JPH0239002A - Production of color filter - Google Patents

Abstract

PURPOSE:To facilitate control of developing reaction and setting of reaction conditions and to prepare a color filter stably by performing a silver dye bleach process after completing whole developing stages for forming at least two color parts by an external developing process. CONSTITUTION:A photomask 14 is disposed on a silver halide photosensitive material 13 having a photosensitive material layer 12 contg. a silver dye bleach effect laminated on a light transmittive substrate 11, and the photosensitive material layer 12 is exposed to light irradiating from above the photomask 14. By this operation, the silver halide photosensitive material is exposed selectively at a predetermined part 16 for exposure of the photosensitive material layer corresponding to an opening part 15 provided to the photomask 14, and the exposed silver halide photosensitive material is treated by an external color developing process and a silver dye bleach process successively in the described order. Thus, reduction of developed color density from a coupler is prevented, and a color filter permitting easy control of the reaction and setting of reaction conditions having also superior color reproducibility is obtd.

Description

[Detailed Description of the Invention] [Fields of Application of If and Hi] This invention relates to a method for producing a color filter, and more specifically, to a method for manufacturing a color filter, which has excellent color reproducibility based on good spectral characteristics, and is particularly suitable for color filters. The present invention relates to a method for manufacturing a color filter that can easily and stably manufacture a color filter that can be suitably used for sprays, color image pickup tubes, and the like.

[Prior Art and Problems to be Solved by the Invention] As a method for manufacturing color filters, there is a method using a color silver salt photographic material and an external color development method.

In a method for producing a polychromatic optical filter using an external development method, for example, as described in JP-A-55-6342, a photographic material in which a photosensitive silver halide emulsion layer is provided on a support is used. The emulsion layer is subjected to pattern exposure of the first color 11, and then external color development is carried out to form a pattern consisting of the dye of the first color [I] and silver. A pattern of the second color is exposed, and a pattern consisting of the second color dye and silver is formed by external color development.
By repeating the same step 1 to form a pattern consisting of a dye and silver, a pattern of at least two colors is formed, and a desilvering process is performed after the final color development process.

By performing silver salt dye bleaching treatment in the out-of-plane color development method, tM1'! ! We are proposing a method for producing a color filter by combining a color JG's own color and a coloring dye from a coupler. L is completely different, so if a production method is adopted in which an external development process is performed after a silver salt dye bleaching process, the dye density based on the external development process will be 1! There was a problem that I couldn't read it.

This invention was made based on the above-mentioned situation No. 111.

An object of the present invention is to easily and stably manufacture a color filter that has excellent color reproducibility based on good spectral characteristics and can be used particularly in TLF and NF for color displays, color image pickup tubes, etc. It is an object of the present invention to provide a method for producing a color filter that is easy to control the reaction, set reaction conditions, etc., and has excellent production efficiency.

[Means for Solving the Problems] In order to solve the problems described in No. 1'67, the present inventor has made extensive studies and has developed a method for forming a color filter layer on a transparent IJ+ substrate using external color development method and silver salt. When formed by performing the dye bleaching method in a specific order, good spectral characteristics are obtained.
(4Z has excellent color reproducibility and is particularly suitable for use in color display displays and color image pickup tubes. This invention was achieved by discovering that the reaction conditions can be easily set and the production efficiency is excellent.

The structure of the present invention includes a step of pattern-exposing a photosensitive agent layer provided on L of a light-transmitting substrate and containing a dye having a silver salt dye bleaching action, and then developing the pattern-exposed portion by an external development method. This method of producing a color filter is characterized in that a silver salt dye bleaching treatment is carried out after the completion of the entire development stage in which colored parts of at least two or more colors are repeatedly formed.

One of the important points in the method of this invention is that a silver halide photosensitive material formed by coating a photosensitive agent on a light-transmitting substrate is processed by an external color development method and a silver salt color J bleaching method. The purpose is to perform the processing in this order.

Regarding Halon In the method of the present invention, a silver halide photosensitive material having a photosensitive agent layer formed by coating a photosensitive agent on a light-transmitting substrate is used.

The light transmitting substrate to be 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:
Shokai I compounds such as polyethylene terephthalate, polyphthylene terephthalate, polystyrene, polycarbonate, polyether sulfone, polyvinyl alcohol and cellulose acetate, glasses such as soda glass and borosilicate glass, non-metallic substances such as quartz and sapphire, etc. can.

ItI-written light-transmissive substrate Using the above-mentioned material, plate-shaped,
It can be used in the form of a sheet or film.

The length of the light-transmissive substrate can be set appropriately depending on the application and material, but it is usually 0.57L.
It is within the range of m to lom m. In particular, when glass is used as a light-transmissive substrate for a liquid crystal color display device, the thickness is preferably within the range of 0.3 to 2 mm.

Further, the surface of the light-transmitting substrate forming the photosensitive agent layer is
There may be no particular restriction as long as the surface precision is the same as that of the light-transmitting substrates conventionally used for color filters.In order to achieve even higher image quality, it may be necessary to It is preferable that the surface accuracy is ±0.1 lumen.In addition, in the present invention, a light-transmitting layer for antihalation is provided on the surface of the light-transmitting substrate opposite to the surface on which the photosensitive agent layer is formed. Preferably, a backing layer is provided.

In this case, it is preferable that the dye or pigment contained in the hasokink layer is a non-diffusible dye or pigment. Specifically, a carbon black dispersion can be suitably used.

The carbon black dispersion liquid may be produced by either the furnace method or the channel method; for example, r
"Dia Black" (trade name: manufactured by Mitsubishi Kasei ■) etc. can be suitably used.

The above-mentioned non-diffusible dye or pigment must be contained in the backing layer in a state dispersed in a wood-philic colloid, or must not be eluted into each processing solution even after development. It won't happen.

Also, do the light absorption properties of the above-mentioned non-diffusible dyes or pigments differ depending on the spectral absorption properties of the silver halide emulsion used in this IJI method? When a silver halide emulsion is used, it is preferable that it absorbs light of 50 (I n1 or less).

Furthermore, the para-kink layer may contain an ultraviolet absorber, such as 'IJVIII
LILMS-411) (product name; manufactured by BASF),
'TINUVINPJ (product name: Chiha Geigy M) is one example.

The non-diffusible dye or pigment and the ultraviolet absorber described in tWj can be combined with known high-boiling point organic solvents such as methyl acetate, ethyl acetate, propyl acetate, propyl acetate, butyl acetate,
After dissolving in a low boiling point organic solvent such as cyclohexane, tetrahydrofuran, carbon tetrachloride, chloroform, etc., it is mixed with an aqueous gelatin solution containing a surfactant, and then processed using a Wl stirrer, homogenizer, colloid mill flowchette. After emulsifying and dispersing it using a dispersing means such as a mixer or an ultrasonic dispersion device, it is added to a coating material for the wood-philic colloid harakink layer and used.

In addition, the above-mentioned non-diffusible dye 4 or pigment is used for pickling.
The amount is preferably 1.1 mg or more, particularly preferably lsg or more per 100 cm 2 of the light-transmitting substrate.

A photosensitive agent layer may be directly coated on the surface of the light-transmitting substrate (iii), or a subbing layer may be provided between the photosensitive agent layer and the light-transmitting substrate. The undercoat layer strengthens the adhesion between the photosensitive material layer and the light-transmitting substrate, and if the surface of the light-transmitting substrate is rough, the rough surface is f'? t'
tjl'j.

Materials forming this F'EI layer include, for example, gelatin, altumin, casein, cellulose, conductor,
Starch derivative, sodium alginate.

Mention may be made of bosohinyl alcohol, bobbinylpyrrolitone polyacrylic acid copolymer, polyvinylidene chloride copolymer and polyacrylamide.

Considering the spectral characteristics of the color filter layer, the thickness of the undercoat layer is preferably 1 μm or less, and preferably within the range of 0.05 to 0.5 pm.

The photosensitizer according to l) u to be used contains at least silver tetrahalide, a water-soluble binder, and a dye having a dye exhibiting silver salt dye bleaching action.

Examples of the silver halide include silver chloride, silver iodide,
Examples include 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 the silver halide having a small average grain size, and it is particularly preferable to use a so-called Lippmann emulsion having a average grain size of 0.1 μmm.

If the average particle diameter of the silver halide described in Iij is large, the image quality, mainly the graininess, of the resulting color filter may be reduced.

Examples of water-soluble binders include gelatin, albumin, casein, and cellulose conductors.

Examples include starch derivatives, sodium alginate, polyvinyl alcohol, polyvinylpyrrolidone, polyacrylic acid 71 combination, and polyacrylamide. These may be used alone or in combination of two or more types. Among these, gelatin is preferred.

The important point in this invention is that the dye has a silver halide color,
The purpose is to contain a dye that exhibits KH self-activity.

For example, phthalocyanine dyes, azo dyes, etc. can be suitably used as the dye. Among the azo dyes,
Particularly preferred are bisazo dyes.

Physically, for example, compounds represented by the following formula [I] in combination with any one of 0 to 2 can be exemplified.

(0, In the above formula [11], R' or -(ll is '1. R2 is water, k[7-te is present, D(, in the above formula [1], R1 or -CQ, and R2 is wood , NU child is R2 and D is a tree J atom, and in the above formula [1], -N02 (0, in the above formula [I], R' is -502NH, and R2 and D are water) a certain compound.

(2) In the above formula [], R' and R2 are <d), in the above formula [T], R' is -So, CH, and R2 is a water atom (r), and the above formula [I] Ft' or -No2 in R2 and D are water J atoms <h
, +if7 In the formula [I], R' or -COCH,
and R2 is a hydrogen atom, and the photosensitizer is composed of IrI silver halide, a water-soluble binder, and dye 4 in a ratio of (silver halide) = (water-soluble binder): 1; 4 or 1. =6\8 l
, 171O compared to J +1 of the dye to silver halide.
It is desirable that the ratio of dye 1 to the water-soluble binder is 1/100 to 2.

The photosensitive agent layer r'67 can be formed using a conventionally known "11tJ)jυ method, such as a spinner coating method or a soubreike cloth method."
The photosensitive material may be formed by applying the photosensitive agent onto the light-transmitting substrate using the following method.

The thickness of the photosensitive agent layer formed in this way is usually within the range of 0.3 to 10 lm in terms of dry thickness. If the thickness of the photosensitive agent layer is less than 0.3 m, sufficient color development may not be achieved. On the other hand, if it exceeds 10 μm, the light transmittance may decrease and the IJI degree of the color filter may become insufficient. In particular, in the present invention, the spectral characteristics of the resulting color filter tend to improve by controlling the I depth of the photosensitive agent layer within the range of 0.5 to 3 gm.

In the method of the present invention, a silver halide photosensitive material having a photosensitive layer as detailed above is used, and after [7] of all processing steps by external color development method, processing by AK11 color JQ white method is carried out. Let's do it.

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

(Processing step using external color development method) One of the important points in the method of the present invention is that all the colored parts formed on the light-transmitting substrate by external color development method are
#i It is necessary to form the salt dye in advance before applying the bleaching treatment.

Specifically, the halogenated S 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.

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

The pattern exposure is performed, for example, on the light-transmitting substrate 11 as shown in the first [ ]! A halogenated 1M photosensitive material 13 having a photosensitive layer 12 containing the dye described above and exhibiting a silver salt dye bleaching action. ．． A photomask 14 is placed on the surface of the photomask 14, and light is applied from the L side of the photomask 14. Through this operation, the exposed portions 16 of the photosensitive layer corresponding to the openings 15 provided in the photomask 14 are exposed. Can be selectively exposed. The size of the constant exposure 7 portion 16, 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 this wavelength. Silver halide is 3
Since the width of the open Ij portion 15 is normally 340 nm, the width of the open Ij portion 15 is determined by the 4I effective photosensitivity to light within the range of 40 to 420 nm.
n- or higher, and considering its use as a color filter, it is preferable to set it to lpm or higher, and
In the case of a color filter for a liquid crystal display, the width of the aperture 15 should be set to 100 mm in order to effectively reproduce colors by additively mixing red, blue, and green colored parts.
It is desirable to set the height to 0 m or less (particularly preferably 500 pm or less).

Other conditions such as exposure time and light source may follow conventional conditions.

The external color development method is a method in which a dye is dyed or precipitated into the photosensitive agent layer by performing development using a developer containing one or more color couplers. be.

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

The Theory
ofI'hoLographic Process
3rd EdiLaion, C, E, Meesan
Examples include (1) 4-amino-3-methyl-N-(2-hydroxyethyl). Aniline 11! Acid acid salt (2) N-ethyl-N-methoxyethyl-3-methyl-
p-phenylenecyamine/P-toluenesulfonate (3) 4-amifoucaultmethyl-N-ethyl-N-(2
(methylsulfonamidoethyl) aniline sulfate hydrate (4) N,N-diethyl-p-phenylenecyamine sulfate, and (5) H,N-diethyl-cortacyl-p-phenylenecyamine hydrochloride I can list the following.

In the developer, it is preferable to select and use one type of developing agent from among the developing agents mentioned above.The selection of the developing agent is usually based on the type and combination of color forming couplers. etc. shall be taken into consideration.

The developing agent in the developer is usually used so that the content rl is within the range of 0.1 to 10g per developer. If the content of the developing agent is less than 0.1 g, effective development may not be possible, and IOg
Even if a larger amount is used, not only no significant improvement in developability is observed, but also the developing agent may not be sufficiently dissolved depending on the type of developing agent.

Especially developer i! In the range of 0.5 to 7 g per l
It is preferable to use a 1'F agent, and it is particularly preferable to use a developing agent within 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 temperature is within an appropriate range (e.g. 1 to 1
(within the range of 0 minutes), resulting in very good workability. Furthermore, by keeping it within this range, there is a tendency for particularly good coloring properties.

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 is at least partially dissolved in the developer. This is a foreign coupler, and any known external coupler can be used.

Examples of yellow coloring couplers include ring-opened ketomethylene compound C, 2-(
p=carboxyphenoxy)-2-piguaroyl-2'
, 4°-dichloroacetanilide, etc.], and furthermore, in this invention, U.S. Pat. No. 3,510,306;
No. 189, Special Publication No. 4G-33775 and No. 44-3
Those described in various publications such as 664 Gin can be used.

Examples of magenta color-forming couplers include hydrazones such as active methylene compounds [e.g., I-(2,4,6-)-lichlorophenyl)-3-Cp-nitroanilino)-2-pyrazolino-5-one, Furthermore, in this Part II, German Patent Publication (01,S) No. 2,016゜5
No. 87, U.S. Patent No. 3,152,896, i.
615.50215 and 0 public II? (It is also possible to use the numbers listed in each publication, such as No. 44-133 No. I.

Furthermore, examples of cyan color-forming couplers include phenolic compounds (e.g., 2-acetamido-4,6-dichloro-5
-methyl-phenol) or naphthol compounds [e.g., tho(0-acetamidophenoethyl)-2-hydroxy-2-naphthamide]. '16, Co., No. 542,552 and British Patent No. 1,062
, No. 190, etc. can be used.

In addition to the above-mentioned color couplers that can be used in this external color development method, r Th
e Theory of Photographic
Process3rd HidiLaion, Capt.
er 17 C, E, ni, Mees and
J.T.

James 3) pages 82 to 95 can also be used.

In the developer, it is preferable that the total content of color-forming couplers in one developer is set within the range of 0.5 to 20 g.If it is less than 0.sg, the color may not develop sufficiently; On the other hand, if more than 520 g is used, so-called fog may occur. Particularly in this special external development method, a color filter layer with less color turbidity and good spectral characteristics can be obtained by controlling the total amount of color forming couplers in the developer to be within the range of 1 to 10 g. I can do it.

The blending ratio of color-forming couplers exhibiting different color development in this developer can be appropriately set in consideration of the color-forming properties of the color-forming couplers used. For example, when combining a cyan coloring coupler and a magenta coloring coupler, the Tohani ratio of both is usually 1:9 to 73.
Preferably it is within the range of 1:9 to 4:6. In addition, when combining a cyan coloring coupler and a yellow coloring coupler, the weight ratio of both is usually 1:9 to 7:3.
Preferably l: is within the range of 9 to 446. Furthermore, when combining a magenta color-forming coupler and a yellow color-forming coupler, the ratio of both is 1:1, usually 9:1.
~2:8. llT or preferably within the range of 8:2 to 6:4. When combining the kings of color-forming couplers, magenta color-forming couplers, and yellow color-forming couplers, it is preferable to mix approximately the same amount of Tamana.

Further, the blending weight ratio of the total amount of the color forming coupler and the developing agent in the developing solution that can be suitably used in the external color developing method in the method of this invention is as follows: The amount of the color-forming coupler and the developing agent can be set appropriately considering the type and content of the color forming coupler and the developing agent. .

Furthermore, the developer solution includes a preservative (e.g., sodium sulfite, diethylhydroxylamine), an accelerator (e.g., an alkaline agent such as sodium hydroxide), a control agent (e.g., potassium bromide, potassium iodide), and an auxiliary agent. (For example, a water quality conditioner such as polyethylene glycol, a color such as citrazic acid or an imitazole derivative, and an il agent) may also contain additives included in ordinary external developers.

The developer solution can be prepared by dissolving the components described above in wood.

In addition, the developer solution has a temperature of 1 normal usage temperature (for example, 10 to
Adjust the pH using sodium hydroxide etc. so that the pH value at 40°C is within the range of 9.0113.0.
It is used after adjusting I.

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

First, the photosensitive agent layer is pattern-exposed by a conventional method (first exposure).

Perform the first development of the exposed area using a developer that carries out the first pattern exposure. By performing development using a solution (blue developer solution), the exposed areas are developed in 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.

In general, by using a developer (red developer) containing a magenta color-forming coupler and a yellow color-forming coupler, the exposed areas are developed into red.

Also, a developer containing a cyan coloring coupler (cyan developer), a developer containing a magenta coloring coupler? By using i-liquid (magenta developer) and a developer containing a yellow color coupler (yellow developer), the exposed areas are developed into 11 cyan colors, magenta colors, and yellow colors.

The first exposed area is filled with cyan developer depending on the purpose.

Develop using any one of a magenta developer, a yellow developer, a blue developer, a green developer, and a red developer.

After the first exposed area is developed in this way, the photosensitive layer is usually immersed in a stop solution containing an acid such as acetic acid to stop the reaction accompanying the development, and then the photosensitive layer is washed with water. After that, the silver halide photosensitive material is usually immersed in a bleaching solution or a black-and-white developer to prevent color turbidity in the first development area during the subsequent development processing, and then washed with water and then dried. As a result, a first colored portion having pixels of any one of red, eight colors, green, cyan developer, magenta developer, and yellow developer is formed.

Next, using a photomask, the unexposed area adjacent to the first exposed area is exposed in a pattern similar to 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 portions adjacent to the second 41 color portions are pattern exposed, and then developed using a developer other than that used in the first and second L portions. Furthermore, if desired, it may be subjected to steps such as immersion in a bleaching solution or a black and white developer, washing with water, and drying.

It is possible to form a second colored part.

In the method of this invention, after forming the first to third colored parts as described above, the silver salt dye bleaching treatment described in detail is first performed.

(Processing step using lJi salt dye bleaching method) The important point in the method of this invention is that after forming all the colored parts by the Jij outside color development method, tMIi! Color Ad
The object of the present invention is to carry out self-processing to erase the coloring matter that exhibits the silver salt color Jii bleaching action contained in the halogenated tM light-sensitive material.

The processing steps according to the silver salt color spot bleaching method include at least black and white development, dye bleaching, and S bleaching in this order.

Next, the processing steps according to the 1R salt color JH white method will be divided into black and white development processing, dye bleaching processing, and tM bleaching processing, and will be explained in this order.

11 In the method of the present invention, the silver halide photosensitive material is image-exposed in the same pattern as a desired colored part pattern among the patterns of each colored part formed by the external color development method. Next, a black-and-white development process is performed using a black-and-white developer to form a reduced silver image on the silver halide photosensitive material.

The black and white developer to be used may contain, for example, a developing agent [
Hereinafter, developing agent (D), development aid, preservative,
It contains a so-called development antifoggant, an alkaline buffer, and, if necessary, a solvent for the developing agent (D) and development aid.

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

Examples of the development auxiliary agent a) include pyrazone, pyrazone regulator, metol, and the like.

Examples of the preservative include sulfites, ascorbic acid, and the like.

The antifogging agent for development and development includes, for example, bromides,
Examples include benzotriazole.

Examples of the alkaline buffer 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.

III. Content of the various components in the black and white developer jj
An example is ftj developing agent) 1-2f1g
/l of the above-mentioned development aid 0.05~8g/l, above-mentioned preservative 1~
120 g/view, the above-mentioned development fog inhibitor 0.001-5
The amount of the alkaline buffer is 0.1 to 50 g/kg, and when a solvent for the developing agent and the development aid is used, the amount of the solvent is 1 to 201 g/kg.

Black and white development processing is usually carried out at a temperature of 20 to 60°C.
This is carried out by immersing the image-exposed photosensitive agent layer in a developing bath containing the black and white developer for 10 to 200 seconds.

This black-and-white development process produces a reduced copper image (silver negative image) in the image-exposed photosensitive agent layer (A).

In this invention, after the black and white development process, a water washing process is usually performed, and then a dye bleaching process, which will be described in detail below, is performed.

Moxibustion Company Ruioka 11 In the dye bleaching process: l? The dye contained in the dye book 1 contained in the halogenated 1M light-sensitive material is bleached using a dye bleaching solution.

That is, this dye bleaching process removes the dyes contained in the image-exposed silver halide light-sensitive material.
This is a process of bleaching the dye in areas with a large amount of silver in the image to form a positive image of the dye.

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-promoting catalyst.

Examples of the bleaching agent include mineral acids such as hydrochloric acid, sulfuric acid, and VI acid, and organic acids such as sulfamic acid, succinic acid, and acetic acid IV.

Examples of the acid salt or the compound forming the fM complex include potassium bromide, potassium iodide, urea, thiourea, semicarbazide, and thiosemicarbazide.

Examples of the dye bleaching accelerating catalyst include pyrazine, naphthazine, quinoline, and quinoxaline.

Phenazines, anthraquinones, naphthoquinones, indophenazines, N2ff-substituted isoalloxazines, floquinoxalines, chietukizalines, diphenyl derivatives, triphenylmethane derivatives, lumazines, alloxazines, cinnolines, orthophenylenediamine visiting conductors etc. are listed as 6rels (X-Country 4.7 permission 17S2,2
No. 70.118 IJJ [IJt, IRIm2.41
0.025 Specification, 2.51.884 Ginmeijinsu, 2,627,461 Specification Old, 2. [i6
9,517 Specification, 1:, British [I4 Patent No. 657,37
4 Specification, No. 711,247 No. 11 Part 1), Japanese Patent Publication No. 45-22195, etc.).

Examples of the contents of the various components in the dye bleaching solution include 1 to 20 g of the bleaching agent, 0.1 to 20 g of the silver salt or silver complex-forming compound, and 0 of the dye bleaching accelerating catalyst. .001~10g/love.

In this invention, the dye bleaching treatment is usually carried out at a temperature of 20°C.
This is carried out by immersion in a dye bleaching solution for 10 to 200 seconds under condition F at ~60°C.

By this dye bleaching treatment, the image-rich portions of the image-exposed silver halide photosensitive material I'f1 are erased to form a positive image of the dye. Black steel that has not been used to bleach the dye may remain as it is.

In this invention, 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.

The bleaching process is a process of re-halogenating all the black silver remaining in the image-exposed silver halide photosensitive material that has been subjected to the dye bleaching process.

A 1M bleaching solution is used for this silver bleaching process.

1jjl +i! ! The silver bleaching solution may be one conventionally known, such as ethylenediaminetetraacetate secondary bleaching solution.
Bleaching solutions containing iron chelates can be suitably used.

In this invention, the silver bleaching treatment is usually carried out at a temperature of 18 to
It is carried out for 5 to 500 seconds at 60°C.

After performing the above processing, the film is washed with water, followed by a fixing process to remove silver halide in the photosensitive agent layer, further washed with water, and dried.

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

For example, the second (B shown in 4)
G (pixel for transmitting green light) and R (pixel J for transmitting red light)
Table i1 shows the pattern of the exposure/processing process when forming a color filter having the following properties.

Each colored part shown in Table 2 contains two different pigments: yellow pigment (l!11 or M2), magenta color J (Y, or Y2), and cyan color (c+ or C2). do.

Table 1 shows the method for forming each of these dyes.

That is, in the method of this invention, GA is applied to the first cover.
After forming a dye image in the areas indicated by the external color development method, a silver salt dye bleaching method was used to remove the dye in areas other than the areas indicated by SDR to create a dye that exhibits silver salt dye bleaching action. Perform erasing.

For example, in the pixel formation pattern shown in Pattern Example 1 in Table 1, first, the n-color light transmitting pixel is formed by the first exposure/processing process. +Expose the pattern as described above. After that, a development process is performed using an external developer containing a magenta color coupler.Next, the green light transmitting pixels are pattern-exposed in a second exposure/processing process, and then a yellow color coupler and a cyan color coupler are applied. Development processing is performed using an external developer containing a yellow coloring coupler and a magenta coloring coupler. A development process is performed using a developer.Finally, the green light transmitting pixels and the red light transmitting pixels are exposed in a pattern, and then the silver salt dye bleaching process is performed.

Here, regarding the order of exposure and processing of the blue light transmitting pixel, the green light transmitting image J, and the red light transmitting pixel, the silver salt dye bleaching treatment is performed after all external color development treatments are completed. For example, there is no particular restriction, and the arrangement of the Ilt color light transmitting pixels, the green light transmitting pixels, and the red light transmitting pixels is not defined as shown in FIG.

(Others) In the method of this invention II, for example, a red part (R), an iν color part (B
) and a green part (G) are formed with a gap of J9 between them, pattern exposure is applied to this gap, and then a cyan coloring coupler, a magenta coloring coupler and a yellow coloring coupler are applied. By performing a development process using a solution containing a developer, the red part (R) of the colored part 32, the /7 color part (B) and the II part of the green part (G)
It is also possible to form a light-transmitting section (black stripe) 33 in the JI gap. Also in this case, the fII salt dye bleaching process is carried out after all external development processes are completed.

Furthermore, in this IJ method, it is also possible to perform an etching process on the color filter layer to remove defective portions of the color filter layer, depending on the use of the color filter.

Further, the four pixels may be formed in either a mosaic pattern or a stripe pattern.

The color filter obtained in this way is, for example, a liquid crystal color display ff+ as shown in B4UA.
It can be suitably used as a filter. That is, as shown in FIG. 4, six polarizing plates 45a and 45b
Accordingly, the color filter 43 and the electrodes 48a, 4
If the color filter 43 is arranged so as to sandwich the liquid crystal 47 controlled by the filter 8b, it can be used as a filter for a liquid crystal color display.

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

[Example] Next, an example of the present invention will be shown and the present invention will be explained in more detail.

(Example 1) Adding a silver nitrate aqueous solution to a 1OiFIit% aqueous solution of halogen gelatin,
By simultaneously adding an aqueous solution containing potassium bromide and potassium iodide, a silver iodobromide emulsion containing 4 mol% of iodized steel (f average grain size 0.05 m, gelatin C degree 9 hair volume %)
) was prepared. The addition conditions were regulated so as to obtain a Lippmann emulsion with a mean grain size of 0.05 μm.

To the obtained silver iodobromide emulsion, t! 28.3m per 41mol
Add 5 g of sodium thiosulfate wood salt and bring to a temperature of 59.5
Chemical ripening was carried out at 1"l for 145 minutes at .degree.

Next, 1. In the emulsion, l-phenyl-5-mercapto-tetrazole and l-carboxyethyl: l, 4
．． S-hydroxy-benzene was added in an amount of 6 x 10-' mol per 1 mol% silver, 3 AOg, and 1411 mol 5 x 15.9 g of the compound 5C-1 was added, and the following compound H was added as a hardening agent. An emulsion coating solution was prepared by adding 40 mg and 5 ml of H-1 and H-2, respectively, per 1 g of gelatin.

Compound SC-1 Compound %1H-1 Clla -Cl1CllzO (CIlz).

The addition rate of the compound described above as Si(OClli)i Compound H-2 was 135%.

The obtained emulsion coating solution was coated to a thickness of 1. Imm Toru [gI
A halogenated M photosensitive material having a photosensitive agent layer was prepared by coating the dried film on a borosilicate glass substrate (30 cm x 30 cm) to a thickness of 34 m. Gintsuki Hani is 1.5 g/
The wood edge of Go5 dye was 0.24 g/cut.

This silver halide photosensitive material has a backing layer on the surface of the borosilicate glass substrate opposite to the surface on which the photosensitive agent layer is provided.

The formation of this huffing layer will be explained below.

A dispersion of the following compound Y-1 was added to an aqueous gelatin solution, and 40 mL of each of the compounds H-1 and H-2 was added.
g, 5 mg was added. Here, the gelatin weight f% of these gelatin aqueous solutions was adjusted in advance so that the gelatin weight f% was 5 tonne weight%. Further, after adding it to 100 cc of gelatin aqueous solution, this gelatin aqueous solution was applied to the borosilicate glass substrate and dried to form a backing layer. The weight of Compound Y-1 of Irj was 101 g 7 d2.

In addition, the above-mentioned dispersion liquid has a tri-percentage per gram of compound Y-1.
Talesyl phosphate 1g, ethyl acid resistant 4.29c
After dissolving gelatin in C, add 0.83 g of gelatin to a 5% aqueous solution of sodium triisopropyl β-naphthalene sulfonate.
．． 63cc and 8.4cc of wood were added and mixed into a wood e liquid containing 8.4cc of wood, ultrasonically dispersed at a temperature of 50°C, ethyl acetate was removed, and water was further added to make 17.5cc of wood.
I used the one that I made.

As shown in Figure 2 of Color (/l), G (green), R
A method for manufacturing a color filter that forms a mosaic pattern of three colors (red) will be described below. The size of each pixel is 150 x 15 (1).

A first exposure was carried out using a tungsten lamp using a chromium mask for color filters having a square opening of +50 p, * on one side for −L of the photographic material. The W light was applied to a position corresponding to 8 portions in FIG.

Place the exposed photographic material in the following magenta color developer at 25°C.
It was immersed for 1111 minutes for 3 minutes.

Magenta ＾ ゛Magenta coupler −・・・・・・・・・Axis・・・・・・
・・Old-2,0g1-(2,4,6-1-lichlorophenyl)3(p-nitroanilino)-pyrazolin 5-one developer 1 drug ・・・・・・・・・・・・・
・・Old・・ 1.86g4-amino-3-methyl-N-
Ethyl~t(2hydroxyethyl)aniline [I'l
Nitrotrimethylene sulfonic acid salt...1001
Bunsenki & lts sodium ・・・・・・・・・・・・−・
・・・・・・6.66 ------0
,86g6-nitropenzimidazole・・・0
．． 02g side sulfur sulfate resistant lium...
・・・・・・・・・・・・20.00g Hexylene glycol・・・・・・・・・・・・・・・・・・S, OOI
Text polyethylene glycol・・・・・・・・・・・・・・・
・・0.60ml diethylhydroxylamine・・・・
... o, 271 sentences Hydroquinone monosulfonic acid ... 0.1 (1) H tertiary-butylaminoborane ... 0.07 g Sodium thiocyanate ...
・・・・・・Old-1,00g anhydrous sodium carbonate・・
・・・・・・・・・・・・・・・・・・16.67g
Woodless sodium bicarbonate・・・・・・・・・・・・・・・
・4.0111H In addition, by adding water oxidation sodium to the magenta color developer described in L, the pH value at 27°C is 1.
Adjusted to 2.0.

Next, immerse in Stop F solution (triple acetic acid aqueous solution) for 1 minute, wash with water, immerse in silver source white liquor with the following composition for 1 minute to perform bleaching, wash with water for 1 minute, and then dry. By doing so, a blue portion was formed on the substrate (first treatment).

Guanko U [Hongyu ethylenecyaminetetraacetic acid iron ammonium salt...
・・・・・・・・・・・・・・・200.0g Ammonium bromide・・・・・・・・・・・・・・・・・・・
・・・・・・lo, 0g glacial acetic acid ・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・
...Add lO and raw wood to make 11L, and adjust the pH to 5.0 using ammonia wood.

Next, another chrome mask for a color filter was placed on the photographic material after the processing described in L so that the exposed area corresponded to the area G in FIG.

Below are the photographic materials that were used for this second exposure! l′
After immersing it in a yellow color developing solution of II& for 3 minutes at 25°C, it was soaked in a writing stop solution F for 1 minute, and then washed with water.
The substrate was bleached once, washed with water, and dried in the same manner as in step 1 to form a green area on the substrate (second treatment).

Yellow hl l Yellow coupler・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・1.5g2-[P-carboxyphenoxy)-2-pyraaroyl-2”,4'-dichloroacetanilide developer ・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・1.85g 4-Amino-3-methyltoethyl-N-(2-hydroxyethyl)aniline sulfate Nitrotrimethylenesulfonic acid・・・3.00 yen Anhydrous sulfur-ugly sodium ・・・・・・・・・・・・・・・
...6.66go, H potassium iodide aqueous solution...
・・・・・・・・・I 1. oOm Sodium bromide...................................................................IJ,
85g6-nitropenzimidazole...a
, OZ g Sodium sulfite・・・・・・・・・・・・
・・・・・−・−・・・・−20,00g Hexylene glycol・・・・・・・・・・・・・・・・5.0
0sJlj polyethylene glycol・・・・・・・・・
......0.60sjL diethylhydroxylamine......L], 27si hydroquinone monosulfonic acid...-0,10g tert-butylaminoborane...0.07g thiocyanine Sodium acid・・・・・・・・・・・・・・・ 1. Old 1g anhydrous sodium carbonate・・・・・・・・・・・・・・・・・・・・・
...16.67g anhydrous sodium bicarbonate...
・－・・・・・・・・・4. OOg Note that sodium hydroxide was added to the above yellow color developer to adjust the pH (f) to 12.0 at 27°C.

First, another chrome mask for a color filter was placed on the photographic material E 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 the third exposure was immersed for 3 minutes at 25° C. in a red color developing solution of M1 composition, followed by stop I: water washing, original white, and water washing in the same manner as the second exposure.

After drying, a black part was formed on the substrate (: fS Sansho FP)
.

(h 63”-1・Magenta coupler ・・・・・・・・・・・・・・・・・・
...old-3,00g+-(2,4,6-dolichlorophenyl)3-(p-nitroanisono)-pyranrin-5
-On yellow coupler ・・・・・・・・・・・・・・・・・・
・・・・・・・・・1.00g 2-(P-carboxyphenoxy)-2 bivaloyl-2=,4'-dichloroacetanilide developing agent E ・・・・・・・・・・・・・・・・・・・・・−・
・・・・・・・・・・・・・・・＋, 85g 4-amino-3-methyl-N-ethyl-! 1-(2-hydroxyethyl)aniline sulfate nitrotrimethylene sulfonic acid 3. Old 1m
JL Jiao Shui! Sodium acid ・・・・・・・・・・・・・・・
...6.66go, 1z potassium iodide aqueous solution・
························································································L+
86g6-nidropenzimitazole・・・0.
02g Sodium sulfite・・・・・・・・・・・・・・・
・・・・・・－・・・20.100g Hexylene glycol・・・・・・・・・・・・・・・5.00m
1 Polyethylene glycol・・・・・・・・・・・・
...0.60 days diethylhydroxylamine...
...0.27su Hydroquinone monosulfonic acid ... -0.10g Tertiary-butylaminoborane ...0.07g Sodium thiocyanate ...
・・・・・・・・・・1. OOg anhydrous sodium carbonate-・
・・・・・・・・・・・・・・・・・・・16.67g
Anhydrous sodium bicarbonate・・・・・・・・・・・・・・・
・4.00g In addition, sodium hydroxide was added to the above red color developing solution to adjust the pH at 27°C to 1 (from 1 to 12.
I adjusted it so that it was 0.

Next, a chromium mask for a color filter was placed on the photosensitive material after the process described above so that the exposed area corresponded to Ri in FIG. 2, and the fourth exposure [1] was performed.

This photographic material, which has been exposed to 4 times 11 times of tS, is heated to 1
C Under the condition of 33°C, by processing as follows to form a red part (fourth processing), B (t'?),
One set of color filters that create a mosaic pattern of three colors: G (M) and R (red).

Black and white color R Stop for 1 minute Wash with water for 1 minute Color patch bleach for 1 minute Wash with water for 1 minute 1 molecule 1111M standard
1 minute II (1 water wash, 4 minutes drying) Here, the bath used for each treatment had the following composition.

<Black and white developer composition> Sodium bisulfate 10 g Hydroquinone 10 g Potassium hydroxide (48% aqueous solution) 5 cc Diethylene glycol 20 cc
Dimedone 0.7g Sodium carbonate 20g Potassium bromide
2g Thiadiazole O, OS
g Add wood I see color bleaching solution composition > 96% potassium iodide sulfate 0 cc 5 g 2,co,6-drimethylquinoxaline 2 g Add wood: After the 4th treatment, the composition shown below at a solution temperature of 25°C 1 in fixer
It was immersed for 4 minutes, washed with water for 4 minutes, and then dried.

<8 Bleach solution composition> The silver source white liquor composition and rotation described above were used.

<Fixer composition> ammonium thiosulfate anhydrous d/p, sodium sulfate sodium metasulfite add water (Adjust the pH to -5.0 using acetic acid.

175.0g 8.5g 2.3g 1 sentence Regarding the color filter obtained in this way,
i' was determined by scanning with a microdensitometer (aperture scanning area: 250 p-m'') using color light, green light, and red light, respectively, and the C degree of each color pixel portion.

Regarding the measurement C degree of each color drawing area 1. Table 2 shows the measurement results when 'I' color light was used as the measurement light, and Table 3 shows the measurement results when green light was used as the measurement light.

(Comparative Example 1) In the above Example 1, the order of exposure processing was as follows: 1st=processing using magenta external color developer after light (first process)→2nd*yt, post-yellow external color development rIl Processing using a liquid (second processing) → Processing using a red external color developer after the third exposure (third processing) - After the fourth exposure, silver halide color J bleaching process Jly
(4th process) to 7 zenta after il exposure Processing using external color developer (1st process FP) → Processing using yellow external color developer (1st process) → After 4th exposure silver salt dye Bleaching treatment (fourth treatment) = ? S3S3 Color filters were produced in the same manner as in the example work described above, except that the treatment using an external light color developer after exposure (third treatment) was performed. was measured.

The results are shown in Tables 2 and 3.

(Comparative Example 2) In the above-mentioned Example g41, the order of the 'A light treatment was changed to JII! using a magenta external color developer after the first exposure. (First treatment) → After the second exposure, use a yellow external color developer (Second treatment) → After the third exposure, use a red external color developer
treatment (third treatment) → 4th A light silver salt dye bleaching treatment (4th treatment) to 1st exposure magenta treatment using external color developer (first treatment) →: JS 45A light?& Silver salt dye bleaching treatment (fourth treatment) → treatment using a yellow external color developer after the second exposure (second treatment) → treatment using a red external color developer after the third exposure (third treatment) A color filter was produced in the same manner as in Example 1, except that the color filter was changed to , and the C degree of each color image JM was measured for the obtained color filter.

The results are shown in Tables 2 and 3.

(Comparison M3) In Example 1 of Erj, the order of exposure treatment was changed to treatment using a magenta external color developer after the first exposure (first treatment P).
P) → 2'A Treatment using a yellow external color developer after exposure (second treatment) - 4- Treatment using a red external color developer after third exposure (third treatment) → Third Post-exposure red salt dye bleaching place J9! (4th processing) to fk4 dye bleaching after 4th exposure (4th processing) → Processing using magenta external color developer after 1st exposure (first processing) → 2'A yellow external method after exposure Processing using a color developing solution (first processing) → 3'I! A color filter was produced in the same manner as in Example 1, except that the treatment using an external red color developing solution after a light (third treatment) was changed.

The C degree of each color pixel portion of the polished color filter was measured.

The results are shown in Tables 2 and 3.

(Margin below) Table 3 (Jf value) As is clear from Tables 2 and 3, Example 1 and 1
1) It was confirmed that the obtained color filters were more e-colored than the color filters obtained in Comparative Examples 1 to 3.

〔Effect of the invention〕

According to this FFI III method, (1) Since the silver salt dye bleaching treatment is performed after the entire process of external coupler development treatment, it is possible to prevent the low degree of color development from the coupler, and (2) It is easy to control the reaction and set reaction conditions, resulting in excellent production efficiency, and (3) excellent color + LF based on good spectral characteristics.
A method for producing an industrially useful color filter, which has the advantages of being able to obtain a color filter that has a developing property of 41 and can be particularly used suitably for color display and color image pickup tubes. can be provided.

4. Brief Description of the Drawings Figure 1 is a cross-sectional view showing an example of pattern exposure in the manufacturing method of the present invention, and Figure 2A is a cross-sectional view showing an example of a color filter obtained by the manufacturing method of this invention III. Yes, Figure 53 is a cross-sectional view showing another example, and No. 41'4 is this 3? FIG. 2 is an explanatory cross-sectional view showing an example of a liquid crystal color display using a color filter obtained by the manufacturing method of S-ming.

11... Light-transmissive substrate, 12... Photosensitive agent layer 3...
Silver halide photosensitive material l, 14...) Odo7sk, 15
...opening, 16...exposed r-leg part, 21, :ll...light transmittance) & plate, 22.32...
- Colored portion 43...color filter, 46a, 46b...biased plate.

7N ・・Liquid crystal, 48a, 48b ···electrode.

, hehe stomach.

Go to funeral map 43 Figure 2 Figure 3 Happy 4N Display of procedural amendments 11 yen 1988 Patent application No. 188632 Name of the invention Process for manufacturing color filters Relationship with the 19 cases Patent applicant address 1-26-2 Nishi-Shinjuku, Shinjuku-ku, Tokyo Name (127) Konica Co., Ltd. Representative Benko
Keio

Claims (1)

[Claims] (1) After pattern-exposing a photosensitive agent layer provided on a light-transmitting substrate and containing a dye having a silver salt dye bleaching action, the process of developing this pattern-exposed portion by an external development method is repeated to at least A method for producing a color filter, which comprises performing a silver salt dye bleaching treatment after completing all development steps to form colored parts of two or more colors.