JPS6250828A - Method for replenishing processing liquid - Google Patents

Abstract

PURPOSE:To simplify liquid replenishment and to obtain a good image by making the replenishers to respective development processing tanks for an internal latent image type silver halide photographic sensitive material and surface latent image type silver halide photographic sensitive material common and setting the Br' concn. in the former processing tank at a specific value. CONSTITUTION:The replenishers to the respective development processing tanks for processing lines for the internal latent image type AgX photographic sensitive material having >=1 layers of emulsion layers incorporated therein with internal latent image type silver halide (AgX) particles having preliminarily unfogged particle surfaces and the surface latent image type AgX photographic sensitive material having >=1 layers of the emulsion layers incorporated therein with the surface latent image type AgX particles are made common in the stage of replenishing the replenishers to the processing tanks for both materials in order to process the development of said materials in the respectively separate processing lines. The amt. of the replenisher is so set that the Br' concn. in the development processing tank for the internal latent image type AgX photographic sensitive material is maintained at 5.0X10<-3>-2.0X10<-2>g ion/l. The space for installing the replenisher tank is thereby lessened and the administration thereof is made easy. The good positive image is stably obtd. at high sensitivity with both photographic sensitive materials.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for replenishing a processing solution, and more particularly to a method for replenishing a processing solution when processing an internal latent image type silver halide photosensitive material.

- [Background of the Invention] Methods used to create positive images using internal latent image type silver halide photographic materials can be mainly divided into two types in consideration of their practical usefulness.

One type uses a silver halide emulsion that has been fogged in advance and uses solarization or the Burschel effect to destroy fog nuclei (latent images) in exposed areas, thereby obtaining a positive image after development. be.

The other type uses an internal latent image type silver halide emulsion that has not been fogged in advance, and performs surface development after or while performing fogging treatment after image exposure to obtain a positive image.

The internal latent image type silver halide photographic emulsion is a silver halide photographic emulsion which has photosensitive nuclei mainly inside the silver halide grains and forms a latent image inside the grains upon exposure.

This latter type of method is generally more sensitive than the former type of method and is suitable for applications requiring sensitivity, and the present invention relates to this latter type of method.

Various techniques are known to date in this technical field. For example, US Patent No. 2,592,250, US Patent No. 2,466.957, US Patent No. 2,497,875,
Same No. 2.588,982, Same No. 3,761,266, Same No. 3,761,276@, Same No. 3.796.577
The main ones are those described in the specifications of British Patent No. 1.151.363 and British Patent No. 1.151.363.

By using these known methods, it is possible to produce direct positive type photographic materials with relatively high sensitivity.

Furthermore, although it cannot be said that a clear explanation has been given regarding the details of the direct positive image formation mechanism, for example, in ``The Theory of the Photographic Process J'' by Mies and James, TheTheo
ry of the Photographic Pro
The process by which a positive image is formed can be understood to some extent by the ``desensitizing effect of an internal latent image'' as discussed in page 161 of the 3rd edition.

In other words, fog nuclei are selectively generated only on the surface of unexposed silver halide grains by the surface desensitization effect based on the so-called internal latent image generated inside the silver halide grains by the first image exposure, and then normally It is thought that a photographic image is formed in the unexposed area by development.

As mentioned above, methods for selectively forming fog nuclei include a method of fogging the entire surface of the photosensitive layer by exposing it to light, which is usually called photofogging, and a fogging agent, which is called chemical fogging. A known method is to cover the skin with a chemical.

Among these methods, there is a severe condition in the chemical fogging method that the effect of the fogging agent can only be obtained by using a high 1)H processing solution with a pH of 1±pH12 or more, so the deterioration of the fogging agent due to air oxidation is difficult. This has the disadvantage that the fogging effect is significantly reduced. In addition, when a chemical fogging agent is stored in a tank or the like for a certain period of time before being used, such as a replenishment processing solution, the chemical fogging agent becomes oxidized and the activity of the replenisher decreases, causing automatic processors, etc. With the continuous processing used, it is not possible to always obtain stable positive images.

The photofogging method, as described in Japanese Patent Publication No. 45-12709, involves forming a positive image by applying photofogging and developing in a normal surface developer after image exposure. Unlike the fogging method, the fogging effect is less degraded by air oxidation, and the replenisher is less likely to be oxidized, making it more suitable for continuous processing.

In addition, the photofogging method is based on the formation of fog nuclei through photodecomposition of silver halide, so in addition to the type of silver halide used, fog characteristics also depend on the atmosphere in which the photosensitive material is placed during fog exposure. is greatly affected.

Normally, when sequentially processing internal latent image type silver halide photographic light-sensitive materials and surface latent image type silver halide photographic light-sensitive materials, it is necessary to dissolve and prepare processing solutions and replenishers for each step in each processing line. In addition, a replenishment tank and the like must be installed separately, which increases the installation area. In particular, when processing internal latent image type silver halide color photographic light-sensitive materials and surface latent image type silver halide color photographic light-sensitive materials, it is recommended to As a result, the processing line consists of the following steps: color development, bleaching, fixing, and washing (or bleach-fixing instead of bleaching and fixing, or stabilizing instead of washing). , dissolving is complicated and storage of replenisher becomes more complicated.

Therefore, good positive images can be stably obtained by continuously processing the internal latent image type silver halide photographic light-sensitive material and the surface latent image type silver halide photographic light-sensitive material in separate processing lines. A space-saving method for replenishing processing liquid that is simple and requires less installation of a replenisher tank is desired.

[Object of the Invention] Therefore, the object of the present invention is to process an internal latent image type silver halide photographic light-sensitive material and a surface latent image type silver halide photographic light-sensitive material continuously in at least the development process in separate processing lines. This method allows you to stably obtain good positive images.
Furthermore, it is an object of the present invention to provide a simple and space-saving method for replenishing a processing liquid that requires less installation of replenishment tanks.

[Structure of the Invention] In order to achieve the above object, the present inventors conducted various studies and found that at least one emulsion layer containing internal latent image type silver balogen grains whose grain surfaces are not fogged in advance. An internal latent image type silver halide photographic light-sensitive material having an internal latent image type silver halide photographic light-sensitive material and a surface latent image type silver halide photographic light-sensitive material having at least one emulsion layer containing surface latent image type silver halide grains are each subjected to at least separate development treatments. A processing method in which a processing tank is refilled with a replenisher in a processing line, in which at least the internal latent image type silver halide photographic light-sensitive material and the surface latent image type silver halide photographic light-sensitive material are respectively developed. A common replenisher is used for the internal latent image type silver halide photographic light-sensitive material, and the bromide ion concentration in the development tank of the internal latent image type silver halide photographic light-sensitive material is maintained at 5.0 x 10''3 to 2.0 x 10-2 gram ions/l. It has been found that the object of the present invention can be achieved by a processing liquid replenishment method in which the amount of replenisher is set such that the amount of the replenisher is set as follows.

[Specific Structure of the Invention] The processing steps of the silver halide photographic light-sensitive material in the present invention include, for example, color development processing, a color development processing step, a bleaching processing step, a fixing processing step, and if necessary a water washing processing step, and/or a color development processing step. Alternatively, a stabilization process is performed, but instead of a process using a bleach solution and a process using a fixer, a bleach-fix process can be performed using a one-bath bleach-fix solution.

In combination with these processing steps, a pre-hardening process, its neutralization process, a stop-fixing process, a post-hardening process, etc. may be performed. In these treatments, an activator treatment step in which a color developing agent or its precursor is contained in the material and development is performed with an activator solution may be performed instead of the color development treatment step, or an activator treatment step may be performed in place of the monobath treatment. The processing may be carried out simultaneously with bleaching and fixing processing. Typical treatments during these treatments are shown a. (These treatments include a water washing process as the final process,
Either a stabilization treatment step, a water washing treatment step, or a stabilization treatment step is performed. ) ・Color development process - Bleach process Constant fixation process ・Color development process - Bleach-fix process ・Preliminary film process - Neutralization process - Color development process - Stop fixation process - Washing process - Bleaching process Fixed fixing process - Water washing process - Post-hardening process - Color image processing process - Water washing process - Supplementary color development process - Stopping process - Bleaching process Fixed fixing process/Activator Processing process - Bleach-fixing process / Activator treatment ■ Process - Bleaching process Constant coloring process In the present invention, the color development process is a process of forming a color image, and specifically, the oxidation of a color developing agent. This is a process in which a color image is formed by a coupling reaction between the body and a color coupler.

Therefore, in the color development process, it is usually necessary to include a color developing agent in the color developing solution, but it is necessary to incorporate the color developing agent into the silver halide color photographic light-sensitive material. It also includes treatment with a color developer or alkaline solution (activator solution).

The color developing solution used in the present invention means a surface developing solution that does not substantially contain a silver halide solvent,
The color developing agent contained in the color developing solution is an aromatic primary amine color developing agent, and includes amine phenol derivatives and p-phenylezine amine derivatives. These color developing agents can be used as organic acids and non-INN salts, such as hydrochloric acids, sulfates, p-toluenesulfonates, sulfites, oxalates, benzenesulfonates, etc. can.

These compounds are generally about 0.0% in color developer 12.
A concentration of 1 g to about 30 g, more preferably color developer 1
! ; used at a concentration of about 1 g to about 15° per liter. 0
．． If less than 1 g is added, sufficient color density cannot be obtained.

Further, the temperature of the processing solution in the color developing tank is 10°C to 65°C, more preferably 25°C to 45°C.

Examples of the above amine phenol developer include 0-amine phenol, p-aminophenol, 5-amino-phenol,
Included are 2-oxy-toluene, 2-amino-3-oxy-toluene, 2-oxy-3-amino-1,4-dimethyl-benzene, and the like.

A particularly useful primary aromatic amine color developer is N-N'
-Dialkyl-p-phenylenediamine type compound, and the alkyl group and phenyl group may be substituted or unsubstituted. Among them, an example of a particularly useful compound is N.

N'-dimethyl-p-phenylenediamine hydrochloride, N-
Methyl-p-phenylenediamine hydrochloride, N.

N'-dimethyl-p-phenylenediamine hydrochloride, 2-
Amino-5-(N-ethyl-N-dodecylamino)-toluene, N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate, N-ethyl-N-β-hydroxy Ethylaminoaniline, 4-
Amino-3-methyl-N,N'-diethylaniline, 4
-amino-N-(2-methoxyethyl)-N-ethyl-
Examples include 3-methylaniline-〇-toluenesulfonate.

Compounds that provide bromide ions used in color developing solutions include known water-soluble bromides, such as sodium bromide,
Potassium bromide, lithium bromide, rubidium bromide, ammonium bromide, etc. are used. Since bromide is used to provide bromide ions, the type of bromide is not particularly limited. Furthermore, two or more bromides may be used in combination.

In the present invention, the bromine ion concentration in the development tank of the internal latent image type silver halide photographic light-sensitive material is maintained at 5.0 x 10' gram ions/4 to 2.0 x 10' gram ions/l. 0x10-3 gram ions/li~1.
More preferably 5×10 −2 gram ions/l. The positive image density has a bromide ion concentration of 5.0X10-
Even if it is less than 3 g ions/l, it is also 2.0X10-
Even if it is larger than 2, it will decrease.

Normally, when the bromide ion concentration in the developer is increased, image density decreases in surface latent image type silver chlorobromide photosensitive materials, but within the bromide ion concentration range of the present invention, the bromide ion Even though the density is old, a positive image with high density and high sensitivity can be obtained.

The above color developing agents may be used alone or in combination of two or more. Furthermore, the above color developing agents may be incorporated into color photographic materials. For example, U.S. Pat.
No. 9,492, a method of incorporating a color developing agent into a metal salt, U.S. Patent No. 3.342.559 and Research Disclosure (Research [) 1s
closure ) 1976 No. 0. 1515
9, a method of incorporating a color developing agent into a Schiff salt, JP-A-58-65429 and JP-A-58-58-
A method of incorporating the dye precursor as a dye precursor as shown in US Pat. No. 24137, a method of incorporating the color developing agent precursor as a color developing agent precursor as shown in US Pat. In this case, it is also possible to process the silver halide color photographic light-sensitive material with an alkaline solution (activator solution) instead of a color developing solution, and the bleach-fixing process is carried out immediately after the alkaline solution treatment.

The color developing solution used in the present invention may contain alkaline agents commonly used in developing solutions, such as sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium carbonate, potassium carbonate, sodium sulfate, sodium metaborate, or borax. It may also contain various additives such as benzyl alcohol, alkali metal halides, such as potassium chloride, development regulators such as citrazic acid, preservatives such as droxylamine or sulfites, etc. good.

Furthermore, various antifoaming agents and surfactants, as well as wired solvents such as methanol, dimethylformamide or dimethyl sulfoxide, etc. can be appropriately contained.

The pH of the color developing solution used in the present invention is usually 7 or more,
Preferably it is about 9-13.

In addition, the color developing solution used in the present invention may contain antioxidants such as diethylhydroxyamine, tetronic acid, tetronimide, 2-anilinoethanol, dihydroxyacetone, aromatic secondary alcohol, hydroxamic acid, pentose, or hexose, pyrogallol-1,
3-dimethyl ether etc. may be contained.

In the color developing solution used in the present invention, various chelating agents can be used in combination as metal ion sequestering agents. For example, as the chelating agent, amine polycarboxylic acids such as ethylenediaminetetraacetic acid and diethylenetriaminopentaacetic acid,
-Organic phosphonic acids such as hydroxyethylidene-1,1'-diphosphonic acid, aminopolyphosphonic acids such as aminotri(methylenephosphonic acid) or ethylenediaminetetraphosphonic acid, oxycarboxylic acids such as citric acid or gluconic acid, 2-phosphonobutane1. Examples include phosphonocarboxylic acids such as 2.4-tricarboxylic acid, polyphosphoric acids such as tripolyphosphoric acid or hexametaphosphoric acid, and polyhydroxy compounds.

In the present invention, the internal latent image type silver halide photographic light-sensitive material is subjected to full-surface exposure at any time during the development process after image exposure, but exposure at the early stage of development means that the development time is shortened. In that case, it is advantageous to start exposure after the developer has sufficiently penetrated the emulsion layer.

The illuminance for full-surface exposure, that is, for light fogging in the present invention, is preferably an illuminance that does not cause illuminance failure during fogging, and although it varies depending on the photosensitive material, it is generally 0.01 to 2000 lux, preferably 0.05 to 3 o lux, and more preferably can use light of 0.1 to 5 lux. Adjustment of the light fogging illuminance may be carried out by changing the altitude of the light source, by attenuating light using various filters, by changing the distance between the light-sensitive material and the light source, by changing the angle between the light-sensitive material and the light source, and the like.

Furthermore, in order to shorten the exposure time for light fog, a method may be adopted in which light fog is fogged with weak light at the initial stage of exposure, and then with stronger light at a later stage. Mata Tokko 1987
As described in Japanese Patent Publication No. 6936, there is a method of full exposure while increasing the illuminance, and
The method described in No. 521 can also be carried out advantageously.

In the present invention, as a light source for light fogging, at least one light source within the sensitivity wavelength of the photographic light-sensitive material may be used. It is desirable to use at least one light source with a wide spectral distribution, and a fluorescent lamp with high color rendering properties as described in Japanese Patent Application Laid-Open No. 17350/1983 may also be used. Furthermore, a combination of two or more types of light sources with different emission distributions and color temperatures may be used, and various filters such as color temperature conversion filters may be used.

In the present invention, the bleaching process refers to a process of bleaching the developed silver image after the color development process with an oxidizing agent (bleaching agent).

As bleaching agents, metal complex salts of m-acids are used, such as polycarboxylic acids, aminopolycarboxylic acids, or organic acids such as oxalic acid and citric acid, coordinated with metal ions such as iron, cobalt, and copper. It will be done.

Among the above organic acids, the most preferable If is polycarboxylic acid or aminopolycarboxylic acid.

These polycarboxylic acids may be alkali metal salts, ammonium salts or water-soluble amine salts. Specific examples of these include the following.

[1] Ethylenediaminetetraacetic acid [2] Diethylenetriaminepentaacetic acid [3] Ethylenediamine-N-(β-oxyethyl)-N, N', N
' -Triacetic acid [4] Propylenediaminetetraacetic acid [5] Nitrilotriacetic acid [6] Cyclohexanediaminetetraacetic acid [7] Iminodiacetic acid [8] Dihydroxyethylglycincitric acid (or tartaric acid 1
1j) [9] Ethyl ether diamine tetraacetic acid [10] Glycol ether diamine tetraacetic acid [11] Ethylene diamine tetrapropionic acid [12]
Phenylenediaminetetraacetic acid [13 Coethylenediaminetetraacetic acid disodium salt [14] Ethylenediaminetetraacetic acid tetra(trimethylammonium) salt [15] Ethylenediaminetetraacetic acid tetrasodium salt [16] Diethylenetriaminepentaacetic acid pentasodium salt [17] Ethylenediamine-N -(β-oxyethyl)
-N,N',N'-Triacetic acid sodium salt [18] Propylene diamine tetraacetic acid sodium salt [19] Nitriloacetic acid sodium salt [20] Cyclohexanediamine tetraacetic acid sodium salt Preferably 2
Use at 0 to 250o/ffi.

In addition to the above-mentioned bleaching agent, the bleaching solution may contain a sulfite salt as a preservative, if necessary. Alternatively, it may be a bleaching solution containing an ethylenediaminetetraacetate iron complex salt bleaching agent and a large amount of a halide such as ammonium bromide. As the halides, in addition to ammonium bromide, hydrochloric acid, hydrobromic acid, lithium bromide, sodium bromide, potassium bromide, sodium iodide, potassium iodide, ammonium iodide, etc. can also be used. can.

The bleaching solution used in the present invention includes JP-A No. 46-280, JP-B No. 45-8506, JP-B No. 46-556, Belgian Patent No. 770,910, JP-A No. 45-8836,
No. 53-[54], JP-A-54-71634 and No. 4
Various bleaching accelerators such as those described in No. 9-42349 can be added.

The pH of the bleaching solution used is 2.0 or higher, but generally D
Used at a pH of I-44.0 or higher and pH 9.5 or lower, preferably I) H4.5 or higher +) l-18.0 or lower,
More specifically, the most preferable PL is 5.0 or more and 7.0 or less. The processing temperature is 80'C or less, which is 3°C or more, preferably 5°C or more lower than the temperature of the processing solution in the color developing tank. Although it is used at a temperature of 55° C. or lower, it is preferably used to prevent evaporation.

In the present invention, the fixing process refers to a process of desilvering and fixing using a fixing solution containing a silver halide fixing agent. Silver halide fixing agents used in the fixing solution include compounds that react with silver halide to form water-soluble complex salts, such as potassium thiosulfate, sodium thiosulfate, and dioxin used in ordinary fixing processes. ThioVAm salts such as ammonium sulfate, thiocyanine M such as potassium thiocyanate, sodium thiocyanate, ammonium thiocyanate
Typical examples include salts, thioureas, and thioethers. These fixatives are 5! ;L/I1 or more, used in an amount that can be dissolved, but generally 70g to 250Q/I
A part of the fixing agent can be contained in the bleaching tank, or conversely, a part of the bleaching agent can also be contained in the fixing tank.

The bleaching solution and/or fixing solution may contain various DH buffers such as boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, and ammonium hydroxide. These agents may be contained alone or in combination of two or more. In addition, various optical brighteners, antifoaming agents, or surfactants can be contained. In addition, preservatives such as hydroxylamine, hydrazine, and bisulfite adducts of aldehyde compounds, organic chelating agents such as aminopolycarboxylic acids, stabilizers such as nitroalcohols and nitrates, and organic agents such as methanol, dimethyl sulfoxide, and dimethyl sulfoxide. A solvent and the like can be contained as appropriate.

The pH of the fixer is used at 3.0 or higher, but generally the pH is 3.0 or higher.
Used at pH 4.5 or higher and pH 10 or lower, preferably pH
5 or more p)l is used at 9.5 or less, and more specifically, the most preferable pl-1 is treated at 6 or more and 9 or less. The processing temperature is 80℃ or less, which is 3 degrees higher than the temperature of the processing solution in the color developing tank.
It is used at temperatures lower than ℃, preferably lower than 5℃,
It is preferably used at a temperature of 55° C. or lower to prevent evaporation.

In the present invention, the bleach-fix treatment step is a step in which metallic silver produced by development is oxidized to replace it with silver halide, and then a water-soluble complex is formed and uncolored areas of the color former are colored.

A metal complex salt of an organic acid as a bleaching agent used in a bleach-fix solution is one in which metal ions such as iron, cobalt, copper, etc. are coordinated with an aminopolycarboxylic acid or an organic acid such as oxalic acid or citric acid. The most preferred organic acids used to form such v1 acid metal complexes include polycarboxylic acids. These polycarboxylic acids or aminopolycarboxylic acids may be alkali metal salts, ammonium salts or water-soluble amine salts. Specific examples of these include the following.

[1] Ethylenediaminetetraacetic acid [2] Diethylenetriaminepentaacetic acid [3] Ethylenediamine-N-(β-oxyethyl)-N, N', N
' -Triacetic acid [4] Propylenediaminetetraacetic acid [5] Nitrilotriacetic acid [6] Cyclohexanediaminetetraacetic acid [7] Iminodiacetic acid [8] Dihydroxyedylglycincitric acid (or tartaric acid) [9] Ethyl ether diamine tetraacetic acid [ 10] Glycol ether diamine tetraacetic acid [11] Ethylenediamine tetrabrobionic acid [12]
Phenylenediaminetetraacetic acid [13] Ethylenediaminetetraacetic acid disodium salt [14] Ethylenediaminetetraacetic acid tetra(trimethylammonium) salt [15 Coethylenediaminetetraacetic acid tetrasodium salt [16] Diethylenetriaminepentaacetic acid bentanatri-C cum salt [17] Ethylenediamine- N-(β-oxyethyl)
-N,N',N'-Triacetic acid sodium salt [18] Propylene diamine tetraacetic acid sodium salt [19] Nitriloacetic acid sodium salt [20] Cyclohexanediamine tetraacetic acid sodium salt These bleaches are 5-450 (1#! , more preferably 20 to 250 (1/4).

The bleach-fixing solution contains a silver halide fixing agent in addition to the above bleaching agent, and if necessary, a sulfite M salt as a preservative. Also, a bleach-fix solution consisting of an ethylene diamine tetraacetate iron (I [ A bleach-fix solution containing a large amount of a halide, such as a bleach-fix solution, and a special bleach-fix solution containing a combination of an ethylenediaminetetraacetic acid iron(III) complex salt bleach and a large amount of a halide, such as ammonium bromide, etc. can also be used. In addition to ammonium bromide, the halides include hydrochloric acid, hydrobromic acid,
Lithium bromide, sodium bromide, potassium bromide, sodium iodide, potassium iodide, ammonium iodide, and the like can also be used.

The silver halide fixing agents contained in the bleach-fixing solution include compounds that react with silver halide to form water-soluble complex salts, such as potassium thiosulfate, sodium thiosulfate, and thiosulfate, which are used in ordinary fixing processes. Thiosulfate like ammonium sulfate! l! Typical examples include salts, thiocyanates such as potassium thiocyanate, sodium thiocyanate, and ammonium thiocyanate, thioureas, thioethers, and the like. These fixing agents are used in an amount of 5o/1 or more, within the range that can be dissolved, but generally 70a to 25
Use at 0o/Il.

In addition, various FIH buffers such as 1llllf, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, and ammonium hydroxide may be used alone or in the bleach-fix solution. Two or more kinds can be contained in combination. Furthermore, various optical brighteners, antifoaming agents, or surfactants can be contained. In addition, preservatives such as hydroxylamine, hydrazine, bisulfite adducts of aldehyde compounds, organic chelating agents such as aminopolycarboxylic acids, stabilizers such as nitroalcohols and nitrates, and organic Melt or the like can be contained as appropriate.

The bleach-fix solution used in the present invention includes JP-A-46-280, JP-B No. 45-8506, JP-B No. 46-556, Belgian Patent No. 770.910, JP-B No. 45-8836,
Various bleach accelerators described in JP-A-53-9854, JP-A-54-71634 and JP-A-49-42349 can be added.

The pH of the bleach-fix solution is used at 4.0 or higher, but generally it is used at pH 5.0 or higher and pH 9.5 or lower, preferably at pH 16.0 or higher and pH 8.5 or lower. A preferable DH is 6.5 or more and 8.5 or less. The processing temperature is 80° C. or lower, which is lower than the processing temperature of the color developing tank by 3° C. or more, preferably 5° C. or more, but preferably 55° C. or lower to prevent evaporation.

In the present invention, an aldehyde derivative is added to the stabilizing solution used in the stabilization treatment step in order to improve the storage stability of photographic images.

The aldehyde derivative is an aldehyde compound or aldehyde adduct represented by the following general formula <1), (2) or (3), and at least one selected from these is used. These additions stabilize the dye image and improve the physical properties of the light-sensitive material.

General formula (1) R1-Ct-1° General formula (2) Ra? R2-C-OH 803M General formula (3) In the formula, R1 is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a formyl group, an acetyl group, an acetonyl group, and a hydroxy group or an alkoxy group, a formyl group, an amine group, Represents a hydroxyimino group, an alkyl group having 1 to 5 carbon atoms which may be substituted with a halogen atom, etc. R2 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R3 is an optionally substituted alkyl group having 1 to 5 carbon atoms, M is an alkali metal, R4, R
5 represents a hydrogen atom or an optionally substituted alkyl group having 1 to 5 carbon atoms, and n represents an integer of 0 to 4.

Specific examples of compounds represented by the above general formula are described below, but the present invention is not limited thereto.

[Exemplary compounds represented by general formula (1)] 1, formaldehyde 2, acetaldehyde 3, propionaldehyde 4, inbutyraldehyde 5, n-butyraldehyde 5, n-valeraldehyde 7, isovaleraldehyde 8, methylethyl acetaldehyde 9 , trimethylaldehyde 10, n-hexanaldehyde 11, methyl-n-propylaldehyde 12, isohexaldehyde 136, glyoxal 14, malonaldehyde 15, succinic aldehyde 16, glutaraldehyde 17, asianaldehyde 18, methylglyoxal 19, acetoacetic aldehyde 20. Glycolaldehyde 21, Ethoxyacetaldehyde 22, Aminoacetaldehyde 23, Betainaldehyde 24, Chloral 25, Chloracetaldehyde 26, Dichloroacetaldehyde 27, Promal 28, Dichloroacetaldehyde 29, Iodoacetaldehyde 30, α-Chlorpropionacetaldehyde 31, α
- Bromopropion acetaldehyde [exemplified compound represented by general formula (2)] 1, formaldehyde sodium bisulfite 2, acetaldehyde sodium bisulfite 36
Probionaldehyde TiAm sodium bisulfite 4, butyraldehyde sodium bisulfite [exemplified compound represented by general formula (3)] 1, succinic aldehyde sodium bisulfite 2, glutaraldehyde sodium bisulfite 3, β-methylcultaraldehyde Sodium bisbisulfite 4.7 Reic acid dialdehyde Sodium bisbisulfite The compound represented by the above general formula is 0.0 per 12 stabilizers.
It is preferable to use the amount in the range of 1Q to 50g, more preferably 0, osg to 20g to obtain good results.

Various additives can be added to the stabilizing liquid as necessary. For example, water droplet prevention agents such as siloxane derivatives, boric acid, citric acid, phosphoric acid, acetic acid, or pH 1 of sodium hydroxide, sodium acetate, potassium citrate, etc.
Conditioning agents, hardening agents such as potash alum and chromium alum, organic solvents such as methanol, ethanol, dimethyl sulfoxide,
It is optional to add additives to improve or extend the processing effect, such as humidity conditioners such as ethylene glycol and polyethylene glycol, and other color tone agents.

Further, the stabilizing liquid may be partitioned into two or more compartments to lengthen the countercurrent flow path.

The temperature of the stabilization treatment is 80° C. or lower, which is lower than the temperature of the processing solution in the color developing tank by 3° C. or more, preferably 5° C. or more, but preferably 55° C. or lower to prevent evaporation.

The stabilization treatment step in the present invention can be performed using at least two types of stabilization liquid tanks having different functions.

In the present invention, the "different functions" of the "two types of stabilizing liquid tanks with different functions" refers to pre-bath components (for example, bleach-fix solution components, A function that neutralizes, 112 salt, and inactivates fixing solution components) to prevent deterioration of the storage stability of dyes, a draining bath function that prevents contamination such as uneven washing, and a function that blocks the active sites of unreacted couplers to preserve color images. The functions include a stabilizing function, a coloring adjustment function for coloring a color image, an antistatic function by containing an antistatic agent, and two or more of these functions may be combined. This means that they have different functions as a result.

For example, the first stabilizing liquid is a stabilizing liquid that has the function of neutralizing, desalting, and inactivating the dye and does not deteriorate the storage stability of the dye, and the second stabilizing liquid is a stabilizing liquid that prevents contamination such as uneven washing with water. Examples include stabilizing liquids that have both the function of a draining bath and the function of blocking the active sites of unreacted couplers and stabilizing color images.

Further, the surface tension of the first stabilizing liquid is 20 to 78 dyne,
' Cal and the surface tension of the second stable liquid is 8 to 6.
0 dyne/cm is particularly preferred since it has the additional effect of improving the stability of the dye, especially during long-term high-humidity storage of the processed photosensitive material.

After the stabilizing solution used in the present invention is treated with a processing solution having fixing ability, such as a fixing solution or a bleach-fixing solution, the internal Latent image type silver halide color light-sensitive materials and surface latent image type silver halide color light-sensitive materials are preferably used because they both have good dye image storage stability.

Furthermore, when the stabilizing solution used in the present invention contains at least one compound selected from the group below, the generation of silver sulfide in the stabilizing solution is improved in low update rate processing, and the processed photosensitive material It is particularly preferably used because it also has the effect of improving staining in unexposed areas.

[Compound] (A) Amzozoic acid compound (B) Phenol compound (C) Thiazoline compound (D) Imidazole compound (E) Guanidine compound (F) Carbamate compound (G) Morpholine compound (1) -1) Quaternary phosphonium compounds (1) Quaternary ammonium compounds (J) Urea compounds (K) Isoxazole compounds (L) Proparturamine compounds (M) Amino acid compounds (N) Triazine compounds (0 ) Pyridine compound In the present invention, the above compound (A) contained in the stabilizing liquid
Specific compounds of ~(0) include, but are not limited to, the following.

[Exemplary compounds] (1): Sodium orthophenylphenol (2):
2-octyl-4-isothiazoline (3): benzisothiazolin-3-one (4): 2-methyl-4-isothiazolin-3-one (5): 5-chloro-2-methyl-4-isothiazolin-3- (6): 2-thiomethyl-4-ethylamino-6-(1
, 2-dimethylpropylamino)-3-triazine (7): hexahydro-1,3,5-tris(2-hydroxyethyl)-8-triazine (8): 4-(2-nitrobutyl)morpholine (9) : 4- (3-nitrobutyl) mol, foline (1G) : 2- (4-thiazolyl)benzimidazole (11) Nidodecylguanidine! W! i salt (12)
: Hydroxybenzoic acid methyl ester (13) : Hydroxybenzoic acid butyl ester (14) : Hydroxybenzoic acid n-butyl ester (15) : I)-Hydroxybenzoic acid (16) Dibenzoic acid methyl ester (17) : Orthocyclohexylphenol (18)
: 1.2-benzisothiazolin-3-one (19): 2-octyl-4-isothiazolin-3-one (20): 2-(4-thiazolyl)-benzimidazole (21): 2.6-dimethyl Viridin (22):
2.4.6-Dolimethylpyridine (23): Radium-2-pyridinethiol-1-oxide (24) Nidichlorohexidine (25): Polyhexamethylene biguanidine salt I! (
26): Methyl-1-(butylcarbamoyl)-2-
Benzimidazole carbamate (27): Methylimidazole carbamate (28)
: )-Di-n-butyl-tetradecylphosphonium chloride (29) :)-IJ phenyl-nitrophenylphosphonium chloride (3G) Nidodecyldimethylbenzylammonium chloride (31) Nididecyldimethylammonium chloride (32) : Lauryl pyridine Nium chloride (33)
:N-(3,4-dichlorophenyl)N'-(4-chlorophenyl)urea (34) :N-(3-trifluoromethyl-4-di0
lophenyl)-N'-(4-chlorophenyl)urea (35): 3-hydroxy-5-methyl-isoxazole (36): D,L-2-benzylamino-1-propanol (37): 3-diethylamino-1 -Property Tools (3
8): 2-dimethylamine-2-methyl-1-propatol (39): 3-amino-1-propatol (40):
Isopropanolamine (41) Nidiisopropanolamine (42) :N
, N-dimethylisopropanolamine (43): N-lauryl-β-aniline Among the above compounds, compounds preferably used in the present invention are thiazoline compounds, benzoic acid compounds, pyridine compounds, guanidine compounds, It is a quaternary ammonium compound. Furthermore, preferred are thiazoline compounds or benzoic acid compounds.

The amount of the above compounds (A) to (0) added to the stabilizing solution is preferably in the range of 0.002Q to 5(l), more preferably 0.005g to 5(l) per liter of the stabilizing solution.
Used in the range of 10g.

When a specific chelating agent is used in a stabilizing solution in a stabilizing tank, the storage stability of the stabilizing solution is improved.

The chelating agent preferably used in the first stabilizing liquid has a chelate stability constant of 8 or more with iron (I[I) ions.

The chelate stability constant indicates the stability of a complex formed by a metal ion and a chelate in a solution.
means a constant defined as the reciprocal of the dissociation constant of a complex,
L.G. Siren, A.E. -? -7/L/ (
L, G, 5illen,, A, E.

Martin Martell, “Stability Constance”
Of Metalion Complex Is (3tabil
ityConstants of Metaltonc
complexes)”, The Chemical Society
London (The Chemical Society
yLondon) (1964), Nis Chaberek, A.E. Martill (S, Chaberek)
, , A. E. Martell), ``Organic Securing Agents''
nic 5equesterina Agents
) "Chelating agents that are generally known by Wiley (1959) and others and have a chelate stability constant of 8 or more with iron (III) ions include polyphosphates, aminopolycarboxylates, Oxycarboxylic acid salts, polyhydroxy compounds, organic phosphates, synthetic phosphates, etc. are used, but particularly good results can be obtained when aminopolycarboxylic acid salts and organic phosphates are used in the present invention. Specific examples of chelating agents include, but are not limited to, the following.

(1) CH3 Summer H203P-G-POa H2 H CH3 HOOC-C-PO3H2 0 days One or more chelating agents may be used in combination, and the amount added is in the range of o, osg to 40 o per stabilizing solution. can be used, preferably in the range of 0.1 to 20 g.

Among these chelating agents, particularly preferably used are diebulenetriaminepentaacetic acid and 1-hydroxyethylidene-1,1-diphosphonic acid.

The DH of the stabilizer used in the present invention is not particularly limited, but is preferably in the range of pHo, s to 12.0, more preferably in the range of pHs, o to 9.0, and particularly preferably in the range of I) H6 ,0 to 9.0.

l) that can be contained in the stabilizing solution used in the present invention
As the H adjuster, any commonly known alkaline agent or acid agent can be used, but it is generally preferable to use a small amount.

In addition to the above, various stabilizer additives may be added to the stabilizer, and these additives include, for example, optical brighteners, surfactants, organic sulfur compounds, onium salts, and formalin.

The treatment temperature during the stabilization treatment is preferably in the range of 15°C to 60°C, preferably 20°C to 45°C.

In addition, from the viewpoint of rapid processing, the shorter the treatment time, the better, but it is usually 20 seconds to 10 minutes, most preferably 1 minute to 5 minutes, and in the case of multiple tank stabilization treatment, the first stage tank should be used in a shorter time. It is preferable that the treatment time in the subsequent tank is long. In particular, it is desirable to perform the treatment sequentially with a treatment time 20% to 50% longer than in the previous tank.

Although the temperature of the drying step can be arbitrarily selected, it is preferably 50°C or higher, more preferably 70°C or higher.

The method of bringing the stabilizing liquid into contact with the photosensitive material is to immerse the photosensitive material in the liquid in the same way as with general processing liquids, but it is best to use a sponge, synthetic fiber, cloth, etc. to contact both the emulsion surface of the photosensitive material and the transport leader. It may be applied to the conveyor belt, or it may be sprayed onto the conveyor belt.

Note that when the stabilizing solution contains a soluble silver salt, silver can also be recovered from the solution. As a silver recovery method, an ion exchange resin method, a metal substitution method, an electrolysis method, a silver sulfide precipitation method, etc. can be used.

In addition to these treatments, there are methods in which the developer produced by color development is subjected to herogenation bleaching and then color development is performed again, various intensification treatments (amplification treatments) described in JP-A-58-154839, etc. , processing may be performed using a development method that increases the amount of dye produced.

Each processing step is usually carried out by immersing the photosensitive material in a processing solution, but other methods are also available, such as a spray method in which the processing solution is supplied in the form of a spray, or a method in which the material is brought into contact with a carrier impregnated with the processing solution. A web method, a method of viscous development processing, etc. may be used.

The composition of the replenisher for the processing solution used in the present invention is such that the composition of the processing solution in which the light-sensitive material used in the present invention is continuously processed is maintained at an activity level that provides constant image performance. , so that the processing liquid components can be adjusted.

Also, the components of the processing liquid and the replenisher are the same. In the present invention, since at least the replenisher solution is supplied to the development processing tanks for developing the internal latent image type silver halide photographic light-sensitive material and the surface latent image type silver halide photographic light-sensitive material, the replenisher tank is filled accordingly. There is less installation, management, etc.

Furthermore, in the present invention, when replenishing the development tank with the internal latent image type silver halide photographic light-sensitive material, the bromide ion concentration is maintained at 5.0X10-3 to 2.0X10-2 gram ions/l as described above. The replenisher m is set so that

The internal latent image type silver halide emulsion in the present invention is an emulsion having silver halide grains which form a latent image mainly inside the silver halide grains and have most of the photosensitive nuclei inside the grains, and which has arbitrary Silver halides such as silver bromide, silver chloride, silver chlorobromide, silver iodobromide, silver chloroiodobromide, and the like are included. In particular, silver chloride, silver chlorobromide, silver chloroiodobromide, and silver iodochloride are preferred from the viewpoint of grains with a high development speed.

In the internal latent image type silver halide grains of the present invention, it is preferable that the grain surface is not chemically sensitized, or even if it is sensitized, it is only to a small extent.

The meaning that the grain surfaces are not prefogged means that the emulsion used in the present invention is coated on a transparent film support with a thickness of 35 m
The density obtained when a test piece coated to give gA (+ /d v') is developed with the following surface developer A for 10 minutes at 20°C without exposure to light should not exceed 0°6, preferably 0.4. means.

Surface developer A Metol 2.5g! -Ascorbic acid io gNaB02 ・
4H2035Q KBr 1 a Add water 12 Furthermore, the silver halide emulsion according to the present invention has a sufficient density when the test piece prepared as described above is exposed and then developed with internal developer B having the following formulation. It is something to give.

Internal developer B Metol 2g Sodium sulfite (anhydrous) 90° Hydroquinone 8g Soda carbonate (-hydrogen) 52.5 to IKBr
5 QKl
o, add sg water
11 More specifically, when a portion of the specimen is exposed to a light intensity scale for a defined period of time up to about 1 second and developed in internal developer B at 20° C. for 4 minutes, exhibiting a maximum density that is at least 5 times, preferably at least 10 times, that obtained when another portion of the specimen exposed under the same conditions is developed with surface developer A at 20° C. for 4 minutes. be.

Specifically, for example, conversion type silver halide emulsions described in U.S. Pat. No. 2,592,250, U.S. Pat.
．． Core/shell type silver halide emulsion doped with internal chemical sensitizing liquid or polyvalent metal ions as described in No. 276, JP-A-50-8524, JP-A-50-38525
Examples include the laminated silver halide emulsion described in Japanese Patent Application No. 53-2408, and the emulsions described in JP-A-52-156614 and Japanese Patent Application No. 54-35361. can.

The internal latent image type silver halide emulsion and the surface latent image type silver halide emulsion used in the present invention will hereinafter be abbreviated as the silver halide emulsion of the present invention unless otherwise specified.

The silver halide emulsion of the present invention includes any silver halide used in conventional silver halide emulsions, such as silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, and silver chloride. can be used.

The silver halide grains used in the silver halide emulsion of the present invention may be obtained by any of the acid method, neutral method, and ammonia method. The particles may be grown all at once, or may be grown after seed particles are created. The method of creating and growing the seed particles may be the same or different.

In the silver halide emulsion, halide ions and silver ions may be mixed simultaneously, or one may be mixed in a liquid in which the other is present. Also, while considering the critical growth rate of silver halide crystals, halide ions and silver ions were mixed in a DH in a pot.

Growth may be performed by sequentially and simultaneously adding pAg while controlling it. By this method, silver halide grains having a regular crystal shape and a nearly uniform grain size can be obtained. After growth, a conversion method may be used to change the halogen composition of the particles.

During production of the silver halide emulsion of the present invention, it is possible to control the grain size, grain shape, grain size distribution, and grain growth rate of silver halide grains by using a silver halide solvent as necessary. can.

The silver halide grains used in the silver halide emulsion of the present invention are formed by cadmium salt, zinc salt, lead salt, thallium salt, iridium salt (complex salts containing), rhodium salt, Metal ions can be added using at least one selected from salts (including lead salts) and iron salts (complex salts including) to contain these metal elements inside the particles and/or on the surface of the particles, Further, by placing the particles in an appropriate reducing atmosphere, reduction sensitizing nuclei can be provided inside the particles and/or on the particle surfaces.

In the silver halide emulsion of the present invention, unnecessary soluble salts may be removed after the growth of silver halide grains is completed, or they may remain contained. When removing the salts, please refer to Research Disc.
It can be carried out based on the method described in D1closure) No. 17643.

The silver halide grains used in the silver halide emulsion of the present invention may have a uniform silver halide composition distribution within the grain, or may be core/shell grains in which the silver halide composition differs between the grain interior and the surface layer. There may be.

The silver halide grains used in the silver halide emulsion of the present invention may have a regular crystal shape such as a cube, octahedron, or dodecahedron, or may have an irregular crystal shape such as a spherical or plate shape. It may also have a crystalline form.

In these particles, any ratio of the (100) plane to the (111) plane can be used. Further, the particles may have a composite form of these crystal forms, or particles of various crystal forms may be mixed.

The average grain size (grain size represents the diameter of a circle with an area equal to the projected area) of the silver halide grains used in the silver halide emulsion of the present invention is preferably 5 μm or less, and particularly preferably 3 μm or less. .

The silver halide emulsion of the present invention may have any grain size distribution. An emulsion with a wide grain size distribution (referred to as a polydisperse emulsion) may be used, or an emulsion with a narrow grain size distribution (referred to as a monodisperse emulsion). When divided by the average grain size, the value is 0.20 or less.Here, the grain size is the diameter in the case of spherical silver halide, and the diameter in the case of grains with shapes other than spherical. This indicates the diameter when the projected image is converted into a circular image of the same area.) may be used alone or in combination. Further, a mixture of a polydisperse emulsion and a monodisperse emulsion may be used.

The silver halide emulsion of the present invention may be a mixture of two or more separately formed silver halide emulsions.

The silver halide emulsion of the present invention can be chemically sensitized by conventional methods. That is, a sulfur sensitization method, a selenium sensitization method, a reduction sensitization method, a noble metal sensitization method using gold or other noble metal compounds, etc. can be used alone or in combination.

The silver halide emulsion of the present invention can be optically sensitized to a desired wavelength range using dyes known as sensitizing dyes in the photographic industry. Sensitizing dyes may be used alone, but
You may use two or more types in combination. Along with the sensitizing dye, the emulsion contains a dye that itself does not have a spectral sensitizing effect, or a supersensitizer, which is a compound that does not substantially absorb visible light and enhances the sensitizing effect of the sensitizing dye. Good too.

The silver halide emulsion of the present invention includes steps for producing light-sensitive materials,
During chemical ripening, at the end of chemical ripening, and/or after chemical ripening, until silver halide emulsion is applied, for the purpose of preventing fog during storage or photographic processing, or to maintain stable photographic performance. In addition, compounds known in the photographic industry as antifoggants or stabilizers can be added.

Gelatin is advantageously used as a binder (or protective colloid) for the silver halide emulsion of the present invention, but
Hydrophilic colloids such as synthetic hydrophilic polymer substances such as gelatin derivatives, graft polymers of gelatin and other polymers, other proteins, sugar derivatives, cellulose derivatives, and single or copolymers can also be used. .

When gelatin is used as a binder for the silver halide emulsion of the present invention, the jelly strength of the gelatin is not limited, but it is preferably 250 g or more (value measured by the buggy method).

Photographic emulsion layers and other hydrophilic colloid layers of light-sensitive materials using Mizumoto's silver halide emulsions contain one or two hardeners that crosslink binder (or protective colloid) molecules and increase film strength. By using the above, hardening can be achieved. A hardening agent can be added in an amount that can harden the photosensitive material to the extent that there is no need to add a hardening agent to the processing solution.
It is also possible to add a hardening agent to the processing solution.

A plasticizer can be added to the silver halide emulsion layer and/or other hydrophilic colloid layer of a light-sensitive material using the silver halide emulsion of the present invention for the purpose of increasing flexibility.

The photographic emulsion layer and other hydrophilic colloid layers of the light-sensitive material using the silver halide emulsion of the present invention contain a dispersion (latex) of a water-insoluble or poorly soluble synthetic polymer for the purpose of improving dimensional stability. can be done.

In the emulsion layer of a light-sensitive material using the silver halide emulsion of the present invention, an oxidized product of an aromatic primary amine developer (for example, a p-phenylenediamine derivative, an aminephenol derivative, etc.) and a cup are used in the color development process. A dye-forming coupler is used that undergoes a ring reaction to form a dye. The dye-forming couplers are typically selected for each emulsion layer such that a dye is formed that absorbs light in the light-sensitive spectrum of the emulsion layer, with a yellow dye-forming coupler for the blue-sensitive emulsion layer and a dye for the green-sensitive emulsion layer. A magenta dye-forming coupler is used in the sensitive emulsion layer and a cyan dye-forming coupler is used in the red-sensitive emulsion layer. However, depending on the purpose, silver halide color photographic materials may be produced using different combinations from the above.

These dye-forming couplers have 8 LJ carbon atoms and make the coupler non-diffusive, which is called a ballast group in the molecule.

It is desirable to have the above groups. In addition, even if these dye-forming couplers are 4-equivalent, in which 4 molecules of silver ions need to be reduced in order to form 1 molecule of dye, only 2 molecules of silver ions need to be reduced. Either equivalence is acceptable. Dye-forming couplers can be combined with the oxidized form of a developing agent to produce development accelerators, bleach accelerators, developers, silver halide solvents, toning agents, hardeners, fogging agents, antifoggants, chemical sensitizers, Compounds that release photographically useful fragments, such as spectral sensitizers and desensitizers, can be included. These dye-forming couplers may be used in combination with colored couplers that have a color correction effect or DIR couplers that release a development inhibitor during development and improve image sharpness and image graininess. In this case, it is preferable that the dye formed from the DIR coupler is of the same type as the dye formed from the dye-forming coupler used in the same emulsion layer, but if the color turbidity is not noticeable, a different type of dye may be used. It may also be one that forms a pigment. Instead of the DIR coupler, a DIR compound may be used which, when used with or in combination with the coupler, undergoes a coupling reaction with the oxidized form of the developing agent to produce a colorless compound and at the same time releases a development inhibitor.

A colorless coupler that undergoes a coupling reaction with an oxidized aromatic primary amine developer, but does not form a dye, can also be used in combination with a dye-forming coupler.

Dye-forming couplers, colored couplers, DIR couplers, DIR that do not need to be adsorbed on the silver halide crystal surface
compounds, image stabilizers, color antifoggants, ultraviolet absorbers,
Among fluorescent brighteners, hydrophobic compounds can be prepared using various methods such as solid dispersion method, latex dispersion method, and oil-in-water emulsion dispersion method. It can be selected as appropriate. For the oil-in-water emulsion dispersion method, conventionally known methods for dispersing hydrophobic additives such as couplers can be applied, and the boiling point is usually about 150°C.
Dissolve the above-mentioned high-boiling point organic solvent in combination with a low-boiling point and/or water-soluble organic solvent as necessary, and use a stirrer, homogenizer, colloid mill, etc. in a hydrophilic binder such as gelatin aqueous solution using a surfactant. flowit mixer,
It may be emulsified and dispersed using a dispersion means such as an ultrasonic device, and then added to the desired hydrophilic colloid layer. A step of removing the low boiling point organic solvent may be included simultaneously with the dispersion or dispersion.

When dye-forming couplers, DIR couplers, colored couplers, DIR compounds, image stabilizers, color antifoggants, ultraviolet absorbers, optical brighteners, etc. have acid groups such as carboxylic acid or sulfonic acid, they can be used as an alkaline aqueous solution. They can also be incorporated into hydrophilic colloids.

Anionic surfactants, nonionic surfactants, Cationic surfactants can be used.

Between the emulsion layers (between the same color-sensitive layers and/or between different color-sensitive layers) of a light-sensitive material using the silver halide emulsion of the present invention,
A color antifogging agent can be used to prevent color turbidity, deterioration of sharpness, and noticeable graininess due to migration of the oxidized product of the developing agent or the electron transfer agent.

The color antifoggant may be contained in the emulsion layer itself, or
An interlayer may be provided between adjacent emulsion layers and contained in the interlayer.

In the light-sensitive material using the silver halide emulsion of the present invention, an image stabilizer can be used to prevent deterioration of the dye image.

A protective layer of a photosensitive material using the silver halide emulsion of the present invention,
The hydrophilic colloid layer such as the intermediate layer may contain an ultraviolet absorber in order to prevent fogging due to discharge caused by charging of the photosensitive material due to friction, etc., and to prevent image deterioration due to UV light.

In order to prevent deterioration of magenta dye-forming couplers and the like due to formalin during storage of a light-sensitive material using the silver halide emulsion of the present invention, a formalin scavenger can be used in the light-sensitive material.

The silver halide emulsion layer and/or other hydrophilic colloid layer of a light-sensitive material using the silver halide emulsion of the present invention is matted with the aim of reducing the gloss of the light-sensitive material, improving the ease of writing, and preventing the light-sensitive materials from sticking to each other. agent can be added.

A lubricant can be added to reduce the sliding friction of the light-sensitive material using the silver halide emulsion of the present invention.

An antistatic agent for the purpose of preventing static electricity can be added to a light-sensitive material using the silver halide emulsion of the present invention.

The antistatic agent may be used in the antistatic layer on the side of the support on which the emulsion is not laminated, and the protective colloid layer other than the emulsion layer on the side on which the emulsion layer is laminated with respect to the emulsion layer and/or the support. May be used for.

The photographic emulsion layer and/or the hydrophilic colloid layer of the light-sensitive material using the silver halide emulsion of the present invention may include improved coatability,
For the purpose of preventing static electricity, improving slipperiness, emulsification dispersion, preventing adhesion, improving photographic properties (promotion of development, hardening, sensitization, etc.), etc.
A variety of surfactants can be used.

The support used in the photosensitive material using the silver halide emulsion of the present invention is a flexible reflective support such as paper laminated with an α-olefin polymer (for example, polyethylene, polypropylene, ethylene/butene combination), or synthetic paper. Films made of semi-synthetic or synthetic polymers such as cellulose acetate, cellulose nitrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, polyamide, flexible supports with reflective layers on these films, glass, Includes metals, ceramics, etc.

The light-sensitive material using the silver halide emulsion of the present invention can be prepared by subjecting the support surface to corona discharge, ultraviolet irradiation, flame treatment, etc., if necessary, and then applying the adhesive properties, antistatic properties, and dimensions of the support surface directly or to the surface of the support. It may be applied through one subbing layer to improve stability, abrasion resistance, hardness, antihalation, friction properties and/or other properties.

When coating a photosensitive dye using the silver halide emulsion of the present invention, thickening (1) may be used to improve coating properties. Also, for things like hardeners, which have quick reactivity and will cause gelation if added to the coating solution before coating, it is best to mix them using a static mixer or the like just before coating. preferable.

In preparing the photosensitive material using the silver halide of the present invention, the silver halide emulsion layer and other protective colloid layers are prepared according to Research Disclosure.
[)isclosure) It can be applied by the method described in Section A of Xv of No. 17463, and dried by the method described in Section B of the same.

The photosensitive material using the silver halide of the present invention can be exposed using electromagnetic waves in the spectral region to which the emulsion layer constituting the photosensitive material has sensitivity. Light sources include natural light (sunlight), tungsten electric lamps, fluorescent lamps, mercury lamps, xenon arc lamps, carbon arc lamps, xenon flash lamps, cathode ray tube flying spots, various laser beams, light emitting diode lights, electron beams, X-rays, and gamma rays. Any known light source can be used, such as light emitted from a phosphor excited by alpha rays or the like.

The exposure time is not only the 1 millisecond to 1 second exposure time normally used in cameras, but also the exposure shorter than 1 microsecond, for example, 100 nanoseconds to 1 microsecond exposure using a cathode ray tube or xenon flash lamp. However, exposures longer than 1 second are also possible. The exposure may be performed continuously or intermittently.

[Examples] Specific examples of the present invention will be described in detail below, but the present invention is not limited to these embodiments.

Example-1 The following three types of silver chlorobromide emulsions A and BSC were prepared by the method described in Japanese Patent Publication No. 46-7772, and each was chemically sensitized using sodium thiosulfate pentahydrate, and then treated as a stabilizer. 4-Hydroxy-1,'1,3a,7-titrazyden was added.

For B, more pigment ゛)n・ was added to prepare a green-sensitive silver chlorobromide emulsion (B').

For C, further pigment Old 7. I+ was added to prepare a red-sensitive silver chlorobromide emulsion (C').

On a paper support laminated on both sides with polyethylene, the following layers were sequentially coated from the support side to prepare a surface latent image type silver halide color photographic light-sensitive material sample (2).

Layer 1...1.29/i2 gelatin, 0.32o/f
Blue-sensitive silver chlorobromide emulsion (silver bromide content 80 mol%) (A) of 0.80 (+/n' yellow) dissolved in 0.50 g/f of dioctyl phthalate. A layer containing coupler (Y-1).

Layer 2...0.70g/lz gelatin, 12mg/
1' anti-irradiation dye (A I-1),
Intermediate layer consisting of (AI-2) of 6ffl (1/l').

Layer 3...1.25+1/1m" gelatin, 0.25
0/i2 green-sensitive silver chlorobromide emulsion (silver bromide content 70 mol%) (B'), 0.30! A layer containing a magenta coupler (M-1) of 0,621)/l' dissolved in dioctyl phthalate of II/f.

Layer 4: Intermediate layer made of gelatin of 1.20Q/f.

Layer 5...1.20 (1/i' gelatin, 0.300
/i2 red-sensitive silver chlorobromide emulsion (silver bromide content 80 mol%
) (C') A layer containing a cyan coupler (C-1) of 0.45Q/f dissolved in dioctyl phthalate of 0.200/v'.

Layer 6...1.00(]/ml' gelatin and 0.2
0,30 dissolved in 00/f dioctyl phthalate
A layer containing a C1/i' ultraviolet absorber (UV-1).

Layer 7: A layer containing gelatin of 0.50Q/t'.

In addition, as a hardening agent, 2,4-dichloro-6-hydroxy-S-triazine sodium was added in layers 2.4 and 7.
Each was added in an amount of 0.017 (l) per 1 g of gelatin.

(Y-1) (AI-1) (AI-2) (UV-1) Cut the sample ■ into 8211 width, and cut the color negative film into A
Using a negative obtained by photographing with a camera using SAloo and performing color development processing, uniform image exposure was applied to the above cut sample using an auto color printer, and the following processing N001 was performed.

Processing conditions for Processing No. 11 Processing process Processing temperature ('C) Processing time 1 Color development 38.0 3 minutes 15 seconds 2 Bleach constant @ 3
8.0 1 minute 30 seconds 3 stable 32.0
The composition of the color developing solution used for 2 minutes is as follows.

Benzyl alcohol 16d diethylene glycol 16t12 optical brightener (
Note 2) 2g hydroxylamine sulfate 4g 3-methyl-4-amino-N-edyl-N-(β-methanesulfonamidoethyl)aniline sulfate 5.7g potassium carbonate 25 C1 potassium sulfite (50% solution) 5 potassium bromide 0.620 potassium chloride
0.5g potassium hydroxide
2.90 water
12 (pH 10, 2) (Note 2) Tinopal MSP (manufactured by CibaKykey) was used as a fluorescent whitening agent.

[Color developer replenisher] Benzyl alcohol 201e Diethylene glycol 201g Optical brightener (
Note 2) 2g hydroxylamine sulfate 4g 3-methyl-4-amino-N
- Ethyl-N-(β-methanesulfonamidoethyl)aniline sulfate 6.8g potassium carbonate
25g potassium sulfite (50%
solution) 6th grade potassium bromide
0.2g potassium hydroxide
1 with 2.3g water! (+) 810.42 ) [Bleach-fix solution] Iron ethylenediaminetetraacetate (I
) Finish to 12 with 10vQ water,
Adjusted to pl-17.5 with acetic acid and aqueous ammonia.

[Bleach-fixing replenisher] Iron ethylenediaminetetraacetate (I [[) Ammonium salt 80 Q Ammonium sulfite 10 Q Ammonium diosulfate 1800 Aqueous ammonia (28
%) 1 in 10mff1 water! ; pH was adjusted to 7.0 with acetic acid and aqueous ammonia.

[Stabilizing solution and stable replenishing solution] 2-Methyl-4-isothiazolin-3-one 0101 g 1-hydroxyethylidene-1,1-diphosphonic acid 1.5 g Finished up to 11 with water, pl-17 using potassium hydroxide, 0
Adjusted to.

The color developing replenisher is replenished into a 61Q color developing bath per 100 C1' of the light-sensitive material, and the bleach-fixing replenisher is replenished per 100 C1' of the light-sensitive material.
8. per cf. The Oi bleach-fix bath is replenished. Further, the stable replenisher is replenished at 10 d per 100 C of photosensitive material.

On the processing day, the sample was processed 20f per day. This treatment was carried out continuously for 30 days.

Further, the automatic developing machine used was an automatic developing machine RP-1200 manufactured by Noritsu Koki Co., Ltd.

In order to observe the photographic properties, the wedge-exposed sample was processed at the beginning of Process No. I and at the end of the 30-day process. The maximum yellow (Y), magenta (M), and cyan (C) densities and relative sensitivities of the processed samples are shown in Table 1 below.

Next, the following layers were sequentially coated on a resin-coated paper support from the support side to prepare an internal latent image type silver halide color photographic material sample (2).

Layer 1: cyan-forming red-sensitive silver halide emulsion layer according to the method described in JP-A-55-127549.
An internal latent image type silver halide emulsion was prepared.

That is, to 220 i12 of a 1 molar aqueous solution of potassium chloride containing 10 g of gelatin, 20 g of a 1 molar aqueous solution of silver nitrate was added at 60°C.
0. Q was added immediately. After physical aging for 10 minutes, a mixed solution of 200 iR of a 1 molar aqueous solution of potassium bromide and 50 vi of a 0.1 molar aqueous solution of potassium iodide was added. In order to coat the obtained conversion type silver chloroiodobromide grains with a silver chloride shell, 150 g of a 1 molar aqueous solution of silver nitrate was added.
1Q was added over a period of 5 minutes, and the mixture was physically aged for 20 minutes, followed by washing with water.

2,4-dichloro-3-methyl-6-[α-(2,4-di-tert-amyldeenoxy)butyramide]phenol 70o,2,5-di-t as cyan coupler
2 g of ert-octylhydroquinone, 50 g of dibutyl phthalate, and 140 g of ethyl acetate were mixed and dissolved, and added to a gelatin solution containing sodium isopropylnaphthalene sulfonate for emulsification and dispersion.

Next, the dispersion was added to the emulsion that had been spectrally sensitized with a dye, 1 g of potassium 2,5-dihydroxy-4-5eC-octadecyl-benzenesulfonate was added, and the bis(vinylsulfonylmethyl) ether was hardened. Added as a film agent, silver amount 400mQ/f
, the amount of coupler was 4601Q/1".

Layer 2: Intermediate layer 5 g of gray colloidal silver and 1 2,5-di-tert--octylhydroquinone dispersed in dibutyl phthalate
100 iQ of a 2.5% gelatin solution containing 0(+) was applied so that the amount of colloidal silver was 140010/1'.

Layer 3...Magenta-forming green-sensitive silver halide emulsion layer 1-(2,4,6-dolichlorophenyl)-3-(2-chloro-5-octadecylsuccinimidoanilino)-5-pyrazolone as magenta coupler 40g, 2.5
-G-tert-- 1 g of octylhydroquinone, 75 g of dioctyl phthalate, and 30111 ethyl acetate were mixed and dissolved, and added to a gelatin solution containing sodium isopropylnaphthalene sulfonate for emulsification and dispersion. Next, the dispersion was added to the emulsion that had been spectrally sensitized with the dye F+, and 1 g of potassium 2,5-di-hydroxy-4-5ec-octadecylbenzenesulfonate was added to harden the bis(vinylsulfonylmethyl) ether. Added as a film agent, silver amount 400 rao
/f, and the coupler was once applied so that it became 400Il+J/w'.

Layer 4...Yellow filter 1 yellow layer A 2.5% gelatin solution containing 5 g of colloidal silver and 5 g of 2,5-di-tert-octylhydroquinone dispersed in dibutyl phthalate was mixed with 200 g of colloidal silver.
1 (J/m').

Layer 5... Yellow-forming blue-sensitive silver halide emulsion layer α-[4-(1-benzyl-) as a yellow coupler
2-phenyl-3,5-dioxo-1゜2,4-driazolidinyl)]-]α-bivalyl-2-chloro-5-γ
-(2,4-di-tert-amylphenoxy)butylamitocoacetanilide 80 g, 2,5-di-tart
1 g of quinone and 200 g of dibutyl phthalate 80o1 ethyl acetate were mixed and dissolved, added to a gelatin solution containing sodium isopropylnaphthalene sulfonate, and emulsified and dispersed. The dispersion was then added to the emulsion and 2°5-dihydroxy-4-5ec-
Potassium octadecyl-benzenesulfonate 10 was added, bis(vinylsulfonylmethyl)ether was added as a hardener, silver ff 1380!11! ] /f, coupler fi1530m(]/v'.

Layer 6...protective layer It was applied so that the gelatin thickness was 200 ma/f.

Note that Layer 1, Layer 2, Layer 3, Layer 4, Layer 5, and Layer 6 contained saponin as a coating aid.

The sample (2) thus obtained was cut to a width of 82 mm, photographed on color reversal film, and using the positive obtained by color development processing, the cut sample was given a uniform image exposure using an auto color printer. Automatic developing machine R P 1200 manufactured by A4 Machine Co., Ltd.
The following processing No. was carried out using a modified automatic processor.

2, 3, 4, 5, 6, 7, 8, 9 and 10 were performed.

(Processing conditions for processing No. 2, 3, 4, 5, 6, 7, 8, 9 and 10) Processing process Processing temperature ('C) Processing time 1 Color development Change 3 minutes (Full surface (Table 2) Exposure was set so that 10 seconds after the sample entered the color developer, it was irradiated with 1 LuX light for 10 seconds) 2 Bleach-fixing 35.0 1 minute 30 seconds 3 Ans.
Constant 32.0 Except for changing the bromide ion concentration (degree of Brm at the start of treatment) of the 2-minute color developer as shown in Table 2, the composition of the color developer was the same as the treatment No. Same as 1.

The replenisher for the color developer is Process No. The same as 1,
Processing No. 2, 3 from the color developer replenisher tank of Processing No. 1
, 4, 5, 6, 7, 8, 9 and 10, respectively. The amount of replenisher for the color developing solution was set as shown in Table 2 so that the bromide ion concentration at the start of the process was maintained.

The processing temperature of the color developer was adjusted at the start of each treatment as shown in Table 2 so as to obtain equivalent positive densities.

The compositions of the bleach-fix solution, bleach-fix replenisher, stabilizer, and stable replenisher were the same as in Process No. 11, and the amount of replenisher and the number of processing ports per day were also the same as in Process-1, and the treatment was continued for 30 days. .

As replenishers for bleach-fixing and stabilizing solution, those contained in the bleach-fixing replenisher tank and the stabilizing replenisher tank of Processing-1 were used in the same manner as for the color developing replenisher.

The above sample (1), which had been exposed to wedge light in order to examine its photographic properties, was processed at the start of processing and at the end of 30 days of processing.

The maximum densities and relative sensitivities of yellow (Y), magenta (M), and cyan (C) of the processed samples are shown in Table 2 below.

From the results in Table 1, it can be seen that good images were obtained with the surface latent image type silver halide photographic light-sensitive materials.

On the other hand, from the results in Table 2, it can be seen that for internal latent image type silver halide photographic light-sensitive materials, the processing liquid replenishment method according to the present invention (
It can be seen that according to processing Nos. 094 to 8), the processing ability of the processing liquid does not change even if continuous processing is performed, and high-sensitivity and good positive images can be stably obtained. Furthermore, since the same replenisher as that used in surface latent image type silver halide photographic light-sensitive materials is used, installation and management of replenisher tanks can be reduced accordingly.

Claims (1)

[Claims] An internal latent image type silver halide photographic light-sensitive material having at least one emulsion layer containing internal latent image type silver halide grains whose grain surfaces are not fogged in advance, and a surface latent image type silver halide grain. A method of processing surface latent image type silver halide photographic light-sensitive materials having at least one emulsion layer in separate processing lines, in which at least the internal latent image is The same replenishment solution is supplied to the development tanks for developing the type silver halide photographic light-sensitive material and the surface latent image type silver halide photographic light-sensitive material, and the development processing of the internal latent image type silver halide photographic light-sensitive material. A treatment liquid characterized in that the amount of replenisher is set so that the bromide ion concentration in the tank is maintained at 5.0 x 10^-^3 to 2.0 x 10^-^2 gram ions/l. How to replenish.