JPH03252605A - Production of color filter - Google Patents

Abstract

PURPOSE:To obtain the color filter having good spectral characteristics by executing at least one time of color developments in the presence of a specific yellow coupler. CONSTITUTION:The color filter is produced by executing at least one time of the color developments in the presence of the yellow coupler expressed by formula I. In the formula, R1 denotes 3 to 6C branched alkyl group; R2 denotes <=12C alkane amide group or alkane sulfone amide group; X denotes a halogen atom or 1 to 4C alkoxy group; M denotes a hydrogen atom or the cation inert to photographic processing. The color filter having the good spectral characteristics and excellent color reproducibility is stably obtd. in this way.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for manufacturing a color filter, and particularly to a method for manufacturing a color filter suitable for use in color displays and image pickup tubes.

[Background of the invention]

Conventionally known color filters include those described in Japanese Patent Publication No. 53-248, in which polymeric materials are dyed with dyes, but the manufacturing process for these color filters requires seven steps for each color. There are complicated manufacturing steps such as coating of photoresist, image exposure, development, coloring, and removal of resist, and the resulting color filter is extremely expensive.

In order to overcome these drawbacks, a method for producing color filters using a color silver salt photographic material using an external development method was investigated. For example, Japanese Patent Application Laid-open No. 55-6342 describes a method for producing color filters by external development.

In the production of color filters by such an external color development method, several basic characteristics are required, and it is necessary to use couplers that meet these purposes.

For example, firstly, the resulting image has excellent spectral characteristics, and secondly, color filters are manufactured through a complex process that repeats exposure, development, bleaching, and fixing steps.
It has high color development and little fog in unexposed areas, and thirdly, it has excellent stability with little variation in properties after preparing the external developer, and furthermore, the resulting image has sufficient thermal stability. Characteristics such as reaching a certain level are important.

From this point of view, for yellow color developing solutions for color filters, for example, JP-A-58-129430
Useful are external color developer compositions of the type described in Japanese Patent Publication No. 55-9697.

However, the color developer compositions still have insufficient properties in several respects, and further improvements are desired. For example, these color developer compositions tend to cause fogging, which is particularly noticeable when yellow development is carried out after the preceding color development of another color, and color filter production by external color development method. This is a big problem in law.

Furthermore, when the color developing composition is used for development, there is a problem in that the coloring dye is deposited on the surface of the color filter.

[Purpose of the invention]

The present invention has been made in view of the above circumstances, and a first object of the present invention is to provide a color filter with good spectral characteristics using external color development in photographic technology. A second object of the present invention is to provide a color filter with excellent color reproducibility and stable quality.

[Structure of the invention]

The above object of the present invention is to provide at least one
After the emulsion layer of the light-sensitive material provided with the silver halide emulsion layer of the layer is pattern-exposed, a dye image corresponding to the pattern is formed by color development, and at least two colors are formed at once or by repeating the same process. In a method for producing a color filter obtained by forming a pattern and performing a desilvering treatment after final color development, at least one of the color development steps is performed.
This was achieved by a method for manufacturing a color filter, which is characterized in that the color filter is produced in the presence of a yellow coupler represented by the following general formula (1).

In the formula, R1 represents a branched alkyl group having 3 to 6 carbon atoms, and R
2 represents an alkanamide group or an alkanesulfonamide group having 12 or less carbon atoms. X represents a norogen atom or an alkoxy group having 1 to 4 carbon atoms, and M represents a hydrogen atom or a cation inert to photographic processing.

The substituents of the compound represented by general formula [I] will be explained in more detail.

The branched alkyl group represented by R□ is 1-propyl, 5e
Examples include e-butyl, [-butyl, neo-pentyl, etc., and t-butyl is preferable.

Preferred halogen atoms represented by Of these, methoxy group is particularly preferred.

The alkanamide group or alkanesulfonamide group having 12 or less carbon atoms represented by R2 may be linear or branched, and is preferably acetamide, propionamide, 2-methylbutanamide, 2,2-dimethylpropionamide, or octaneamide. , 2-ethylhexanamide, decaneamide, methanesulfonamide, butanesulfonamide, and the like.

Although the position of -C00M is not particularly limited, the m + p position is preferred, and the p position is particularly preferred.

Examples of cations inert to photographic processing represented by M include ions such as sodium, potassium, and ammonium.

Typical specific examples of the yellow coupler represented by the general formula [I] (referred to as the yellow coupler of the present invention) are shown below, but the invention is not limited thereto.

8 yellow of the invention The coupler is can be synthesized by

Synthesis Example (Synthesis of Compound 4) α-pivaloyl-α-chloro-2-chloro-5-(3-
Methylbutane)amide acetanilide 42-5g5p-
28.6 g of carboxyphenol and 17.4 g of triethylamine were mixed with 300 mQ of acetonitrile.
Boil for an hour.

After distilling off acetonitrile under reduced pressure, the residue was dissolved in ethyl acetate and thoroughly washed with water. The ethyl acetate layer was dehydrated with anhydrous magnesium sulfate, concentrated, and crystallized with acetonitrile to obtain crude crystals.

It was used as it was in the next reaction.

Yield 32.1g0 Synthesis of crude α-pivaloyl-α-p-ethoxycarbonyl90 phenoxy-2-chloro-5-(3-methylbutane)amide acetanilide in 22.5g sodium hydroxide, 300m alcohol (1, 100mQ water) The mixture was mixed with 50°C and reacted for 20 minutes at 50°C.The reaction was stopped when a pale yellow transparent solution was obtained, and the temperature was lowered.The mixture was then poured into ice water containing 60mC of glacial acetic acid to obtain a crude target coupler.

Since it solidified, it was filtered, thoroughly washed with water, dried, and recrystallized from methanol. Yield: 18.5g.

Melting point 218-221°CO It was confirmed by NMR that it was the desired product.

When the coupler of the present invention is used by being added to an external developer, the amount to be added will be clarified in the description of the external developer below. Further, yellow couplers other than those of the present invention may be used in combination without impairing the effects of the present invention.

Furthermore, examples of the magenta coupler used in the present invention include active methylene compounds (for example, 1-(2,4,6-trichlorophenyl)-3-(4-nitroanilino)-5-hyrazolone, acylacetonitrile). ,
Furthermore, West German Patent Publication (0LS) No. 2,016,587, U.S. Patent No. 3,152.896, U.S. Patent No. 3,615,50
2, Japanese Patent Publication No. 44-133111, etc. can be used.

Furthermore, cyan couplers used in the present invention include phenols (for example, 2-acylaminophenol, 2.5-
dianruaminophenol) and hinaphthols (e.g. 2-alkylcarbamoyl-naph-1-hel), as well as U.S. Pat.
, 474, 293, etc. can be used.

Typical examples of magenta couplers, dian couplers, and yellow couplers other than the present invention that can be used in the present invention are shown below, but the invention is not limited thereto.

(Magenta coupler) 1 2 (Cyan coupler) 3 4 In the present invention, a silver halide photosensitive material is used, which has a photosensitive layer (referred to as an emulsion layer) formed by coating a silver halide emulsion on a light-transmitting substrate. do.

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

Examples of materials that make up such a light-transmissive substrate include:
Polymer compounds such as polyethylene terephthalate-1, polybutylene terephthalate, polystyrene, polycarbonate-1, polyether sulfone, polyvinyl alcohol and cellulose acetate, glasses such as sorter glass and borosilicate glass, inorganic substances such as quartz and zaphire, etc. can be mentioned.

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 the light-transmitting substrate for a liquid crystal color display, the thickness is preferably within the range of 3 to 2 mm.

In addition, there are no particular restrictions on the surface of the light-transmitting substrate that forms the emulsion layer, as long as it has the same level of surface precision as the light-transmitting substrate conventionally used for color filters, or even higher surface precision. 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 that a backing layer for antihalation is provided on the surface of the light-transmitting substrate opposite to the surface on which the emulsion layer is formed. In this case, it is preferable that the dye or pigment contained in the backing layer is a non-diffusible dye or pigment. Specifically, a carbon black dispersion can be suitably used. The carbon black dispersion may be produced by either a furnace method or a channel method, and for example, Diablack J (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 characteristics of the dye or pigment used vary depending on the spectral absorption characteristics 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 can be combined with known high-resolution point organic solvents such as methyl acetate, ethyl acetate, propyl acetate, butyl acetate, cyclohexane, and tetrahydro-7.
After dissolving in a low-boiling point organic solvent such as oran, carbon tetrachloride, chloroform, etc., it is mixed with an aqueous gelatin solution containing a surfactant, and then a stirrer and a homogenizer are used.
After emulsifying and dispersing it using a dispersing means such as a colloid mill, a flow jet mixer, or an ultrasonic dispersion device, it is used by adding it to a hydrophilic colloid backing footwear coating composition.

The amount of non-diffusible dye or pigment used is preferably 0.1 mg or more, particularly preferably 1 mg or more per 100 cm 2 of the light-transmitting substrate.

The emulsion layer can be directly coated on the surface of the light-transmitting substrate, or a subbing layer can 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, polyhynylidene chloride copolymer, and polyvinylidene chloride copolymer. Mention may be made of acrylamide.

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 μnl.

The silver halide emulsion layer used contains at least silver halide and a water-soluble binder, but may further contain a dye having a silver dye bleaching action.

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

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

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

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

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

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

9 0 I( Q 02NH2 02CH3 2 5-NO□ 3 C83 0CI(3 CH3 0CH.

0CH2CH20H CH3 0CH.

4 CH3 0CH.

CH3 0CH.

1 CH3 o2 COCH.

0 C02 CH It is preferable that the weight ratio of dye to silver halide is 1/10 to 50, and the weight ratio of dye to water-soluble binder is 1/100 to 2.

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

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

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

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 employed, it is preferable to carry out processing using the silver dye bleaching method after all processing steps using the external color development method are completed.

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

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

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

Exposure Processing Exposure methods that can be employed in the present invention include, for example, methods used in normal pattern exposure such as contact exposure, proximity exposure, and step exposure.

In pattern exposure, for example, as shown in FIG. 1, a photomask 14 is placed on a silver halide photosensitive material 13 having an emulsion layer 12 containing the dye exhibiting a silver dye bleaching action and laminated on a light-transmissive substrate 11. This is done by applying light 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 opening 15 is narrower than the wavelength of the light source used for exposure, effective exposure cannot be performed, so the width of the opening 15 is made wider than the wavelength. Since silver halide has effective photosensitivity to light in the range of 340 to 420 nm, the width of the opening 15 is usually 340 nm or more, and further considering its use as a color filter, The thickness is preferably 1 μm or more. In addition, in the case of a color filter for liquid crystal spray, in order to effectively reproduce colors by additively mixing red, blue, and green colored parts, the width of the opening 15 should be 1000 μm or less.
Particularly preferably, it is set to 500 μo1 or less.

Other conditions such as exposure time and light source can follow normal conditions.

The non-processing color development method is a method in which a dye is dyed or precipitated into an emulsion layer by performing development using a developer containing one or more color couplers.

The developer used contains at least a color forming coupler and a developing agent.

As developing agents, C.E.K. Mees, T.H. James (C, E, Ni, Mees and
T.

The Theory of the Photographic Process, 3rd Edition, by James H.
of the Photographic Process
ss 3rd, Edition) J, pages 293 to 298, and specific examples include: (1) 4-amino-3-methyl-N-(2-hydroxyethyl)aniline sulfate Salt (2) N-ethyl-N-methoxyethyl-3-medyl p-phenylenediamine p-toluenesulfonate (3) 4-amino-3-methyl-N-ethyl-N-(2
-methylsulfonamidoethyl) aniline sulfate hydrate (4) N,N-diethyl-p-7 22-diamine sulfate (5) N,N-diethyl-3-methyl-p-ph22 Examples include diamine hydrochloride.

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

The developing agent in the developer is usually used so that it is contained in the developer 5 6 IQ in a content within the range of 0.1-log. If the content of the developing agent is less than 0.1 g, effective development may not be possible, and even if more than log is used, there is no significant improvement in developability. , it 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 I
(within a range of 0 minutes), resulting in very good workability. Furthermore, by keeping it within this range, the coloring property becomes particularly good.

The color-forming coupler is different from the internal coupler (ballast type coupler) used in ordinary color photography, and is used in a state where it is added to the developer and at least partially dissolved in the developer. It is an external coupler, and any known external coupler can be used.

In the developer, the total content of color forming couplers in the developer 112 is preferably set within a 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 couplers in the developer IQ within the range of 0.2 to 10 g, a color filter with less color fading 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. When a cyan coupler and a yellow coupler are combined, the weight ratio of the two is usually 1:9 to 7:3, preferably 1:9 to 4:6.

Furthermore, when combining a magenta coloring coupler and a yellow coloring coupler, the weight ratio of both is usually 9:
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.

Furthermore, the developer may contain preservatives (e.g., 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, citradinic acid) , color toning agents such as imidazole derivatives), etc., which are included in ordinary external developers, may also be included.

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

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

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

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

After performing the first pattern exposure, a first development of the exposed area is performed using a developer containing the color forming coupler. For example, by performing 0-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 into green color. 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 /un 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.

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, the unexposed area adjacent to the first exposed area is pattern-exposed using a photo mask in the same manner as the first exposure, and then a developer other than that used in the first step is used. Develop using one of the following.

Further, if desired, a second colored portion can be formed by performing steps such as immersion in a bleach solution or a black and white developer, washing with water, and drying.

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

2 In one example of a preferred embodiment of the present invention, after forming the first to third colored portions 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, each image formed by the above-mentioned external color development method is subjected to image exposure in the same pattern as the desired colored part pattern among the colored part patterns.
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, developing agent E, 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 ethylene glycol, triethanol, and jetanol.

3 4 An example of the content of the various components in the black and white developer is 1 to 20 g/+2. Development aid 0.05-8 g/L Preservative 1-120 g/(2, Development antifoggant 0.001-5 g/L Alkaline buffer 0.
The amount is 1 to 50 g/Q, and when a solvent for a developing agent and a developing aid is used, the amount is 1 to 20 mff/ff.

Black and white development processing is usually done at 20-60°C and 10-200°C.
This is carried out by immersing the image-exposed photosensitive material in a black and white developer for a second.

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

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

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

That is, this dye bleaching process is a process in which a positive image 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, and thiosemicarbazide.

Examples of dye bleaching accelerating catalysts include pyrazine, naphthazine, quinoline, quinoxalines, phenazines, anthraquinones, naphthoquinones, indophenazines, N
Examples include -substituted isoalloxazines, floquinogyzalines, chietukizalines, diphenyl derivatives, triphenylmethane derivatives, lumazines, alloxazines, cinnolines, or]-phenylenediamine derivatives (U.S. Pat. No. 2,270,118) , 2,410,0
No. 25, No. 2,541゜884, No. 2,627,46
No. 1, British Patent No. 2,669,517, British Patent No. 56, British Patent No. 657,374, British Patent No. 711,247, British Pat.
See No.-22195, etc. ).

Examples of the contents of the various components in the dye bleaching solution include: 1 to 20 g IQ of bleach, 1.0 to 20 g IQ of compound forming a silver salt or silver complex, and 0 dye bleach accelerating catalyst.
．． 001 to IOg, l.

The dye bleaching process is usually 20-60'O, 10-2
This is done by immersion in a dye bleaching solution for 00 seconds.

By this dye bleaching process, the silver-rich portions of the image-exposed photosensitive material are bleached to produce a positive dye image. The black silver that has not been used to bleach the dye may remain as it is. After the dye bleaching process, the silver bleaching process described below can be carried out after washing with water.

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

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

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

Silver bleaching is usually carried out at 18-60°C for 5-500 seconds.

After performing the above processing, washing with water, fixing processing to remove silver halide in the photosensitive material, and further washing with water.
dry.

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

For example, Table A shows the pattern of the exposure 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. show.

7 8 Table A Each colored part shown in Figure 2 is a yellow dye (y r or Y2
), magenta dye (M or M2) and cyan dye (C
Contains two different color pigments of I or C2).

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, SD
A silver dye bleaching method is used to remove the color of the dye in areas other than the area indicated by B, which exhibits a silver dye bleaching effect.

For example, in the image forming pattern shown in Pattern Example 1 in Table A, the blue light transmitting pixels are first exposed in the first exposure/processing process in the manner described above. after that,
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.

Finally, after the green light transmitting pixels and the red light transmitting pixels are exposed in a pattern, the silver dye bleaching treatment is performed. here,
Regarding the order 90 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 developer treatments are completed, There are no particular restrictions.

Further, the arrangement of the blue light transmitting pixels, the green light transmitting pixels, and the red light transmitting pixels is not defined as shown in FIG. 2. (Others) In the method of the present invention, for example, a light-transmitting substrate 31 as shown in FIG. After forming the colored portions 32 with gaps between them, pattern exposure is applied to the gaps, and then development is performed using a developer containing a cyan coloring coupler, a magenta coloring coupler, and a yellow coloring coupler. The red part (R) of the colored part 32,
A light-impermeable section (black stripe) 33 can also be formed in the gap between the blue part (B) and the green part (G). Also in this case, it is preferable that the silver dye bleaching process is carried out after all the external development processes are completed.

Further, in the method of the present invention, it is also possible to perform etching treatment 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 148b are sandwiched by the polarizing plate 46a1461.
If placed, it can be used as a filter for LCD color display.

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.

1 2 Example 1 Preparation of SC silver halide photosensitive material By simultaneously adding a silver nitrate aqueous solution and an aqueous solution containing potassium bromide and potassium iodide to a 10% aqueous gelatin solution, an iodine containing 4 mol% silver iodide was prepared. A silver bromide emulsion (average particle size: 0.05 μm, gelatin concentration: 9%) was prepared.

Addition conditions were regulated to obtain a Lippmann emulsion having an average grain size of 0.05+zm.

The resulting silver iodobromide emulsion contained 28.3 mg per mole of silver.
of sodium thiosulfate pentahydrate was added thereto and chemically aged at 59.5°C for 45 minutes.

Next, 1-phenyl-5-mercaptotetrazole and 1-carboxyethyl-3,4,5-hydroxybenzene were added to the above emulsion at 141.5% per mole of silver, respectively.
mg, 3.40g, and the following compound SC1
An emulsion coating solution was prepared by adding 15.9 g of the following compounds per mole of silver, and further adding 40 mg and 5 mg of the following compounds H-1 and -2 per 1 g of gelatin as hardeners.

H-2 ((CH2=CH5OzCHz)3ccH□5o2CH
The emulsion coating solution obtained in 2CH2) 2NCH2CH2SO, was applied to a transparent borosilicate glass substrate with a thickness of 1.1 mm (30
A silver halogenide photosensitive material having an emulsion layer was prepared by coating the film on a 30 cm x 30 cm film to a dry film thickness of 3 μm. Silver coating amount is 1.5g/m2, pigment coating amount is 0.2
4 g/m''.

A photosensitive material was thus produced.

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

Formation of this backing layer will be explained next.

4:3 4 Add the following dispersion of compound Y-1 to an aqueous gelatin solution, and add 40 mg each of hardeners H-1 and H-2.
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 Yl added to the gelatin aqueous solution Loomil was 1.35%.

-1 Thereafter, this aqueous gelatin solution was applied to the borosilicate glass substrate and dried to form a 7(.7 king layer).

The amount of Y-1 applied was 10 mg/dm2.

The above-mentioned dispersion was prepared by dissolving 11 g of Y-1 into 1 g of tricresyl phosphate, 4.29 m+2 of ethyl acetate, and then 0.83 g of gelatin and 0.83 g of triisopropyl-β.
- 5% aqueous solution of sodium naphthalene sulfonate 2.6
The mixture was added and mixed into an aqueous solution containing 3 m12 and water 8.4 m12, subjected to ultrasonic dispersion at 50°C, ethyl acetate was removed, and water was added to make a total volume of 17.6 mQ.

Preparation of color filters As shown in Figure 2, three colors (blue), G (green), and R (red) are prepared.
A method for manufacturing a color filter having a color mosaic pattern will be described below. Furthermore, the size of each pixel is 15
It is 0 μm x 150 μm.

On each of the above silver halide photosensitive materials, one side or 150+
A chromium mask for a color filter having a Zm square opening was placed on top of the mask, and a first exposure was performed using a tungsten lamp. Exposure was carried out at a position corresponding to part B in FIG.

2. Add the exposed photosensitive material to the magenta color developing solution shown below.
Soaked at 3°C for 3 minutes.

Magenta color developer composition Magenta coupler 0.26g5-
t-Butyl-7-chloro-3-(3-methylbutyl)-
IH-pyrazolo[3,2,-all, 2.4 triazole WE-10,6g 46 Developing agent 2.0g4-amino-3-methyl-N-ethyl-N-βmethanesulfonamide ethylaniline 11/2 sulfuric acid Salt monohydrate Sodium nitrilotrimethylenephosphonate (40% aqueous solution) 3.09 m4 Anhydrous sodium sulfate 20.0 g Thorium bromide 1.0 g Thorium sulfite Io, 00 g Ethylene glycol IO, 0 m12 Polyethylene glycol 2.0 g Add water hand
1° In addition, sodium hydroxide was added to the above magenta color developer to adjust the pH value at 25° C. to 12.0.

E-1 Next, after washing with water for 1 minute, bleaching was performed by immersing it in a silver source white liquor of the following composition for 3 minutes, washing with water for 4 minutes, and then drying to form a blue part on the substrate ( 1st process)
.

Silver source White liquor composition Ethylenediaminetetraacetic acid iron (Itl) Ammonium salt 200.0g Ammonium bromide lo, 0g Glacial acetic acid 10.0mρ Add water to make IQ, and adjust to pH = 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 that had been exposed for the second time was immersed in a yellow color developing solution having the following composition for 3 minutes at 23°C.
The substrate was washed with water for a minute, then bleached, washed with water, and dried in the same manner as the first time to form a green portion on the substrate (second treatment).

7 8- Yellow color developer composition Yellow coupler (Comparison-A) 1.5g
α-(4-carboxyphenoxy)-α-piparoyl-
2,4-dichloroacetanilide developing agent
2.0g4-aminol3-methyl-
N-ethyl-N-β methanesulfonamide ethylaniline 1172 sulfate monohydrate Sodium nitrilotrimethylenephosphonate (40% aqueous solution) 3.0 m12 Anhydrous sodium sulfate 20.0 g Thorium bromide 3.0 g Sodium sulfite lo, 0 g ethylene glycol
10. Add O+n12 polyethylene glycol 2.0g water
ItlNote that by adding sodium hydroxide to the above yellow color developer, the pI at 25°C (
The value is 12. It was adjusted to be O.

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

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

Red color developer composition Magenta coupler 0.28g6
-t-butyl-7-chloro-3-(3-methylbutyl)
-1H-pyrazolo[3,2-c]-1,2,4-1-lyazole W E -10,32g Yellow coupler (comparison-A) 1.42
gα-(4-carboxyphenoxy)-α-pivaloyl-2,4-dichloroacetanilide developing agent
2.0g 4-Amino-3-methyl-N-ethyl-N-β-methanesulfonamide ethylaniline Q11/2 sulfate monohydrate Sodium nitrilotrimethylenephosphonate 9 (40% aqueous solution) ' 3.0
mQ anhydrous sodium sulfate 20.0g
Sodium bromide 3.0g Sodium sulfite lo, 0g ethylene glycol lo, 0mff Polyethylene glycol 2.0g Add water
IL1 Note that sodium hydroxide was added to the above red color developing solution to adjust the pH value at 25°C to 12.0.Next, the exposed area was A chrome mask for a color filter was placed so as to correspond to the R section in FIG. 2, and a fourth exposure was performed.

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

Black and white development 1 minute water wash 1 minute dye bleach 1 minute water wash 1 minute silver bleach 6 minutes water wash 1 minute hole
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 Sothorium sulfite 10g Hydroquinone 10g Potassium hydroxide (48% aqueous solution) 5m4 Diethylene glycol 20mQ Dimaison
0.7g sodium carbonate
20g potassium bromide
2g Thiadiazole
Add 0.05g water
1a1-52 Dye bleaching solution composition 96% sulfuric acid 40mQ Potassium iodide 15g2.3.
6- Trimethylquinoxaline Add 2g water and make IQ silver silver white liquor composition water 800m (t
Sodium ferricyanide 206g Thorium bromide 15g Borax
Add 1g water
IQ (Adjust the pH to 8.0 using an aqueous potassium hydroxide solution.) Fixer composition Ammonium thiosulfate 175.0 g Sodium sulfite 8.5 g Sodium metasulfite 2.3 g Add water and adjust the pH to 1 (1 (pH using acetic acid) = 6.0.) Also, after creating a color filter,
The backing layer was completely removed by impregnating the backing layer with a 3% sulfur-IJium hypochlorite aqueous solution and wiping it with gauze.

The color filters obtained in this way were sample No.
Let it be l.

Further, samples No. 2.3° and 4.5 were prepared in exactly the same manner except that the yellow couplers used in the yellow color developing solution and the red developing solution were changed as shown in Table 1.

Regarding the obtained color filter samples N011-5,
Using blue light to measure the density of the B pixel with an aperture scanning area of 250 μm
It was determined by scanning with a microdensitometer.

The results are shown in Table 1.

3 4 Comparative coupler table 2 The comparative coupler has large fog, so sample No. 1 B
It can be seen that although the B density in the pixels is quite high, it is considerably improved in Samples Nos. 2 to 5 using the yellow coupler of the present invention.

Example 2 The photosensitive material prepared in Example 1 was exposed solidly, and similarly developed with the yellow color developing solution used in Example 1. Then,
Samples from which the 71-inking layer was removed in the same manner after being treated with silver source white liquor and fixer were designated as Nos. 1 and 2, respectively.

6.7.8.9 and 10. The surface of each sample was visually observed.

As shown in Table 2, in the samples developed using the comparative coupler, it was observed that the coloring dye adhered to the surface of the photosensitive material like a powder, but in the sample developed using the coupler of the present invention, this was observed. The degree of powder adhesion was low.

It is presumed that this phenomenon occurs probably because the coloring dye moves from the inside of the gelatin matrix to the surface.

〔Effect of the invention〕

The present invention makes it possible to stably provide color filters with good spectral characteristics and excellent color reproducibility.

5 6 Note that by performing color development at least once in the presence of the yellow coupler according to the present invention, the B density in the B pixels of the filter could be suppressed considerably and the filter characteristics could be greatly improved.

Furthermore, no precipitation of coloring dyes is observed, and the filter 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. 11...Light-transmitting substrate 12...Emulsion layer 13...Silver halide photosensitive material 14...Photomask 15...Opening 16...Exposed portion 21.31...Light transmission Colored substrate 22.32 Colored portion 33 Black stripe 43 Color filters 46a, 46b Polarizing plate 47 Liquid crystal 48a, 48b Electrode

Claims (1)

[Scope of Claims] After exposing the emulsion layer of a light-sensitive material in which at least one silver halide emulsion layer is provided on a light-transmitting support in a pattern, a dye image corresponding to the pattern is formed by color development. at least two times at once or by repeating the same process.
In a method for producing a color filter obtained by forming a color pattern and performing desilvering treatment after final color development,
At least once of the above color development is performed using the following general formula [I
] A method for producing a color filter, characterized in that it is carried out in the presence of a yellow coupler represented by: General formula [I] ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ [In the formula, R_1 represents a branched alkyl group with 3 to 6 carbon atoms, and R_2 represents an alkanamide group or alkanesulfonamide group with 12 or less carbon atoms. . X represents a halogen atom or an alkoxy group having 1 to 4 carbon atoms, and M represents a hydrogen atom or a cation inert to photographic processing. ]