JPH03212602A - Production of color filter - Google Patents

Abstract

PURPOSE:To produce a color filter having improved color reproducibility and heat resistance by incorporating at least one kind of high b.p. solvent into a layer of a silver halide photosensitive material laminated on a light transmissive substrate by 0.1-20mg/dm<2>. CONSTITUTION:A photomask 14 is set above a silver halide photosensitive material 13 having a dye-contg. emulsion layer 12 laminated on a light transmissive substrate 11, parts 16 of the emulsion layer 12 corresponding to the openings 15 in the mask 14 are selectively exposed by irradiation with light from the top of the mask 14 and a color image corresponding to a pattern is formed by coupler-in-developer type color development to produce a color filter. At this time, at least one kind of high b.p. solvent is incorporated into the photosensitive material layer or a coupler-in-developer typer developer. The solvent may be used in both the material layer and the developer but is preferably used in the material layer. When the solvent is used in the material layer, 0.1-20mg/dm<2> is required but the pref. amt. is 0.5-10 mg/dm<2>. When the solvent is used in the developer, the pref. amt. is 0.1-30g/l. The heat resistance and color reproducibility of the resulting color are improved.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for manufacturing a color filter, and more particularly, to a method for manufacturing a color filter with excellent color reproducibility and heat resistance. The present invention also relates to a method of manufacturing a color filter that is particularly suitable for color displays and can also be used as a color filter for image pickup tubes.

[Background of the invention]

As a method for manufacturing color filters, for example, Japanese Patent Application Laid-open No. 5
As shown in No. 5-6342, there is an external color development method using color silver salt photosensitive materials.

However, the color filter manufactured by the method described in the above patent did not have sufficient color reproducibility and also had problems in heat resistance.

Therefore, in order to solve the above problem, we proposed a method for manufacturing a color filter using pyrazoloazoles as magenta couplers and improved color reproducibility, but this method was not yet fully satisfactory.

[Purpose of the invention]

Therefore, an object of the present invention is to provide a method for manufacturing a color filter with improved color reproducibility and improved heat resistance.

[Structure of the invention]

The object of the present invention is to provide a color filter having a process of exposing a silver halide photosensitive material having a photosensitive layer on a light-transmitting substrate in a pattern and then externally developing it to form a dye image corresponding to the pattern. In the manufacturing method of
g/dm" and/or by a method for producing a color filter, which is characterized in that the color filter is contained in an external developer.

[Specific structure of the invention]

The high boiling point solvent (hereinafter abbreviated as HBS) according to the present invention can be used in the photosensitive agent layer or in the external developer, or both in the photosensitive agent layer and in the external developer. However, it is preferable to use it in the photosensitive agent layer.

Here, the high boiling point solvent refers to a compound having a boiling point of 200°C or higher. When using a compound with a boiling point of less than 200°C, polyimide,
When providing a protective layer containing polyacrylamide or the like as a main component, there is a risk that the compound will vaporize and disappear from the photosensitive material. Also, when providing a light-transmitting electrode or an alignment film on a sample after creating a protective layer, it is treated at high temperature, so the boiling point is 20.
The use of compounds below 0°C is not preferred.

The amount of HBS used is 0 to 1 when used in the photosensitive layer.
~20mg/dm" is required, but 0.5~10mg
/dm" is more preferable. When used in an external developer, it is preferably 0.1 to 30 g per lα, more preferably 0.5 to log.

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. Note that f(BS used in the present invention may be a mixture of two or more types.

Examples of the heptatarate used in the present invention include those represented by the following general formula CI).

General Formula [I] In the formula, R□ and R2 each represent an alkyl group, an alkenyl group, or an aryl group. However, the total number of carbon atoms in the groups represented by R2 and R2 is 2 to 36.

More preferably, the total number of carbon atoms is 6 to 24.

The alkyl group represented by R1 and R2 may be linear or branched, such as butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, Examples include groups such as eicosyl.

Examples of the alkenyl group represented by R1 and R2 include allyl, hexenyl, heptenyl, octenyl, and octadecenyl, and examples of the aryl group include phenyl and naphthyl groups.

These alkyl groups, alkenyl groups and aryl groups may have single or multiple substituents.

Examples of substituents for alkyl and alkenyl groups include halogen atoms and groups such as alkoxy, aryl, aryloxy, alkenyl, and alkoxycarbonyl; examples of substituents for aryl groups include halogen atoms and alkyl, alkoxy, aryl, Examples include groups such as aryloxy, alkenyl, and alkoxycarbonyl. Two or more of these substituents may be introduced.

Phosphoric esters advantageously used in the present invention include those represented by the following general formula (1).

General formula (I[) In the formula, R3, R4 and R6 each represent an alkyl group, an alkenyl group or an aryl group. However, the total number of carbon atoms in the groups represented by R1, R6 and R6 is 3 to 54.

The alkyl groups represented by R8, R4 and R6 may be linear or branched, and specifically, R1 and R of the general formula CI)
Examples of the alkyl group represented by 2 include the same groups as those listed above.

As the alkenyl group represented by R3, R4 and R3,
Examples of the aryl group include a vinyl group, an allyl group, a butenyl group, and a phenyl group, a tolyl group, a xylyl group, and the like.

These alkyl groups, alkenyl groups and aryl groups may have single or multiple substituents.

R3, R4 and R1 are preferably alkyl groups, such as butyl, 2-ethylhexyl, octyl, t-
Groups such as octyl, 3.5.5-1-limethylhexyl, nonyl, decyl, 5ec-decyl, 5ec-dodecyl and the like can be mentioned.

As the phenolic HBS used in the present invention, any conventionally known HBS can be applied;
Or, it is liquid at room temperature and has a boiling point of 200 at normal pressure (1 atm).
It is preferable that the 4-position of the phenol is substituted with a group that does not leave by coupling so that it cannot react with the oxidation product of the color developing agent at temperatures above .degree. Furthermore, those having a diffusion-resistant group (hereinafter referred to as a ballast group) are preferable,
Particularly preferred is one represented by the following general formula (I[[).

In the formula, R1 and R7 are each a hydrogen atom or a carbon number of 1 to 2
0 linear or branched alkyl group (e.g. methyl, ethyl, t-butyl, t-pentyl, t-octyl, dodecyl, pentadecyl, etc.), and Ra represents a carbon number of 1 to 20
represents a straight-chain or branched alkyl group (the same groups as those listed above for R6 and R7) or a cycloalkyl group (for example, cyclopentyl, cyclohexyl, etc.). However, the total number of carbon atoms in the groups represented by R7 and R8 is 6 to 24.

Typical specific examples of HBS according to the present invention are shown below.
-1 B5-3 HBS HBS B5-9 B5-2 B5-4 B5-6 B5-8 B5-10 B5-11 B5-12 B5-14 B5-16 B5-13 ) fBs-15 HBS-17 HBS-18 HBS-20 HBS-22 HBS 4 HBS-26 B5-19 C2H.

嘗 CH3CHO,H.

C2H.

HBS-21 HBS-23 HBS 5 HBS-27 HBS 8 HBS 9 HBS 0 HBS 1 B5-32 HBS-33 The HBS according to the present invention can be used as a dispersion of hydrophilic colloids such as gelatin, surfactants, water, etc. preferable.

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, 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 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 based on either the 7 Arnes method or the channel method, and for example, "Dia Black" (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, is 500nm
It is preferable that it absorbs the following light. Furthermore,
The backing layer may contain a UV absorber.

UV absorbers, such as rUVINUL MS-
40J (manufactured by BASF), rTINUVIN-PJ (
(manufactured by 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 emulsified and dispersed using a dispersion means such as a stirrer, a homogenizer, a colloid mill, a flow jet mixer, and an ultrasonic dispersion device. It is used by adding it to a coating composition that requires a colloidal backing.

The amount of non-diffusible dye or pigment used is preferably 0.1 mg or more, particularly preferably L mg or more per light-transmissive substrate 100c+n2.

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 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 Rigman 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 silver dye bleaching action.

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

(m and n each represent 1 or 2) Width below\ Compound R'R"R' R
'J R'2 2 No2H0C
Hs 0CHs Co Hb
2NOx 5NO20CHx 0CHs
CO, Hc 2 CQ HOCH
30CHs Co Hd H
HOCH30CH3Co He 2-C
Q H-OCH, CH20HH-3O, -Hf
2-3o2NH2H-OCH, H-3Oz-Hg
2 5O2CH3HOCH30CHs C
o Hi 2NOx H0CHx
CH20HH5O2H2COCH3H0CHx
0CHx CoH 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) of 6 to 8:11. The weight ratio of dye to
10-50, the weight ratio of dye to water-soluble binder is 1/
It is desirable that it be contained in a ratio of 100 to 2.

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

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

In particular, in the present invention, the thickness of the emulsion layer is set to 0.5 to 3 μm.
By keeping it within this range, the spectral characteristics of the resulting color filter can be improved.

One of the preferred embodiments of the present invention is a method in which the emulsion layer detailed above is processed using a silver halide photosensitive material by a combination of an external color development method and a silver dye bleaching method. When this method is adopted, it is preferable to carry out the treatment by the silver dye bleaching method after all the processing steps by the external color development method are completed.

Next, a preferred embodiment of the production method of the present invention will be explained in this order by dividing it into a processing step using an external color development method and a processing step using a silver dye bleaching method.

(Processing step using external color development method) In this method, it is preferable that all colored parts formed on the light-transmitting substrate by external color development method be formed in advance before applying the silver dye bleaching action.

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, seven otomasks 14 are placed on a silver halide photosensitive material 13 having an emulsion layer 12 containing the dye exhibiting silver dye bleaching action and laminated on a light-transmissive substrate 11. This is done by applying light from above the 7-otomask 14.

By this operation, the exposure element fixed portions 16 of the emulsion layer corresponding to the openings 15 provided in the photomask 14 can be selectively exposed.

The size of the exposure element fixed portion 16, ie, the size of the opening 15, can be appropriately set depending on the use of the color filter to be manufactured. However, if the width of the aperture 150 is narrower than the wavelength of the light source used for exposure, effective exposure cannot be performed, so the width of the aperture 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 Kaglar 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 (The Theory of the Photographic Process) by James H.
of the Photographic Process
ss 3rd, Edition) J, pages 293 to 298, and specific examples include (1) 4-amino-3-methyl-N=(2-hydroxyethyl)aniline sulfate Salt (2) N-ethyl-N-methoxyethyl-3-methyl-
p-phenylenediamine/p-toluenesulfonate (3
) 4-amino-3-methyl-N-ethyl-N-(2-
Methylsulfonamidoethyl) aniline sulfate/aquarium (4) N,N-diethyl-p-p-p-22-diamine sulfate (5) N,N-diethyl-3-methyl-p-7-22-diamine Examples include hydrochloride.

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

The developing agent in the developer is usually used in a content within the range of 0.1 to 10 g in the developer IQ. If the content of the developing agent is less than 0.1 g, effective development may not be possible, and even if more than 10 g is used, not only will no significant improvement in developability be observed, but depending on the type of developing agent. may not dissolve sufficiently.

In particular, it is preferable to use the developing agent in the range of 0.5 to 7 g in the developer IQ, 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 couplers, examples of yellow couplers include ketomethylene compounds (e.g. α-(4-
carboxyphenoxy)-a-pivaloyl-2,4-dichloroacetanilide);
, No. 3,619.189, Japanese Patent Publication No. 40-33775 and No. 44-3664, etc. can be used.

Examples of magenta color-forming couplers include active methylene compounds (for example, pyrazolones such as 1-(2,4,6-dolichlorophenyl)-3-(p-nitroanilino)-5-pyrazolone, 7-chloro-3 -7znyl-6-ituprobyl-IH-pyrazol:l [5,l -el-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, Special Publication No. 4
4-133111 etc. can be used.

Furthermore, examples of cyan color-forming couplers include phenolic compounds (e.g., 2-acetamido-4,6-dichloro-
5-methylphenol) or a 7-tolyl compound (for example, N-(2-acetamido-7enethyl)-1-hydroxy-2-7-tamide);
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 la is preferably set within the range of 0.1 to 20 g. If it is less than 0.1 g, sufficient color development may not be achieved, while if it is used in excess of 20 g, so-called fogging may occur. In particular, in the present invention, by controlling the total content of color-forming Kadalar in the developer IQ to be within the range of 0.2 to 10 g, a color filter with less color turbidity and good spectral characteristics can be obtained.

The blending ratio of color-forming couplers exhibiting different color development in this developer can be appropriately set in consideration of the color-forming properties of the color-forming couplers used. For example, when combining a cyan coloring coupler and a magenta coloring coupler, the weight ratio of both is usually I:9 to 7:3.
Preferably it is within the range of I: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:
l-1:9, preferably within the range of 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), auxiliary agents (e.g. water conditioners such as polyethylene glycol, citrazic acid, imidazole) It may also contain additives contained in ordinary external developers, such as color toning agents such as derivatives.

A developer can be prepared by dissolving the above components in water.

Note that the developer should be used at a normal operating temperature (for example, 10 to 40°C).
It is used after adjusting the pH value in C) using sodium hydroxide or the like so that the pH value falls within the range of 9.0 to 13.0.

In the method of the present invention, pixels can be formed by external color development using the developer as described below, for example.

First, the silver halide photosensitive material is pattern-exposed by a conventional method (Jth 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 using silver salt 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). ], a developing aid, a preservative, a so-called developing antifoggant, an alkaline buffer, and, if necessary, a solvent for the developing agent (D) and the developing aid.

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

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

Preservatives include sulfites, ascorbic acid, and the like.

Examples of the development antifogging agent include 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 evaporated ethylene glycol, triethanol, and jetanol.

An example of the contents of the various components in the black and white developer is as follows: 1 to 20 g IQ of developing agent (D) and 0 g of developing aid.
．． 05 to 8 g/(1, preservative 1 to 120 g/+2, development antifoggant 0.001 to 5 g IQ, alkaline buffer 0.1 to 50 g IQ, and further uses a developing agent and a developing aid solvent. In case of solvent 1-20II112/Q
It is.

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

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

After the black-and-white development process, a washing process is usually performed, and then a dye bleaching process, which will be described in detail below, is performed.

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

That is, this dye bleaching process is a process in which a positive image of the dye is formed by bleaching the dye in the dye contained in the image-exposed light-sensitive material in the portion containing a large amount of image silver.

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

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

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

Examples of dye bleach accelerating catalysts include pyrazine, naphthazine, quinoline, quinoxalines, phenazines, anthraquinones, naphthoquinones, indoorenazines, N
-Substituted isoalloxazines, floquinoxalines, chietukizalines, diphenyl derivatives, triphenylmethane derivatives, lumazines, alloxazines, cinnolines, orthophenylenediamine derivatives, etc. (US Pat. No. 2,270.118, 2,410,02
No. 5, No. 2,541.884, No. 2,627,461
No. 2,669.517, British Patent No. 657.374
No. 711,247, Japanese Patent Publication No. 45-22195, etc. ).

Examples of the contents of the various components in the dye bleaching solution include: 1 to 20 g IQ of bleach, 0.1 to 20 g, l of a compound forming a silver salt or silver complex, and 0 dye bleach accelerating catalyst.
．． 001 to 10g/Q.

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 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, when forming a color filter having B (pixel for transmitting blue light), G (pixel for transmitting green light), and R (pixel for transmitting red light) shown in FIG. 2, each exposure table shown in FIG. The colored part is yellow pigment (y+ or yz)
, a magenta dye (M+ or M-li) and a cyan dye (C or CZ).

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,
The silver dye bleaching method is used to remove the color of the dye in areas other than the areas indicated by SDR, which exhibits a silver salt dye bleaching effect.

For example, in the pixel forming pattern shown in Pattern Example 1 in Table A, first, the blue light transmitting pixels are pattern-exposed in the manner described above in the first exposure/processing process. Thereafter, development is performed using an external developer containing a magenta color-forming coupler. Next, after the green light transmitting pixels are pattern-exposed in a second exposure/processing process, a development process is performed using an external developer containing a yellow color-forming coupler and a cyan color-forming coupler. 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-impermeable section (black stripe) 33 can also be formed in the gap between the red part (R), the blue part (B), and the green part (G).

Also in this case, the silver dye bleaching process is preferably carried out after all external development processes have been completed.

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

Furthermore, the pixel formation mode may be either 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, the color filter 43 is arranged so that the color filter 43 and the liquid crystal 47 controlled by the electrodes 48a and 48b are sandwiched between the polarizing plates 46a and 46b.
If placed, it can be used as a filter for liquid crystal color displays.

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

〔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: O, OS μm 1, 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 aged for 5 minutes.

Then, 14b5 mg of l-phenyl-5-mercaptotetrazole and l-carboxyethyl-4,5-hydroxybenzene were added to the emulsion per mole of silver, respectively.
x 3.40g, and the following compound SC-1 was added in an amount of 15.9g per mol of silver, and the following compounds H-1 and H-2 were added as hardeners at a rate of 4% each per 1g of gelatin.
By adding 0 mg and 5 mg, C-1-1-2 [(CH2=CH302CHx)3ccH2sO2cH
The emulsion coating solution obtained on 2cH2]2NCR2CH2SO3 was applied to a transparent borosilicate glass substrate (30
A silver halide photosensitive material having an emulsion layer was prepared by coating the film on a 30 cm x 30 cm film to give a dry film thickness of 3 μm. Bank clerk: 1.5g/m”, amount of pigment applied: 0.24g
/m2.

The photosensitive material thus produced was designated as Photosensitive Material-1.

In addition, in the manufacturing process of photosensitive material-1, photosensitive materials-2 to 9 in Table 1
A dispersion containing each of the compounds shown in is added to the emulsion coating solution,
Photosensitive materials-2 to 2 were prepared in the same manner, except that the amount of water added was adjusted so that the volume of the emulsion coating solution per mole of silver was the same as the volume of the emulsion coating solution in the manufacturing process of photosensitive material-1.
9 was produced.

For bank employees, 1.5g/m2, amount of pigment applied is 0.2
4g/m2, and the amount of HBS applied was 0.18g/m''.

As the dispersion liquid, each of HBS shown in Table 1 was used at 13°5.
A solution of 8 g dissolved in 136.3 m4 of ethyl acetate was added to 27.34 g of gelatin and 170.5 m of a 5% aqueous solution of sodium triisopropyl-β-naphthalenesulfonate.
I2 and 458.2 m of water were added and mixed into an aqueous solution containing 2, subjected to ultrasonic dispersion at 50'O, ethyl acetate was removed, and water was further added to make a total of 818.4 m++2.

The silver halide photosensitive materials mentioned above all have a backing layer on the surface of the borosilicate glass substrate opposite to the surface having the emulsion layer.

The formation of this buffing layer will be explained below.

A dispersion of compound Y-1 below was added to an aqueous gelatin solution, and 40 mg each of hardeners H-1 and H-2 were added.
5 mg was added. Here, the amount of gelatin added to the gelatin aqueous solution was adjusted in advance to be 5%. Further, the amount of Y-1 added to 100 mff of gelatin aqueous solution was 1.35%.

-1 Thereafter, this aqueous gelatin solution was applied to the borosilicate glass substrate and dried to form a backing layer. Y-
The amount of No. 1 applied was 10 mg/dm2.

The above-mentioned dispersion was prepared by dissolving 1 g of Y-1 in 1 g of tricresyl phosphate, 4.29 m of ethyl acetate (2), 0.83 g of gelatin, and 0.83 g of triisopropyl-β.
- 5% aqueous solution of sodium naphthalene sulfonate 2-6
An aqueous solution containing 3 m (2) and 3.4 m (2) of water was added and mixed, subjected to ultrasonic dispersion at 50°C, ethyl acetate was removed, and water was added to make a total volume of 17.6 mQ.

Table 1 HBS in silver halide photosensitive materials A method for producing a color filter having a mosaic pattern of three colors (blue), G (green), and R (red) as shown in FIG. 2 will be described below. The size of each pixel is 150μm×150
It is 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 of m in size was overlaid, and a first exposure was performed using a tungsten lamp. Exposure was carried out at a position corresponding to part B in FIG.

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

Magenta color developer composition Magenta coupler・0.3g6-ituprobyl-7-chloro-3-phenyl-IH pyrazolo[3,2-c]-1,2,4-triazole developing agent・
2.0g4-amino-3-
Methyl-N-ethyl-N-β-methanesulfonamide ethylaniline 11/2 sulfate monohydrate Sodium nitrilotrimethylenephosphonate (40% aqueous solution) 3.00 ma anhydrous sodium sulfate
・20.0g sodium bromide・
1.0g sodium sulfite...
IO, 00g ethylene glycol ・ ・ 10
．． 0mQ polyethylene glycol・2.0
g Add water and H2Additionally, add sodium hydroxide to the above magenta color developer and make H2.
The pa value at 5°C was adjusted to 12.0.

Next, after immersing in a stop solution (3% acetic acid aqueous solution) for 1 minute, washing with water, and bleaching by immersing in a silver source white liquor of the following composition for 9 minutes, washing with water for 1 minute, and then drying. , a blue portion was formed on the substrate (first treatment).

Silver source White liquor composition Ethylenediaminetetraacetic acid iron (I[) ammonium salt 2
Add 00.0 g ammonium bromide, 10.0 g glacial acetic acid, and 10.0 mg water to make 112, 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 part G in FIG. 2, and a second exposure was performed.

The photosensitive material subjected to the second exposure was immersed in a yellow color developing solution having the composition shown below at 23°C for 3 minutes, then immersed in the stop solution for 1 minute, and then washed with water. A green area was formed on the substrate by bleaching, washing with water, and drying (second
process).

Yellow color developer composition Yellow coupler・1.5g α-
(4-carboxyphenoxy)-α-pivaloyl-2,
4-dichloroacetanilide developing agent・・
2.0g4-amino-3-methyl-N-ethyl-N-β-methanesulfonamidoethylaniline.
11/2 Sulfate monohydrate Sodium nitrilotrimethylenephosphonate (40% aqueous solution) ・3.00 mQ Anhydrous sodium sulfate ・ 20.0 g sodium bromide ・ 3.0 g sodium sulfite ・ ・ 10.00 g ethylene glycol ・ 10. Add 0m12 polyethylene glycol and 2.0g water
112Additionally, add sodium hydroxide +'y/-4 repulsion r+lr' to the above yellow color developing solution.
('ρ I'' 廿1+ ＾ niJ value A; +9-11
11 I adjusted it so that it looked like this.

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

The photographic material subjected to this third exposure was immersed in a red color developer having the composition shown below at 23°C for 3 minutes, then stopped, washed with water, bleached, washed with water, dried, and placed on a substrate in the same manner as the second time. A black part was formed on the surface (third process).

Red color developer composition Magenta coupler・0.3g6-Ingloby-7-chloro-3-phenyl-IH-pyrazolo[3,2-c]-1,2,4-triazole Yellow coupler・1.5ga-(4-carboxyphenoxy )-σ-pivaloyl 2,4-dichloroacetanilide developing agent
・2.0g4-amino-3-methyl-N-ethyl-N
-β Methanesulfonamidoethylaniline・+1/91
Sodium Nitrilotrimethylenephosphonate (40% aqueous solution)...3.00m12 Anhydrous sodium sulfate, 20.0g sodium bromide...3.0g sodium sulfite, IO, 00g ethylene glycol, 10.00m12 Polyethylene Glycol・Add 2.0g water
112 Furthermore, by adding sodium hydroxide to the above red color developing solution, the pH at 25 °C
The value was adjusted to 12.0.

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 subjected to the fourth exposure is processed at 33°C as follows to form a red part (fourth exposure).
A color filter having a mosaic pattern of three colors, B (blue), G (green), and R (red) was obtained.

Black and white development Stop for 1 minute Water for 1 minute
Wash and bleach for 1 minute
Wash with water for 1 minute, wash with water for 1 minute
Bleach for 1 minute in water
Wash for 4 minutes
Wash 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) 5m12 diethylene glycol
20m+2jimaison
0.7g sodium carbonate 20
g Potassium bromide 2 g Thiadiazole 0.05 g Add water
10 Dye bleaching solution composition 96% sulfuric acid 40ml 12 Potassium iodide 15g 2.3.6-Trimethylquinoxaline 2g Add water
The same silver source white liquor composition as in IQ Silver Silver White Liquor Composition was used.

Fixer composition Ammonium thiosulfate 175.0g Sodium sulfite 8.5g Sodium metasulfite 2.3g Add water
IQ (adjusted to pH=6.0 using acetic acid.

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

The color filter obtained in this way was used as sample No.
1 to 9.

Samples No. 1 to 9 except that the types and amounts of couplers and developing agents in the magenta color developer, yellow color developer, and red color developer were changed as shown in Table 2 in the manufacturing process of Samples No. 1 to 9. Color filter samples Nos. 10 to 18 were prepared in the same manner as Table 2. Types and amounts of couplers and developing agents in each external developer For the obtained color filter samples Nos. 1 to 18, blue light (B) Using green light (G) and red light (R), the density of blue light-transmitting pixels was determined by scanning with a microdensitometer having an aperture scanning area of 250 μm 2 . Concentration by blue light measurement / Concentration by green light measurement (
B/G'') is shown in Table 3. The smaller this value is, the better the color reproducibility is.

In addition, as a heat resistance test, blue light measurement and green light measurement of blue light transmitting pixels and red light transmitting pixels after aging for 0 hours, 2 hours, 4 hours, and 6 hours under the condition of 180 ° C using open circuit. The change in concentration was calculated as a relative value with the concentration of the sample at 0 hours as 1. The results are shown in Table 4-1.4-2.

However, the display of density change values based on blue light measurement of red light transmitting pixels was omitted.

Table 3 B/G of blue light transmitting pixel Table 4-1 Heat resistance performance (blue light transmitting pixel) Table 4-2 Heat resistance performance (red light transmitting pixel) The color filter manufactured by the manufacturing method of the present invention is as shown in Table 3. As is clear from the results, in the blue light transmitting pixels, the ratio of blue density to green density is small, and color reproducibility is improved.

In addition, as is clear from the results in Table 4-11 and Table 4-2, heat resistance has improved, and in blue light transmitting pixels, the increase in blue density after heat-resistant treatment is low, and the color reproducibility after heat-resistant treatment is improved. is also good.

Example 2 Samples No. 002 to 9 and No. shown in Table 4-1 of Example 1,
Regarding "ll" 18, the amount of HBS applied in advance at the time of preparing the photosensitive material was 0.001.0.01.0.05.1, respectively.
, 2 and 5 g/m2, except that the light-sensitive materials were prepared in the same manner.

Each of the obtained samples was subjected to the same heat resistance test as shown in Table 4-1 to examine changes in density of blue light transmitting pixels and green light transmitting pixels.

Although there are some differences for each sample, the amount of HBS applied was 0.01, 0.05. 1 and 2 g/m2 both showed similar results to the examples in Table 4-1.

In addition, for the HBS applied amount of 0.001 g/m'', the concentration change due to the heat resistance test was not large for comparative samples No. 1 or 10, but for the samples of this example (No. 2 to 9, 11 to
18), the concentration change was quite large and the heat resistance could not be said to be good. Also, the amount of HBS applied is 5 g/m2
The sample was not only devitrified, but also had fine cracks on the filter surface, making it unsuitable for use as a color filter.

[Brief explanation of drawings]

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-transparent substrate 12... Emulsion layer 13. ・
Silver halide photosensitive material 14... Photomask 15... Opening 16... Area to be exposed 21
．． 31... Light transmitting substrate 22. 32... Colored portion 33... Black stripe 43... Color filters 46a, 46b, Polarizing plate 47, Liquid crystal 48a, 48b, Electrode

Claims (1)

[Claims] A method for producing a color filter comprising the steps of exposing a silver halide photosensitive material having a photosensitive agent layer on a light-transmitting substrate in a pattern, and then externally developing to form a dye image corresponding to the pattern. A method for producing a color filter, characterized in that one kind of high boiling point solvent is contained in the photosensitive agent layer at a concentration of 0.1 to 20 mg/dm^2 and/or in an external developer.