JPH03214103A - Production of color filter - Google Patents

Abstract

PURPOSE:To obtain a color filter having improved surface smoothness and adaptable to use for a color liq. crystal display by utilizing a silver halide emulsion sensitized with a noble metal and carrying out silver bleaching after final-stage color development. CONSTITUTION:A silver halide emulsion sensitized with a noble metal such as Au, Pd or Ir is utilized. After a silver halide photosensitive material is color- developed to form all of colored parts, coloring matter having silver-coloring matter bleaching action contained in the photosensitive material is decolored by silver-coloring matter bleaching. This processing is attained by successively carrying out at least black-and-white development, dye bleaching and silver bleaching. A color filter having a small difference in level between color image elements and superior surface smoothness is obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for manufacturing a color filter, and more particularly to a method for manufacturing a color filter suitable for use in a color liquid crystal display.

[Background of the invention]

As a method for manufacturing color filters, JP-A-55-63
As disclosed in No. 42, there is an external color development method using a color silver salt photographic material.

When producing a black matrix (hereinafter abbreviated as BM) between each red, green, and blue pixel by this external color development method, there is a method that uses, for example, three dyes of yellow dye, magenta dye, and cyan dye. However, when exposing the color silver halide photographic material through a mask during the production of each pixel, due to alignment accuracy problems and developability problems inherent to silver salt, a line of BM is created at the boundary between each pixel and BM. A protrusion is formed in the center of the Therefore, the smoothness of the color filter deteriorates, leading to deterioration of the image quality after manufacturing the color liquid crystal display, and also causing wiring defects in the common electrode provided during the manufacturing of the color liquid crystal display.

[Purpose of the invention]

An object of the present invention is to provide a method for manufacturing a color filter that has improved surface smoothness and is suitable for use in color liquid crystal displays.

[Structure of the invention]

The above-mentioned object of the present invention is to pattern-expose a photosensitive material having a silver halide emulsion layer on a light-transmitting substrate, and then use a developer containing a coupler and a color developing agent to form a dye image corresponding to the pattern. A color filter manufacturing method comprising at least two steps of forming a color filter, wherein the silver halide emulsion is a silver halide emulsion sensitized with a noble metal, and after color development is performed in the final stage of the development process. , is achieved by a method for producing a color filter, which is characterized by carrying out silver bleaching.

[Specific structure of the invention]

Examples of the noble metal compound according to the present invention include gold, palladium, iridium, and the like.

As the gold compound, the oxidation number of gold may be +1 or +3, and various types of gold compounds are used. Representative examples include chlorauric acid salt, potassium chloroaurate, auric trichloride, potassium auric thiocyanate,
Potassium iodo-oleate, ammonium aurothiocyanate, pyridyl trichlorogold, gold sulfide, gold selenide and the like can be mentioned.

As a palladium compound, the oxidation number of palladium is +2
Preferred are those with a valence of +4, such as potassium tetrachloropalladate, potassium hexachloropalladate, and the like.

In addition, as an iridium compound, the M number of iridium +
3. +4 is suitable for use, and specific examples include potassium hexachloroiridate (II) and potassium hexachloroiridate (IV).

The amount of the noble metal compound added varies depending on various conditions, but as a guideline, it is from IO-@ to 10-' mol, preferably from 10-' to 1 O-2 mol, per mol of silver halide.

Nu, these compounds are added at the time of AgX particle formation,
Any step during physical ripening, during chemical ripening, or after completion of chemical ripening may be used.

The silver halide emulsion according to the present invention is noble metal sensitized using the above-mentioned noble metal compound, but may be sensitized in combination with the following sensitization method.

These include a sulfur sensitization method using a compound containing sulfur that can react with silver ions or active gelatin, a selenium sensitization method using a selenium compound, and a reduction sensitization method using a reducing substance.

Among these, sensitization is preferably carried out in combination with a sulfur sensitizer or a selenium sensitizer.

Examples of the sulfur sensitizer include thiosulfate, allylthiocarbazide, thiourea, allylisothiocyanate, cystine, p-toluenethiosulfonate, and rhodanine. Others: U.S. Patent No. 1,574゜944, U.S. Patent No. 2
゜410.689, 2,278.947, 2.
728゜668, 3,501,313, 3,6
No. 56.955, West German Publication (OLS) 1,422
, No. 869, JP-A-56-24937, JP-A No. 55-45
Sulfur sensitizers described in No. 016 and the like can also be used.

Examples of selenium sensitizers include aliphatic inselenocyanates such as allyl isoselenocyanate, selenoureas, selenoketones, selenoamides, selenocarboxylic acid salts and esters, selenophosphates, and selenides such as diethylselenide. Examples thereof include U.S. Pat. Nos. 1,574,944 and 1,602.
, No. 592 and No. 1,623.499.

Silver halide photosensitive material In the present invention, a silver halide photosensitive material having an emulsion layer formed by coating a light-transmitting substrate with a silver halide emulsion is used.

The light transmitting substrate used may be transparent or semitransparent as long as it has light transmittance. Furthermore, since the color filter is sometimes exposed to high temperatures during the vapor deposition process of transparent electrodes, it is preferable that the material of the light-transmitting substrate has good heat resistance.

Examples of materials that make up such a light-transmissive substrate include:
Examples include glasses such as polyethylene terephthalate, polybutylene terephthalate, polystyrene, polycarbonate, polyether sulfone, polyvinyl alcohol soda glass, and borosilicate glass, and inorganic substances such as quartz and sapphire.

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

The thickness of the light-transmissive substrate can be set appropriately depending on the application and material, but it is usually 0.5μ+i”10.
It is within a range of 1m. In particular, when glass is used as a light-transmissive substrate for a liquid crystal color display,
It is preferable that the thickness is within the range of 0.3 to 21111.

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 accuracy of the light-transmitting substrate be ±0.1 μl.

In the present invention, it is preferable to provide a backing layer for antihalation on the surface of the light-transmissive substrate opposite to the surface on which the emulsion layer is formed. In this case, the dye or pigment contained in the backing layer is preferably a non-diffusible dye or pigment. Specifically, a carbon black dispersion can be suitably used. The carbon black dispersion may be produced by either the furnace method or the channel method, and for example, "Diablack" (manufactured by Mitsubishi Kasei Corporation) can be suitably used.

The non-diffusible dye or pigment is contained in the backing layer in a state dispersed in a hydrophilic colloid, but it must not be eluted into each processing solution even after development. The light absorption properties of the dye or pigment used vary depending on the spectral absorption properties of the silver halide emulsion used in the present invention, but for example, when using a silver halide emulsion that has not been spectral sensitized with a sensitizing dye, It is preferable that it absorbs light of 500 mm or less. Furthermore, the backing layer may contain a UV absorber.

UV absorbers, such as rUVINUL MS-
40J (manufactured by BASF), rTIN[IVIN-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, globyl 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 light-transmissive substrate 100c++''.

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 in consideration of the spectral characteristics of the color filter, and is usually less than 1 μm, preferably within the range of 0.05 to 0.5 μm.

The silver halide emulsion layer used contains at least silver halide and a water-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 desirable to use a silver halide having a small average grain size, and it is particularly preferable to use a so-called Lippmann emulsion having an average grain size of 0.1 μm or less. If the average particle size of silver halide is large, the image quality, mainly in terms of graininess, of the resulting color filter may deteriorate.

Examples of the water-soluble binder include gelatin, albumin, casein, cellulose derivatives, starch derivatives, sodium alginate, polyvinyl alcohol, polyvinylpyrrolidone, polyacrylic acid copolymers, and polyacrylamide.

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

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

Examples of such dyes include phthalocyanine dyes,
Examples include azo dyes. Among azo dyes, particularly preferred are bisazo dyes, such as R' R2 2-NO, H 2-NO, 5-No.

2-CQ H 81( 2-CQ H 2-5O! NH!　H 2-So, C) I, H 3 -OCH.

-0CI(.

10 CI.

100) l.

QC)ItCHtOH -OCI(.

-OCH.

4 -OCI(.

0CHs -OCH.

-OCH! ■ 1 -OCR.

C.O. C0- CQ -C〇- -SO,- -50° C0- 2-No.

+1 -　ocn, CH, OH -SO1 2-〇〇C)Is 10CR.

OCR.

-C〇- 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 120 to 8:1. The weight ratio of dye to silver halide is 1/10 to 50. It is desirable that the weight ratio of the dye to the water-soluble binder is 1/100 to 2.

The emulsion layer can be formed by applying the emulsion 1j on the light-transmitting substrate using a conventionally known coating method such as a spinner coating method or a spray coating method.

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

In particular, in the present invention, the thickness of the emulsion layer at °C is 0.5 to 3 μm.
By keeping it within the range of l, 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 described in detail above is processed by a combination of an external color development method and a silver dye bleaching method using a silver halide photosensitive material. However, when this method is adopted, it is preferable to carry out the treatment by the silver dye bleaching method after all the processing steps by the external color development method are completed.

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

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

Specifically, the silver halide photosensitive material is subjected to mask exposure for forming pixels, and then developed with a developer containing a color-forming coupler to form a colored portion.

Exposure Processing Exposure methods that can be employed in the present invention include, for example, methods used in normal pattern exposure such as direct 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 portions 16 of the emulsion layer to be exposed corresponding to the openings 15 provided in the photomask 14 can be selectively exposed.

The size of the portion 16 to be exposed, that is, the size of the opening 15, can be appropriately set depending on the use of the color filter to be manufactured. However, if the width of the opening 15 is narrower than the wavelength of the light source used for exposure, effective exposure cannot be performed, so the width of the opening 15 is made wider than the wavelength. Since silver halide has effective photosensitivity to light in the range of 340 to 420 nm, the width of the opening 15 is usually 340 nm or more, and considering its use as a color filter, It is preferable to set it to 1 u@ or more. In addition, in the case of a color filter for a liquid crystal display, in order to perform color reproduction through additive color mixing of red, blue, and green colored parts, the width of the opening 15 should be set to 1.
It is preferable to set the thickness to 000 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, 293N298
Specific examples include (1) 4-amino-3-methyl-N-(2-hydroxyethyl)aniline sulfate (2) N-ethyl-N- Methoxyethyl-3-methyl-p-7 22-diamine p-toluenesulfonate (3) 4-amino-3-methyl-N-ethyl-N-(2
-methylsulfonamidoethyl) aniline sulfate hydrate (4) N,N-diethylnyl-phenylenediamine sulfate (5) N,N-diethyl-3-methyl-p-
Examples include phenylenediamine hydrochloride.

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

The developing agent in the developing solution is usually used so that it is contained in the developing solution la in an amount within the range of 0.1 to 10g. If the content of the developing agent is less than 1g, effective development may not be possible, and even if more than 10g 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 la 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 CI [) as described in Japanese Patent Publication No. 55-9697.

General formula [I[) In the formula, R represents a branched alkyl group having 3 to 6 carbon atoms, xl
and X! each represents 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 X□ are preferably a chlorine atom, X is preferably a hydrogen atom,
A chlorine atom is mentioned, and the carboxyl group of the phenoxy group substituted at the active site of the coupler is preferably in the meta or bara position with respect to the bonded oxygen atom.

Compound RX+ Xs X3 C
00HY 1 (CH3)3CCQ Cl2(3
) H4 position Y-2(CH,)3CCQ Cl2(
4) H3 position Y 3 (CHs)sCCQ
C(2(4) H4 position y-4(CH3)3Cc12
cQ(4) cQ(5) 4th position y-5(CHI)3
Cca cc(4) cc(5) 3rd place Y-6(
CHs)sCBr Br(4) CH, 4th position A particularly preferred compound among the above yellow coloring couplers is Y-
This is a compound represented by No. 4.

Magenta coloring couplers include active methylene compounds,
for example! -(2,4,6-dolichlorophenyl)-3-
Examples include pyrazolones such as troanilino-5-pyrazolone and cyanoacetanilides, which are further disclosed in West German Patent Publication (OLS) 2. O12,587,
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 preferred pyrazoloazole magenta color-forming couplers are shown below, but the invention is not limited thereto.

Furthermore, U.S. Patent Nos. 3,510.306 and 3,619;
No. 189, Special Publication No. 40-33775 and No. 44-36
Those described in No. 64 etc. can be used.

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-naphthamide);
U.S. Patent No. 3,002,836, U.S. Patent No. 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 Edf
tionJ (cited above), Chapter 17.

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

In the developer, the total content of color forming couplers in the developer IQ is preferably set within the range of 0.1 to 20 g. If it is less than 0.1 g, the color may not develop sufficiently, while if it is more than 20 g, so-called capri may occur. In particular, in the present invention, by controlling the total content of color-forming couplers in the developing solution la 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), auxiliary agents (e.g. water conditioners such as polyethylene glycol, citrazic acid, imidazole) It may also contain additives contained in ordinary external developers, such as color toning agents such as derivatives.

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

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

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

First, the silver halide photosensitive material is pattern-exposed by a conventional method (first exposure).

After performing the first pattern exposure, a first development of the exposed portion is performed using a developer containing the color forming coupler. For example, 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.

Also, a developer containing a cyan color forming coupler (cyan developer)
, by using a developer containing a magenta color-forming coupler (magenta developer) and a developer containing a yellow color-forming coupler (yellow developer), the exposed areas become cyan and cyan, respectively.
Developed to magenta and yellow colors.

The first exposed 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 bleach solution or a black and white developer, washing with water, and drying.

Similarly, the unexposed portion adjacent to the second colored portion is exposed in a pattern, and then developed using a developer other than that used in the first and second steps. Further, if desired, a third colored portion can be formed by performing steps such as dipping in a bleach solution or a black and white developer, washing with water, and drying.

In one example of a preferred embodiment of the present invention, after the first to third colored portions are formed as described above, a silver dye bleaching treatment described in detail below is performed.

(Processing step using silver dye bleaching method) In this method, after forming all the colored parts by the external color development method, a silver dye bleaching process is performed to remove the silver dye bleaching effect contained in the silver halide photosensitive material. Decolorize the dye that shows.

The processing steps by the silver dye bleaching method include at least black and white development, dye bleaching, and silver bleaching in this order.

Next, processing steps using the silver dye bleaching method, black and white development processing,
Dye bleaching treatment and silver bleaching treatment will be explained separately in this order.

Black-and-white development processing In this method, the photosensitive material is subjected to image exposure in the same pattern as the desired colored part pattern among the patterns of each colored part formed by the above-mentioned external color development method.
A black-and-white development process using a black-and-white developer is performed to form a reduced silver image on the light-sensitive material.

The black and white developer used is, for example, a developing agent [hereinafter referred to as developing agent (D). ], a developing aid, a preservative, a so-called developing antifoggant, an alkaline buffer, and, if necessary, a solvent for the developing agent (D) and the developing aid.

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

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

Preservatives include sulfites, ascorbic acid, and the like.

Examples of the development antifogging agent include bromide and benzotriazole.

Examples of alkaline buffers include carbonates, hydroxides, phosphates, borates, and metaborates.

Examples of the solvent for the developing agent (D) and the developing aid include ethylene glyfur, triethanol, and jetanol.

An example of the content of the various components in the black and white developer is 1 to 20 g, 1 of the developing agent (D).

Development aid 0.05-8 g/Q, preservative 1-120 g/
12. Developing anti-fogging agent 0.001-5 g/Q, alkaline buffer 0.1-50 g#, and when using a solvent for the developing agent and development aid, the solvent 1-20 m+12
/12.

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

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

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

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

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

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

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

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

Examples of dye bleach accelerating catalysts include pyrazine, naphthazine, quinoline, quinoxalines, phenazines, anthraquinones, naphthoquinones, indoorenazines, N
-Substituted isoalloxazines, floquinoxalines, chietukizalines, diphenyl derivatives, triphenylmethane derivatives, lumazines, alloxazines, cinnolines, orthophenylenediamine derivatives, etc. (U.S. Pat. No. 2,270,118, 2,410,02
No. 5, No. 2,541,884, No. 2,627,461
No. 2,669,517, British Patent No. 657.374
No. 711,247, Japanese Patent Publication No. 45-22195, etc.).

An example of the contents of the various components in the dye bleaching solution is: 1 to 20 g of bleach IQ, 0.1 to 20 g of a compound forming a silver salt or silver complex/(2, dye bleach accelerating catalyst o, ooi to It is lOg/12.

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 water washing treatment 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 an image that has been subjected to the above dye bleaching process! This process re-halogenates all the black silver remaining in the photosensitive material.

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 two processes, the photosensitive material is washed with water, followed by a fixing process to remove silver halide in the photosensitive material, further washed with water, and dried.

(Regarding Exposure/Treatment Process) Next, a preferred exposure/treatment process in the present invention will be described.

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

Each colored part shown in Figure 2 is a yellow dye (y r or Y2
), magenta dye (M, or M-li 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 SDR, which exhibits a silver dye bleaching effect.

For example, in the pixel forming pattern shown in Pattern Example 1 in Table A, first, the blue light transmitting pixels are pattern-exposed in the manner described above in the first exposure/processing process. Thereafter, development is performed using an external developer containing a magenta color-forming coupler. Next, after the green light transmitting pixels are pattern-exposed in a second exposure/processing process, a development process is performed using an external developer containing a yellow color-forming coupler and a cyan color-forming coupler. After the red light transmitting pixels are pattern-exposed in a third exposure/processing process, a development process is performed using an external developer containing a yellow color-forming coupler and a magenta color-forming coupler. 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 salt 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.

Furthermore, in the present invention, in order to alleviate or substantially eliminate the relief that occurs in each pixel, particularly in each color pixel, a substantially colorless compound is selectively added to each pixel by coupling reaction with an oxidized form of a developing agent. may be included in

〔Example〕

EXAMPLES Next, the present invention will be explained in more detail with reference to Examples. Note that % in the examples represents weight % unless otherwise specified.

Example 1 Preparation of silver halide photosensitive material Silver iodobromide containing 4 mol% silver iodide was prepared by simultaneously adding a silver nitrate aqueous solution and an aqueous solution containing potassium bromide and potassium iodide to a 10% aqueous solution of gelatin. An emulsion (average particle size: 0.05 μm, gelatin concentration: 9%) was prepared.

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

The obtained silver iodobromide emulsion was designated as Emulsion No. Em-1.

Emulsion Em-1 was subjected to chemical ripening as shown below.

(Emulsion No., Ell 2) To emulsion Em-1, 28.3 ag of sodium thiosulfate pentahydrate per mole of silver was added and chemically ripened at 59.5°C for 45 minutes.

(Emulsion No., Em 3) Emulsion Em-1 was brought to 55° C. without stirring, and sodium thiosulfate pentahydrate of 1 g of 43II per mole of silver was added. After another 5 minutes, 21.0% per mole of silver. An aqueous solution containing lag of chloroauric acid and 280 mg of ammonium thiocyanate was added, and stirring was continued for an additional 50 minutes at 55°C.

(Emulsion No., Em-4) Chemical procedures were carried out in the same manner as in Emulsion Em-3, except that 39 mg of allyl isoselenone anate was added per mole of silver in place of sodium thiosulfate, and the stirring temperature was changed to 61°C. Aged.

(Emulsion No., Em-5) Emulsion E+o-1 was brought to 53°C with stirring, an aqueous solution containing 200 mg of ammonium thiocyanate per mole of silver was added, and after 20 minutes, 45 μg of thiosulfate per mole of silver was added. Sodium pentahydrate was added, and after another 5 minutes, an aqueous solution containing 22.3 mg of chloroauric acid and 80 g of ammonium thiocyanate per mole of silver was added, and stirring was continued at 53° C. for another 35 minutes. .

(Emulsion N0-Ell-6) Emulsion Em-1 was heated to 50°C with stirring, and 45 mg of sodium thiosulfate pentahydrate per 1 mole of silver was added, and after 5 minutes, potassium hexachloroiridate (IV) was added to silver 1 A 25% by weight aqueous sodium chloride solution containing 24.8 g per mole was added and stirred for an additional 55 minutes at 50°C.

Then, immediately after chemical ripening, 1-phenyl-5-mercagutotetrazole and 1-carboxyethyl-3,4,5-hydroxybenzene were added to each of the above emulsions at a rate of 14l41-5ya 3-40g per mole of silver. At the same time, the following compound SC-1 was added at 15% per mole of silver.
．． Each emulsion coating solution was prepared by adding 9 g of each of the following compounds H-1 and H-2 as hardeners, each in an amount of 40 mg and 5 g per 1 g of gelatin.

C- H-1 [■-2 ((CH2=CIISO□CHz)xccHzso□C
HzCHz) zN(JlzCH2SOJ) Each of the obtained emulsion coating solutions was coated on a transparent borosilicate glass substrate (30ca+ x 30cm) with a thickness of 1.1 mm to a dry film thickness of 3 μm.
/% silver halide photosensitive materials having an emulsion layer were prepared by coating the materials in such a manner that the photosensitive materials Nos. 1 to 6 were used, respectively. Silver coating amount is 1.5g/m'', pigment coating amount is 0.24g/l11
It was 2.

All of these silver halide photosensitive materials have a backing layer on the surface of the borosilicate glass substrate opposite to the surface on which the emulsion layer is provided.

Formation of this backing layer will be explained next.

A dispersion of compound Y-1 below was added to an aqueous gelatin solution, and 40 mg 55 mg each of hardeners H-1 and H-2 were added.
B was added. Here, the amount of gelatin added to the gelatin aqueous solution was adjusted in advance to be 5%. Also, the amount of Y-1 added to 100 μQ of gelatin aqueous solution was 1.3
It was 5%.

Compound Y-1 Thereafter, this aqueous gelatin solution was applied to the borosilicate glass substrate and dried to form a backing layer. Y-
The amount applied of No. 1 was 10 mg/d2.

The above-mentioned dispersion was prepared by dissolving 1 g of Y-1 in 1 g of tricresyl phosphate, 4.29 μa of ethyl acetate, and then 0.83 g of gelatin, 11 g of gelatin, and 2.63 va of a 5% aqueous solution of sodium beta-naphthalene sulfonate.
Add and mix into an aqueous solution containing 8.4 mQ of water and 50 mQ of water.
After ultrasonic dispersion at °C, ethyl acetate was removed, and water was added to make the solution 17.6 m<1.

Preparation of color filters As shown in Figure 3, 3 (blue), G (green), and R (red) are prepared.
A method for producing a color filter having a color mosaic pattern and BM will be described below. The size of each pixel is 150 μm x 150 μm, and the line width of BM is 30 μm.
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 placed on top of the mask, and a first exposure was performed using a mercury lamp. Exposure was carried out at positions corresponding to 8 portions in FIG. Further, the exposure amount is changed depending on the type of photosensitive material.

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...0.26g6-
t-Butyl-7-chloro-3-(3-methylbutyl) I
H-pyrazolo[3,2-cL-1,2,4-triazole biscoupler 0.48g1
-(2,4,6-trichloro)phenyl-3-(4-methoxyph!nyl)-4-methylpyrazolone developing agent...
...... 2.0g 4-amino-3-methyl-N-ethyl-N-β-methanesulfonamide ethylaniline 11/2 sulfate l hydrate Sodium nitrilotrimethylenephosphonate (40% aqueous solution) )... 3-03-0O anhydrous sodium sulfate... 20.0g Sodium bromide... 160g sodium sulfite
・・・・IO,00g ethylene glycol・・
...10.0+n (2 polyethylene glycol・
・・・ ・ Add 2.0g water
Note that sodium hydroxide was added to the above magenta color developing solution to adjust the pH value at 25° C. to 12.0.

Next, a blue portion was formed on the substrate by washing with water for 4 minutes and drying (first treatment).

Next, another chromium 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. 3, and a second exposure was performed. The amount of exposure varies depending on the type of photosensitive material.

The photosensitive material that had been exposed for the second time was immersed in a yellow color developing solution having the following composition for 3 minutes at 23°C.
A green portion was formed on the substrate by washing with water for a minute (second treatment).

Yellow color developer composition Yellow coupler... 1.5ga-(
4-carboxyphenoquine)-αpivaloyl-24-dichloroacetanilide developing agent...
... 2.0g4-amino-3-methyl-N-ethyl-N~βmethanesulfonamidoethylaniline・11/
Disulfate l hydrate Sodium nitrilotrimethylenephosphonate (40% aqueous solution) 3. OOmQ anhydrous sodium sulfate... 20.0g sodium bromide... 3.0g sodium sulfite...
・・・ ・・ 10.00g ethylene glycol・・
... 10.0m12 polyethylene glycol ... Add 2.0g water
IO Note that by adding sodium hydroxide to the above yellow color developing solution, the pH value at 25°C is 12.
I adjusted it so that it was 0.

Next, another chrome mask for a color filter was placed on the photosensitive material after the above processing so that the exposed areas were the R area and the BM area in FIG. 3, and a third exposure was performed. The amount of exposure varies depending on the type of photosensitive material.

The photographic material subjected to the third exposure was immersed in a red color developing solution having the following composition at 23°C for 3 minutes, washed with water for 4 minutes, and immersed in a bleaching solution having the following composition for 6 minutes. After washing with water for a minute, it was dried to form a black part on the substrate (third
process).

Red color developer composition Magenta coupler 0.28g 6-t-butyl-7-chloro-3-(3-methylbutyl)-18-pyrazolo[3,2-C]-1,2,4-triazole biscoupler...・ ・ ・ ・ 0.
18g1-(2,4,6-trichloro)phenyl-3-
(4methoxyphenyl)-4-methylpyrazolone yellow coupler... ・ ・ 1.42gσ-(
4-carboxyphenoxy)-σ-pivaloyl 2,4
-Dichloroacetanilide developing agent...
・・2.0g4-amino-3-methyl-N-ethyl-N-β methanesulfonamidoethylaniline・11
/2ffl salt hydrate Sodium nitrilotrimethylenephosphonate (40% aqueous solution) 100+off anhydrous sodium sulfate 20.0g sodium bromide ... 3.0g sodium sulfite
・・・ ・・・ IO, 00g ethylene glycol・
・ ・ ・ 10.00+off polyethylene glycol ・ ・ ・ Add 2.0g water
IOIncidentally, sodium hydroxide was added to the above red color developing solution so that the pH value at 25°C was 12.
I adjusted it so that it was 0.

Silver source White liquor composition Ethylenediaminetetraacetic acid iron (1) ammonium salt...
...200.0 g ammonium bromide ... IO, 0 g glacial acetic acid ...... 10.0-g water was added to make IQ, and aqueous ammonia was used to make pI (- Adjust to 6.0.

Next, a chrome mask for a color filter was placed on the photosensitive material after the above processing so that the exposed area was the R area in FIG. 3, and a fourth exposure was performed. The amount of exposure varies depending on the type of photosensitive material.

The photosensitive material subjected to this fourth wc exposure was heated at 33°C.
By processing as follows to form a red part (fourth processing), a color filter having a mosaic pattern of three colors of B (blue), G (green), and R (red) and BM is created. G.

Black and white development 1 minute water wash 1 minute dye bleach 1 minute water wash 1 minute silver Bleach 6 minutes water
Wash for 1 minute
Arrival 1 minute water
Washing: Drying for 4 minutes The bath used for each treatment had the following composition.

Black and white developer composition Sothorium sulfite 10g Hydroquinone 10g Potassium hydroxide (4
8% aqueous solution) 5IIIQ diethylene glycol
20m12 Jimaison
0.7g Sodium carbonate 20g
Potassium bromide 2g Thiadiazole 0.05g Add water
1g Dye bleaching solution composition 96% sulfuric acid 40ml Potassium iodide 15g 2.3.6-1-
Limethylquinoxaline 2g Add water
1g silver silver white liquid pure water 800sff sodium ferricyanide 206g sodium bromide 15g borax
Add 1g water
1a (adjusted to pH = 8.0 using an aqueous potassium hydroxide solution) Fixer composition Ammonium thiosulfate 175.0g Sodium sulfite 8.5g Sodium metasulfite 2.3g Add water
la (adjusted to pH -6.0 using acetic acid) Also, after making the color filter, add 3% to the backing layer.
The backing layer was completely removed by impregnating it with an aqueous sodium hypochlorite solution and wiping it off with gauze.

The color filters obtained in this way were sample No.
1 to 6. The photosensitive materials used for samples No. 1 to 6 are photosensitive materials No. 1 to 6, respectively.

For each R (red), G (green), B (blue) pixel and BM (black matrix) of each sample obtained, each pixel and BM were measured at 30 locations per sample by Top Co., Ltd. When the spectral absorption density was measured using Kohn's SR-1, there was almost no variation in the spectral absorption density of each pixel and BM between samples, and the density distribution ((standard deviation)/(
The average concentration))X100(%) was all within 1 to 3%.

Further, the difference in average density of each pixel and BM between each sample was small, and the difference in density was within 2 to 4%. Here, when calculating the average density, 435ns of the measured spectral absorption density, 5
Concentration values at 45 nm and 610 ns are used, respectively.

Further, for each sample, the level difference between each pixel and 81 was determined using a Tally Step manufactured by Rank Taylor Hobson Co., Ltd. The results obtained are shown in Table 1.

Here, the difference in level between pixel 2 and 81 is omitted because there was almost no difference in each sample.

S...Sodium thiosulfate Au...Chlorauric acid Se...Allyl isoselenocyanate Ir...Potassium hexachloroiridate (IV) As is clear from the results in Table 1, the color filter based on the present invention The sample has a small surface level difference between each color pixel and 81, and has excellent surface smoothness.

[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. ]1... Light-transmitting substrate 12... Emulsion layer 13...
Silver halide photosensitive material 14...7 Otomask 15...opening 16...exposure scheduled area 21
．． 31... Light transmitting substrate 22. 32... Colored portion 43... Color filters 46a, 46b... Polarizing plate 47... Liquid crystal 48a,
48b--electrode

Claims (1)

[Claims] After exposing a light-sensitive material having a silver halide emulsion layer on a light-transmitting substrate in a pattern, a step of forming a dye image corresponding to the pattern using a developer containing a coupler and a color developing agent is performed at least two times. In the method for manufacturing a color filter, the silver halide emulsion is a silver halide emulsion sensitized with a noble metal, and after the final stage of color development in the development process, silver bleaching is performed. Characteristic color filter manufacturing method.