JPH01189652A - Color developer for silver halide color photographic sensitive material and method for processing said material using same - Google Patents

Abstract

PURPOSE:To stabilize the photographic characteristic of an image even in case of reducing the replenishing amount of a replenisher by incorporating a specified compd. and a prescribed amount of a chloride in the color developer. CONSTITUTION:One or more kinds of the compds. shown by the formula and the halide such as KCl of >=3X10<-2>mol./l are incorporated in the color developer. In the formula, A1-A5 are each -COOM1, or -PO3M2M3 group (M1-M3 are hydrogen atom. or an alkali metal, etc.), (n) is 1 or 2. The compd. shown by the formula is exemplified by a diethylene triamine penta acetic acid (salt), etc., and the developer may contain a hydroxyl amine compd. And, the sensitive material provided an emulsion layer comprising a silver halide particle contg. >=70mol.% of AgCl is preferably developed with the color developer.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a color developing solution for silver halide color photographic light-sensitive materials and a method for processing silver halide color photographic light-sensitive materials using the color developer, and further relates to More specifically, the present invention relates to a color developing solution for silver halide color photographic materials and a processing method that dramatically reduces the amount of replenishment and continuously forms stable color photographic images.

[Background of the invention]

Generally, when processing silver halide color photographic materials (hereinafter referred to as photographic materials), a fixed amount of developer replenisher is supplied per unit area of the photographic material in order to keep the composition of the color developer constant and maintain photographic performance. Ru.

The composition of the developer changes due to photographic processing, and the photographic performance also changes.

For example, the concentration of the color developing agent is consumed and reduced by the reaction, and the concentration of the inhibitory halide is increased by being eluted from the photographic material by the reaction. Therefore, the activity of the developer changes and becomes inactive if nothing is done. As a method for preventing such inactivation, for example, German Patent Application No. 2,007,459 and No. 2,0
Nos. 07,457 and 2.717,674, U.S. Pat. Nos. 3,647,461 and 3,647.
No. 462 and No. 4,186,007 and European Patent Application No. 00029722.

These methods are called replenishment methods and are performed by replenishing the replenisher.

The substances consumed in the development process are maintained at the desired concentration by the addition of such replenishers, while at the same time the amount of fluid lost from the developer bath is reduced in order to prevent undesirable build-up of halides in the developer solution. A larger volume of replenisher is added.

In this case, the concentration of halide in the replenisher is low, and although recent efforts have been made to reduce the amount of replenishment by using replenishers that do not contain any halides, this still results in a relatively large amount of overflow fluid. is bringing. Another method is to reduce the replenishment amount by removing the halide concentration from the developer by specific means,
In some cases, a method is frequently used in which halides in the overflow liquid are removed, deficient components are supplemented, and the overflow liquid is used again as a replenisher, thereby reducing the overflow liquid.

The former has the disadvantage that the halide concentration increases and development is inhibited, so it is necessary to perform a high activation treatment to eliminate the inhibitory effect, and furthermore, the amount of liquid to be discharged is relatively large.

The latter uses an ion exchange tower or an electrodialysis tower, and is generally expensive. Furthermore, there is a drawback that maintenance work is extremely complicated, such as requiring analysis operations in order to keep the developing composition constant.

Therefore, a low replenishment system (LR system), which can easily reduce replenishment, is generally employed especially in minilabs and the like. However, the disadvantage of this method is that bromide accumulates in fairly high concentrations.

As a result, high-temperature treatment is performed to overcome the inhibitory effect as described above. In this case, the influence of evaporation cannot be ignored, and the toxic components are concentrated and increased, and the disadvantage is that the liquid is easily oxidized.

As a method to solve the drawbacks of these methods,
No. 70552 discloses that a photographic material consisting of a very high silver halide silver chloride content is processed with a replenishment amount so low that it does not overflow even when replenished, so that the elution of bromide ions is reduced, and as a result, bromide ions are A treatment method has been proposed that does not require high-temperature treatment because it does not result in a high concentration of .

This method has been well known for a long time, and since bromide has a much greater development inhibitory effect than chloride, it is a particularly new method in which chloride ions, which have a small inhibitory effect, are more easily eluted into the developer. However, low replenishment processing can be achieved without high temperature processing.

However, according to research conducted by the present inventors, as the ratio of silver chloride in photographic materials increases, the performance of conventional developing solutions cannot be maintained, resulting in lower color density and problems with aging of color developing solutions. Due to this, the gradation changes significantly over time, and even the slight change in the concentration of sulfite, which is a preservative, due to air oxidation causes a change in photographic performance. It was found that this method could not be put to practical use as it was.

The present inventors further investigated using a photographic material with a high silver chloride content that has the various advantages mentioned above, and found that when processed with a conventional color developing solution, the maximum density did not increase and as a result, the processing time was too short. It turned out that the process could not be achieved.

Furthermore, it has been found that when silver chloride exceeds 90 mol %, not only the maximum density but also the intermediate density does not increase, making it impossible to obtain sufficiently stable development.

The inventors of the present invention conducted numerous studies to analyze the cause of this problem, and found that the main cause was the presence of hydroxylamine sulfate, which was used without exception in conventional color developing solutions.

It has been found that the presence of hydroxylamine sulfate causes more severe development inhibition as the proportion of silver chloride in the photographic material increases; It was also found that the higher the ratio of silver chloride, the easier it is to be physically developed, and the photographic performance changes.

Therefore, even if silver chloride suppresses the elution of bromide generated in the development reaction, if hydroxylamine is present in the developer, photographic performance cannot be stabilized.
Particularly in continuous processing, performance changes due to factors other than the concentration of halogen ions.

In addition, in low replenishment processing, the sulfite ion concentration in the developer tends to change over time, but it was found that photographic performance of photographic materials mainly composed of silver chloride changes sensitively to the sulfite concentration.

In order to prevent these undesirable effects of hydroxylamine, techniques for incorporating various metal chelating agents have been proposed and some have been put into practical use. For example, U.S. Patent No. 3.839
Hydroxyalkylidene m: technology using a phosphonic acid sequestering agent and lithium salt in combination as described in US Pat. No. 3,045, polyhydroxy compound and aminopolycarboxylic acid as described in US Pat. Technology using sequestering agents in combination, US Patent No. 4,264
Examples include the technique of using a polyhydroxy compound and an aminopolyphosphonic acid sequestering agent in combination, as described in No. 716. According to these techniques, the influence of heavy metal ions, particularly iron ions, mixed into the developer can be reduced.

However, the inventors have found that, despite the addition of these chelating agents, continuous processing using an automatic processor may cause fogging and abnormalities in photographic properties, especially in the shoulder areas, in photographic light-sensitive materials. I found out that it leaks. In particular, recent photographic processing is characterized by low replenishment processing and over 7
It has been found that in a recycling process in which the 0-liquid is reused, this abnormality in photographic characteristics occurs to a greater extent as the amount of accumulated heavy metal ions increases.

As a result of intensive investigation into the cause of this problem, the present inventors found the following. In other words, conventionally only iron ions mixed in as impurities have been cited as the causative agent of this phenomenon, but in addition to this, increased mixing of copper ions is also the cause of the above-mentioned abnormalities in photographic characteristics. It was also found that the use of conventional chelating agents or combinations of chelating agents is almost ineffective against this copper ion, and it is difficult to render it harmless. That is, copper ions in a color developing solution subjected to ordinary processing are contained in an amount of at least 0.1 ppm, and generally as much as 0.3 ppm. Conventional chelating agents used in color developers, hydroxyalkylidene m:phosphonic acid sequestering agents, have no effect on copper ions, and polyhydroxy compounds and aminopolymers containing three or more carpoquinyl groups In combination with carboxylic acid sequestering agents, the catalytic action of copper ions cannot be completely prevented and may even accelerate the decomposition of the preservative hydroxylamine.

The present inventors have conducted extensive studies and found that amine compounds containing a total of five or more acetic acid groups or methylene phosphonic acid groups in one molecule minimize the adverse effects of not only iron ions but also copper ions on color developing solutions. If we found that this effect was found to be effective, and then combined with the addition of chloride above a certain concentration, not only would the above effects be further enhanced, but we would also find that the addition of chloride at a certain concentration or higher not only further enhanced the effect, but also improved the ability of the color developing agent, especially under conditions where the sulfite concentration in the color developer was low. The present invention has been made based on the discovery that not only the preservability is improved, but also the effect of accelerating development and the suitability for rapid processing are enhanced.

In particular, this effect is remarkable in photographic materials containing 70 mol % or more of silver chloride, and the effect of low fog density in unexposed areas has also been observed, which led to the present invention.

Conventionally, a technique has been used to add diethylenetriaminepentaacetic acid or triethylenetetraminehexaacetic acid to a color developing solution in order to prevent the decomposition of 111 components such as hydroxylamine due to the presence of heavy metal ions such as iron and copper in the color developing solution. However, Japanese Patent Publication No. 108250/1983, Japanese Patent Publication No. 44-30
These are known from Japanese Patent Publication No. 232, Japanese Patent Publication No. 54-16861, Japanese Patent Publication No. 48-30496, etc., but they cannot be used alone in recent years for low replenishment processing, rapid processing, and low sulfite concentration. The reality is that stable photographic properties cannot be achieved during processing and the like.

Based on these analyses, the present inventors have conducted extensive research,
By containing a specific aminopolycarboxylic acid derivative or aminopolyphosphoric acid derivative and chloride at a specific concentration or higher in the color developing solution, all of the above-mentioned drawbacks can be solved and continuous processing with sufficiently high photographic density can be achieved. They have also discovered that the above effects can be further enhanced by using 70 mol% or more of silver chloride particles in a photographic material, and have accomplished the present invention. This is what we have come to.

[Purpose of the invention]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a color developing solution and a processing method which eliminate the above-mentioned drawbacks and which consistently provide stable photographic performance even when the amount of replenishment is significantly reduced.

[Structure of the invention]

The above objects of the present invention have been achieved by a color developer containing at least one compound represented by the following general formula [1] and at least 3×10 −2 mol/α of chloride.

General formula [1] H2A5 In the formula, AI to A5 may be the same or different and -CO
OM represents + or -P03M2M3. M3, M2 and M3 may be the same or different and represent a hydrogen atom, an alkali metal atom or an ammonium ion, and n is 1
or 2.

Furthermore, as another aspect of achieving the object of the present invention,
A photographic material in which the silver halide emulsion layer contains silver halide grains containing at least 70 mol% of silver chloride is mixed with at least one of the compounds represented by the general formula [1] at least 3 x 10-2 mol/Q. A method of processing a photographic material in which the photographic material is processed with a color developing solution containing chloride.

[Specific structure of the invention]

Specific compounds represented by the general formula [1] are known as diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, diethylenetriaminepentamethylenephosphonic acid, and triethylenetetraminehexamethylenephosphonic acid, and their salts (potassium, sodium, lithium Alkali metal salts and ammonium salts (such as alkali metal salts and ammonium salts) are also known and can be obtained as commercial products.

These compounds represented by general formula [l] can be used in color developer l
Preferably in the range of 0.1 to 209, particularly preferably in the range of 0.5 to 10g, particularly preferably in the range of 1 to 209, per Q
A range of 5g is used.

Among the compounds represented by the general formula (1), diethylenetriaminepentaacetic acid and its salts are particularly preferably used from the viewpoint of the desired effects of the present invention.

The chloride used in the present invention may be any compound as long as it releases chloride ions in a color developer, and specific examples include potassium chloride, sodium chloride, lithium chloride, magnesium chloride, and the like.

Further, in the present invention, the chloride is added to the color developing solution 112.
The desired effect of the present invention can be obtained when the content is at least 3X to 2 moles per color developer, but especially 3.3X 10-2-20X10-2 moles per color developer la t7
>In particular, especially 3.5X per color developer tff
Good results can be obtained with 10-2 to 12X 10-2 mol.

When the color developing solution of the present invention contains a compound represented by the following general formula [2], not only the desired effects of the present invention are better achieved, but also the fog density in the unexposed areas of the photographic material is lowered. Therefore, it is preferable to use it in combination with the color developing solution of the present invention.

General formula [2] In the formula, R1 and R2 each represent an alkyl group or a hydrogen atom. However, both R1 and R2 are not hydrogen atoms at the same time. Further, R1 and R2 may form a ring.

In general formula [2], R1 and R2 each represent an alkyl group or a hydrogen atom that is not a hydrogen atom,
The alkyl groups represented by R1 and R2 may be the same or different, and each is preferably an alkyl group having 1 to 3 carbon atoms. The alkyl groups of R1 and R2 include those having substituents, and examples of the ring formed by bonding R1 and R2 include heterocycles such as piperidine and morpholine.

Specific compounds of the hydroxylamine compound represented by general formula [2] are described in U.S. Patent Nos. 3,287,125, 3,293,034, and 3,287,124, However, particularly preferred specific exemplary compounds are shown below.

These hydroxylamine compounds are usually used in the form of hydrochloride, sulfate, p-toluenesulfonate, oxalate, phosphate, acetate, and those to which no salt is attached.

The concentration of the compound represented by the general formula [2] of the present invention in the color developer is usually 0.2 to 50 g/(2, preferably 0
．． 5-30g10. , more preferably 1 to 15 g/(
It is 2.

Further, the compounds represented by the general formula [2] may be used alone or in combination of two or more.

Usually, a sulfite is used as a preservative in a color developer, but the sulfite concentration in the color developer according to the present invention is
When used at 1.6X 10-2 mol or less per color developer ID, it is possible to suppress the decrease in color density that is thought to be caused by dissolution physical development of high silver chloride-containing photosensitive materials, and to improve the preservation ability. Since the deterioration is extremely slight, it is possible to provide a color developing solution that enables rapid processing using photosensitive materials containing high silver chloride, and a method for processing silver halide color photographs using this solution. A sulfite concentration in the developer of 1.6×10 −2 mol/Q or less is preferably used. Furthermore, this effect is better exhibited by I X 10-2 mol 10. It is not more than 4×10″3 mol 10.0% or less.

Examples of the sulfite include sodium sulfite, potassium sulfite, sodium bisulfite, potassium bisulfite, and the like.

As the color developing agent used in the color developer of the present invention, a p-phenylenediamine compound having a water-soluble group is preferably used because it satisfactorily achieves the desired effects of the present invention and causes less fogging.

A p-phenylenediamine compound having a water-soluble group is
Compared to paraphenylenediamine compounds that do not have water-soluble groups such as N,N-diethyl-p-phenylenediamine,
Not only does it have the advantage that it does not contaminate photosensitive materials and does not cause skin irritation, but it can also achieve the objects of the present invention more efficiently, especially when combined with the color developing solution of the present invention.

Examples of the water-soluble group include those having at least one on the amino group or benzene nucleus of the p-phenylenediamine compound, and specific examples of the water-soluble group include (CH2)
n' -CH20f(, -(CH2)m' -NH30
2-(CH2)n' CH3, -(CH2)m'o
-(CH2)n' -CH3, (CH2CH209'
Preferred examples include Cm'Hx m'++ (m' and n' each represent an integer of 0 or more), -COOH group, -5O3H group, and the like.

Specific examples of color developing agents preferably used in the present invention are shown below.

Exemplary color developing agent (C-1) C2115\7 C2,HI NH302CH3NH2 (C-2) C2)15\/C2H4OH (C-3) C2H5\/C2H10H NH2 (C-4) C2H,\/C2H40CH3 C2H,\ /Cs H6SOs H (C-6) CH3\/C21(40H 2O- (C-7) HOH,C2\/C2H4OH NH2 (c-8) C4H,\/C,H,5O3H N1'12 (C-9 ) H9C4\/C3H6SO3H Nt+2 (C-10) 11\/CHzCOOH (C-11) C2H5\/(CH2CH20)2CH3(C-12) C2HI,\/ (CH2CH20)3CH3NH□ (C-13) C2H5\ /( CH2CH20)3C2H5~■2 (C-14) C2H5\/(CH2CH20)2C2H6 (C-15
) C2H5\/C2H4NH302CH3~112 (C-16) C2H・\, /C2H・OH H2 Among the color developing agents exemplified above, example No. 1, (C-
1), (C-2), (C-3), (C-4), (C-6
), (C-7) and (C-15), with (c-1) being particularly preferred.

The color developing agents mentioned above are usually used in the form of salts such as hydrochloride, sulfate, p-toluenesulfonate and the like.

The color developing agent having a water-soluble group used in the present invention is
Usually, it is preferable to use it in the range of 10-2 to 2-2:t-X 10-' mol per color developer IQ,
From the viewpoint of rapid processing, 1.5X 1 per color developer Iff
A range of 0-22 x 10-' moles is more preferred.

The color developing agent may be used alone or in combination of two or more, and if desired, a black and white developing agent such as phenidone,
4-hydroxymethyl-4-methyl-1-phenyl-3
- May be used in combination with pyrazolidone, metol, etc.

Further, instead of using the above-mentioned color developing agent in the color developing solution, a color developing agent can be added to the photographic material, and the color developing agent used in this case includes a dye precursor. A typical dye precursor is JP-A-58-
Those described in No. 65429 and Item 5g-24137 of the same are used, and specifically, for example, 2',4'-bismethanesulfonamide-4-diethylaminodiphenylamine, 2'-methanesulfonamide-4'' (2 ,4,6-
Doliisobrobyl)benzenesulfonamido-2-methyl-4-N-(2-methanesulfonamidoethyl)ethylaminodiphenylamine, 2'-methanesulfonamido4'-(2,4,6-doliisoprobyl)benzene Sulfonamido-4-(hydroxytrisethoxy)diphenylamine, 4-N-(2-methanesulfonamidoethyl)ethylamino-2-methyl-2',4'-his(2,4,6-doliisoprobyl)benzene Sulfonamido diphenylamine, 2,4'-bismethanesulfonamide-4-N,N-diethylaminodiphenylamine, 4-n-hexyloxy-2'-methanesulfonamide-4'' (2,4,6-dolyisopropyl) Benzenesulfonamide diphenylamine, 4-medoxy 2'
-methanesulfonamide-47-(2,4,6-)liimprovil)benzenesulfonamide diphenylamine, 4-diethylamino-4'-(2,4,6-)liimpropylobenzenesulfonamide)diphenylamine,
4-n-hexyloxy-3'-methyl-4'-(2°4.6-)lyinpropylobenzenesulfonamido) diphenylamine, 4-NIN-diethylamino-4'-
(2,4,6-triimprobylbenzenesulfonamide)diphenylamine, 4-N,N-dimethylamine-
Examples include 2-phenylsulfonyl-4'-(2,4,6-)liisoprobylbenzenesulfonamido)diphenylamine.

The amount of the dye precursor added to the photographic material is preferably 0.5 to 22 mg per 100 cm2 of the photographic material.
More preferably, it is 4 to 12 mg.

When the color developer according to the present invention contains a compound represented by the following general formula [D], it not only exhibits the effects of the present invention better, but also prevents air oxidation of the color developer. It is more preferably used because it shows an improvement effect.

General formula [D] (wherein, R2I is a hydroxyalkyl group having 2 to 6 carbon atoms, R22 and R23 each represent a hydrogen atom, a carbon dialkyl group, a pencil group, or the formula -Cn, H2nl -N, and the above formula nl of
is 1 to ゝZ' The integers X' and Z' of 6 are each a hydrogen atom and a carbon number of 1
-6 alkyl group or a hydroquine alkyl group having 2 to 6 carbon atoms. ) Preferred specific examples of the compound represented by the general formula [D] are as follows.

(D-1) Ethanolamine, (D-2) Jetanolamine, (D-3)) Jetanolamine, (D-4) Di-isopropanolamine, (D=5)2
-Methylaminoethanol, (D-6) 2-ethylaminoethanol, (D-7) 2-dimethylaminoethanol, (1)-8) 2-diethylaminoethanol, (D
-9) l-';ethylamino-2-7' lovanol, (D-10) 3-diethylamino-1-propanol, (D-11) 3-dimethylamino-1-propanol, (D-12) isopropyl Aminoethanol, (D-
13) 3-amino-1-propatol, (I)-14)
2-amino-2-methyl-1,3-propanediol, (D-15) ethylenediaminetetrainpropanol, (D-16) benzyljetanolamine, (D-R
17) 2-amino-2-(hydroxymethyl)■,3-
Propanediol.

These compounds represented by the general formula [D] have an effect of 1 g to 100 g per 14 color developing solution.
It is preferably used in the range of 3g to 5g, more preferably 3g to 5g.
It is used in the range of 0g.

In the present invention, it is preferable to use a triazylstilbene type optical brightener represented by the following general formula [3] in the color developing solution according to the present invention, since the occurrence of fogging is further reduced.

General formula [31 In general formula [31], X + , X 2. Y r
and Y2 are a hydroxyl group, a halogen atom such as chlorine or bromine, a morpholino group, an alkoxy group (e.g. methoxy,
ethoxy, methoxyethoxy, etc.), aryloxy groups (
(e.g., phenoxy, p-sulfophenoxy, etc.), alkyl groups (e.g., methyl, ethyl, etc.), aryl groups (e.g., phenyl, methoxyphenyl, etc.), amine groups, alkylamino groups (e.g., methylamino, ethylamino, propylamino, dimethylamino, Cyclohexylamino, β-
Hydroxyethylamino, di(β-hydroxyethyl)
Amine, β-sulfoethylamino, N-(β-sulfoethyl)-N'-methylamino, N-(β-hydroxyethyl-N'-methylamino, etc.), arylamino group (e.g. anilino, o-1m-1p -Sulfoanilino, 0-
1m-1p-chloroaniline, 0-1m-1I)-triidino, 0-1m-1p-carboxyanilino, 0-1
m-1p-hydroxyanilino, sulfonaphthylamino, 0-1m-1p-aminoanilino, 0-1m-1p-
Anilino, etc.). M represents a hydrogen atom, sodium, potassium, ammonium or lithium.

Specifically, the following compounds can be mentioned.
] The triadylstilbene-based brightener represented by the general formula [3] can be synthesized, for example, by the usual method described in "Fluorescent Brighteners" edited by the Japan Chemical Industry Association (Published in August 1975), page 8. can do.

These triazylstilbene type brighteners are preferably used in an amount of 0.2 to 6 g, particularly preferably 0.4 to 3 g, per color developer IO used in the present invention.

The color developer of the present invention preferably contains poly(alkyleneimine). Poly(alkylene imines) consist of substituted or unsubstituted repeating alkylene chain units connected to each other via nitrogen atoms.

These are well-known commercially available substances. Representative poly(alkyleneimine)s include compounds represented by the following general formula [4].

General formula [4] R2' ■ -CR,'-Nl)-n' (In the formula, RI' represents an alkylene group having 1 to 6 carbon atoms, R2' represents an alkyl group, and n' is 500 to 20.
Represents an integer of 000. ) The alkylene group having 1 to 6 carbon atoms represented by R1' above may be linear or branched, preferably having 2 to 4 carbon atoms.
Examples of alkylene groups include ethylene, propylene, butene, isobutyne, dimethylethylene, and ethylethylene.

The alkyl group represented by R2/ preferably has 1 carbon atom
-4 alkyl group, such as methyl group, ethyl group,
Examples include propyl groups, and also those having substituents (eg, hydroxyl groups). n' represents the number of repeating units in the polymer chain and is an integer from 500 to 20,000, preferably from 500 to 2.000. Poly(ethyleneimine) in which R1' is an ethylene group
is most preferred for the purposes of this invention.

Below, poly(
Examples of alkyleneimine) are shown below, but the invention is not limited thereto.

Exemplary compound (FAI-1) Poly (ethyleneimine) (FAI
-2) Poly (propylene imine) (FAI-3)
Poly (buteneimine) (FA l-4) Poly (imbutene imine) (FAI-5) Poly (N-
methylethyleneimine) (P, Al-6) Poly(N-β-hydroxyethylethyleneimine) CPAI-7) Poly(2,2-dimethylethyleneimine) (PAI-8) Poly(2-ethylethyleneimine) ( FA I-9) Poly(2-methylethyleneimine) The poly(alkyleneimine) can be used in the color developer in any amount that achieves the objectives of the present invention, but generally per 112 parts of the color developer. It is preferably used in an amount of 0.1 to 200 g, more preferably in a range of 0.5 g to 50 g.

JP-A-56-94349 discloses that when poly(alkyleneimine) is used together with hydroxylamine in a color developer, the storage stability of the color developer can be improved and the sulfite concentration can be reduced. Are listed. However, in this method, especially when heavy metal ions are mixed, hydroxylamine or a derivative thereof used as a preservative decomposes, resulting in a decrease in storage stability, and is thus insufficient as a preservation improvement technique. However, when used in combination with a color developing solution containing the specific aminopolycarboxylic acid represented by the general formula [l] and a specific concentration of chloride according to the present invention, the above-mentioned drawbacks are improved, and the present invention It was found that the desired effects of the above were well achieved, and that the effect of accelerating development was also obtained. Therefore, in the present invention, the polyalkyleneimine represented by the general formula [4] is mentioned as a preferred combination in the present invention.

In the present invention, the processing time of the color development step may be any time, but is usually between 5 seconds and 5 minutes. Normally, a color development time of 15 to 60 seconds is used for high silver chloride light-sensitive materials such as those of the present invention. Because it has the effect of reducing differences in photographic characteristics, large-scale laboratories and
It is more preferably used because the photographic processing characteristics of the minilab (small-scale laboratory) are similar and the photographic characteristics of the market are uniform. This effect is particularly evident when the color development process is 150%
This becomes noticeable when the time is longer than seconds.

The replenishment amount is 300mQ -10m0 per 1m2 of photographic material.
However, in order to maximize the effect of the present invention, processing should be performed within the range of 150+nQ to 30mff. Particularly preferably from 120 mff to 40 mQ,
most preferably 100m0. 55m from
It is processed in the range of ff. In addition, processing solution volume losses due to evaporation can be avoided by setting the replenishment rate at a level slightly less than the rate at which the developer is carried away from the equipment, and any remaining volume losses can be accounted for by adding replenisher from a simple automatic replenishment device. It can be easily compensated for by supplementing with

In a preferred embodiment, the concentrated and adjusted kit used for making the replenisher can be directly put into the developing bath, and the water shortage can be managed by lowering the liquid level and supplied from the water replenishing device.

The color developing solution of the present invention preferably does not substantially contain benzyl alcohol. Here, the term "substantially free of benzyl alcohol" refers to a benzyl alcohol content of 2 mQ/Q or less, and in the present invention, it is most preferable that the benzyl alcohol is not contained at all. Benzyl alcohol has extremely low solubility, and in the process of the present invention where the amount of replenishment is extremely small, the liquid tends to be concentrated, resulting in problems such as adhesion failure to photographic materials due to oil precipitation and tar formation due to oxidation of color developing agent. This creates extremely troublesome problems.

Furthermore, since the solubility is extremely low, when the above-mentioned prepared concentration kit is directly put into a developing tank, a mechanical mixing device is required, which is extremely complicated. Therefore, benzyl alcohol is an undesirable additive in order to maximize the effects of the present invention.

In the present invention, after color development processing, processing is performed with a processing liquid having a fixing ability, but if the processing liquid having a fixing ability is a fixing liquid, a bleaching treatment is performed before that. A metal complex salt of an organic acid is used as a bleaching agent in the bleaching solution or bleach-fixing solution used in the bleaching process, and the metal complex salt is oxidized into a metal salt produced by development.
It has the effect of converting it into silver genide, and its composition is a complex formed with an aminopolycarboxylic acid or an organic acid such as oxalic acid or citric acid with a metal ion such as iron, cobalt, or copper. The most preferred organic acids used to form such organic acid metal complexes include polycarboxylic acids or aminopolycarboxylic acids. These polycarboxylic acids or aminopolycarboxylic acids may be alkali metal salts, ammonium salts or water-soluble amine salts.

Specific representative examples of these organic acids include the following.

(1) Ethylenediaminetetraacetic acid (2) Diethylenetriaminepentaacetic acid (3) Ethylenediamine-N-(β-oxyethyl)-N, N', N'
-) diacetic acid (4) 1.3-propylenediaminetetraacetic acid (5) nitrilotriacetic acid (6) cyclohexanediaminetetraacetic acid (7) iminodiacetic acid (8) dihydroxyethylglycinecitric acid (also tartaric acid) ) (9) Ethyl ether diamine tetraacetic acid (10)
J Cono Ether Diamine Tetraacetic Acid (11) Ethylenediamine Tetrapropionic Acid (12) Phenylenediamine Tetraacetic Acid The bleaching solution used contains the above-mentioned metal complex salt of an organic acid as a bleaching agent, as well as various color additives. be able to. Additives include, in particular, alkali halides or ammonium halides, re-chlorination agents such as potassium bromide, sodium bromide, sodium chloride, ammonium bromide, metal salts, chelating agents, nitrates, and It is desirable to include commonly known bleach accelerators. In addition, pH buffering agents such as borates, oxalates, acetates, carbonates, and phosphates, alkylamines, polyethylene oxides, and other substances known to be commonly added to bleaching solutions may be added as appropriate. be able to.

Furthermore, the fixer and bleach-fixer contain ammonium sulfite,
Sulfites such as potassium sulfite, sodium bisulfite, ammonium metabisulfite, potassium metabisulfite, sodium metabisulfite, boric acid, borax, sodium hydroxide,
A pH buffering agent consisting of various salts such as potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, and ammonium hydroxide may be contained alone or in combination. In the present invention, in order to increase the activity of the bleach solution or bleach-fix solution, air or oxygen may be blown into the bleach bath or bleach-fix bath and the bleach replenisher solution or bleach-fix replenisher storage tank, if desired. Alternatively, a suitable oxidizing agent such as hydrogen peroxide, bromate, persulfate, etc. may be added as appropriate.

In the present invention, a bleach-fix solution is preferably used from the viewpoint of rapid processing, and when a high-silver chloride photosensitive material is used as in the present invention and bleach-fix processing is performed immediately after color development, staining called bleach blade blur occurs. Easy to occur. For this reason, as a result of various studies, by using a bleach-fix solution with a pH in the range of 4.5 to 6.8, this drawback can not only be solved, but also
It was found that it also has the effect of speeding up silver bleaching.

Particularly, this effect is obtained when the I)H of the bleach-fix solution is 5 to 6.3.
It is especially good when the pH is 5.2 to 5.9.

In the processing method of the present invention, silver may be recovered by known methods from processing solutions containing soluble silver complexes such as washing or washing substitute stabilizing solutions, fixing solutions, bleach-fixing solutions, and the like. For example, electrolysis method (French Painting Patent No. 2.299,667), precipitation method (Japanese Unexamined Patent Publication No. 52-73037, German Patent No. 2,331)
, No. 220), ion exchange method (JP-A-51-17114)
German Patent No. 2,548,237) and metal replacement method (German Patent No. 2,548,237)
British Patent No. 1,353,805) can be effectively used.

In the processing method of the present invention, after color development, bleaching and fixing (or bleach-fixing), stabilizing treatment may be performed without washing with water, or washing with water may be performed followed by stabilizing processing. In addition to the above steps, known auxiliary steps such as hardening, neutralization, black-and-white development, reversal, and washing with a small amount of water may be added as necessary.

A typical example of a preferred treatment method includes the following steps.

(1) Color development - Bleach-fixing - Washing (2) Color development - Bleach-fixing One small amount of water washing One water wash (3) Color development → Bleach-fixing → Washing → Stable (4) Color development → Bleach-fixing → Stable (5) Color development - Bleach-fixing - 1st stability - 2nd stability (6)
Color development - washing with water (or stable) - bleach-fixing - washing with water (or stable) (7) Color development → stop → bleach-fixing → washing with water (or stable) (8) color development - bleaching, washing with water, washing with water, washing with water (or stabilizing) (8) color development - bleaching, washing with water, constant washing, washing with water, and stabilizing (9) )
Color development → Bleaching → Fixing → Washing - Stable (1O) color development -
Bleach - Wash with a small amount of water Constant fixation → 1st stability → 2nd stability (11) Color development → Bleach → Wash with a small amount of water → Fix → Wash with a small amount of water →
Washing with water → Stable (12) Color development → Washing with a small amount of water → Bleaching → Washing with a small amount of water → Fixation →
A small amount of water washing -> water washing -> stabilization (13) Color development - stop - bleaching - small amount of water washing - constant fixing - small amount of water washing -> water washing -> stabilization Among these steps, especially the steps (4) and (5) are preferably used.

Another preferred embodiment of the processing method of the present invention is a method in which a part or all of the autoflow solution of the color developer according to the present invention is allowed to flow into the subsequent bleaching solution or bleach-fixing solution. It will be done. This is because when a certain amount of the color developing solution according to the present invention is introduced into a bleach solution or a bleach-fix solution, the generation of sludge in the bleach solution or bleach-fix solution can be suppressed. This is because the recovery efficiency of silver is also improved.

Furthermore, in addition to the above-mentioned method, when part or all of the overflow liquid of the stabilizing liquid in the subsequent process is poured into the bleach-fixing liquid or the fixing liquid, the above-mentioned effects are particularly well achieved.

Specific examples of these embodiments include those shown in FIG. 1, for example.

The silver halide grains used in the silver halide emulsion layer of the photographic material used in the processing method of the present invention have a silver chloride content of 70%.
It is necessary that the silver chloride content is 90 mol% or more, and preferably close to 100%, but the effect of the present invention is better achieved when the silver chloride content is 90 mol% or more, and especially when the silver chloride content is 95 mol% or more. The intended effects of the present invention are particularly well achieved.

The silver chloride used in the present invention is at least 70 mol%
The silver halide emulsion layer containing silver halide grains consisting of a color coupler has a color coupler. These color couplers react with color developer oxidation products to form non-diffusible dyes. Color couplers are advantageously incorporated in non-diffusive form in or closely adjacent to the photosensitive layer.

Thus, the red-sensitive layer may contain, for example, a non-diffusing color coupler, generally a phenolic or alpha-naphthol based coupler, which produces a cyan partial color image. The green-sensitive layer contains, for example, at least one non-diffusive color coupler, usually 5-, which produces a magenta partial color image.
Pyrazolone color couplers and pyrazolotriazoles may be included. The blue-sensitive layer may contain, for example, at least one non-diffusive color coupler that produces a yellow color image. For example, the color coupler is 6-
It can be a 14- or 2-equivalent coupler.

In the present invention, 2-equivalent couplers are particularly preferred.

Suitable couplers are disclosed, for example, in the following publications:
Abfu research report (Mitteilungen au)
sden Forschungslaboratori
Germany (en der Agfa), Leh 7 Erkusen/Munich (Leverkusen/Miinchen),
Vol, II [, p, 111 (1961) by W. Pe1z [Color Coupler J
(Farbkuppler); Kay Benriki Taraman (
K. Venkataraman), “The Chemistry of Nuncthetic Dice” (The Chem
irsry of 5ynthetic Dyes),
Vol, 4.341-387, Academic Press (
Academic Press), (1971); T.H.

James), rThe Theory of the Photographic Process J
f the Photographic Processes
s), 4th edition, pp. 353-362; and the journal Research Disclosure (Res6rchDisclosure)
) No. 17643, Section ■.

According to a particularly preferred embodiment, a color coupler is used which can sufficiently couple even without the usual addition of benzyl alcohol. Benzyl alcohol is commonly used as a development accelerator which allows the coupling between the oxidized color developer and coupler 2 to proceed at the desired rate to form the image dye. However, while
In practical use, benzyl alcohol is always the cause of the complaints mentioned above, especially problems due to the formation of tar. A suitable coupler that can be used without benzyl alcohol is described in German Patent Application No. 3,209,71.
No. 0, No. 2,441,779, No. 2,640,601
and European Patent Application No. 0067689.

In the present invention, as the magenta coupler, a pyrazolotriazole magenta coupler is more preferably used than the pyrazolone magenta coupler. This has the drawback that stains tend to occur in unexposed areas when bleaching or bleach-fixing is performed immediately after color development using high silver chloride photosensitive materials, but a pyrazolotriazole magenta coupler is used as the magenta coupler. This is because not only this drawback is improved, but also the magenta dye density at the highest density portion during short-time processing becomes better. Among the pyrazolotriazole couplers, couplers represented by the following general formula [M-I] are particularly preferably used.

General formula [M-I] In the general formula [M-I], Z represents a group of nonmetallic atoms necessary to form a nitrogen-containing heterocycle, and the ring formed by Z may have a substituent. good. X represents a hydrogen atom or a group that can be separated by reaction with an oxidized product of a color developing agent.

Moreover, R represents a hydrogen atom or a substituent.

The substituent represented by R is not particularly limited, but typical examples include alkyl, aryl, anilino, acylamino, sulfonamide, alkylthio, arylthio, alkenyl, and cycloalkyl, but in addition to these, halogen Atoms and cycloalkenyl, alkynyl, heterocycle, sulfonyl, sulfinyl, phosphonyl, acyl, carbamoyl, sulfamoyl, cyano, alkoxy, aryloxy, heterocycleoxy, siloxy, acyloxy, carbamoyloxy, amino, alkylamino, imide, ureido, sulfonyl Also included are famoylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl, and heterocyclic thio groups, as well as spiro compound residues, bridged hydrocarbon compound residues, and the like.

The alkyl group represented by R preferably has 1 to 32 carbon atoms, and may be linear or branched.

The aryl group represented by R is preferably a phenyl group.

Examples of the acylamino group represented by R include an alkylcarbonylamino group and an arylcarbonylamino group.

Examples of the sulfonamide group represented by R include an alkylsulfonylamino group and an arylsulfonylamino group.

Examples of the alkyl component and aryl component in the alkylthio group and arylthio group represented by R include the alkyl group and aryl group represented by R above.

The alkenyl group represented by R preferably has 2 to 32 carbon atoms, and the cycloalkyl group preferably has 3 to 12 carbon atoms, particularly 5 to 7 carbon atoms, and the alkenyl group may be linear or branched.

The cycloalkenyl group represented by R has 3 to 3 carbon atoms.
12, especially those of 5 to 7 are preferred.

Sulfonyl groups represented by R include alkylsulfonyl groups, arylsulfonyl groups, etc.; sulfinyl groups include alkylsulfinyl groups, arylsulfinyl groups, etc.; phosphonyl groups include alkylphosphonyl groups, alkoxyphosphonyl groups, and aryloxyphosphonyl groups. , arylphosphonyl group, etc.; Anru group includes alkylcarbonyl group, arylcarbonyl group, etc.; carbamoyl group includes alkylcarbamoyl group, arylcarbamoyl group, etc.; sulfamoyl group includes alkylsulfamoyl group,
Arylsulfamoyl groups, etc.; Acyloxy groups include alkylcarbonyloxy groups, arylcarbonyloxy groups, etc.; carbamoyloxy groups include alkylcarbamoyloxy groups, arylcarbamoyloxy groups, etc.; ureido groups include alkylureido groups, arylureido groups, etc. : Examples of the sulfamoylamino group include an alkylsulfamoylamino group and an arylsulfamoylamino group; Preferably the heterocyclic group is a 5- to 7-membered one, specifically a 2-furyl group and a 2-thienyl group. , 2-pyrimidinyl group, 2-benzothiazolyl group, etc.; as the heterocyclic oxy group, those having a 5- to 7-membered heterocycle are preferred, for example 3.
4,5.6-tetrahydropyranyl-2-oxy group, ■
-Phenyltetrazole-5-oxy group, etc.: The heterocyclic thio group is preferably a 5- to 7-membered heterocyclic thio group, such as 2-pyridylthio group, 2-penzothiazolylthio group, 2,4-diphenoxy- 1,3,5-) lyazole-6 monothio group, etc.; as a siloxy group, a trimethylsiloxy group, a trimethylsiloxy group, a dimethylbutylsiloxy group, etc.; as an imide group, a succinimide group, a 3-heptadecylsuccinimide group , 7-thalimide group, glutarimide group, etc.; examples of spiro compound residues include spiro [3,3]hebutan-1-yl; examples of bridged hydrocarbon compound residues include hiscyclo [2゜2.
1] Hebutan-1-yl, tricyclo [3°3.1.
13.7]decane-1-yl, 7.7-dimethyl-bicyclo[2,2,1]heptane-1-yl, and the like.

Groups that can be separated by reaction with the oxidized product of the color developing agent represented by X include, for example, halogen atoms (chlorine atom, bromine atom, fluorine atom, etc.), alkoxy, aryloxy, heterocyclic oxy, acyloxy, sulfonyloxy, alkoxy Carbonyloxy, aryloxycarbonyl, alkyloxalyloxy, alkoxyoxalyloxy, alkylthio, arylthio, heterocyclic thio, alkyloxythiocarbonylthio, acylamino, sulfonamide, nitrogen-containing heterocycle bonded via N atom, alkyloxycarbonylamino , aryloxycarbonylamino,
carboxyl, (R,' is the same as R in the above general formula [M-IF, Z' is the same as Z in the above general formula [M-IF, R2' and R3' are hydrogen atoms, aryl groups, represents an alkyl group or a heterocyclic group),
Preferred is a halogen atom, especially a chlorine atom.

Examples of the nitrogen-containing heterocycle formed by Z or Z' include a pyrazole ring, imidazole ring, triazole ring, or tetrazole ring, and examples of the substituents that the ring may have include those described for R above. can be mentioned.

What is represented by the general formula [M-II is more specifically represented by, for example, the following general formulas [M-I[] to [M-■].

General formula [M-1111 In the above general formula [M-I11~[M-■], R□~
R8 and X have the same meanings as R and X in the general formula [M-IF].

Among the couplers represented by the general formula [M-IF], those represented by the following general formula [M-■] are preferred.

In the formula, R, , X and Zl are the general formula [R in M-11
, X and Z.

Among the magenta couplers represented by the general formulas [M-II] to [M-■], particularly preferred ones are those represented by the general formula
It is a magenta coupler represented by [M-I[].

General formula [Ring formed by Z in M-IF and general formula [M-■] Substituents that the ring formed by Zl in [M-■] may have, and general formula [M-II]
R2 to R8 in ~[M-VI] are preferably those represented by the following general formula [M-ff].

General formula [M-ff]-R'-3o□-R2 In the formula, R1 represents an alkylene group, and R2 represents an alkyl group, a cycloalkyl group, or an aryl group.

The alkylene group represented by R1 preferably has 2 or more carbon atoms in the straight chain portion, more preferably 3 to 6 carbon atoms, and it does not matter whether the straight chain has one branch or not.

The cycloalkyl group represented by R2 is preferably a 5- to 6-membered one.

Furthermore, when used for positive image formation, the most preferable substituents R and R1 on the heterocycle in the general formulas [M-Il to [M-■] are those represented by the following general formula [M-Xl] It is.

General formula [M-Xl Ro R8゜-〇- R9, R, o and R11 in the formula [M
-■] has the same meaning as R.

Also, two of the above R9+R1O and R1, for example, R5
and Rlo may be combined to form a saturated or unsaturated ring (e.g., cycloalkane, cycloalkene, heterocycle), and R1□ may be combined with the ring to form a bridged hydrocarbon compound residue. You can.

Among the general formulas [M −X ], (+)R
When at least two of 9-R1 are alkyl groups,
(■) One of R3-R1, for example, R1, is a hydrogen atom, and the other two R3 and Rlo combine to form a cycloalkyl together with the root carbon atom.

Furthermore, in (1), it is preferable that two of R9 to R1□ are alkyl groups and the other one is a hydrogen atom or an alkyl group.

In addition, when used for negative image formation, the substituent R on the heterocycle
and R1 are most preferably represented by the following general formula [M-
XI].

General formula [M-XI] R12CH2- In the formula, R1□ has the same meaning as R in the general formula [M-Il.

Preferred as R12 is a hydrogen atom or an alkyl group.

Typical specific examples of the coupler represented by the general formula [M-1] are shown below.

■ CH3 ■ CH3 H3 Shi H3 H3 Cs Hl 3 Shifu H15 Shi@tl17(L) H3 ■ H3 ρθ Shit-131Nl-1ssu2 Shi16 H33IN-I
N-~ (,l-(,l
Q-Oll In addition to the above typical examples of compounds preferably used in the present invention, specific examples of compounds preferably used in the present invention include pages 66 to 1 of the specification of Japanese Patent Application No. 61-9791.
Among the compounds described on page 22, No. 1-4.
6.8-17.19-24.26-43.45-59.
61-104.106-121.

Compounds represented by 123 to 162 and 164 to 223 can be mentioned.

Also, the coupler is described in the Journal of the Chemical
Society (Journal of the Ch)
chemical society), Parkin (P e
rkin) I (1977), 2047-2052
, U.S. Patent No. 3,725,067, JP-A-59-994
No. 37, No. 58-42045, No. 59-162548
No. 59-171956, No. 60-33552,
It can be synthesized by referring to No. 60-43659, No. 60-172982, No. 60-190779, etc.

The above couplers usually contain IX 10 per mole of silver halide.
-3 mol to 1 mol, preferably I X 10-2 mol-
A range of 8×10-' moles can be used.

The magenta power puller preferably used in the present invention can also be used in combination with other types of magenta couplers.

The embodiment in which a nitrogen-containing heterocyclic mercapto compound is used in combination with the high silver chloride photographic material used in the processing method of the present invention not only achieves the desired effects of the present invention well, but also allows the bleach-fix solution to be contained in the color developer. This can be cited as a more preferred embodiment of the present invention because it has the additional effect of minimizing the influence on photographic performance that occurs when mixed.

The nitrogen-containing heterocyclic mercapto compound has the following general formula [S]
Compounds represented by are preferably used.

General formula [5] (In formula [S], Zo is a heterocyclic residue, and M is a hydrogen atom, an alkali metal atom, or ammonium.) More preferably, the general formula [Sol] represented by the following general formula [
Sol 5・per′・, (In the formula [Sol, Q represents an atomic group necessary to form a 5- or 6-membered heterocycle or a 5- or 6-membered heterocycle fused with a benzene ring, (M represents a hydrogen atom or a cation.) The mercapto compound represented by the general formula [Sol] will be described below.

In the general formula [Sol, Q represents an atomic group necessary to form a 5- or 6-membered heterocycle or a 5- or 6-membered heterocycle fused with benzene rings; Examples include imidazole ring, tetrazole ring, thiazole ring, oxazole ring, selenazole ring,
Examples include a benzimidazole ring, a naphthoimidazole ring, a benzothiazole ring, a naphthothiazole ring, a benzoselenazole ring, a naphthoselenazole ring, and a benzoxazole ring.

Examples of the cation represented by M include alkali metals (
Examples include sulfur, lithium, potassium, etc.), ammonium groups, and the like.

Among the mercapto compounds represented by the general formula [So], the following general formula [SA], [SB], [SC] or [SD
] are more preferable.

General formula [SA,] In formula [SA], RA represents a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, a halogen atom, a carboxyl group or a salt thereof, a sulfo group or a salt thereof, or an amine group, and Z is - It represents NH-1-〇-1 or -S-, and M has the same meaning as M in general formula [S].

General formula [SB] Ar In the formula [SB], Ar represents an alkyl group, an alkoxy group, a carboxyl group or a salt thereof, a sulfo group or a salt thereof, a hydroxyl group, an amine group, an acylamino group, a carbamoyl group, or Represents a sulfonamide group. n represents an integer from 0 to 2. M has the same meaning as M in general formula [S].

In general formulas [SA] and [SB], RA and R
Examples of the alkyl group represented by B include methyl group, ethyl group, butyl group, etc.; examples of alkoxy groups include methoxy group, ethoxy group, etc.; examples of salts of carboxyl group or sulfo group include sodium salt, Examples include ammonium salts. Furthermore, RA and R
B may be a hydroxyl group.

In the general formula [SA], examples of the aryl group represented by RA include a phenyl group and a naphthyl group, and examples of the halogen atom include a chlorine atom and a bromine atom.

Examples of the acylamino group represented by RB in the general formula [S B] include methylcarbonylamino group and benzoylamino group, examples of the carbamoyl group include ethylcarbamoyl group and phenylcarbamoyl group, and examples of the sulfonamide group include Examples include methylsulfonamide group and phenylsulfonamide group.

The above-mentioned alkyl groups, alkoxy groups, aryl groups, amino groups, acylamino groups, carbamoyl groups, sulfonamide groups, etc. further include those having substituents.

General formula [SC] RA In formula [SC], Z represents -N-1 oxygen atom or sulfur atom. RAl represents a hydrogen atom, an alkyl group, or a heterocyclic group, RA□ represents a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, -CORA, or -3OQRA6, and RA2 and RA3 represent a hydrogen atom, It represents an alkyl group or an aryl group, and R□ and RAS represent an alkyl group or an aryl group. M has the same meaning as M in general formula [S].

RA in general formula [SC], RAl+ RA2+
Examples of the alkyl groups represented by RA3, RA4, and RAS include methyl, benzyl, ethyl, and propyl groups, and examples of the aryl groups include phenyl and naphthyl groups.

Examples of the alkenyl group represented by RA and RAI include a propenyl group, and examples of the cycloalkyl group include a cyclohexyl group.

Examples of the heterocyclic group represented by RA include furyl group and pyridinyl group.

Above RA, RA□, RA2+ RA3. R□ and R
The alkyl group and aryl group represented by A5, the alkenyl group and cycloalkyl group represented by RA and RAI, and the heterocyclic group represented by RAI further include those having a substituent.

General formula [SD] In the formula [SDl, RA and M are each represented by the general formula [
SC] represents a group having the same meaning as RA and M in [SC]. Also R
BI and RB□ represent the same groups as RAI and RA2 in the general formula [SC], respectively.

Specific examples of purine derivatives and compounds represented by the general formula [SDl are shown below, but are limited to these.
3-4 S-53-6 S-73-8 HH 5A-I 5A-2S
A-33A-4 SA-55A-6 SA-75A-8 SB-I SB-2B-
7 Carp 96 - Compounds represented by the above general formula (SO) are described, for example, in Japanese Patent Publication No. 40-28496, Japanese Patent Application Laid-Open No. 50-89034, Journal of Chemical Society (J, Chem,
Soc, ) 49.1748 (1927), 4237 (
1952), Journal of Organic Chemistry (J, Org, Chem,) 39.2469 (1
965), U.S. Patent No. 2,824,001, Journal of the Chemical Society, 1723 (195
1), Japanese Patent Application Publication No. 56-111846, British Patent Nos. 1 and 2
No. 75,701, U.S. Pat. No. 3,266,897, U.S. Pat.

The compound represented by the general formula [So] (hereinafter referred to as compound (
In order to incorporate silver halide emulsion layers containing silver halide grains according to the present invention, water or an organic solvent miscible with water (for example, methanol,
It can be added after being dissolved in ethanol, etc.). Compound Cs o) may be used alone, or in combination of two or more compounds represented by the general formula [So], or in combination with the general formula [So].
] The compound may be combined with other stabilizers or anti-braking agents other than the compounds shown.

The compound (So) is generally added at the end of the chemical sensitization of silver halide, but it can be added during the formation of silver halide grains, from after the formation of silver halide grains to before chemical sensitization. It is also possible to add it at any time selected from the start of chemical sensitization, during chemical sensitization, at the end of chemical sensitization, and after the end of chemical sensitization during the coating solution preparation step. Although it can be added to one or both of the beginning and end of chemical sensitization, the method of adding it to both is most preferred in order to enhance the effect of the present invention.

There is no particular restriction on the amount added, but it is usually from 1 x 10-' mol to 1 x 10-1 mol per mol of silver halide.
moles, preferably l x 10-5 moles to l x 10
- It is added in a range of 2 moles.

The silver halide grains used in the silver halide emulsion layer of the photographic material used in the processing method of the present invention contain at least 70 mol% of silver chloride, and the remainder may contain bromide and iodide; Silver is preferable, and bromide and iodide are preferably contained in extremely small amounts. In a special case, it is also a preferred embodiment that the blue-sensitive layer is made of silver halide containing about 30 mol% of bromide, and the other two layers, for example, the green-sensitive layer and the red-sensitive layer, contain about 99% of chloride. It is one.

The silver halide is preferably a core-shell particle and has a double layer structure.

The grains consist of at least two regions differing in halide composition, such as one core and at least one shell, with at least one region B containing at least 10 mol% silver bromide, preferably at least 25 mol% silver bromide. silver bromide, preferably at least 25 mole % silver bromide, with the proviso that 5
Contains 0 mol% or less of silver bromide.

Region B can be present as a core or as a shell around the core. The particles preferably include a core surrounded by at least one region B. In that case, region B can be present in the silver halide grain as a shell or on the surface of the crystal.

In other embodiments, the grains have at least one zone ZBr having a high content of at least one mole percent bromide and no bromide-rich zone ZBr on the surface of the silver halide grains.

The silver bromide rich zone ZBr in these grains can exist either as a core or as a layer within the silver halide grains.

Silver halide emulsions may be prepared by conventional methods (eg, single flow or double flow with constant or accelerated feeding of material). I) Preparation method by double inflow method with Ag adjustment is particularly preferred; Research Disclosure No.
17643, Sections I and ■.

Emulsions can be chemically sensitized. Particularly preferred are sulfur-containing compounds such as allyl isothiocyanate, allylthiourea or thiosulfate. Reducing agents can also be used as chemical sensitizers, and they are described, for example, in Belgian patents 493,464 and 568,687.
tin compounds such as those described in Belgian Patent No.
Polyamines such as diethyllenetriamine or aminomethylsulfinic acid derivatives according to No. 47,323. Noble metals and precious metal compounds such as gold, platinum, palladium, iridium, ruthenium or rhodium are also suitable sensitizers. This chemical sensitization method was developed by the Coitschrift Ver Bissenschaftliche Photography (
Z, Wiss, Photo, ) 46.65-72 (1
951) Earl Koslovsky (R, Kos 1o
Vsky): See also Research Disclosure No. 17643, Section 2 above.

The emulsions can be sensitized by optically known methods, for example using common polymethine dyes such as neutrocyanines, basic or acidic carbocyanines, rhodacyanines, hemicyanines, styryl dyes, oxonols and the like;・M Hammer (F, M, Hamer
)'s "The Cyanine Dyes and Related Compounder J"
and related compounds) (19
64) Ullmanns Enzyklpad
ie der technischen chemie
) 4th edition, volume 18, page 431 and the following, and see Research Disclosure No. 17643, section ① above.

Conventional antifoggants and stabilizers can be used in the photographic materials according to the invention. Azaindenes are particularly suitable stabilizers, with tetra- and penta-azaindenes being preferred, especially those substituted with hydroxyl or amino groups. Compounds of this type are described, for example, in the paper by Birr, Zeitschrift Ver.
Bissenschaftliche Photograph ((Z, Wis
s, Photo) 47.1952, p, 2-58, and the above Research Disclosure No. 17643,
As shown in Section ■.

The components of the photographic material can be combined by conventional known methods; for example, U.S. Pat. See No. 3,765,897. Components of photographic materials, such as couplers and UV absorbers, can also be combined in the form of charged latexes; see DE 2,541,274 and EP 14,921. The components can also be immobilized in photographic materials as polymers; for example, German Patent Application No. 2,044,992, US Pat. No. 3,370.

See No. 952 and No. 4,080,211.

Customary supports can be used for the photographic material according to the invention, for example supports of cellulose esters, such as cellulose acetate, and supports of polyesters. Paper supports are also suitable and these can be coated, for example, with polyolefins, in particular polyethylene or polypropylene; in this regard see Research Disclosure No. 17643, Section X■, supra.

Common hydrophilic film-forming agents can be used as protective colloids or binders for the layers of photographic materials, such as proteins, especially gelatin, alginic acid or its derivatives such as esters, amides or salts, carboxymethyl cellulose and cellulose. cellulose derivatives such as sulfates, starch or derivatives thereof, or hydrophilic synthetic binders; see also the binders set out in Research Disclosure 17643, supra, Section 1.

The layers of the photographic material on the support can be hardened using conventional methods, for example using epoxides, heterocyclic ethyleneimines or acroyl type thickeners.

Furthermore, the nuclear layer is described in German Patent Application No. 2,218,009
A photographic material suitable for high temperature operation can be made by curing by the method according to the patent. The photographic layer can also be hardened with a diazine, triazine or 1,2-dihydroquinoline hardening agent or a vinyl sulfone type coining agent. Other suitable curing agents include German Patent Application No. 2,439
, No. 551, No. 2,225.230 and No. 2,31
No. 7,672 and the above Research Disclosure
No. 17643, Section ■.

[Specific Effects of the Invention] As explained above, the present invention eliminates the need for additional means such as reprocessing the color developer, making it economically inexpensive, and without deteriorating photographic performance. It has been possible to provide a method for processing a silver halogenide color photographic light-sensitive material in which the photographic performance of the resulting image can always be stably provided even if the amount of replenishment is significantly reduced.

[Specific Examples of the Invention] Hereinafter, the present invention will be specifically explained with reference to Examples, but the embodiments of the present invention are limited thereto.Example 1 The following color developing solution (No. 1) ~No, (122
)) was created and an experiment was conducted.

[Color developer] Potassium carbonate 30g Sulfite
0.5g 3-methyl-4
-Amino-N-ethyl-(β-methanesulfonamidoethyl) -Aniline sulfate 5.5g Hydroxylamine sulfate 2.5g Sodium chloride Listed in Table 1 Chelating agent (listed in Table 1) 3g Add water to bring the total amount IQ,
Adjust the pH to 10.1 using potassium hydroxide and 50% sulfuric acid.

Add 1 ppm of copper ions (added in the form of copper sulfate) and 1 ppm of iron ions (added in the form of iron chloride) to the adjusted color developer No. (1-1)-(1-22), and open the aperture. 35°C1 in a hard vinyl chloride container with a ratio of 150cm2/α (air contact area for IQ color developer is 100cm")
The amount of residual color developing agent (3-methyl-4-amino-N-ethyl-(β-methanesulfonamidoethyl)-aniline sulfate) in the color developing solution before and after storage after storage at 50% relative humidity for 2 weeks. was determined by redox titration method using cerium salt. The results are summarized in Table 1 below. In Table 1, chelating agents A-1 to A-6 represent the following comparative chelating agents.

A-1: l-hydroxyethylidene-1,1-diphosphonic acid A-2 = sodium nitrilotriacetate A-3: sodium ethylenediaminetetraacetate A-4:2
-phosphonobutane-1,3,4-)licarponic acid A-5 = sodium hexametaphosphate A-6; hydroxyethyliminodiacetic acid Also, in Table 1,
DTPA, TTHA, DTPMP and TTHMP
represents the following chelating agent of the present invention.

DTPA Sodium diethylenetriaminepentaacetate T
THA Nitriethylenetetramine Sodium Hexaacetate DT
PMP Sodium diethylenetriaminepentamethylenephosphonate TTHMP: Sodium triethylenetetraminepentamethylenephosphonate From Table 1 above, the chelating agents related to the present invention (
DTPA, TTHAXDTPMP and TTHMP)
It can be seen that the remaining amount of the color developing agent is good when using 3 x 10-2 mol/Q or more of chloride.

Example 2 A photographic material was prepared by sequentially coating the following layers on a paper support laminated with polyethylene from the support side.

Layer 1 - 1.10 g/m2 gelatin, 0.38 g/m2
Blue-sensitive silver halide emulsion (in terms of silver, the same applies hereinafter) and 0
．． 1 dissolved in 55 g/m2 of dioctyl phthalate,
A layer containing 3 mol g/m2 of the following yellow coupler.

Layer 2: Intermediate layer consisting of 0.65 g/m2 gelatin.

Layer 3-1-10g/m2 gelatin, 0.22g/m2
10-3 mol g of 1,OX dissolved in a green-sensitive silver halide emulsion and 0.28 g/m2 of dioctyl phthalate
/m2 of the following magenta coupler.

Layer 4: Intermediate layer consisting of 0.70 g/m2 of gelatin.

Layer 5 - 1.20 g/m2 gelatin, 0.29 g/m2
a red-sensitive silver halide emulsion and 1,75X 10-3 mole g/m2 of the following cyan coupler dissolved in 0.25 g/m2 dibutyl phthalate.

Layer 6 - 1.0 g/m2 gelatin and 0.25 g/m
0.30 g/m2 dissolved in dioctyl phthalate of 2
A layer containing Tinuvin 328 (ultraviolet absorber manufactured by Ciba Kaigy).

Layer 7: Layer containing 0.48 g/m2 of gelatin.

As a hardening agent, 2,4-dichloro-〇-hydroxy-5-sodium triazine was added to layers 2.4 and 7 in an amount of 0.016 per IO of gelatin, respectively.

The average silver halide composition in the silver halide emulsion is shown in Table 2.

Yellow coupler: α-r 4-(1-benzyl-2-
7enyl-3,5-dioxo'-1,2,4-driazolidinyl)]-]αvivalyl-2-chloro-5-γ-(
2,4-di-tert-amylphenoxy)butyramido]acetanilide magenta coupler: 1-(2,4
,6-trichloropher)-3-(2-chloro-
5-octadecylsuccinimideanilino)-5-pyrazolone cyan coupler = 2,4-dichloro-3-methyl-6-
[α-(2,4-Di-tert-amylphenoxy)butyramide]phenol The thus prepared color paper sample was printed and then subjected to running processing using an automatic processor according to the following processing steps.

Processing steps (1) Color development 35°C 45 seconds (2) Bleach fixing 35°C 45 seconds (3) Water washing alternative stabilization 30°
0 90 seconds (4) Drying 60~
The composition of the treatment solution used at 80° C. for 1 minute and 30 seconds is as follows.

[Color developing tank liquid] Potassium bromide 20 mg Potassium chloride Amount listed in Table 2 Potassium sulfite (50% solution) 1.0 m 123-Methyl-
4-Amino-N-ethyl-N-(β-methanesulfonamidoethyl)-aniline sulfate 4.5 g diethylhydroxylamine (85%) 5.0 g triethanolamine 1. Og Potassium carbonate 30g Chelating agent (listed in Table 2) 2.0g Finished with water and adjusted to pH 10.5 with potassium hydroxide or 50% sulfuric acid.

[Color development replenisher] Potassium chloride Amount listed in Table 2 Potassium sulfite (50% solution) 2.0 mQ3-Methyl-4-amino-N-ethyl-N-(β-methanesulfonamidoethyl) -aniline sulfate 7.5 g Diethylhydroxylamine (85%) 7.0g Triethanolamine 10.0g Potassium carbonate 30g Chelating agent (Table 2
2.0g of water to make II2, and the pH was adjusted to 10.40 with potassium hydroxide or sulfuric acid.

[Bleach-fix tank solution] Ethylenediaminetetraacetic acid ferric ammonium dihydrate 60.0g Ethylenediaminetetraacetic acid 3.0g Ammonium thiosulfate (70% solution) 100. OmQ ammonium sulfite (40% solution) Adjust the pH to 5.50 with 27.5 mQ ammonia water or glacial acetic acid, and add water to make the total amount B.

[Bleach-fixing replenisher] Ethylenediaminetetraacetic acid ferric ammonium dihydrate 70.0g Ethylenediaminetetraacetic acid 3.0g Ammonium thiosulfate (70% solution) 120.0ml 11 Ammonium sulfite (40% solution) 35mα pH 5 with aqueous ammonia or glacial acetic acid , 40, and let the total amount be IQ.

[Water wash alternative stable tank liquid and replenisher] 5-chloro-2-methyl-4-isothiazolin-3-one 0.02g2
-Methyl-4-inchazolin-3-one 0.02
g ethylene glycol 1.0g2-
Octyl-4-inchazolin-3-one 0.01g
1-Hydroxyethylidene-1,1-diphosphonic acid (60% aqueous solution) 3.0g
B1Cff3 (45% aqueous solution) 0
．． 65gMg5O, 7H20 (L2g aqueous ammonia (25% ammonium hydroxide aqueous solution) 2.5g nitrilotriacetic acid trisodium salt 1.5g 10% with water
．． and adjust to T)H7.0 with aqueous ammonia and sulfuric acid.

In the running process, the automatic processor is filled with the above-mentioned color developing tank liquid, bleach-fixing tank liquid and stabilizing tank liquid, and the above-mentioned color developing replenisher and bleach-fixing replenisher are added every 2 minutes while processing the color paper sample. This was done without replenishing the water washing alternative stable replenishment solution through a metering pump.

The amount of replenishment to the color development tank is 70m0 per 1m2 of color paper. The amount of replenishment to the bleaching tank was 100 mθ of bleach-fixing replenisher per 1 m 2 of color paper, and the amount of replenishment to the stabilization tank was 200 m 12 of washing substitute stabilizing replenisher.

The stabilization processing baths of the automatic processor are the first to third stabilization baths in the direction of the flow of the photosensitive material. Further, this over-70-liquid was allowed to flow into the previous tank to form a multi-tank countercurrent system.

In addition, the opening ratio of the color developing tank is 50cm2/(2
I conducted an experiment.

When the amount of color developer replenisher added to the color developer tank solution is twice the capacity of the color developer tank, measure the maximum color density of the yellow dye through the wedge-exposed check sample and start. The activity of the developer was evaluated by calculating a relative value with the maximum color density at 100 as 100. Furthermore, the magenta fog density in the unexposed area at the end of the running process was measured.

＼－・） Table 2 In Table 2, the abbreviations 1 for chelating agents have the same meaning as in Example 1.

From Table 2 above, it can be seen that stable running processing characteristics can be obtained by using the chelating agent of the present invention and a color developing solution having a chloride concentration, and by having a silver oxide composition of 70 mol % or more.

Example 3 Experiment No. 2-1, No. 2-9 and No. of Example 2
, 2-11, the same experiment as in Example 2 was conducted except that the amount of replenishment of the color developer was changed as in Example 3 below.

\-1' The chelating agent DTPA in Table 3 means sodium diethylenetriaminepentaacetate as in Example 1.

From Table 3 above, it can be seen that in the processing of the present invention, sufficient photographic density can be obtained even with low replenishment processing.

Example 4 The same procedure as in Example 1 was carried out except that the hydroxylamine sulfate used in Experiment No. 1-3 of Example 1 was changed to the same number of moles of the hydroxylamine derivative represented by the general formula [2]. We conducted an experiment. Using the color developing solution before storage, using the same processing steps and processing solution as in Example 2, and using the color paper (silver chloride content: 70 mol%) used in Experiment No. 2-4. A developing process was performed. The yellow reflection density of the highest density part of the color paper sample after processing was measured using a Konica densitometer PDA-65 (manufactured by Konica Corporation).
Measured using

Table 4 From Table 4, the desired effect of the present invention is further promoted by using the hydroxylamine derivative represented by the general formula [2] in place of hydroxylamine sulfate in combination with the color developer of the present invention. I understand that.

Example 5 A similar experiment was conducted by changing the color developing agent in the color developing solution used in Example 1 to the following (B-1) or (B-2). are both 0
．． 03 It got worse. Similarly, the color developing agent of Example 1 was added to exemplified compounds (C-2), (C-4), and (C-5).
When the same experiment as in Example 1 was carried out by changing to (C-15) and (C-15), almost the same results were obtained.

H2 Example 6 The fluorescent whitening agent (represented by the general formula (3) above) was changed as shown in Table 5 below in the color developing solution used in Experiment No. 2-8 of Example 2, and other was developed according to Example 2. The yellow stain in the unexposed area after processing was measured using a Konica densitometer PDA-65 (manufactured by Konica Corporation).
Measured using

The results are summarized in Table 5.

Table 5 (F-1) (Fluorescent Brightener) From Table 5, yellow stain can be further improved by using the triazylstilbene fluorescent brightener represented by the general formula [3] in combination with the present invention. It turns out that

Example 7 The I)H of the bleach-fix solution used in Example 2 was changed as shown in Table 6 below, and the other values were the color paper sample and processing solution (before running) used in Experiment No. 2-6 of Example 2. processing liquid)
Development processing was performed using. The minimum reflection density and desilvering property of the yellow dye after treatment were evaluated. Note that the minimum reflection density was measured using the PDA-65 described above, and the desilvering property was measured by a fluorescent X-ray method.

Table 6 As is clear from Table 6 above, when the pH of the bleach-fix solution increases, both the minimum reflection density and desilvering performance deteriorate, and when the pH is too low, the minimum reflection density increases.

When I)H of the bleach-fix solution is 5-6.3 (No, 3-7), both the minimum reflection density and desilvering property are good, and especially good when the pH is 5.2-5.9, This can be said to be a preferred embodiment of the present invention.

Example 8 As shown in Table 7 below, the color developer used in Experiment No. 29 of Example 2 contained an alkanolamine (the general formula [D
) or polyalkyleneimine (compound represented by the general formula [4]) at 5 g/each.
(l) was added to the color developer, and the color developer was stored at 38°C in a glass container with an open area ratio of 100 cm2/12 (air contact area is 100 cm2 for the IQ color developer), and the tar property of the color developer was evaluated after 3 weeks. .

However, the appearance of the liquid was divided into the following four levels.

10 + 1 A large amount of tar generated 10 Tar attached to the wall (black) 1 Slight tar generated on the surface - No tar generated. Each color developer was used before storage, and the others were Experiment No. 2-9 of Example 2. Development was performed in the same manner as above, and the yellow reflection density of the highest density area was measured.

Table 7 From Table 7 above, by using alkanolamine or polyalkyleneimine in combination with the present invention, the storage stability of the color developing solution is improved, a sufficient dye concentration can be obtained, and the suitability for rapid processing is promoted. It turns out that it will be done.

Example 9 A sample was prepared by changing the magenta coupler of the color paper used in Experiment No. 2-8 of Example 2 to the magenta coupler listed in Table 8 below, and the others were Experiment No. 2 of Example 2. An experiment similar to 2-8 was conducted.

The magenta dye reflection density of the unexposed area and the maximum density area after processing was measured.

The results are shown in Table 8.

U From Table 8, by using the present invention in combination with a pyrazolotriazole coupler as a magenta coupler, the stain in the unexposed area is further improved and the maximum strength density is also improved.

Example 1O Experimental color paper was created by using the nitrogen-containing heterocyclic mercapto compound listed in Table 9 below in layer 11, layer 3, and layer 5 in addition to the color paper used in Experiment No. 2-9 of Example 2. . Using this color paper, 0.5 mQ of the bleach-fix solution used in Example 2 was added per 10 color developing solutions, and the other conditions were developed in the same manner as in Experiment No. 29 of Example 2, and then the gamma value of the dye was determined. (slope value between density 0.8 and density 1.8) is calculated, and the one without bleach-fixing solution is 100
As is clear from Table 9, by using the specific heterocyclic mercapto compound according to the present invention in the present invention, the relative gamma value does not change much even when the bleach-fix solution is mixed into the color developing solution. It can be seen that the film exhibits stable photographic characteristics.

[Brief explanation of the drawing]

FIG. 1 is a schematic diagram showing an example of processing steps including the processing method of the present invention. ■...Color developing tank 2...Bleach fixing tank 3...
・Bleaching tank 4...Fixing tank 5...Stabilizing tank

Claims (2)

[Claims] (1) A color-forming silver halide color photographic material containing at least one compound represented by the following general formula [1] and at least 3×10^-^2 mol/l of chloride. developer. General formula [1] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, A_1, A_2, A_3, A_4 and A_5
may be the same or different, -COOM_1 or -P
Represents O_3M_2M_3. M_1, M_2 and M_
3 may be the same or different and represent a hydrogen atom, an alkali metal atom or an ammonium ion, and n is 1 or 2.
represents. ] (2) A silver halide color photographic light-sensitive material whose silver halide emulsion layer contains silver halide grains containing at least 70 mol % of silver chloride is processed with the color developing solution according to claim 1. A method for processing silver halide color photographic materials.