JPH0468347A - Processing method for silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To shorten the processing time for washing or stabilizing and to prevent the degradation in preservable property by subjecting the silver halide color photosensitive material having a high silver chloride content to development processing by using a specific developing agent. CONSTITUTION:A silver halide emulsion contains >=90mol% silver chloride and the color developing soln. contains at least one kind of the compds. expressed by formula I. In addition, the processing time for washing and/or stabilizing is confined within 40 seconds. In the formula I, R1 denotes a substituent; (n) denotes 0 to 4 integer; R2 denotes an alkyl group; R3 denotes an alkylene group of >=2C main chain; R4 denotes a hydrogen atom or alkyl group. X denotes the compd. of formula II. In the formula II, R5 and R7 respectively denote a hydrogen atom. alkyl group or aryl group; R6 denotes alkyl group or aryl group. The images which have the high image density in the rapid processing and lessen the generation of stains in the rinsing treatment of a short period of time are obtd. in this way.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a method for processing silver halide color photographic materials, and more specifically, to a method for processing a silver halide color photographic light-sensitive material, and more specifically, to produce an image that has excellent color image fastness and less staining after image storage. The present invention relates to a rapid processing method for photosensitive materials capable of capturing and supplying.

(Prior Art) In recent years, higher efficiency and higher productivity have been required for processing color photographic materials. This trend is especially noticeable for color print production.
There is a strong desire to shorten printing processing time due to the need for quick finishing.

As is well known, the process of finishing a color print consists of exposure and color development. Using highly sensitive photosensitive materials leads to shorter exposure times. On the other hand, in order to shorten the color development processing time, it is essential to realize a system that combines a photosensitive material and a processing solution or processing method that can speed up development.

As a technology to achieve these issues, we have proposed an alternative to silver chlorobromide emulsion with a high silver bromide content, which has been widely used in conventional photosensitive materials for color printing (hereinafter referred to as color photographic paper). A method of processing a color photographic light-sensitive material containing an emulsion (high silver chloride emulsion) is known.For example, International Patent Publication No. WO87-04534 discloses a method of processing a color photographic light-sensitive material containing a high silver chloride emulsion. A method of rapid processing with a color developer free of sulfite ions and Hensyl alcohol is disclosed.

In addition to the above-mentioned patent, JP-A No. 61-70552 discloses a method for reducing the developer solution by using a high-silver chloride color photographic light-sensitive material and adding a replenishing amount to prevent overflow into the developer bath during development. A method for replenishment is described, and furthermore,
3-106655, for the purpose of stabilizing the process,
A method is disclosed in which a high-silver chloride color photographic material is processed with a color developing solution containing a hydroxylamine compound and a chloride ion concentration above a certain level.

In this way, by using a high silver chloride emulsion and devising a developing processing solution, development time can be improved from 3 minutes and 30 seconds in the conventional silver chloride bromide emulsion system (for example, Fuji Photo Film ■ color processing CP-20) to 45 seconds. Although the total processing time was shortened to 4 minutes (e.g. Fuji Photo Film's color processing CP-40FMS), compared to the total processing time of other single color methods (e.g. electrostatic transfer method, thermal transfer method, inkjet method). However, it is still difficult to say that the level is satisfactory.

Therefore, it is desired to develop a silver halide color photosensitive material for ultra-rapid processing that significantly shortens the total processing time by using a silver halide color development method that allows high-quality color prints to be obtained at low cost. .

On the other hand, there have been many proposals to use paraphenylenediamine compounds, particularly N,N-dialkyl-substituted paraphenylenediamine compounds, as color developing agents added to color developing solutions. For example, as examples of devised alkyl groups substituted at the N-position, U.S. Pat.
No. 015, No. 2,552.240, No. 2,566.2
No. 71, U.S. Pat. No. 2,193.015 regarding N-sulfamoylalkyl groups, U.S. Pat. No. 2,552,242, U.S. Pat.
No. 2.363, U.S. Patent No. 2,374.337 regarding N-acylalkyl groups, U.S. Patent No. 2,603,656 regarding N-flukoxyalkyl groups, etc.
No. 1534, No. 47-11535, Special Publication No. 54-16
No. 860, No. 58-14670, No. 58-23618
British Patent No. 81L67 relating to N-sulfoalkyl groups
No. 9, U.S. Pat. No. 2,716 regarding N-aralkyl groups.
It is described in No. 132, etc. In addition, as for substituents on Hensen's nucleus, U.S. Pat. No. 2,304,953 and U.S. Pat.
U.S. Pat. No. 2,552,240, U.S. Pat. No. 2,592,364, regarding nuclear acylamino sulfonamide groups, U.S. Pat. Regarding alkyl groups, U.S. Patent Nos. 2,552,241 and 2.556271
No. 2,592,364; U.S. Patent Nos. 2,570.116 and 2,575,027 regarding nuclear amino groups;
No. 2,652,331 and British Patent No. 872,683 regarding the nuclear thiosulfonic acid group. Regarding the use of analogs of phenylenediamine as color developing agents, U.S. Pat. No. 2.196.739 and U.S. Pat. U.S. Patent No. 2,612 for phenyl)hexamethyleneimine series
, 500, and US Pat. No. 2,707,681, etc. regarding the 9-aminojulolidine system.

Under these circumstances, in order to effectively shorten not only the color development processing time but also the total processing time, it was necessary to reduce the time not only in the color development step but also in the steps after bleach-fixing.

(Problem to be Solved by the Invention) However, with conventional developing agents, even if it is possible to shorten the development time, if you try to shorten the time of the subsequent processing steps, the shelf life of the prints will be significantly impaired. The current situation is that speed and other performance are not satisfied, such as deterioration.

In particular, when the water washing or stabilization process is simplified and speeded up, the amount of developer components and bleach-fix solution components remaining in the photosensitive material is significantly greater than when the water washing or stabilization processing is carried out using conventional processing times.

It has been known for a long time that the residual components of the developer and bleach-fixer on the photosensitive material affect the storage stability of prints. Residual color developing agent reacts with unreacted coupler over time, resulting in undesirable staining. Further, if the bleaching component remains, the photosensitive material becomes an oxidizing atmosphere, which causes yellow stain, especially under high humidity and high temperature.

Regarding the removal of these residual chemicals from photosensitive materials, Haruhiko Iwano, Takatoshi Ishikawa, and Moto Furusawa et al. presented a paper entitled "The Chemistry of Wonthing" at the 5th International Symposium on Photofining Technology (Chicago, 1986). The Way to Ensure Photoprocessing Quality at Minilab J (The Chemlst
ry of Washing'The hJa
yt.

ensure Photoprocessing Qu
arity at Minilabs J), it is effective to set the washing time, washing temperature, and stirring speed appropriately to remove the developing agent. Increasing the amount of washing water and multistage countercurrent flow are effective, and this difference (difference between means for promoting the removal of developing agent and means for promoting the removal of bleach)
There is knowledge that it depends on the magnitude of interaction with the binder.

Particularly in ultra-rapid processing, it has been found that the shelf life (increase in staining, decrease in dye density) of prints subjected to continuous processing is extremely deteriorated due to the reduction in washing time that accompanies ultra-rapid processing.

These stains tend to be improved if the pH of the photosensitive material is kept low, but if the pi is lowered, the fading of cyan and yellow becomes worse under high humidity and high temperature.

JP 58-14834, JP 61-20864, JP 60263939, JP 61-170742, JP 58-132743 and JP 61-151538
The publication discloses a technique for preventing coloring components from being introduced into a light-sensitive material or rendering the material colorless when washing with water is not sufficient. However, in either case, ultra-quick processing requires much less washing or stabilization time and the amount of washing, so it inevitably introduces a larger amount of developer and bleach-fixer components than conventional washing, making it less effective. , especially in continuous processing, more coloring components remain in the photosensitive material, and as a result, if the finished print is stored under high temperature and high humidity, staining may occur in white areas and color usage of dyes may deteriorate. The value of the product had declined.

On the other hand, if the processing time of the desilvering process is shortened, so-called desilvering failure and staining in unexposed areas are likely to occur.

For example, a method has been disclosed in which a photosensitive material using a silver halide emulsion with a high silver chloride content is processed with a specific bleach-fix solution (JP-A-1-196052, JP-A-63-4).
No. 0154, No. 63-14149, No. 62-2491
No. 47, No. 62-246055). These specifications describe a method for maintaining the PL+ of the bleach-fixing bath at 4.5 to 6.8 and a method for containing bromide ions and iodide ions at appropriate concentrations in order to suppress desilvering failure and staining in unexposed areas. Although methods are disclosed, according to the examples described therein, both color development and bleach-fixing are performed at 45 to
The processing time was approximately 60 seconds, which was still insufficient to meet the market's demand for rapid processing.

In addition, a technique has been disclosed that discloses that a specific bleach-fixing solution is preferable in relation to the color development process (Japanese Patent Application Laid-Open No. 63-1989-1).
According to their specifications (No. 46455, No. 62-229144), after a development process is performed using a color developer with an extremely low sulfite concentration or a color developer containing a specific color developing agent and solvent. , a method of suppressing staining in unexposed areas by treating with a specific bleach-fixing solution has been shown.

According to the experience of the present inventors, when speeding up the bleach-fixing process, the influence of the color development process, which is the preceding stage, is extremely large; It is desired that a technology with high image storage stability even after fixing be developed.6 Furthermore, as a technology to shorten the hot bath processing time from color development to water washing in the development process, high silver chloride emulsions can be converted into henol alcohol. A special method is to process with a color developing solution that does not contain . Although disclosed in Japanese Patent Publication No. 1-196044, it has been found that this technique alone is still insufficient to solve the above problems.

As is clear from the foregoing, the purpose of the present invention is to provide high quality prints that can be processed extremely quickly, and to provide finished prints with excellent storage stability under high temperature and high humidity conditions, especially with no increase in stain. The object of the present invention is to provide a method for processing silver halide color photographic materials that have a small amount of color and have excellent color image fastness.

(Means for Solving the Problem) The above object of the present invention is to provide a color photographic material having at least one silver halide emulsion layer on a support, after exposure, color development, and desilvering treatment, followed by washing with water and/or Alternatively, in a processing method in which the silver halide emulsion is stabilized and dried, the silver halide emulsion is
Contains 0 mol% or more of silver chloride, the color developing solution contains at least one compound represented by the following general 2 (1), and the water washing and/or stabilization treatment time is within 40 seconds. It has been found that the problem can be solved by a method for processing silver halide color photographic material 4 characterized by the following.

-Ritual (1: R25, /R1-N-×H2 (In the formula, R1 represents a substituent. n represents an integer from 0 to 4. When n is 2 or more, R1 may be the same or different. Good.R2 represents an alkyl group.R3 represents an alkylene group whose main chain has 2 or more carbon atoms.R4 represents a hydrogen atom or an alkyl group.X represents.In this case, R1 and R1 in the formula are each Represents a hydrogen atom, an alkyl group, or an aryl group.R.

represents an alkyl group or an aryl group. ) That is, according to the present invention, a silver halide color photosensitive material Zero 4 with a high silver chloride content is prepared by using the novel developing agent represented by the above-mentioned formula N).
Surprisingly, even if the subsequent washing or stabilization time is shortened to 40 seconds or less, the deterioration in storage stability that is thought to be caused by the residual coloring components as described above can be resolved. found.

In the present invention, the water washing process (including the stabilization process, that is, the water washing process, the water washing and stabilization process, and the stabilization process) is shortened to within 40 seconds. It has been known for a long time that if the washing process is carried out very quickly, the remaining color developing agents, bleaching agents, and fixing agents will significantly deteriorate the shelf life of the prints.

The developing agent, which is one of the major causes of staining, is that by using the new developing agent of formula (1) of the present invention, the amount used can be relatively small, and that the scales can be considerably removed even in the next step, the bleach-fixing bath. It is presumed that this invention works advantageously in shortening the water washing step according to the present invention because the removal rate can be reduced by adjusting the temperature, stirring speed, etc.

The invention will be further explained below.

First, the compound represented by the above-mentioned form N) in the present invention will be described in detail.

In the present invention, R1, R2, R3, R4, R5, R6, R1, X and n in the compound represented by general 2 [I] will be described in detail below.

R1 is a substituent; more specifically, R1 is a nor\logen atom, an alkyl group, an aryl group, a heterocyclic group, a cyano group,
Nitro group, hydroxyl group, carboxyl group, alkoxy group, aryloxy group, acylamino group, alkylamino group, anilino group, ureido group, sulfamoylamino group, alkylthio group, arylthio group, alkoxycarbonylamino group, sulfonamide group, Carbamoyl group, sulfamoyl group, sulfonyl group, alkoxycarbonyl group, heterocyclic oxy group, azo group, acyloxy group,
Carbamoyloxy group, silyl group, silyloxy 45,
It represents an aryloquinolponylamino group, an imide group, a heterocyclic thio group, a sulfinyl group, a phosphonyl group, an aryloxycarbonyl group, or an anlu group.

More specifically, R5 is a halogen atom (for example, a fluorine atom,
chlorine atom), alkyl group, (preferably 1 to 16 carbon atoms)
linear, branched or cyclic alkyl groups, including alkenyl, alkynyl, hydroxyl, nitro,
It may be substituted with a cyano group, a halogen atom, or another substituent linked to an oxygen atom, nitrogen atom, sulfur atom, or carbonyl group, such as methyl, ethyl, propyl, isopropyl, t-butyl, 2-hydroxyethyl, 3 -Hydroxypropyl, 2-methanesulfonamidoethyl, 3-methanesulfonamidopropyl, 2-methanesulfonylethyl, 2-methoxyethyl, cyclopentyl, 2-acetamidoethyl, 2-carboxyethyl, 2-carbamoylethyl, 3-carbamoylpropyl , n-hexyl, 2-hydroxypropyl, 4-hydroxybutyl, 2-carbamoylaminoethyl, 3-carbamoylaminopropyl, 4-carbamoylamino/butyl, 4-carbamoylbutyl, 2-carbamoyl(1-
(methyl)ethyl, 4-nitrobutyl), aryl groups (e.g. phenyl, naphthyl, Pmethquinphenyl), heterocyclic groups (e.g. 2furyl, 2-thienyl, 2-pyrimidinyl, 2hencytriazolyl, imidazolyl, pyrazolyl) ), cyano group, nitro group, hydroxyl group, carboxyl group, alkoxy group (e.g., methoxy, ethyne, 2-methoxyethoxy, 2-methanesulfonylethoxy), aryloxy group (e.g., phenoxy), acylamino group (e.g., acetamide, 2-methoxypropionamide), alkylamino groups (e.g. dimethylamino, diethylamino), anilino groups (e.g. anilino, m-nitroanilino), ureido groups (e.g. methylureido, N,N-diethylureido), sulfamoylamino groups (e.g. dimethylsulfamoylamino), alkylthio groups (e.g. methylthio, ethylthio), arylthio groups (e.g. phenylthio), alkoxycarbonylamino groups (e.g. methoxycarbonylamino, ethoxycarbonylamino), sulfonamyl groups (e.g. methanesulfonamide), carbamoyl group (e.g. NN-dimethylcarbamoyl, N-ethylcarbamoyl), sulfamoyl group (e.g. dimethylsulfamoyl), sulfonyl group (e.g. methanesulfonyl, ethanesulfonyl), alkoxycarbonyl group (e.g. methoxycarbonyl, ethoxycarbonyl), heterocyclic oxy groups (e.g. 1-phenyltetra-
zolyl-5-oxy, 2-tetrahydrobilanyloquino), ab groups (e.g., phenylazo, 2-hydroquine-
4-propanoylphenylazo), acyloxy groups (e.g. acetoxy), carbamoyloxy groups (e.g.
NN-dimethylcarbamoyl group, silyl group (e.g., trimethylsilyl), nitrogenyloxy group (e.g., trimethylnoryloxyquino), aryloquine group (e.g., phenoxocarbonylamino), imide group (e.g., N-scunnimide), petro ring Thio group (
For example, 2-hendithiazolylthio, 2-pyridylthio), sulfinyl groups (e.g. ethanesulfinyl),
It represents a phosphonyl group (for example, methoxyphosphonyl), an aryloquine group (for example, phenoxycarbonyl), an anlu group (for example, acetyl, hendyl).

Among these substituents, R1 is preferably an alkyl group, an alkoxy group, an alkoxycarbonylamino group, or a ureido group, more preferably an alkyl group, and among these, a methyl group and an ethyl group are particularly preferred.

n represents an integer from 0 to 4. When n is 2 or more, R5 may be the same or different. Preferably n is O or 1, more preferably n is 1.

R2 is an alkyl group, more specifically, R2 is an alkyl group (a linear, branched, or cyclic alkyl group having 1 to 16 carbon atoms; these include an alkenyl group, an alkynyl group, a hydroxyl group, a nitro group, an ano group, a halogen It may be substituted with a substituent linked to an atom or other oxygen atom, nitrogen atom, sulfur atom or carbonyl group, such as methyl, ethyl, propyl, isopropyl, butyl, 2
-Hydroxyethyl, 3-hydroquinepropyl, 2-methanesulfonamidoethyl, 3-methanesulfonamidopropyl, 2-methanesulfonylethyl, 2-methoxyethyl, nclopentyl, 2-acetamidoethyl, 2
-Carboxylethyl, 2-carbamoylethyl, 3-carbamoylpropyl, n-hexyl, 2-hydroxypropyl, 4-hydroxybutyl, hensyl, 2-carbamoylaminoethyl, 3-carbamoylaminopropyl, 4-carbamoylaminobutyl, 4-carbamoyl butyl, 2-carbamoyl(1-methyl)ethyl, 4-nitrobutyl).

Among these substituents, preferred R2 is methyl,
Ethyl, propyl, isopropyl, t-butyl, 2-hydroxyethyl, 3-hydroxypropyl, 2-methochinoethyl, 2-methanesulfonamidoethyl, 2-acetamidoethyl groups, more preferably methyl, ethyl, propyl, isopropyl, It is a t-butyl group.

R3 is an alkylene group, more specifically, R3 is an alkylene group whose main chain has two or more carbon atoms (a straight or branched alkylene group, and these include a hydroxyl group, a nitro group, an ano group, a halogen atom or other oxygen atom, It may be substituted with a substituent linked to a nitrogen atom, a sulfur atom, or a carbonyl group (for example, ethylene, 2-methylethylene, 2-fluoropropylene, propylene, tetramethylene, pentamethylene, hexamethylene, 2-methylpropylene). , 2-methoxypropylene, -methylbutylene, l-methylethylene).

Among these substituents, preferred R1 is ethylene, 2-methylethylene, propylene, tetramethylene,
2-methylpropylene and 1-methylethylene groups.

R4 is a hydrogen atom or an alkyl group, more specifically, R4 is a hydrogen atom or an alkyl group (a straight-chain or branched alkyl group having 1 to 16 carbon atoms, which is a hydroxyl group,
It may be substituted with a nitro group, carboxyl group, soano group, halogen atom, or other substituents linked to an oxygen atom, nitrogen atom, sulfur atom or carbonyl group, such as methyl, ethyl, propyl, butyl, 2- hydroxyethyl, 2-carboxyethyl, 3-sulfopropyl, isopropyl, 3-(11,11-dimethyl)aminopropyl).

Among these, R4 is preferably a hydrogen atom, methyl, or ethyl group, and more preferably a hydrogen atom.

Here, R1 and R7 each represent a hydrogen atom, an alkyl group, or an aryl group; more specifically, R1 and R7 each represent a hydrogen atom, an alkyl group (a straight-chain or branched alkyl group having 1 to 16 carbon atoms, and may be substituted with a hydroquine group, a nitro group, a carboxyl group, a cyano group, a halogen atom, or other substituents linked to an oxygen atom, a nitrogen atom, a sulfur atom or a carbonyl group, such as methyl, ethyl, propyl, t- butyl, 2-hydroquinethyl, 2-carboxyethyl, 3-sulfopropyl, isopropyl, 3-(N,N-dimethyl)aminopropyl), aryl group (e.g. phenyl, naphthyl, p-methquinphenyl) .

Among these, preferred R1 is a hydrogen atom or an alkyl group, with a hydrogen atom being particularly preferred.

R7 is also preferably an alkyl group or an aryl group, more preferably an alkyl group, with methyl and ethyl groups being particularly preferred.

R6 represents an alkyl group or an aryl group; more specifically, R6 represents an alkyl group (a linear or branched alkyl group having 1 to 16 carbon atoms; these include a hydroquinyl group, a nidotetra group, a carboxyl group, a cyano group, a halogen atom, or It may also be substituted with a substituent linked to an oxygen atom, nitrogen atom, sulfur atom, or carbonyl group, such as methyl,
ethyl, propyl, butyl, 2-hydroxyethyl, 2-carboxyethyl, 3-sulfopropyl, isopropyl, 3-(N,N-dimethyl)aminopropyl),
Aryl groups (eg, phenyl, naphthyl, pmethoxyphenyl) are represented.

Among these, preferred R6 is an alkyl group, with methyl and ethyl groups being particularly preferred.

Among the compounds represented by the -format [■], particularly preferred compounds include the compounds represented by the following general formula CII).

General formula (If) H2 (In the formula, R1, R2, R3, R4 and X have the same meanings as above.) Compounds represented by general formulas (1) and (II) can be Since it is very unstable, it is generally preferable to produce and store it as a salt of an inorganic acid or an organic acid so that it becomes a free amine only when it is added to the processing solution. Examples of inorganic and organic acids for forming salts of compounds of formats [1] and (II) include hydrochloric acid, sulfuric acid, phosphoric acid, p-toluenesulfonic acid, methanesulfonic acid, and naphthalene-15-disulfonic acid.

Next, specific examples of typical developing agents in the present invention will be shown, but the present invention is not limited thereto.

(1) C) I:+\/CHzCHJHCONH
zKO'C311fu\ / CH2CHz CHz N HC
ON H2~ H2 C1h C,)ll,,, ,CHzGHzCl(zcHzN)
ICONHCzt(sH3 'CzHz\yCHzCH2NCONHztC1111
17\/Ct(zcHzc)I2NHC(IN)Icm
171)Hz NH! υ CzHCHzCHzCHJHCONL 5\/ Nfl.

Nut Ntlχ N11= NH2 Regarding the general method for synthesizing the developing agent of the present invention, the developing agent of the present invention can be synthesized according to the method described, for example, on page 3100 of Journal of the American Chemical Society 73t=. You can.

The amount of the aromatic primary amine developing agent used is preferably 1 mmol to 200 mmol, more preferably 5 mmol to 100 mmol, per developer solution 11.

In the present invention, furthermore, a silver halide color photosensitive material having a high silver chloride content is developed using a novel developing agent represented by the above-mentioned format (1), and the color developing agent in the photosensitive material film is removed from the photosensitive material 1rrf. It has been found that when desilvering is carried out in a bleach or bleach-fixing solution at a concentration of 1 mmol or less per unit, images with less staining and less staining can be obtained even if desilvering is performed within 30 seconds.

It is presumed that the reason is the same as the factor that made it possible to shorten the water washing step by using the novel developing agent of formula (1) according to the present invention.

In order to reduce the amount of color developing agent in the photosensitive material film to 1 mmol/po or less, for example, the swollen film thickness of the photosensitive material is reduced (
For example, adjusting the amount of gelatin, which is a hydrophilic binder, and the amount of hardening agent), after color developing the photosensitive material, washing it with water or spreading it in less than neutral water or a buffer solution to remove the color developing agent; Examples include a method of reducing the amount of a high boiling point organic solvent as a dispersion medium.

It is also possible to carry out bleach-fixing after removing the color developing agent by washing with the color developing agent, but this is not preferable for ultra-rapid processing because of the increased number of baths and processing time.

In the present invention, since bleach-fixing can be performed while limiting the color developing agent in the light-sensitive material film, the amount of replenishment of bleach-fix solution and washing solution during continuous processing can also be greatly reduced.

Therefore, by further taking the above measures, it has become possible to simultaneously achieve processing with low replenishment of each processing solution and ultra-rapid processing.

For example, the amount of replenishment of color developer is 120
d or less, and further replenish the amount of bleach or bleach-fix solution and washing water or stabilizing solution by 3 times the amount of pre-bath brought in per unit area of light-sensitive material.
It can be up to twice as much.

Color photographic materials contain hydrophilic binders (for example, gelatin, polymeric compounds such as polyacrylamide), and the swelling characteristics of the film in the processing solution can be changed depending on the type and amount of the hardening agent. I can do it. In the present invention, in order to allow the processing liquid to penetrate quickly, the membrane swelling time (the time to reach 80% of the maximum swollen membrane thickness when measured using a color developer with a known swelling membrane) is 15 seconds or less. It is preferable that the maximum swelling film thickness is 20 or less. By this adjustment, the remaining amount of various components in the photosensitive material film can be reduced, and elution to the outside of the film can also be achieved quickly. Additionally, the drying load can be greatly reduced.

Furthermore, the alkali consumption of the photosensitive material was reduced to 3.0 m5 ol/
It has been found that by setting the rrf or less, it is possible to further speed up the processing, and even if the color development processing time in the development processing step is shortened to 25 seconds or less, a very high quality image can be obtained.

In the present invention, the "alkali consumption amount" of a photosensitive material is measured and calculated by the following measuring method.

The means for calculating the "alkali consumption" is as follows: First, a certain area (specifically, one area) of the photosensitive material of the present invention is sampled, and the sample is peeled off between the support and the coating layer. A typical support is paper laminated with polyethylene, which can be peeled off between the eyebrows. Next, crush the coating layer side finely and add a certain amount of water (specifically 100 mN).
). Next, add this liquid to alkaline water/8 liquid (
Specifically, 0. Titrated with IN potassium hydroxide solution) and p
H6,0 to ρ)110. (The amount of potassium hydroxide required to reach 1 is defined as the "alkali consumption amount" in millimole units.

If the support contains an acid component and cannot be removed as described above, evaluation can be made by subtracting the measured value of the support alone.

This alkali consumption rate evaluates the acid component contained in the photosensitive material and its pH buffering ability.
Specifically, it is affected by gelatin, which is a hydrophilic binder, and other organic compounds in the photosensitive material.

In the present invention, if the amount of alkali consumed is large, the high alkalinity during initial development cannot be maintained, so the initial development is delayed and it is not possible to shorten the development processing time. This is thought to have an effect on the occurrence of staining when ultra-rapid treatment is performed, and by using the compound of the present invention in combination, unexpected effects were obtained.

In order to reduce "alkali consumption" which is a feature of the present invention, the following method is preferred.

First, hydrophilic colloids having acidic groups in the sensitive material layer are reduced.

Gelatin is most preferably used as the hydrophilic colloid in a color photographic light-sensitive material using a silver halide emulsion as a photosensor. However, gelatin has a pH buffering capacity against the penetration of alkaline solutions due to its functional groups.

Lowering this buffering capacity is important for speeding up the initial development in rapid processing, and a method of reducing the amount of gelatin is preferred.

Second, gelatin reduction alone may deteriorate membrane physical properties, and therefore is used in combination with a hydrophilic polymer that does not have acidic functional groups.

As the hydrophilic polymer that can be used in the present invention, those exemplified in the present specification can be used, and polyacrylamide, polydextran, polyvinyl alcohol, and the like are particularly preferably used.

Thirdly, the type of gelatin used as the hydrophilic colloid is changed.

Specifically, by changing the processing method during gelatin production, or by using esterified gelatin or amidated gelatin with fewer acid groups in gelatin, we can change the number of functional groups and change the isoelectric point, thereby reducing alkali consumption. It can be suppressed.

Fourth, the amount of organic compound materials other than gelatin (specifically, couplers, hydroquinone, phenolic compounds, etc.) used is reduced. When such means are used in combination with a hardening agent, it is also possible to form a photosensitive material with a rapid initial swelling rate.

Fifth, the alkali consumption can be reduced by adjusting the pka value of the organic compound mentioned in the fourth section.

As described above, in the present invention, it is preferable to suppress the "alkali consumption" of the photosensitive material. The alkali consumption amount is 3.0 mmol/rrr or less, but preferably 2.0 mmol/rrr or less.
．． 8mm to 17mm below, more preferably 2.6 fights of/
or less, particularly preferably 1.9 mmol/rr? It is as follows.

The color photographic light-sensitive material of the present invention can be constructed by coating at least one pre-malignant silver halide emulsion layer, one green-sensitive silver halide emulsion layer, and one red-sensitive silver halide emulsion layer on a support. . In general color photographic paper, the layers are usually coated on the support in the above order, but they may be applied in a different order.

Imaging systems including the useable photosensitive materials and processes of the present invention can be used for the rapid processing of commonly used color prints, but can also be used for intelligent color hardcopy applications where speed is more desired.

In particular, as an embodiment of the intelligent color hard copy, an embodiment in which scanning exposure is performed using high-density light such as a laser (for example, a semiconductor laser) or a light emitting diode is preferable.

Many semiconductor lasers have high photosensitivity in the infrared region, and in the photosensitive material used for this purpose, an infrared window-sensitive silver halide emulsion layer can be used in place of at least one of the above-mentioned emulsion layers. These photosensitive emulsion layers contain silver halide emulsions sensitive to respective wavelength ranges, and dyes that are complementary colors to the light to which they are exposed - yellow for blue, magenta for green, and cyan for red. By containing a so-called color coupler, subtractive color reproduction can be performed. However, the coloring hues of the photosensitive layer and the coupler may not correspond as described above.

Furthermore, depending on the required image quality and quality, the color coupler may be of two colors. In this case, the number of silver halide emulsion layers corresponding to each layer may be two.

In this case, although a full-color direct image is not obtained, it is possible to form an image more quickly.

As the silver halide emulsion used in the present invention, one consisting of silver chlorobromide or silver chloride that does not substantially contain silver iodide can be preferably used. Here, "substantially free of silver iodide" means that the silver iodide content is 1 mol% or less, preferably 0.2 mol% or less. The halogen composition of the emulsion may be different or the same among the grains, but if an emulsion having the same halogen composition among the grains is used, it is easy to make the properties of each grain uniform. In addition, regarding the halogen composition distribution inside silver halide emulsion grains, there are grains with a so-called uniform structure in which the composition is the same in every part of the silver halide grain, and grains with a core inside the silver halide grain and a shell surrounding it. (Shell) [-layer or multiple layers] Particles with a so-called laminated structure in which the halogen composition is different, or
Particles with a structure that has parts with different halogen compositions in a non-layered manner inside or on the particle surface (if it is on the surface of the particle, parts with different compositions are joined on the grain, corner, or surface of the particle) are appropriately selected. It can be used as In order to obtain high sensitivity, it is more advantageous to use one of the latter than particles with a uniform structure, and it is also preferable from the viewpoint of pressure resistance. When the silver halide grains have the above structure, the boundaries between the parts that differ in halogen composition are
The boundaries may be clear, or may be unclear due to the formation of mixed crystals due to compositional differences, or may have continuous structural changes.

Regarding the halogen composition of these silver chlorobromide emulsions, any silver bromide/silver chloride ratio can be used. Although this ratio can vary widely depending on the purpose, a silver chloride ratio of 2% or more is preferably used.

Further, so-called high-silver chloride emulsions having a high silver chloride content are preferably used in light-sensitive materials suitable for rapid processing. The silver chloride content of these high silver chloride emulsions is preferably 90 mol% or more, more preferably 95 mol% or more.

Such a high silver chloride emulsion preferably has a structure in which the silver bromide localized phase is present inside and/or on the surface of the silver halide grains in a layered or non-layered manner as described above. The halogen composition of the localized phase preferably has a silver bromide content of at least 10 mol%, more preferably more than 20 mol%. These localized phases can be located inside the particles, or on the edges, corners, or surfaces of the particle surfaces, but one preferred example is one in which they are grown in an epitaxial manner at the corner of the particles.

On the other hand, in order to minimize the decrease in sensitivity when a photosensitive material is subjected to pressure, even in high silver chloride emulsions with a silver chloride content of 90 mol% or more, grains with a uniform structure with a small distribution of halogen composition within the grains are used. It is also preferable to use

Furthermore, it is also effective to further increase the silver chloride content of the silver halide emulsion for the purpose of reducing the amount of replenishment of the development processing solution.

In such cases, the silver chloride content is 98 mol% to 10
Emulsions of almost pure silver chloride, such as 0 mol %, are also preferably used.

Average grain size of the silver halide grains contained in the silver halide emulsion used in the present invention (the grain size is defined as the diameter of a circle equivalent to the projected area of the grain, and the number average thereof is taken)
is preferably 0.1 μ to 2 μ, and their particle size distribution has a coefficient of variation (standard deviation of particle size distribution divided by average particle size) of 20% or less, preferably 15%.
The following so-called monodisperse ones are preferred. At this time, in order to obtain a wide latitude F, it is preferable to blend the above-mentioned monodispersed emulsions in the same layer or to apply multilayer coating.

The shape of the silver halide grains contained in the photographic hole side is regular such as a cube, a tetradecahedron, or an octahedron.
lar) those with crystal shapes, those with irregular crystal shapes such as spherical, plate-like, etc.
Alternatively, a composite form of these can be used. Moreover, it may be made of a mixture of crystals having various crystal forms. In the present invention, among these particles, it is preferable to contain particles having the above-mentioned regular crystal shape in an amount of 50% or more, preferably 70% or more, and more preferably 90% or more.

In addition to these, the average aspect ratio (yen equivalent diameter/
Emulsions in which the projected area of tabular grains having a thickness of 5 or more, preferably 8 or more, exceeds 50% of the total grains can also be preferably used.

In the photosensitive material according to the present invention, a hydrophilic colloid layer is incorporated in a hydrophilic colloid layer for the purpose of improving the sharpness of images.
．． No. 337.49OA2, pages 27 to 76, dyes that can be decolorized by processing (among them oxonol dyes) are used when the optical reflection density at 680 nm of the sensitive material is 0.7.
0 or more, or 12% by weight or more (more preferably 14% by weight) of titanium oxide surface-treated with a di- to tetrahydric alcohol (for example, trimethylolethane) in the water-resistant resin layer of the support. (wt% or more) is preferably contained.

Further, in the light-sensitive material according to the present invention, it is preferable to use a color image preservation improving compound as described in European Patent EP 0,277.589A2 together with a coupler.

Particularly preferred is the combination with a pyrazoloazole coupler.

That is, a compound (F) that chemically bonds with the aromatic amine developing agent remaining after the color development process to produce a chemically inert and substantially colorless compound and/or a compound that remains after the color development process. For example, the use of a compound (G) that chemically bonds with the oxidized product of an aromatic amine color developing agent to produce a chemically inert and substantially colorless compound may be used simultaneously or singly, for example, during storage after processing. This is preferable in order to prevent staining and other side effects caused by the formation of a coloring dye due to the reaction between the color developing agent or its oxidized product remaining in the film and the coupler.

Furthermore, in order to prevent various types of mold and bacteria that propagate in the hydrophilic colloid layer and cause image deterioration, the light-sensitive material according to the present invention contains an anti-mold agent as described in JP-A No. 63-271247. It is preferable to do so.

The support used in the photosensitive material according to the present invention may be a white polyester support for display or a support in which a layer containing a white pigment is provided on the support on the side having a silver halide emulsion layer. May be used. In order to further improve sharpness, it is preferable to coat an antihalation layer on the side on which the silver halide emulsion layer is coated or on the back side of the support.

In particular, it is preferable to set the transmission density of the support in the range of 0.35 to 0.8° so that the display can be viewed in both reflected light and transmitted light.

The photosensitive material according to the present invention may be exposed to visible light or infrared light. The exposure method may be low-intensity exposure or high-intensity short-time exposure, and particularly in the latter case, a laser scanning exposure method in which the exposure time per pixel is shorter than to-' seconds is preferred.

Further, during exposure, it is preferable to use a hand stop filter as described in US Pat. No. 4,880,726. This eliminates optical color mixture and significantly improves color reproducibility.

Exposed light-sensitive materials may be subjected to conventional black-and-white or color development, but in the case of color light-sensitive materials, for the purpose of rapid processing, it is preferable to carry out bleach-fixing after color development.

In particular, when the high silver chloride emulsion is used, the pH of the bleach-fix solution is preferably about 6.5 or less, more preferably about 6 or less, for the purpose of promoting desilvering.

Silver halide emulsions and other materials (additives, etc.) and photographic constituent layers (layer arrangement, etc.) applied to the photosensitive material of the present invention, and processing methods and processing materials applied to process this sensitive material. As additives, the following patent publications, especially European Patent EP0.355.66OA2 (Patent Application Hei 1-1)
07011) are preferably used.

(The following is a blank space) In addition to the diphenylimidazole cyan coupler described in JP-A-2-33144, the cyan coupler described in European Patent EP 0,333,185A2 is also
- Hydroxypyridine cyan couplers (particularly preferred are couplers (6) and (9), in which a 4-equivalent coupler of coupler (42) listed as a specific example is made into 2-equivalent couplers by adding a chlorine leaving group), Japanese Patent Publication No. 64-322
60 (including the cyclic active methylene cyan couplers listed as specific examples 3.8.
34 is particularly preferred).

The color photographic material of the present invention is preferably subjected to color development, bleach-fixing, and water washing treatment (or stabilization treatment). Bleaching and fixing may be carried out separately instead of in one bath as described above.

The color developer used in the present invention may contain a conventionally known aromatic primary amine color developing agent in addition to the developing agent represented by (I) above. Preferred examples of other developing agents that can be mixed are p-phenylenediamine derivatives, representative examples of which are shown below, but the invention is not limited thereto.

D-IN, N-diethyl-p-phenylenediamine D-24-amino-N, N-diethyl-3-methylaniline D-34-amino-N-(β-hydroquinethyl)-N
-Methylaniline D-44-amino-N-ethyl-N-(β-hydroxyethyl)aniline D-54-amino-N-ethyl-N-(β-hydroxyethyl)-3-methylaniline D-64-amino -N-
Ethyl-N-(3-hydroxypropyl)-3-methylaniline D-74-amino-N-ethyl-N-(4-hydroxybutyl)-3-methylaniline D-84-amino-N-
Ethyl-N-(β-methanesulfonamidoethyl)-3
-Methylaniline D~11 D~14 4-Amino-N, N-diethyl-3 (β-hydroxyethyl) Aniline 4-amino-N-ethyl-N-(β-methoxyethyl)
-3-Methylaniline 4-amino-N-(β-ethoxyethyl)N-ethyl-
3-Methylaniline 4-amino-N-(3-carbamoylpropyl-N-n
-Propyl-3-methylaniline 4-amino-N-(4-carbamoylbutyl-N-n-
Propyl-3-methylaniline N-(4-amino-3-methylphenyl) = 3-hydroxypyrrolidine N-(4-amino-3-methylphenyl) 3-(hydroxymethyl)pyrrolidine N-(4-amino-3 -Methylphenyl)-3-pyrrolidinecarboxamide Among the above p-phenylenediamine derivatives, particularly preferred are exemplary compounds D-5, D-6, D-7D-8 and D-
It is 12. Further, salts of these p-phenylenediamine derivatives with sulfates, hydrochlorides, sulfites, naphthalenedisulfonic acid, p-toluenesulfonic acid, etc. may also be used.

The amount of the aromatic cylindrical amine developing material used is preferably 0.002 mol to 0.00 mol per p of developer solution. 2 mol, more preferably 0.005 mol to O) mol.

In practicing the present invention, it is preferred to use a developer solution that is substantially free of Hensyl alcohol. Here, "substantially not containing" means preferably 2 relatives/l or less,
More preferably, the hensyl alcohol concentration is 0.5rttR/12 or less, and most preferably, no benzyl alcohol is contained at all.

It is more preferable that the developer used in the present invention does not substantially contain sulfite ions. The sulfite ion functions as a preservative for the developing agent, and at the same time has the effect of dissolving silver halide and reacting with the oxidized product of the developing agent to reduce the dye formation efficiency.

Such an effect is presumed to be one of the causes of increased fluctuations in photographic characteristics due to continuous processing. Here, "substantially not containing" means preferably having a sulfite ion concentration of 3.0 x 10 -'' mol/l or less, and most preferably not containing any sulfite ions.

However, in the present invention, a very small amount of sulfite ion used to prevent oxidation of the processing agent quint in which the developing agent is condensed before being adjusted to a working solution is excluded.

It is preferable that the developer used in the present invention contains substantially no sulfite ions, and more preferably substantially no hydroxylamine. This is because hydroxylamine functions as a preservative for the developing solution and also has silver developing activity itself, and it is thought that fluctuations in the concentration of hydroxylamine greatly affect photographic properties.

Here, "not substantially containing hydroxylamine" preferably means 5. A hydroxylamine concentration of OX 10-' mole/2 or less, and most preferably no hydroxylamine at all.

It is more preferable that the developer used in the present invention contains an organic preservative instead of the hydroxylamine or sulfite ion.

The term "organic preservative" as used herein refers to any organic compound that, when added to a processing solution for a color photographic light-sensitive material, reduces the rate of deterioration of an aromatic primary amine color developing agent. That is, organic compounds that have the function of preventing color developing agents from being oxidized by air, among others, hydroxylamine derivatives (excluding hydroxylamine; the same applies hereinafter), hydroxamic acids, hydrazines, hydrazides, phenols, Especially α-hydroxyketones, α-aminoketones, sugars, monoamines, diamines, polyamines, quaternary ammonium salts, nitroxy radicals, alcohols, oximes, diamide compounds, fused cyclic amines, etc. It is an effective organic preservative. These are JP-A-63
-4235, 6330845, 63-2164
No. 7, No. 63-44655, No. 6353551, No. 63-43140, No. 63-56654, No. 635
No. 8346, No. 63-43138, No. 63-1460
No. 41, No. 6344657, No. 63-44656,
U.S. Patent Nos. 3,615,503 and 2,494,90
No. 3, JP-A No. 52-143020, JP-A No. 48-30
No. 496, etc.

Other preservatives include various metals described in JP-A-57-44148 and JP-A-57-53749;
Salicylic acids described in No. 180588, JP-A-54-35
Alkanolamines described in No. 32, JP-A-56-94
No. 349, the polyethyleneimines described in U.S. Patent No. 3.
If necessary, aromatic polyhydroxy compounds described in No. 746,544 and the like may be contained. In particular, alkanolamines such as triethanolamine, dialkylhydroxylamines such as diethylhydroxylamine,
Preferably, a hydrazine derivative or an aromatic polyhydroxy compound is added.

Among the above-mentioned organic preservatives, hydroxylamine derivatives and hydrazine derivatives (hydrazines and hydrazides) are particularly preferred.
No. 5270, No. 63-9713, No. 639714,
It is described in Mukai No. 63-11300.

Further, it is more preferable to use the above-mentioned hydroxylamine derivative or hydrazine derivative in combination with amines from the viewpoint of improving the stability of the color developer and further improving the stability during continuous processing.

Examples of the above-mentioned amines include cyclic amines as described in JP-A-63-239447 and JP-A-63-128.
Amines such as those described in No. 340 and other patent applications filed in 1983
Examples include amines such as those described in No. 3-9713 and No. 63-11300.

In the present invention, 3.5% of chloride ions are added to the color developer.
It is preferable to contain Xl0-2 to 1.5 Xl0-'mol/l. Particularly preferably 4X10-2 to 1x10
Mol/l. Chlorine ion concentration is 1.5X10-' ~
If the amount is more than 10-1 mol/1, it has the disadvantage of delaying development, which is not preferable in achieving the object of the present invention of rapid development and high maximum density. Further, if it is less than 3.5XIO-''mol/1, it is not preferable in terms of preventing capri.

In the present invention, 3. bromine ions are added to the color developer. O
X 10-' mol/l~t, oxio-3 mol/I!
, is preferably contained. More preferably 5.0X
10-' to 5X10-' mol/l. If the bromide ion concentration is more than 1XIO-3 mol/l, development will be delayed, maximum density and sensitivity will be reduced; 3. OXl0-'mol/
If it is less than 2, fogging cannot be sufficiently prevented.

Here, the chlorine ions and bromine ions may be added directly to the developer, or may be eluted from the photosensitive material into the developer during the development process.

When added directly to a color developer, examples of the chloride ion supplying substance include sodium chloride, potassium chloride, ammonium chloride, lithium chloride, nickel chloride, magnesium chloride, manganese chloride, calcium chloride, and cadmium chloride, among which preferred ones are preferred. are sodium chloride and potassium chloride.

Alternatively, it may be supplied from an optical brightener added to the developer.

As a supply material for bromide ions, sodium bromide, potassium bromide, ammonium bromide, lithium bromide, calcium bromide, magnesium bromide, manganese bromide, nickel bromide, cadmium bromide, cerium bromide, thallium bromide Among these, preferred are potassium bromide and sodium bromide.

When eluted from the light-sensitive material during the development process, both chloride ions and bromine ions may be supplied from the emulsion, or may be supplied from a source other than the emulsion.

The color developer used in the present invention is preferably pl(
9 to 12, more preferably 9 to 11.0, and the color developer may contain other known developer component compounds.

In order to maintain the above pH, it is preferable to use various buffers. Buffers include carbonate, phosphate, borate, tetraborate, hydroquine benzoate, glycyl salt,
N,N-dimethylglycine salt, leucine salt, norleucine salt, guanine salt, 3,4-dihydroxyphenylalanine salt, alanine salt, aminobutyrate, 2-amino-2-
Methyl-1,3-propanediol salt, valine salt, proline salt, trishydroxyaminomethane salt, lysine salt, etc. can be used. In particular, carbonates, phosphates, tetraborates, and hydroxybenzoates are soluble at pH 9.0.
These buffers have excellent buffering ability in the high pH 8I range, do not affect photographic performance (fogging, etc.) even when added to color developers, and are inexpensive. It is particularly preferred to use

Specific examples of these buffers include sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate, sodium borate, and boric acid. Potassium, sodium tetraborate (borax), potassium tetraborate, sodium 0-hydroxybenzoate (sodium salicylate), potassium 0-hydroxybenzoate, sodium 5-sulfo-2-hydroxybenzoate (sodium 5-sulfosalicylate) , potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate), and the like. However, the present invention is not limited to these compounds.

The amount of the buffer added to the color developer is 0.1 mol/i
It is preferable that it is 0.1 mol/mil or more, especially 0.1 mol/mil.
4 mol/I! It is particularly preferable that

In addition, various caloric acid agents can be used in the color developer as agents for preventing precipitation of calcium and magnesium, or for improving the stability of the color developer. For example, nitrilotriacetic acid, diethylenetriaminepentaacetic acid,
Ethylenediaminetetraacetic acid, N,N,N-trimethylenephosphonic acid, ethylenediamine-N,N,N', N'-
Tetramethylene sulfonic acid, transsilohexanediaminetetraacetic acid, 1.2diaminopropanetetraacetic acid, glycol ether diaminetetraacetic acid, ethylenediamine orthohydroxyphenylacetic acid, 2-phosphonobutane-1,2,
4-tricarboxylic acid, 1-hydroxyethylidene-1,
1 diphosphonic acid, N,N'-bis(2-hydroxybenzyl)ethylenediamine-N,N'-diacetic acid, and the like.

Two or more of these chelating agents may be used in combination, if necessary.

These chelating agents may be added in an amount sufficient to sequester metal ions in the color developer. For example 11
It is about 0.1g to 10g per serving.

Any development accelerator can be added to the color developer if necessary.

As a development accelerator, Japanese Patent Publication No. 37-16088 and No. 3
No. 7-5987, No. 3B-7826, No. 44-123
No. 80, No. 45-9019 and U.S. Patent No. 3.813
, p-phenylenediamine compounds shown in JP-A-52-49829 and JP-A-5015554, JP-A-50-1
No. 37726, Japanese Patent Publication No. 1977-30074, Japanese Patent Publication No. 1983
-156826 and 52-43429, etc., U.S. Patent No. 2,494.9
No. 03, No. 3.128.182, No. 4,230,79
No. 6, No. 3,253,919, Special Publication No. 41-1143
No. 1, U.S. Patent No. 2,482,546, U.S. Patent No. 2,596
, 926 and 3.582.346, etc., Japanese Patent Publication No. 37-16088, 42-25
No. 201, U.S. Patent No. 3.128.183, Special Publication No. 4
1-11431, 42-23883, and U.S. Pat. No. 3,532,501, and other 1-phenyl-3-pyrazolidones, imidazoles, etc. may be added as necessary. I can do it.

In the present invention, any antifoggant can be added if necessary. As antifoggants, alkali metal halides such as sodium chloride, potassium bromide, potassium iodide, and organic antifoggants can be used. Examples of the organic antifoggant include hensitriazole, 6-nidrohenzimidazole, 5-nitroisoindazole, 5methylhensitriazole, 5-nitrohensitriazole, 5-chloro-hensitriazole, 2-thiazolylbenzimidazole. Typical examples include nitrogen-containing heterocyclic compounds such as 2-thiazolylmethyl-henzimidazole, indazole, hydroxyazaindolizine, and adenine.

The color developer applicable to the present invention preferably contains an optical brightener. As a fluorescent whitening agent, 4. ■−
- Diaminor 2. (2)--Disulfostilbene compounds are preferred. The amount added is O~5g//! Preferably 0.1g
~4/j2.

Furthermore, various surface active substances such as alkylsulfonic acids, arylsulfonic acids, aliphatic carboxylic acids, and aromatic carboxylic acids may be added as necessary.

The processing temperature of the color developer that can be applied to the present invention is 20~
50°C, preferably 30 to 45°C. The processing time is within 20 seconds, preferably within 15 seconds. The smaller the amount of replenishment, the better, but it is 20 to 60 per photosensitive material.
0d is suitable, preferably 120 l1ll! It is as follows. More preferably, it is 60d or less.

Next, a desilvering process that can be applied to the present invention will be explained.

The desilvering step may generally include any process such as a bleaching step-fixing step, a fixing step-bleach-fixing step, a bleaching step-bleach-fixing step, or a bleach-fixing step.

The bleaching solution, bleach-fixing solution, and fixing solution that can be applied to the present invention will be explained below.

As the bleaching agent used in the bleach or bleach-fix solution, any bleaching agent can be used, but especially iron (
Iff) organic complex salts (e.g. ethylenediaminetetraacetic acid,
Complex salts with aminopolycarboxylic acids such as diethylenetriaminepentaacetic acid, aminopolyphosphonic acid, phosphonocarboxylic acid, and organic phosphonic acids) or organic acids such as citric acid, tartaric acid, and malic acid; persulfates and hydrogen peroxide, etc. preferable.

Among these, complex salts of iron ([[l)] are particularly preferred from the viewpoint of rapid processing and prevention of environmental pollution. Iron (I[I)
Examples of useful aminopolycarboxylic acids, aminopolyphosphonic acids, or organic phosphonic acids or their salts for forming organic complex salts include ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, 1,3-diaminopropanetetraacetic acid, propylene Examples include diaminetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, iminodiacetic acid, glycol ether diaminetetraacetic acid, and the like. These compounds may be sodium, potassium, lithium or ammonium salts. Among these compounds, iron ([1) i! Salt is preferred because of its high bleaching properties. These ferric ion complex salts may be used in the form of complex salts, or ferric salts such as ferric sulfate, ferric chloride, ferric nitrate, ferric ammonium sulfate, and ferric phosphate. A ferric ion complex salt may be formed in a solution using a chelating agent such as aminopolycarboxylic acid, aminopolyphosphonic acid, or phosphonocarboxylic acid. Further, the chelating agent may be used in excess of the amount required to form the ferric ion complex. Among the iron complexes, aminopolycarboxylic acid iron complexes are preferred, and the amount added is 0.01 to 1.0 mol/
l, preferably 0.05 to 0.50 mol/l.

Various compounds can be used as bleach accelerators in the bleach solution, bleach-fix solution and/or their pre-bath. For example, U.S. Pat.
Publication No. 630, Research Disclosure No. 1712
No. 9 (July 1978 issue), compounds having a mercapto group or disulfide bond, and Japanese Patent Publication No. 45-85
No. 06, JP-A-52-20832, JP-A No. 53-3273
Thiourea compounds described in No. 5 and US Pat. No. 3,706,561, or halides such as iodine and bromide ions are preferred because they have excellent bleaching properties.

In addition, the bleaching solution or bleach-fixing solution that can be applied to the present invention contains bromides (for example, potassium bromide, sodium bromide,
Rehalogenating agents such as ammonium bromide) or chlorides (eg, potassium chloride, sodium chloride, ammonium chloride) or iodides (eg, ammonium iodide) can be included. If necessary, one or more inorganic acids having a pH buffering capacity such as borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate, citric acid, sodium citrate, tartaric acid, etc. , organic acids and their alkali metal or ammonium salts, or corrosion inhibitors such as ammonium nitrate and guanidine.

The fixing agent used in the bleach-fixing solution or fixing solution is a known fixing agent, namely thiosulfates such as sodium thiosulfate and ammonium thiosulfate; thiocyanates such as sodium thiocyanate and ammonium thiocyanate; ethylene bisthioglycolic acid. , 36-cythia-1,8-octanediol and other water-soluble silver chloride solubilizers such as thioureas and thioureas, and these can be used alone or in combination of two or more. Further, a special bleach-fixing solution consisting of a combination of a fixing agent and a large amount of a halide such as potassium iodide as described in JP-A-55-155354 can also be used. In the present invention, the use of thiosulfates, particularly ammonium thiosulfates, is preferred. The amount of fixing agent per 11 is 0.3
-2 mol is preferable, and the range of 0.5-1.0 mol is more preferable. The pH range of the bleach-fixing solution or fixing solution is preferably 3 to 10, more preferably 5 to 9.

In addition, the bleach-fix solution contains various other optical brighteners, antifoaming agents, surfactants, polyvinylpyrrolidone, methanol, etc. A solvent can be included.

Bleach-fix solutions and fixing solutions contain sulfites (e.g., sodium sulfite, potassium sulfite, ammonium sulfite, etc.) and bisulfites (e.g., ammonium bisulfite, sodium bisulfite, potassium bisulfite, etc.) as preservatives.
, metabisulfite (eg, potassium metabisulfite, sodium metabisulfite, ammonium metabisulfite, etc.).

These compounds are approximately 0.02 to 0.02 in terms of sulfite ion.
The content is preferably 0.05 mol/l, more preferably 0.04 to 0.40 mol/l.

Sulfites are commonly added as preservatives, but other preservatives include ascorbic acid, carbonyl bisulfite adducts,
Alternatively, a carbonyl compound or the like may be added.

Furthermore, a buffer, a fluorescent whitening agent, a chelating agent, an antifoaming agent, an antifungal agent, etc. may be added as necessary.

After desilvering treatment such as fixing or bleach-fixing, water washing and/or stabilization treatment is performed (hereinafter, unless otherwise specified, water washing includes stabilization treatment).

The amount of water used in the washing process varies widely depending on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), the purpose, the temperature of the washing water, the number of washing tanks (number of stages), the replenishment method such as countercurrent or forward flow, and various other conditions. Can be set. Among these, the relationship between the number of flushing tanks and the amount of water in the multistage countercurrent method is described in the Journal of the Society of Motion Picture and Television Engineers (Jour
nalof the 5ociety of Moti
on Picture and Television
Engineers) Volume 64, p. 248-253
(May 1955 issue).

Generally, the number of stages in the multistage countercurrent system is preferably 2 to 6, particularly preferably 2 to 5.

According to the multistage countercurrent method, the amount of washing water can be greatly reduced, for example, from 0.5 to 12 ρ per photosensitive material, and the effect of the present invention is remarkable. The increased residence time causes problems such as bacteria propagation and the resulting floating matter adhering to the photosensitive material. As a solution to such problems, the method of reducing calcium and magnesium described in JP-A-62-288838 can be used very effectively. Also, JP-A-57-85
Isothiazolone compounds and thiahesidazoles described in No. 42, chlorine-based disinfectants such as chlorinated sodium isocyanurate described in No. 61-120145, JP-A-61-2
Hensitriazole, copper ion, etc. described in No. 67761, written by Hiroshi Horiguchi [Chemistry of antibacterial and anti-mildew J (1986) Sankyo Publishing, Sankyo Gijutsukai ed. "Sterilization of microorganisms, sterilization, and anti-mildew technology" (1982) Industrial technology It is also possible to use the fungicides described in "Encyclopedia of Antibacterial and Antifungal Agents" (1986), edited by the Japan Antibacterial and Antifungal Society.

Further, in the washing water, a surfactant as a draining agent and a chelating agent such as EDTA as a water softener can be used.

The above-mentioned water washing step can be followed or the stabilizing solution can be directly treated without going through the water washing step. A compound having an image stabilizing function is added to the stabilizing liquid, such as an aldehyde compound such as formalin, or a film suitable for stabilizing the dye.
Examples include buffers for preparing H and ammonium compounds. Further, in order to prevent the proliferation of bacteria in the liquid and to impart anti-mold properties to the photographic material after processing, the various disinfectants and anti-mold agents described above can be used.

Furthermore, surfactants, optical brighteners, and hardeners can also be added.

In the processing of the photosensitive material of the present invention, when stabilization is performed directly without passing through a water washing step, Japanese Patent Application Laid-Open No. 57-8543
Any of the known methods described in No. 1, No. 5B-14834, No. 60-220345, etc. can be used.

In the present invention, the washing and/or stabilizing water may be treated with a reverse osmosis membrane. Cellulose acetate, cross-linked polyamide, polyether, polysulfone, polyacrylic acid, polyvinylene carbonate, etc. can be used as the material for the reverse osmosis membrane, but cross-linked polyamide-based composite membranes and polysulfone-based composite membranes are particularly preferred because they are less likely to cause a decrease in the amount of permeated water. Membranes are preferred.

In addition, from the viewpoint of reducing the initial cost of the equipment, reducing running costs, downsizing, and preventing pump noise, 2 to 1
A low-pressure reverse osmosis membrane that can be used at a low liquid delivery pressure of 5 kg/cffl is preferred. Further, the membrane structure is preferably a so-called spiral type in which a flat membrane is rolled up into a spiral shape, since the amount of permeated water is less reduced.

The liquid delivery pressure when using these membranes is within the range mentioned above, but the preferred conditions are 2 to 10 kg/cffl, and the particularly preferred conditions are 3 to 7 kg/cd in order to prevent staining and to prevent a decrease in the amount of permeated water. be.

The water washing and/or stabilization step is preferably connected in a multistage countercurrent system using a plurality of tanks, and it is particularly preferable to use 2 to 5 tanks.

It is preferable that the treatment using the reverse osmosis membrane be performed on the water from the second tank and subsequent tanks of such multistage countercurrent washing and/or stabilization. Specifically, in the case of a two-tank configuration, the second tank,
In the case of a 3-tank configuration, the water in the second or third tank, in the case of a four-tank configuration, the water in the third or fourth tank is treated with a reverse osmosis membrane, and the permeated water is stored in the same tank (water for reverse osmosis membrane treatment). This is done by returning the sample to the tank from which it was collected (hereinafter referred to as the collection tank) or to a subsequent washing and/or stabilization tank. Furthermore, one measure is to return the concentrated washing and/or stabilizing liquid to the bleach-fixing bath upstream of the collection tank.

It is preferable that the washing treatment bath of the present invention contains a chelating agent.

The usable chelating agent can be selected from aminopolycarboxylic acid, aminopolyphosphonic acid, phosphonocarboxylic acid, alkylidene diphosphonic acid, metaphosphoric acid, pyrophosphoric acid, polyphosphoric acid, and the like.

In the present invention, organic phosphonic acids and/or organic phosphonates represented by Funakura (I) to (rV) below can be preferably used. Particularly preferred are compounds represented by formula (n).

General formula (1) In the formula, ? t1) Mt represents a hydrogen atom or a cation that provides water solubility (e.g., alkali metals such as sodium and potassium; ammonium; pyridium nitriethanolammonium, triethylene ammonium ion), and R
1R2 is an alkyl group having 1 to 4 carbon atoms (for example, methyl,
ethyl, propyl, isopropyl, butyl), aryl groups (e.g. phenyl, 0-tolyl, m-tolyl, p-
1-lyl, P-carboxyphenyl, water-soluble salts of p-carboxyphenyl group (e.g., sodium, potassium salts))
, aralkyl groups (e.g. hensyl, β-phenethyl,
O-acetamidohensyl, particularly preferably carbon number 7-
9 aralkyl group), an alicyclic group (e.g., cyclohexyl, cyclopentyl), or a heterocyclic group (e.g., pyrrolyldimethyl, pyrrolidylbutyl, hendithiadiylmethyl, tetrahydroquinolylmethyl), R, RZ (especially preferably when it is an alkyl group) is a hydroxyl group, a carboxyl group, an alkoxy group (for example, methoxy, ethoxy), 0 halogen groups,
0M4 In the formula, Ml and h have the same meaning as defined in general formula (1), R + and Rz are hydrogen atoms, - alkyl groups, aralkyl groups, alicyclic groups, hetero groups defined in Funazura (1) cyclic group, or the general formula (I[[) %formula% In the formula, IL and Mz are the same as the definitions of the general formula (1), R is a hydrogen atom, - Funazura (an alkyl group defined by N) , alicyclic group, heterocyclic group 0M4 elementary atom, hydroxyl group, carboxyl group, alkyl group, - Substituted alkyl group defined in Funakura (Summer) or Mz
M4 In the formula, mon, ~i, is -1, L defined in Funakura (1)
In addition, A1 and M4 may particularly be a hydroxyl group.

Specific examples of chelating agents are listed below. However, the present invention is not limited thereto.

0 gates.

HOOCHzC-, //C)lzcOOHN CH2COOH CH2COOH CH2COOH ,CHzP03Hz N’　CHiPOJz \CH2PO3H2 OH OH OH 1" (i-POJ2 OH cozcoon to [1H2COOH CHzPOJz CH3 0OC (Jl-PO3H.

0OC CHPO3H.

cnzcoon H work 0. P OsL Hz H, C-1i-COOH CH3 to 1”′ H,C 1"' (i-Cool( Hff HOOCCPO3H2 Ht CH.

CH2C00H )10-(i-Coo)l CII2COOH H2NCHzCH2-0-P(OH)zNa )100ccHzc C00H PO, H2 to 1".

HzOsP-CPOJz 0iHtH The amount of ferric ethylenediaminetetraacetate contained in the photosensitive material can be determined by the amount of ferric ethylenediaminetetraacetate contained in the photosensitive material.
, 9m+++o I to 290 mmol is preferred. More preferably 14.6 mmol-146 mm
It is ol. If the amount added is too large, the surface may become sticky (possibly), and if it is added too little, the original stain improvement effect will not be achieved.

It is also a preferable embodiment to use a magnesium compound or a bismuth compound.

In addition, it is also a preferred embodiment to use chelating agents such as 1-hydroxyethylidene-1,1 diphosphonic acid and ethylenediaminetetemethylenephosphonic acid, and magfusium and bismuth compounds.

A so-called rinsing solution is also used as a washing solution or stabilizing solution used after desilvering treatment.

The preferred pH of the water washing step or stabilization step is 4-IO, more preferably 5-8. The temperature can be set in various ways depending on the use and characteristics of the photosensitive material, but generally it is 30 to 45 degrees.
C1 is preferably 35-42°C. Although the time can be set arbitrarily, a shorter time is preferable from the viewpoint of reducing processing time. Preferably 5 seconds to 45 seconds, more preferably 10 seconds to 3 seconds
It is 5 seconds. The smaller the amount of replenishment, the lower the running cost.
Preferable from the viewpoints of reduced emissions, ease of handling, etc.

A specific preferable replenishment amount is 0.5 to 50 times, preferably 2 to 15 times, the amount brought in from the previous bath per unit area of the photosensitive material. Or 1ain of photosensitive material (300-
It is preferably 150 d or less. Further, replenishment may be performed continuously or intermittently.

The liquid used in the water washing and/or stabilization step can also be used in the previous step. An example of this is to reduce the amount of waste liquid by using a multi-stage counter-current system to reduce the overflow of washing water and flow it into the bleach-fix bath, which is the previous bath, and replenish the bleach-fix bath with '4 condensate. It will be done.

In the present invention, so-called jet flow can be performed in the washing water and/or the stabilizing liquid and other arbitrary processing liquids. The jet stream is generated by sucking the processing liquid in the processing bath using a pump.
It can be generated by discharging the processing liquid toward the emulsion surface from a nozzle or slit provided at a position facing the emulsion surface of the photosensitive material. More specifically, a pump is applied through a slit or nozzle provided facing the emulsion surface described in the Examples section of the lower right column on page 3 to the lower right column on page 4 of the specification of JP-A-62183460. A method of discharging the pumped liquid can be adopted.

A drying process that can be used in the present invention will be explained.

In order to complete an image using the ultra-quick processing of the present invention, a drying time of 20 to 40 seconds is desired.

As a means for shortening this drying time, an improvement can be made on the window material side by reducing the amount of hydrophilic binder such as gelatin to reduce the amount of moisture carried into the membrane. In addition, from the perspective of reducing the amount carried in, it is possible to speed up drying by absorbing water with a squeeze roller or cloth immediately after leaving the washing bath. Of course, as an improvement from the dryer, it is possible to speed up drying by increasing the temperature or increasing the drying air. Furthermore, drying can be accelerated by adjusting the angle at which the drying air is irradiated onto the photosensitive material or by removing the exhaust air.

(Examples) Hereinafter, the present invention will be specifically explained with reference to Examples, but the present invention is not limited thereto.

(Synthesis example) Exemplary compound (5) of the present invention was synthesized according to the following formula.

(e) oin Exemplary Compound (5) (Synthesis of Compound Tb) (a) 261 ml (2.85 mol) of n-propylbromide was added to 305 g (2.85 mol), and stirring was continued at room temperature for 10 hours. During this time, the reaction solution became viscous and eventually solidified. Then sodium bicarbonate 2
Add 50 g and 11 parts of water, and extract with ethyl acetate (IIX
1) After drying the sodium sulfate, ethyl acetate was distilled off under reduced pressure to obtain an oil containing compound (b). This was purified by silica gel column chromatography to obtain 200 g (yield: 47%) of (b).

(Synthesis of compound (C)) (b) 88.0 g of 3-bromopropylamine hydrobromide (
4,02 x 10-'mo+) was added and stirring was continued for 2 hours in an oil bath at 120"C. During this time, the reaction solution gradually solidified. To this was added 40 g of sodium bicarbonate, 500 g of water,
and extracted with ethyl acetate (500d x 1),
After drying the Glauber's salt, ethyl acetate was distilled off under reduced pressure to obtain 71.0 g of oil containing compound (C).

(Synthesis of compound (d)) (C) To 54.8 g (2,85 x 10-' mol), add 5 (ld) acetic acid, 4 M water, and add 40 g (4,93 x 10-' mol) of potassium cyanate while stirring at room temperature. Stirring was continued for 1 hour. 500 mL of the drained water was added, extracted with ethyl acetate (500 dXl), dried over Glauber's salt, and ethyl acetate was distilled off under reduced pressure to obtain an oil containing compound (d).

This was purified by silica gel column chromatography and then recrystallized from acetonitrile to yield compound (d) 31.
8 g (yield 47%) was obtained.

(Synthesis of compound (e)) (d) 25.7g<1.03X10 Kanko01),
12N hydrochloric acid 23.4d (2,27X 10-'mol
), add 103 d of water and place in an ice-cooled stirring dish with sodium nitrate.
．． A solution of 12 g (1,03×10 −'mol) in 10 d of water was added dropwise, and stirring was continued for 45 minutes. Thereafter, 20 g of sodium hydrogen carbonate was added and extracted with a mixed solvent of ethyl acetate and acetonitrile. After drying with sodium sulfate, ethyl acetate and acetonitrile were distilled off under reduced pressure to obtain an oil containing compound (e). This was purified by silica gel column chromatography to obtain 23.0 g (yield: 85%) of compound (e).

(Synthesis of Exemplary Compound 5) (d) 23.0g (8,27X10-2 mol)
Approximately 2 g of 10% palladium on carbon was added to a solution of 200 al of ethanol, and hydrogen gas was brought into contact with the solution under stirring at room temperature. Thereafter, the catalyst was filtered through Celite, and the filtrate was treated with 29.8 g of 1.5-dinaphthalenesulfonic acid (tetrahydrate) (8,27X10
The precipitated crystals were filtered to obtain 18.8 g of Exemplary Compound 5 (as a salt with 1,5-dinaphthalenesulfonic acid) as pale pink crystals.

The physical property values are shown below.

Melting point: gradually decomposes into red from 230°C) 1-NMR (D gate 5o-d6): δ-0,85 (t
, 3H), 1.06 (t3B), 1.3-1.6 (
m, 4H), 2.24 (s, 3H), 2.9-3.
0m.

2H), 3.2-3.5 (m, 6H), 5.8-7
．． 0 (brs, 6H), 7.0-7.2 (1,3H)
+ 7.46 (t, 28), 7.96 (d, 2H),
8.87 (d, 2H).

In addition, as can be seen from this 'H-NMR, Exemplary Compound 5
It can also be seen that it is obtained as a crystal in a form containing ethanol in a molar ratio of 1:1.

Example 1 After corona discharge treatment was applied to the surface of a paper support laminated on both sides with polyethylene, a gelatin undercoat layer containing sodium dodecylbenzenesulfonate was provided, and various photographic constituent layers were further applied to form the layer structure shown below. A multilayer color photographic paper was produced. The coating solution was prepared as follows.

19.1 g of yellow coupler (ExY), 4.4 g of color image stabilizer (Cpd-1), and color image stabilizer (Cpd-1) were prepared.
-7) Q, 7 g to 27.2 cc of ethyl acetate and 4 each of solvents (Solv-3) and (Solv-7)
．． 1 g was added and dissolved, and this solution was emulsified and dispersed in 185 cc of a 10% gelatin aqueous solution containing 8 cc of 10% sodium todenruhenzenesulfonate to prepare emulsified dispersion A. On the other hand, silver chlorobromide emulsion A (cubic, average grain size 0
．． 3-near mixture of large size emulsion A of 88- and small size emulsion A of 0.70* 1)! yJ (silver molar ratio). The coefficient of variation of the grain size distribution was 0.08 and 0.10, respectively, and each size emulsion contained 110.3 mol % bromide locally on a part of the grain surface. This emulsion contains 2.0% of the blue seductive enhancing dyes A and B shown below per mole of silver compared to large size emulsion A. OX 10-' mol, and for small size emulsion A, 2.5 x 10-' mol, respectively. Chemical ripening of this emulsion was also carried out with the addition of a sulfur sensitizer and a total enhancer. The above emulsified dispersion A
This silver chlorobromide emulsion A was mixed and dissolved to prepare a first layer coating solution having the composition shown below.

Coating solutions for the second to seventh layers were also prepared in the same manner as the coating solution for the first layer. ■-Oxy-3,5-dichloro-5-triazine sodium salt was used as the gelatin hardening agent for each layer.

Also, the total amount of Cpd-10 and Cpd-11 in each layer was 25.0■/rI? and 50.0 μ/bo.

The following spectral sensitizing dyes were used in the silver chlorobromide emulsion of each light-sensitive emulsion layer.

Sensitizing dye A for the blue-sensitive emulsion layer, Sensitizing dye B for the blue-sensitive emulsion layer, and Sensitizing dye D for the green-sensitive emulsion layer (per mole of silver halide, for large-sized emulsion A, each 2.OX 10 -' mol, and 2.5X10-' mol each for small size emulsion A)SO30503)
1-N(C2)1s)□ (per mole of silver halide, 7°0XIO-' mole for large size emulsion B, and 1.0X10-S mole for small size emulsion B) Green sensitivity Sensitizing dye C for emulsion layer Sensitizing dye E for red-sensitive emulsion layer (per mol of halogenated tM, 4.0X10-4 mol for large size emulsion B4, 5.6XIO for small size emulsion B) -' mole) (per mole of silver halide, 0.9 x 10-' mole for large size emulsion C, and 1.1 x 10-' mole for small size emulsion C) in the red-sensitive emulsion layer. In contrast, the following compound was added in an amount of 2.6 x 10-'' moles per mole of silver halide.

(10■/rl() In addition, for the blue-sensitive emulsion layer, the green-sensitive emulsion layer, and the red-sensitive emulsion layer, ■-(5-methylureidophenyl)5-mercaptotetrazole was added to B per mol of silver halide, respectively.
5xlO-' mol, 7.7 Xl0-' mol, 2.5
X 10-' moles were added.

Furthermore, 1X10-' mol and 2X10-' mol of 4hydroxy-6-methyl-L3,3a and 7-titrazaindene were added to the blue-sensitive emulsion layer and the green-sensitive emulsion layer, respectively, per mol of silver halide.

In addition, the following dyes (coating amounts are shown in parentheses) were added to the emulsion layer to prevent irradiation.

and (10 .mu./rr) (40 .mu./rrr) (Layer structure) The composition of each layer is shown below.The numbers represent the coating amount (g/rrr).The silver halide emulsion represents the coating amount in terms of silver.

Support polyethylene laminate paper [The polyethylene on the first layer side contains a white pigment (TiO□) and a bluish dye (ulmarine blue)] -th layer (blue-sensitive emulsion layer) The above-mentioned silver chlorobromide emulsion A 0.30 gelatin 1.6 yellow coupler (ExY) 0.82 color image stabilizer (Cpd-t) 0.19 color medium (Solv-3)
0.16? Container (Solv-7)
0.16 Color image stabilizer (Cpd-7) 0.06
Second layer (color mixing prevention layer) Gelatin 0.99 Color mixing prevention agent (Cpd-5) 0.08 Solvent (
S01 sea 1) 0.16 inch capacity (Solv-4)
0.08 Third layer (green-sensitive emulsion layer) Silver chlorobromide emulsion (cubic, 1 of large size emulsion B with average grain size 0.55- and small size emulsion B with 0.39ta)
:3 mixture (Ag molar ratio). The coefficient of variation of grain size distribution is 0.10 and 0.08, respectively, and each size emulsion is Ag.
0.12 Gelatin (0.8 mol% Br was locally contained on a part of the particle surface)
1.11 magenta coupler (ExM)
0.23 color image stabilizer (Cpd-2)
0.03 color image stabilizer (Cpd-3)
0.16 color image stabilizer (Cpd-4)
0.02 color image stabilizer (Cpd-9)
0.02? Container (Solv-2)
0.36
Fourth layer (ultraviolet absorption layer) Gelatin 1.26 Ultraviolet absorber (UV-1) 0.47 Color mixing prevention agent (Cpd-5) 0.05? Container (Solv-5)
0.20 Fifth layer (red-sensitive emulsion layer) Silver chlorobromide emulsion (cubic, 1:4 mixture of large emulsion C with an average grain size of 0.584 and small emulsion C with an average grain size of 0.451!m) (Ag molar ratio).The coefficient of variation of the grain size distribution is 0.09 and 0.11, and each size emulsion is AgBr.
(0.6 mol% was locally contained in a part of the particle surface)
0.23 gelatin
1.21 Cyan coupler (ExC)
0.32 color image stabilizer (Cpd-2)
0.03 color image stabilizer (Cpd-4)
0.02 color image stabilizer (Cpd-6)
0.18 color image stabilizer (Cpd-7
) 0.40 color image stabilizer (Cpd-
8) 0.05 solvent (Solv-5
) Sixth layer (ultraviolet absorbing layer) Gelatin ultraviolet absorber (U Sea 1) Color mixing inhibitor (Cpd-5) V medium (Sol Sea 5) Seventh layer (protective layer) Acrylic modified copolymer of gelatin polyvinyl alcohol (Degree of modification 17%) Liquid paraffin (ExY) Yellow coupler zHs 0.45 0.16 0.02 0.08 1.20 0.17 0.03 (Cpd-1) l:1 mixture with color image stabilizer (Mole ratio) (Ex old magenta coupler (Cpd-2) Color image stabilizer (Cpd-3) Color image stabilizer Shi! 1=1 mixture (Mole ratio) (Cpd-4) Color image stabilizer SO□ Na J (Cpd-5) Color mixing inhibitor H H (Cpd-6) Color image stabilizer C4L (t) (cpd Preservative (cpd Preservative (uV) 4:4 mixture of ultraviolet absorbers (weight ratio) c4nq (t) ) 2:4:4 mixture (weight ratio) (Cpd-7) Color image stabilizer -←CH.

CH→CoCO~IC-Hq(n) Average molecular weight 60,000 (Cpd-8) 1:1 mixture with color image stabilizer (weight ratio) (Cpd-9) Color image stabilizer (Solν l) l volume Solv-3 Solv-3 Solv-4 ? Medium (Solv-5) 'l Medium C00CeH+t (CH2)! 1 COOCII+(17 (Solv-6) ?vehicle (Solv-7)) was used as the medium, but the type of developer was changed as shown in Table 1, and each treatment was carried out.

Kabuto 1 has L retention i-degree Katama color development
Bleach and fix at 40°C for 30 seconds 35-40° (15 seconds rinse)
33°C 7 seconds ■ 33°C 7 seconds ■ 33°C 7 seconds Dry 70-80'C 15 seconds (rinse)
→■ The 3-tank countercurrent direction was 2.

The composition of each treatment liquid is as follows.

Takatachi Eririzojunsui Ethylenediamine-N,N,N,N- Tetramethylenephosphonic acid Potassium bromide Triethanolamine Potassium chloride Potassium carbonate Sodium bicarbonate Color developing agent (shown in Table 1) Yueiga color solution 00d 1.5g 0.010g 8.0g 3.1g 0g 3.9g 24 mmol N,N-bis(2-sulfoethyl) Hydroxylamine/lNa 7.7g Fluorescent brightener (WHITEX 4B Add water to 1000 g pH (2
5°C) 10.15 1
(tank liquid and replenisher liquid are the same) water
400mfl ammonium thiosulfate (70χ) 100d ammonium sulfite
15g ethylenediaminetetraacetic acid iron (I[I
) Ammonium 7g Disodium ethylenediaminetetraacetic acid g Next, the same treatment was carried out except that the rinse times ◯◯ and ◯ were changed as shown in Table 2.

The density of the resulting yellow, magenta and soan colors was measured using a densitometer to obtain a so-called characteristic curve.

Furthermore, in order to evaluate the occurrence of stain after aging the treated sample at 80° C. and 70% for 7 days, the minimum concentration increase (ΔDI) over time was determined.

In addition, after exposing the sample to xenon light (300,001 ux) for 8 days, the decrease in image density due to light irradiation was determined (Flash Color Discharge Density (FD): After light irradiation in the exposed area giving an image density of 2.0 ) These results are shown in Tables 1 and 2.

Add water to 10001dpH
(25°C) 6.21i solution (tank solution and refill solution are the same) ion exchange water (calcium, magnesium 3pp each
I! 1 or less) NH□ (U.S. Pat. No. 2,363) Indicated by the number of the listed compound.

17 represents the following compound.

However, as shown in Tables 1 and 2 of the comparative compounds, it can be seen that when the color developing agent of the present invention is used, high image density can be obtained in a short processing time, and the occurrence of image staining is small even in a short time washing with water. .

Furthermore, it can be seen that the yellow color image obtained has better fastness to light than color images produced using conventional color developing agents.

Example 2 According to the present invention, the amount of color developing agent in the photosensitive material film can be restricted by changing the binder (gelatin amount here) and hardener amount of the photosensitive material. Next, exemplified compound N
The effect of changing the swelling characteristics of a light-sensitive material using the color developing agent No. 5 will be explained.

The same material as in Example 1 was used except that the gelatin hardening agent and the amount of 1-oxo-35-dichloro-3-triazine sodium salt in the light-sensitive material were changed.

Table 3 shows the swollen film thickness at 6 seconds when measured using the following developer.

A photosensitive needle (manufactured by Fuji Photo Film Co., Ltd., FWH type, color temperature of light source 320''K) was attached to each sample thus obtained.
) was used to give a staircase exposure through the sensitometry optical shaft. The exposure at this time was 250 with an exposure time of 0.1 seconds.
The exposure amount was set to be that of CMS.

The exposed sample was subjected to continuous processing (running test) using the following processing steps and processing solution composition until three times the color developer tank capacity was replenished.

Processing ■ ■ Single load printing 1°'' color development 45'C 15 seconds 60d 2R bleach fixing
35°C 15 seconds 60ml 2N rinse■
35°C 7 seconds 11 Rinse■ 3
5°C 7 seconds IA rinse ■ 35°C
7 seconds 11 rinse ■ 35°C 7 seconds
60#li! 11 Drying 70-80° CI 5 seconds *The replenishment amount was per one photosensitive material (4 tank countercurrent system from rinsing ■ to ■). The composition of each processing solution was as follows.

Hidachi Nyufi LL2UL Hojo flood 800m
Q 800mR ethylenediamine-NNNN Tetramethylenephosphonic acid 1.5g 2.0g Potassium bromide 0.015g -g Triethanolamine 8.0g 12.0
g Potassium chloride 5.2 g Potassium carbonate 30 g 37 g Color developing agent 12.9 g 20.0
g (Naphthalenedisulfonate of Exemplary Compound No. 5) N,N-bis(carphokyl dimethyl) hydrazine 5.5 g 7.0 g Fluorescent brightener ('dHITEX 4B manufactured by Sumitomo Chemical) 1. og 2.0
g Add water to 1000 ml
1000 ml pH (25°C)
10.30 12.45 I took care of my feet (tank fluid and refill fluid are the same) water
400d ammonium thiosulfate (70χ)
100 ron ammonium sulfite
15g ethylenediaminetetraacetic acid iron(II)
I) Sodium ammonium ethylenediaminetetraacetate 1g 5g MizuwokaF 100010
0O (25°C) 6.0
- The tank liquid and replenisher are the same.In addition, the water washing is done using a four-stage countercurrent system in which the overflow liquid flows from the fourth tank to the first tank.

Sensitometry was performed at the start and end of the running test to measure the amount of silver remaining in the maximum density area after drying. Next, the obtained sample was exposed to xenon light (300,001 ux) for 8 days in a room with a relative humidity of 70%, and the minimum concentration increase (ΔDB') due to light irradiation was determined. These results are shown in Table 3. It was shown to.

As shown in Table 3, if a photosensitive material film contains 1 mmol or more of a color developing agent and is brought into the bleach-fix solution for processing, poor desilvering and deterioration of the light stain of the resulting image may occur. Understood. Also, the swelling film thickness of the photosensitive material is 20
T! It can be seen that it is preferable to perform the treatment while suppressing the amount to below m.

In the present invention, the amount of residual silver and the light stain are small both at the start and end of the run, and images of sufficiently high quality can be obtained at least even with the amount of replenishment.

Example 3 (Preparation of emulsion) 3.3% sodium chloride solution in 3% aqueous solution of lime-processed gelatin
3.2 g of N,N'-dimethylimidazolidine-2-thione (1% aqueous solution) were added. This aqueous solution contains 0.2 mol of silver nitrate and 0.2 mol of sodium chloride.
An aqueous solution containing 2 mol of rhodium trichloride and 15 g of rhodium trichloride was added and mixed with vigorous stirring at 56°C. Subsequently, an aqueous solution containing 0.780 mol of silver nitrate and 0.0 mol of sodium chloride were added.
．． An aqueous solution containing 780 mol of potassium ferrocyanide and 4.2 ml of potassium ferrocyanide was added and mixed at 56°C with vigorous stirring. Five minutes after the addition of the aqueous silver nitrate solution and the aqueous alkali halide solution was completed, an aqueous solution containing 0.020 mol of silver nitrate, 0.015 mol of potassium bromide, 0.005 mol of sodium chloride, and hexachloroiridium (IV
) and an aqueous solution containing 0.8 ml of M potassium were added and mixed at 40°C with vigorous stirring. Thereafter, it was desalted and washed with water. Further, 90.0 g of lime-treated gelatin and triethylthiourea were added to perform optimal chemical sensitization.

The particle shape, particle size, and particle size distribution of the obtained silver chlorobromide (A) were determined from electron micrographs. All of these silver halide grains are cubic,
The particle size was 0.52 IWa and the variation coefficient was 0.08. The particle size was expressed as the average value of the diameter of a circle equivalent to the projected area of the particles, and the particle size distribution was calculated using the value obtained by dividing the standard deviation of the particle size by the average particle size.

Next, the halogen composition of the emulsion grains was determined by measuring xf1 diffraction from silver halide crystals. Using monochromatic Cuk α radiation as a radiation source, the diffraction angle from the 200) plane was measured in detail. A diffraction line from a crystal with a uniform halogen composition gives a single peak, whereas a diffraction line from a crystal having localized phases with different compositions gives a plurality of peaks corresponding to those compositions. By calculating the lattice constant from the diffraction angle of the measured peak, the halogen composition of the silver halide constituting the crystal can be determined.

The measurement results for this silver chlorobromide emulsion (A) were as follows: silver chloride 100χ
In addition to the main peak, a broad diffraction pattern centered at 70% silver chloride (30% silver bromide) and tapered to around 60% silver chloride (40% silver bromide) can be observed.

(Preparation of photosensitive material) A multilayer color photographic paper having the layer structure shown below was prepared on a paper support laminated on both sides with polyethylene. The coating solution was prepared as follows.

No.-FF Coating Solution Preparation Yellow coupler (ExY) 19.1 g, color image stabilizer (Cpd-1>4.4 g and color image stabilizer (Cpd-1)
7) Add 0.7g to 27.2cc of ethyl acetate and solvent (
Solv-1) 8.2g was added and dissolved, and this ? 1 volume of liquid
The mixture was emulsified and dispersed in 185 cc of a 10% gelatin aqueous solution containing 8 cc of 0% sodium todenolhenzenesulfonate.

On the other hand, the red sensitization direct appeal (
An emulsion containing Dye-1) was prepared. The above emulsified dispersion and this emulsion were mixed and dissolved to prepare a first coating solution having the composition shown below.

Coating solutions for the second to seventh layers were also prepared in the same manner as the coating solution for the first layer. As the gelatin hardening agent for each layer, 1-oxy-3,5-dichloro-5-triazine sodium salt was used.

The following compounds were used as spectral sensitizing dyes for each layer (layer - red-sensitive yellow coloring N) (Dye-1) t (Dye-2), (Dye-3) 1.8 x 10- per mole of silver halide
``Mole added.

1.0X10-'mo11 per mole of halogenated i
, OX 10-'mol (Third layer infrared-sensitive magenta coloring layer) (Dye-2) 4.5X10-5a+ol(
5th layer (infrared-sensitive cyan coloring layer) (Dye-3) 1-(5-methylureidophenyl)-5-mercaptotetrazole was added to each of the yellow coloring emulsion layer, magenta coloring emulsion layer, and cyan coloring emulsion layer. 8.0% per mole of halogenated i. 10-' moles of OX were added.

The following dyes were added to the emulsion layer to prevent irradiation.

(0.5×10-' mol per mol of silver halide) and (CH2)4503 (CH2)450:J and (Layer structure) The composition of each layer is shown below. The numbers represent the coating amount (g/bo). The silver halide emulsion represents the coated amount in terms of silver.

Support polyethylene laminate paper [The polyethylene on the first layer side contains a white pigment (TiOz) and a bluish dye (ulmarine blue)] -th layer (red-sensitive yellow coloring layer) Said silver chlorobromide emulsion (A) Gelatin yellow coupler (ExY) Color image stabilizer (Cpd-1) Solvent (Sol Sea 1) Color image stabilizer (Cpd-7) Second layer (color mixing prevention layer) Gelatin color mixing prevention agent (Cpd-51) Vehicle (Sol Sea 1) )? Container (Sol Sea 4) Third layer (Infrared photosensitive magenta coloring layer) Silver chlorobromide emulsion (A) Gelatin magenta coupler (Ex) Color image stabilizer IvI (Cpd-2) Color image stabilizer (Cpd -3) Color image stabilizer (Cpd-4) Color image stabilizer (Cpd-9) 0.30 I, 86 0.19 0.35 0.06 0.99 0.08 0.08 0.12 1. 24 0.20 0.03 0.15 0.02 0.02 Solvent (Solv-2) Fourth layer (ultraviolet absorption layer) Gelatin ultraviolet absorber (UV-1) Color mixing prevention agent (cpa-5) N container (Solv-5) Fifth layer (infrared-sensitive cyan coloring layer) Silver chlorobromide emulsion (A) Gelatin cyan coupler (ExC) Color image stabilizer (Cpd-6) Color image stabilizer (cpd-7) Color Image stabilizer (Cpd-8)? Container (Solv-6) Sixth layer (ultraviolet absorbing layer) Gelatin ultraviolet absorber (UV-1) Color mixing inhibitor (Cpd-5) Solvent (Solv-5) Seventh layer (protective layer) 0.40 1. 58 0.47 0.05 0.24 0.23 1.34 0.32 0.17 0.40 0.04 0.15 0.53 0.16 0.02 0.08 Gelatin 1.33 Polyvinyl alcohol Acrylic 0.17 modified copolymer (degree of modification 17%) Liquid paraffin 0.03 Next, semiconductor laser AlGa1nP (oscillation wavelength, approximately 670
nm), semiconductor laser GaAlAs (oscillation wavelength, approx. 750nm), GaAlAs (oscillation wavelength, approx. 810nm)
m), the laser light is transferred onto color photographic paper moving perpendicularly to the scanning direction by means of a rotating polyhedron.
An apparatus capable of sequential scanning exposure was constructed and used to expose these sensitive materials. The exposure amount was electrically controlled by the exposure time and amount of light emitted from the semiconductor laser.

The exposed sample was processed using the following processing steps and processing solution composition.

However, the types of developing solutions were varied as shown in Table 4, and each treatment was carried out.

Processing process ■ Single load color development 45' CI 5 seconds bleach fixing 35°C 15 seconds rinsing ■ 33°C 7 seconds ■ 33°C 7 seconds ■ Drying at 33°C 7 seconds @ 70-80°C 15 seconds (rinse ■ →
■ A three-tank countercurrent system was adopted. ) The composition of each treatment liquid is as follows.

Standing 2 J-mi LL2i water
800
dEthylenediamine-N,N,N,N Tetramethylenephosphonic acid 1.5g Potassium bromide 0.015g Triethanolamine 8.0g Potassium chloride
5.2g potassium carbonate
29 g sodium bicarbonate
3.9g color developing agent (as shown in Table 4)
24 mmol diethylhydroxyamine
6.3g (80% aqueous solution) Fluorescent image whitening agent (WHITEX 4B, 1
．． Add 0g water 1000
dpH (25°C) 10
．． 25 Tomo 1 (tank fluid and refill fluid are the same) Water 4
00d Ammonium thiosulfate (70χ) 1
00mff1 ammonium sulfite 1
5 g Iron(III) ethylenediaminetetraacetate Ammonium 77 g Disodium ethylenediaminetetraacetate 5 g Ammonium bromide 40 g Add water
1000 pH (25°C)
' 6.2 Sad Ekuoka (tank solution and refill solution are the same) Rinse ■ and ■ are ion-exchanged water (calcium and magnesium are 3 ppm or less each) Rinse ■ is the above rinse solution with 1 part organic phosphonic acid (53)
Liquid composition with 5 mmole/1 added.

The results are shown in Table 4.

This made it possible to display a table of color and obtain high-quality color images.

In addition, high-density images were obtained in a short total processing time. Furthermore, the obtained color image had excellent long-term storage stability.

(3 others) By using the color developing agent of the present invention, it is possible to provide images with high image density through rapid processing and with less staining even during short rinsing processing. It can also be seen that the color images obtained have good fastness to light. As described above, the processing method of the present invention makes it possible to achieve both rapid processing performance, image quality, and image robustness.

(Effects of the Invention) By the method of the present invention, ultra-quick water washing and/or stabilization treatment or ultra-quick desilvering process auxiliary device December 1990

Claims (2)

[Claims] (1) A processing method in which a color photographic light-sensitive material having at least one silver halide emulsion layer on a support is exposed, developed, desilvered, washed with water and/or stabilized, and dried. The silver halide emulsion contains 90 mol% or more of silver chloride, the color developer contains at least one compound represented by the following general formula (I), and the water washing and/or stabilization treatment time is 40 mol % or more. A method for processing a silver halide color photographic material, characterized in that the processing time is within seconds. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R_1 represents a substituent, and n represents an integer from 0 to 4. When n is 2 or more, R_1 may be the same or different. May also be used. R_2 represents an alkyl group. R_3 represents an alkylene group whose main chain has two or more carbon atoms. R_4 represents a hydrogen atom or an alkyl group. There are mathematical formulas, chemical formulas, tables, etc. ▼ represents. At this time, R_5 and R_7 in the formula represent a hydrogen atom, an alkyl group, or an aryl group, respectively. R_6
represents an alkyl group or an aryl group. ) (2) A processing method in which a color photographic light-sensitive material having at least one silver halide emulsion layer on a support is exposed, developed, desilvered, washed with water and/or stabilized, and dried. The silver halide emulsion contains 90 mol% or more of silver chloride, the color developing solution contains at least one compound represented by the general formula (I) according to claim (1), and after color development processing is performed. A silver halide color photograph, characterized in that the color developing agent in the film of the light-sensitive material is brought to a bleaching or bleach-fixing solution in an amount of 1 mmol or less per 1 m^2 of the light-sensitive material, and desilvering is carried out within 30 seconds. How to process photosensitive materials.