained in this way were sample No.
It is set as C-1.

In the manufacturing process of sample No. C-1, magenta color developing solution was used as No. DM-2-DM-1 in Table 1 above.
By changing to the developer shown in O, sample No.
C-2 to C-10 were created.

For each sample obtained, blue light (B), green light CG)
The density of the transmitted light pixel of each color was determined by scanning with a microdensitometer (aperture scanning area: 250 μm).

As for the obtained color filter samples, as well as the results for each pixel, samples No. C-1 to C-6 based on the present invention have lower B density of blue light transmitting pixels than the comparative samples, and the color The reproducibility was good.

[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 transmission 22. 32... Colored portion 43... Color filters 46a, 46b... Polarizing plate 47... Liquid crystal 48a, 48b --- Electrode

Claims (1)

[Claims] In a color filter consisting of three primary colors of light on a light-transmitting substrate, at least one color pixel is subjected to a coupling reaction between a precursor compound represented by the following general formula [I] and an oxidized product of a color developing agent. A color filter, characterized in that it is a product and contains at least one substantially colorless compound. General formula [I] ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ [In the formula, R_0 represents an alkyl group with 4 or less carbon atoms, and R
_1 represents an alkyl group or a cycloalkyl group having 4 or more carbon atoms. R_2 is a halogen atom, a cyano group, a nitro group,
It represents an alkyl group, an alkoxy group, an alkylamido group, an arylamido group, a carbamoyl group, an alkylsulfonamide group, an arylsulfonamide group, or a sulfamoyl group. n represents an integer from 0 to 5, and when n is 2 or more, the plurality of R_2 may be the same or different. ]