JPS63106655A - Processing of silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain stable photographic performance even when the amt. of a replenisher added is remarkably reduced, by incorporating silver halide particles contg. silver chloride into a silver halide emulsion layer and by adding a specified compd. and a chloride to a color developing soln. CONSTITUTION:A silver halide color photographic sensitive material having at least one silver halide emulsion layer on the support is imagewise exposed and continuously developed with a color developing soln. contg. a p- phenylenediamine color developing agent under replenishment. The silver halide emulsion layer contains silver halide particles contg. >=70mol% silver chloride. The color developing soln. further contains a compd. represented by formula I and a chloride. The amt. of the chloride is >=2X10<-2>mol per 1l color developing soln. In the formula I, each of R1 and R2 is alkyl group or hydrogen atom but both of them are not hydrogen atom and they may form a ring. The photographic performance of the resulting images is always stabilized even when the amt. of a replenisher added to the developing soln. is remarkably reduced.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for processing silver halide color photographic materials.

More specifically, the present invention relates to a method for processing silver halide color photographic materials, which drastically reduces the amount of replenishment and continuously forms stable color photographic images.

[Background of the Invention 1] Generally, when processing silver halide color photographic materials (hereinafter referred to as photographic materials), in order to keep the composition of the color developer constant and maintain photographic performance, a certain amount of development is carried out per unit area of the photographic material. Replenishment fluid is replenished.

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 Publication Nos. 2,007,459 and 2,007
, 457 and 2,717,674, U.S. Pat.
S-A) No. 3,647,461, No. 3.647,46
2 and 4.188.007 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 a replenisher that does not contain any halides, this still results in relatively large volumes of overflow liquid. is bringing about. 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 often used in which the halides in the overflow liquid are removed, the missing 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 unit and is generally expensive. Another drawback is that maintenance work is extremely complicated, such as requiring analytical operations 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 is a considerable amount.
have accumulated to a high concentration.

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 having an extremely high silver halide content of 9 silver chloride is processed with a replenishment amount low enough not to 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 the ions do not have a concentration of insects.

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 the results were not significant. It was found that short processing times were not achievable.

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; Due to ammonium ions, it has been found that as the ratio of silver chloride increases, physical development becomes easier and 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.

Based on these analyses, the present inventors have conducted extensive research,
Photographic materials are processed by processing silver chloride using silver halide grains with a specific concentration or higher, by using a specific compound to replace conventional hydroxylamine during color development, and by containing chloride in a specific amount or higher. We have discovered that all of the above-mentioned drawbacks can be solved, that continuous processing with sufficient crystalline photographic density can be performed, and that stable photographic density can always be obtained, leading to the present invention.

[Object of the Invention] Therefore, it is an object of the present invention to provide a processing method that eliminates these drawbacks and allows consistently stable photographic performance even when the amount of replenishment is significantly reduced.

[Structure of the Invention] The above-mentioned object of the present invention is to imagewise expose a silver halide color photographic light-sensitive material having at least one silver halide emulsion layer on a support, and then remove at least a p-phelenediamine color developing agent. In a method for processing a silver halide color photographic light-sensitive material, the silver halide color photographic material is developed with a color developing solution containing at least 70 mol % of the silver halide emulsion layer, and the color developing solution is continuously processed while being replenished with a replenisher. contains silver halide grains containing silver chloride, and the color developer contains a compound represented by the following general formula [I] and 1 fL of the color developer.
This was achieved by a method for processing silver halide color photographic materials containing at least 2.times.10@-2 moles of chloride per chloride.

General Formula [I] 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.

[Specific Structure of the Invention] The method of the present invention comprises at least the following steps: reducing exposed silver halide to silver, bleaching to oxidize the reduced silver, and fixing to remove silver salts from the recording material. Contains one development step. Bleaching and fixing may in some cases be combined in a known manner, such as in a bleach-fix solution.

Color development takes place in an aqueous development bath. The temperature of the developer can be kept at the usual commonly used levels of 25°C to 50°C, and the development time is quite short for photographic materials using silver halide grains containing more than 70 mol % silver chloride. It has the advantage of being processed.

In the present invention, a compound represented by the general formula [I] is used in the color developer instead of the conventional hydroxylamine sulfate.

Therefore, it is important in the present invention that hydroxylamine sulfate is not included.

In general formula [I], 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 R1 and R2 may be combined to form a ring, for example, a heterocyclic ring such as piperidine or morpholine.

Specific compounds of the hydroxyamine compound represented by the general formula [I] are described in U.S. Patent No. 3,287,1l5, U.S. Pat. However, particularly preferred specific exemplary compounds are shown below.

These compounds of the present invention are usually free amines, hydrochlorides,
It is used in the form of sulfate, p-toluenesulfonate, oxalate, phosphate, acetate, etc.

The concentration of the compound represented by the general formula [I] of the present invention in the color developer is usually 0.2Q/l to 50g/11, preferably 0.5L#! ~30a/11 more preferably 1Mf
There are f1 to 15Mff1.

The compound represented by the general formula [I] of the present invention can be used in place of hydroxylamine sulfate, which has been widely used as a preservative in color developing solutions for conventional silver halide color photographic light-sensitive materials. However, among the compounds of the present invention, for example, N,N-diethylhuman Oxylamine is known to be used as a preservative for black and white developing agents in color developing solutions to which black and white developing agents are added. For example, in the so-called external color development method, in which a color photographic material is developed by a reversal method using a color developing solution containing a coupler, there is a technique in which it is used together with phenidone. (Tokuko Showa 4
5-22198).

In particular, it has been found that the compound of the present invention has sufficiently high stability over time of the liquid even when the sulfite ion concentration is lowered, so that changes in concentration over time can be reduced and photographic performance can be stabilized as a result.

According to the invention, the developer bath is replenished by a replenisher.

Preferably, overflow occurs slightly and there is no need to supply replenishment liquid by other means to compensate for evaporation, but economically it is possible to reduce replenishment to the extent that no overflow occurs at all and lower the liquid level. is the bird drinking method (
It is preferable to automatically supply and correct replenishment fluid using a device such as Bird's Fountain. The replenisher in this case may be the color developing solution mentioned above or the color developing solution having a low concentration.

Water may also be used. In either case, it is necessary that the consumed components of the developer components are sufficiently replenished, but in the present invention, among the halides, which are inhibitory components, the elution of bromide, which has a large inhibitory effect, is extremely small; The amount of elution increases significantly. However, this chloride had a large development accelerating effect in conventional photographic materials using silver chlorobromide emulsions with a high silver bromide ratio, but in the silver halide photographic material of the present invention with a high silver chloride ratio. Since chloride does not have an extremely weak inhibitory effect, if chloride is added to the developer in advance at a concentration above a certain level, the development effect will be masked. Changes in concentration can be made extremely small,
Furthermore, by using the compound represented by the general formula [I] in combination, various drawbacks of light-sensitive materials having a high silver chloride content can also be improved.

Based on the above-mentioned surprising discoveries, a low replenishment system has been completed that causes extremely little change in photographic density, rather than a conventional low replenishment system that has its drawbacks. Therefore, bromide ions in the developer solution of the present invention are preferably contained in extremely low concentrations in both the replenisher and the tank solution, but whether the concentrations of bromide ions in the replenisher and the tank solution are substantially the same? It is desirable to have slightly less bromide ions in the replenisher.

The silver halide in the photographic material of the present invention contains only an extremely low concentration of silver bromide, and the amount eluted during development is extremely small. It is necessary to adjust the amount of ions, and in particular to keep the bromide ion concentration in the replenisher low to prevent an increase in bromide ions that are concentrated by evaporation.

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.

The silver halide grains used in the silver halide emulsion layer of the silver halide color photographic light-sensitive material used in the present invention are as follows:
It is necessary that silver chloride is 70 mol% or more, and 10
Although it is preferable that the silver chloride content be close to 0%, it has been found that when the silver chloride content is 90 mol% or more, an effect that is substantially close to 100% silver chloride can be obtained.

In particular, when the silver chloride content is 95 mol % or more, the desired effects of the present invention are particularly well achieved. Developing agent is 0 per liter of developer solution.
．． It is used in the range of 5 g to 100 (J), but preferably in the range of 2 to 15 g.
It is carried out in the range of 0°C to 80°C, preferably 30°C to 50°C.
Processed in the range of °C.

I)H at which development is carried out is generally 8 or more, preferably 9
．． It is 5 or more.

Development should be carried out in the presence of pH1lii agents, development inhibitors, antifoggants, complexing agents for water softening, preservatives, development accelerators, competitive couplers, fogging agents, auxiliary developer compounds and viscosity modifiers. Can: Research Disclosure
17544. January 1978, Section XXI
, Industrial Observations, Inc. (Indu
trial 0ppotunities Ltd,
), Hoiewell Havant, Hampsht
re, published by GrentBritain, and published by U Ilmans Enzyklpudie der Techniques Hemie.
technology), 4th edition, vol. 18, 1979, especially pages 451, 452 and 46.
See pages 3-465. Suitable developer compositions include Grant Haist, Modern Photographic Processing
otography processing),
John Wiley & Sons
1ley and Sans), 1973, Vol.
1 and 2.

In the present invention, when a manganese salt or a cerium salt is used in combination with the color developer of the present invention, the antioxidant performance of the color developer is further improved, and the deterioration of color development during storage over time is also improved. Since it also exhibits the following effects, it is more preferably used in the present invention.

Manganese salts and cerium salts according to the present invention refer to compounds that release manganese ions or cerium ions when dissolved in a developer, and are preferably used as listed below, but are not limited to these. .

Manganese chloride sulfate Manganese sulfite Manganese bromide Manganese phosphate Manganese nitrate Manganese Potassium permancanate Manganese acetate Manganese oxalate Manganese citrate Manganese ethylene diamine Tetraacetate Manganese' @ Cerium nitrate Cerium chloride Cerium carbonate Cerium phosphate Cerium acetate Cerium citrate Cerium oxalate These manganese salts and cerium salts are preferably used in the form of ions (manganese ions and cerium ions) in the range of 0.1+eg to 100 g, more preferably 0.3 mg per 1fL of color developer.
~20 IQ present, especially 0.5+ag~1
From the viewpoint of the desired effect of the present invention, 0.1 is preferably used.

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 in an amount of 1.6 x 10 -2 mol or less per color developer 11, it is possible to suppress a decrease in color density that is thought to be caused by dissolution physical development of high silver chloride-containing photosensitive materials,
Since the deterioration in preservation ability is extremely slight, we can provide a method for processing silver halide color photographs using a color developing solution or transfer, which enables rapid processing using photosensitive materials containing high silver chloride. In the invention, the concentration of sulfite in the color developer is preferably 1.6×1Q-2 mol/i or less. Furthermore, this effect is better exhibited at 1X10-2 mol/2 or less, more preferably at 4X10-3 mol/4 or less.

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

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

A p-phenylenediamine compound having a water-soluble group is
Compared to phenylenediamine-based compounds that do not have water-soluble groups such as N,N-diethyl-p-phenylenediamine,
Not only does it have the advantage that there is no contamination of the photosensitive material and it does not cause skin irritation, but especially in the present invention, by combining it with the compound represented by the general formula [I], the object of the present invention can be efficiently achieved. can be achieved.

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\
-CH20H.

-(CH2), -NH8O2-(CH2), -CH3,
-(CH2)-0-(CH2)--CHs, -(CH2
Preferred examples include CH2o+-n Cm H2l+1 (m and n each represent an integer of 0 or more), -COOH group, -803H group, and the like.

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

Exemplary color development agent (A-1) Hs C2C2H4N HS O2CH2 (A-2) Hs　C2C2H40H (A-3) H, C, C, H, OH (A-4) H, C2C2H, OCH.

(A-5) HsC2C5HaSO*H (A-6) H, CC, H, OH H2 (A-7) HOH, C2C, H40H (A-8) Hs C4C4H* S Os H (A-9) HIC,C3H,SO,H (A-10) HC82COOH \N/ (A-11) H6, GCH2CH* O soup CH:I (A-1l) CH2CH20suCH.

N.H.

(A-13) Hs C< )CHt CH20fCt Hs(A-1
4) H. worm,) CH, CH, 0iC2Hs (A-15) HsCz C2H, NHSO2CH.

\N/ (A-16) HsC2C2H-OH Among the color developing agents exemplified above, exemplification No. (A-
1), (A-2>, (A-3), (A-4), (A-6
), (A-7) and (A-15), with (A-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
1 x 10-2 to 2 x 1 per fl of normal color developer
It is preferable to use the amount in the range of 0" mol, but from the viewpoint of rapid processing, it is 1.5
A range of 2×10” 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 light-sensitive material, and the color developing agent used in this case includes a dye precursor. A typical dye precursor is JP-A No. 5
Those described in No. 8-65429, No. 58-24131, etc. are used, and specifically, for example, 2',4'-bismethanesulfonamide-4-diethylaminodiphenylamine, 2'-methanesulfonamide-4' −(2
,4,6-doliisobrobyl)benzenesulfonamide-2-methyl-4-N-(2-methanesulfonamidoethyl)ethylaminodiphenylamine, 2'-methanesulfonamide-4'-(2,4,6- doliisobrovir)benzenesulfonamido-4-(hydroxytrisethoxy)diphenylamine, 4-N-(2-methanesulfonamidoethyl)ethylamino-2-methyl-2'
, 4'-bis(2,4゜6-doliisobuOvyl)benzenesulfonamide diphenylamine, 2,4'-bismethanesulfonamide-4-N, N-diethylaminodiphenylamine, 4-n-hexyloxy-2'- Methanesulfonamide-4'-(2,4,6-doliisoprobyl)benzenesulfonamide diphenylamine, 4
-methoxy-2'-methanesulfonamide-4' -(
2,4,6-DoliisobuOvir)benzenesulfonamide diphenylamine, 4-diethylamino-4'-(
2,4,6-Dolyisobrobylbenzenesulfonamido)diphenylamine, 4-n-hexyloxy-3'-
Methyl-4'-(2,4,6-doliisopropylbenzenesulfonamido)diphenylamine, 4-N.

N-diethylamino-4'-(2,4,6-tri,isopropylbenzenesulfonamide) Schiff-ruamine,
Examples include 4-N,N-dimethylamino-2-phenylsulfonyl-4'-(2,4,6-doliisobrobylbenzenesulfonamide)diphenylamine.

The amount of the dye precursor added to the photosensitive material is preferably 0.5 to 22+ag, more preferably 4 to 1 lmg per 100 c, r of the photosensitive material.

When the color developer according to the present invention contains a compound represented by the following general formula [01, it not only exhibits the effects of the present invention better, but also improves the color developer against air oxidation. It is more preferably used because it shows the effect.

General formula [D] (In the formula, R21 is a hydroxyalkyl group having 2 to 6 carbon atoms, R22 and R23 are each a hydrogen atom, and 1 to 6 carbon atoms.
an alkyl group, a hydroxyalkyl group having 2 to 6 carbon atoms,
The pencil group or the integers X' and Z' of formula ~6 each represent a hydrogen atom and a carbon number of 1
-6 alkyl group or a hydroxyalkyl group having 2 to 6 carbon atoms. ) Preferred specific examples of the compound represented by the general formula [0] are as follows.

(D-1) Ethanolamine, (D-2) Jetanolamine, (D-3> Triethanolamine, (D-4) Di-isopropanolamine, (D-5) 2
-Methylaminoethanol, (D-6) 2-ethylaminoethanol, (D-7) 2-dimethylaminoethanol, (D-8) 2-diethylaminoethanol, (D-
9) 1-diethylamino-2-propatool, (D-10) 3-diethylamino-1-propatool, (D-11) 3-dimethylamino-1-propatool, (D-1l) Isopropylaminoethanol, ( D-
13) 3-amino-1-propatol, (D-14)
2-amino-2-methyl-1,3-propanediol, (D-15) ethylenediaminetetraisopropanol, (D-16) benzyljetanolamine, (D-1
7) 2-amino-2-(hydroxymethyl)-1,3
-Propanediol.

These compounds represented by the general formula [D] have an effect of 3 g to 100 g per liter of color developer.
It is preferably used in the range of 6g to 5g, more preferably 6g to 5g.
It is used in the range of 0g.

The color developer according to the present invention has the following general formula [8-I]
When the compound represented by [8-IVI] is contained, the objective effects of the present invention are better achieved, and the bleach fog that occurs when bleaching or bleach-fixing is performed immediately after color development is also improved. Since it is effective, it is more preferably used in the present invention.

General formula [8-I] General formula [8-I] In the formula, R11, R1l, R13 and R1'l are each a hydrogen atom, a halogen atom, a sulfonic acid group, or an alkyl group having 1 to 7 carbon atoms. represents a group, -0R1s. Also, R
15, Rls, R17 and R+a each represent a hydrogen atom or an alkyl group having 1 to 18 carbon atoms. however,
When Rj2 represents 10H or a hydrogen atom, R++ represents a halogen atom, a sulfonic acid group, an alkyl group having 1 to 7 carbon atoms, or -0R1s.

The alkyl groups represented by R11, R11, R13 and R include those having substituents, such as methyl group, ethyl group, 1so-propyl group, n-propyl group, t-butyl group, n-butyl group, hydroxyl group, etc. Examples include a methyl group, a hydroxyethyl group, a methylcarboxylic acid group, a benzyl group, and the alkyl group represented by R+5, R+s, R17, and Rla are as defined above, and further examples include an octyl group.

In addition, the phenyl group represented by R11, R1l, R13 and R14 includes a phenyl group, a 2-hydroxyphenyl group,
Examples include 4-aminophenyl group.

Typical specific examples of the chelate of the present invention are listed below, but the invention is not limited thereto.

(B-I-1) 4-isopropyl-1,2-dihydroxybenzene (B-I-2) 1.2-dihydroxybenzene-3,5-disulfonic acid (B-I-3) 1.2.3- Trihydroxybenzene-5-carboxylic acid (B-I-4) 1.2.3-trihydroxybenzene-5-carboxymethyl ester (B-I-5) 1.2.3-trihydroxybenzene-5-carboxy -n-butyl ester (B-I-6) 5-t-butyl-1,2,3-trihydroxybenzene (B-I-7) 1,2-dihydroxybenzene-3,4,6-trisulfonic acid ( B-If-1) 2.3-dihydroxynaphthalene-6-sulfonic acid (B-I-2) 2.3.8-trihydroxynaphthalene-6-sulfonic acid (B-II-3) 2.3-dihydroxy Naphthalene-6-carboxylic acid (B-II-4) 2, 3-dihydrooxy-8-isopropyl-naphthalene (B-I[-5) 2,3-dihydroxy-8-chloro-naphthalene-6-
Among the above-mentioned sulfonic acid compounds, compounds particularly preferably used in the present invention include 1,2-dihydroxybenzene-3,
Examples include 5-disulfonic acid, and it can also be used as alkali metal salts such as sodium salts and potassium salts.

In the present invention, the general formulas [8-IF and [8-II]
The compound represented by I is 510 to 20 per liter of color developer.
It can be used within a range of 0, preferably 10m! I
Good results are obtained by adding 1 to 10 g of I, more preferably 201 to 3 g.

General formula [B-1111 General formula [B-IVI (In the general formula [B-1
a -0-La -0-La -triG;t-Ls
Z represents Ls-. Here 7 is N-Llo-R4o
1-N-L++ -N-1L 1l- R41L 1l
- R41 and 1 to L13 each represent an alkylene group. R33 to R43 each represent a hydrogen atom, a hydroxyl group, a carboxylic acid group (including its salt), or a phosphonic acid group (including its salt). However, at least two of R33 to R36 are carboxylic acid groups (including salts thereof) or phosphonic acid groups (including salts thereof), and R37 to Rss
At least two of them are carboxylic acid groups (including salts thereof) or phosphonic acid groups (including salts thereof). ) In the above general formulas [B-II[] and [B-IVI], the alkylene groups, cycloalkylene groups, and phenylene groups represented by , and the alkylene groups represented by L1 to L13 include those having substituents. Next, these general formulas [
Preferred specific examples of the compounds represented by 8-1 [[] and [B-rV] are listed below.

[Exemplary Compounds] [8-I[1-11 Ethylenediaminetetraacetic acid [8-111-2] Diethylenetriaminepentaacetic acid [8-111-31 Ethylenediamine-N-(β-hydroxyethyl)-N]
, N' , N' -Triacetic acid [B-1[[-4] Propylenediaminetetraacetic acid [B-1[[-51 Triethylenetetraminehexaacetic acid [B-Iff-6] Cyclohexanediaminetetraacetic acid [B-1 [I-7] 1.2-diaminopropanetetraacetic acid [B-1 [[-8] 1.3-diaminopropan-2-ol-tetraacetic acid [B-n[-9] Ethyl ether diamine tetraacetic acid [B -11 [-101 Glycol ether diamine tetraacetic acid [B-1-11
1 Ethylenediaminetetrapropionic acid [8-III-1l1 Phenyldiaminetetraacetic acid [8-1[[-13] Ethylenediaminetetraacetic acid disodium salt [8-II
I-141 Ethylenediaminetetraacetic acid tetra(trimethylammonium) salt [8-1[[-15] Ethylenethiaminetetraacetic acid tetrasodium salt [8-II-161 Diethylenetriaminepentaacetic acid pentasodium salt [B-II-17] Ethylenediamine -N-(β-hydroxyethyl')-
N,N',N'-triacetic acid sodium salt CB-! l [-18] Propylene diamine tetraacetic acid sodium salt [B-1 [
[-191 Ethylenediaminetetramethylenephosphonic acid [8-! l
l-20] Cyclohexanediaminetetraacetic acid sodium salt [B-III-211 Diethylenetriaminepentamethylenephosphonic acid [B-1 [[-22] Cyclohexanediaminetetramethylenephosphonic acid [B-IV-1] Trilotriacetic acid [B-IV- 2] Iminodiacetic acid [B-TV-3] Nitrilotribrobionic acid [8-TV-4] Nitrilotrimethylenephosphonic acid [B-IV-51 Iminodimethylenephosphonic acid [8-IV-6] Trisodium nitrilotriacetate Salt [8-TV-7] Hydroxyethyliminodiacetic acid sodium salt Among these compounds represented by the general formula [8-IF or [B-IVI], the compound particularly preferably used in the present invention is [B-111- 11, [B-In-21, [B-11
1-5], CB-Ill-8], [8-III-191
, [B-rV-11, [B-■-4] and [B-IV-
71 are mentioned. Furthermore, these general formulas [B-11]
The compound represented by [8-IVI] is preferably used in an amount of 0.1 to 20 g per liter of color developing solution, and particularly preferably used in an amount of 0.3 to 5 g from the viewpoint of the purpose of the present invention.

The compounds represented by the general formulas [B-I] to [B-IVI] may be used alone or in combination. Furthermore, other chelating agents such as oxycarboxylic acids such as citric acid or gluconic acid, phosphonocarboxylic acids such as 2-phosphonobutane-1,2,4-tricarboxylic acid, and polyphosphoric acids such as tripolyphosphoric acid or hexametaphosphoric acid may be used in combination. You can use it as well.

In the present invention, it is preferable to use a triazylstilbene fluorescent brightener represented by the following general formula [1] in the color developing solution according to the present invention because fogging will be less likely to occur.

General formula [11[] In the formula, Xl, X2, Yl and Y2 are each a hydroxyl group, a halogen atom such as chlorine or bromine, a morpholino group, an alkoxy group (e.g. methoxy, ethoxy, methoxyethoxy, etc.), an aryloxy group (e.g. phenoxy, p-sulfophenoxy, etc.), alkyl groups (e.g. methyl, ethyl, etc.), aryl groups (e.g. phenyl, methoxyphenyl, etc.), amino 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 groups (e.g. anilino, 0-1■
-1p-sulfoanilino, 0. -1■-1p-riOroanilino, 0-1l-1p-toluidino, O-1di-1D
-carboxyanilino, 0-1-1, p-hydroxyanilino, sulfonaphthylamino, 0-1■-1p-aminoanilino, 0-1l+, p-anilino, etc.). M
represents a hydrogen atom, sodium, potassium, ammonium or lithium.

Specifically, the following compounds may be mentioned, but the invention is not limited thereto.

The triadylstilbene-based brightener represented by the general formula [1111] can be synthesized, for example, by the usual method described in "Fluorescent Brighteners" edited by Japan Chemical Industry Association (published in August 1976), page 8. Can be done.

These triadylstilbene type brighteners are preferably used in an amount of 0.2 to 6 g, particularly preferably 0.4 to 3 g, per liter of the color developing solution used in the present invention.

The color developer of the present invention 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. Typical poly(alkyleneimines) include compounds represented by the following general formula.

General formula [I'] R2'-f-R1'-N+7 (wherein, R1' represents an alkylene group having 1 to 6 carbon atoms, R2' represents an alkyl group, n' is 500 to 20,
Represents an integer of 000. ) The alkylene group having 1 to 6 carbon atoms represented by R1' may be linear or branched, and is preferably an alkylene group having 2 to 4 carbon atoms, such as an ethylene group, a propylene group, a butene group, an isobutyne group, Examples include dimethylethylene group and ethylethylene group. R2
The alkyl group represented by ' preferably has 1 to 4 carbon atoms.
It is an alkyl group such as a methyl group, an ethyl group, a propyl group, etc., and also includes those having a substituent (for example, a hydroxyl group). 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 R+' is an ethylene group is most preferred for the purposes of the present invention. Specific examples of poly(alkylene imine) used in the color developer of the present invention are shown below, but the present invention is not limited thereto. .

Exemplary Compounds FAI-1 Poly(ethyleneimine) PAI-2 Poly(propyleneimine) FAI-3 Poly(buteneimine) FAI-4 Poly(isobutyneimine) FAI-5 Poly(N-methylethyleneimine) PAI-
6 poly(N-β-hydroxyethylethyleneimine) PAI-7 poly(2,2-dimethylethyleneimine) PAI-8 poly(2-ethylethyleneimine) PAI-
9 Poly(2-methylethyleneimine) poly(alkyleneimine) can be used in the color developer in any amount that can achieve the purpose of the present invention, but generally from 0.1 to 1 ffi of the color developer. Soog is preferred, and more preferably used in a range of 0.5g to 300g.

It was disclosed in JP-A-56-94349 that when the poly(alkylene imine) of the present invention 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. It is stated in the No. However, in this method, especially when heavy metals are mixed in, hydroxylamine decomposes and storage stability decreases, so it is not only insufficient as a storage stability improvement technique, but also has an excellent effect as a preservative and prevents heavy metals from mixing. When hydroxylamine derivatives such as diethylhydroxylamine and dimethylhydroxylamine, which the present inventors have discovered as strong preservatives for color developers, are used in color developing solutions, coloring of the solution and the resulting coloring of photosensitive materials, containers, etc. There is no mention in the above-mentioned patent publication that polyalkyleneimine effectively solves the problem of contamination. In other words, the problem of coloring of the liquid and contamination of photosensitive materials and containers due to it does not occur with hydroxylamine, but is a problem that specifically occurs when hydroxylamine derivatives such as diethylhydroxylamine and dimethylhydroxylamine are used. The existence of such a problem has not been known to date, and furthermore, the fact that polyalkyleneimine effectively solves this problem is a completely unexpected and surprising effect.

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 photosensitive materials such as those of the present invention, but when color development is performed for a long time of 150 seconds or more, 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 especially true when the color development process is 180%
This becomes noticeable when the time is longer than seconds.

The replenishment amount is processed in the range of 300 vQ to 1 (h1l) per V of photographic material, but in order to maximize the effect of the present invention, it should be processed in the range of 150 ij2 to 30 ml.

Particularly preferably, the range is from 11G to 150, and most preferably from 100 to 1.

Additionally, volume losses due to evaporation can be avoided by setting the replenishment rate at a level slightly less than the rate at which developer is carried away from the equipment, and any remaining capacity losses can be accounted for by adding replenisher from a simple automatic replenishment device. It has been found that by supplementing, it can be easily compensated automatically.

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.

A preferred developer of the present invention preferably does not substantially contain benzyl alcohol. Here, "substantially free" refers to a benzyl alcohol content of 2 iQ/l 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 failure of adhesion to photographic materials due to oil precipitation, and tar formation due to oxidation of color developing agents. Generate troubling problems.

Furthermore, since the solubility is extremely low, if the above-mentioned prepared concentration kit is directly put into a developing tank, a mechanical mixing device is required, which is extremely complicated. Therefore, it has been found that 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 bleach solution or bleach-fix solution used in the bleaching process, and the metal complex salt oxidizes metallic silver produced by development and converts it into silver halide. It has the effect of coloring the uncolored parts of the coloring agent, and its composition is that metal ions such as iron, cobalt, copper, etc. are coordinated with aminopolycarboxylic acid or organic acids such as oxalic acid and citric acid. The most preferred organic acids used to form such metal complexes of organic acids 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 include the following.

[1] Ethylenediaminetetraacetic acid [2] Diethylenetriaminepentaacetic acid [3] Ethylenediamine-N-(β-oxyethyl)-N, N', N
' -Triacetic acid [4] Propylenediaminetetraacetic acid [5] Nitrilotriacetic acid [6] Cyclohexanediaminetetraacetic acid [7] Iminodiacetic acid [8] Dihydroxyethylglycinecitric acid (or tartaric acid) [9] Ethyl etherdiamine tetraacetic acid [ 10] Glycol ether diamine tetraacetic acid [11] Ethylenediamine tetrapropionic acid [1l]
Phenylenediaminetetraacetic acid [13] Ethylenediaminetetraacetic acid disodium salt [14] Ethylenediaminetetraacetic acid tra(trimethylammonium) salt [15] Ethylenediaminetetraacetic acid tetrasodium salt [16] Diethylenetriaminepentaacetic acid pentasodium salt [17] Ethylenediamine- N-(β-oxyethyl)
-N,N',N'-Sodium triacetate [18] Sodium propylene diamine tetraacetate [19] Sodium nitriloacetate [20] Sodium cyclohexanediamine tetraacetate The bleaching solution used is an organic acid such as those mentioned above. In addition to containing a metal complex salt as a bleaching agent, it can also contain various additives. As additives, it is desirable to include rehalogenating agents, metal salts, and chelating agents such as alkali halides or ammonium halides, such as potassium bromide, sodium bromide, sodium chloride, and ammonium bromide.

Also borate, oxalate, acetate, carbon I! p of salts, phosphates, etc.
H[i agents, alkylamines, polyethylene oxides, etc., which are known to be added to normal bleaching solutions, can be added as appropriate.

Furthermore, the fixer and bleach-fixer contain ammonium sulfite,
Sulfites such as potassium sulfite, sodium bia, ammonium metabisulfite, potassium metabisulfite, sodium metabisulfite, boric acid, borax, sodium hydroxide,
pH1lj consisting of various salts such as potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, ammonium hydroxide, etc.
A single WB agent or two or more types of WB agents can be included.

When processing is carried out while replenishing the bleach-fixing solution (bath) with a bleach-fix replenisher, the bleach-fixing solution (bath) may contain thiosulfate, thiocyanate, sulfite, etc. These salts may be added to the replenisher to replenish the processing bath.

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.
Good when.

In the process 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, etc. For example, electrolysis National Patent No. 2,299.667), precipitation method (Japanese Unexamined Patent Publication No. 52-73037, National Patent No. 2.331,2)
20), ion exchange method (JP-A-51-17114,
The Japanese Patent No. 2.548.237) and the metal substitution method (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 → water washing (2) color development → bleach fixing → small amount of water washing → water washing (3) color development → bleach fixing → water washing → stable (4) color development → bleach fixing → stable (5) color development → Bleach-fix → 1st stable → 2nd stable (6) Color development → Washing with water (or stable) → Bleach-fixing → Washing with water (
(7) Color development → stop → bleach-fix → water washing (or stable) (8) color development → bleach → water washing → fixing → water washing → stable (9) color development → bleaching → fixing → water washing → stable (10) ) Color development → bleaching → washing with small amount of water → fixing → first stable → second stable (11) color development → bleaching → washing with small amount of water → fixing → washing with small amount of water →
Washing with water → stable (1l) color development → washing with a small amount of water → bleaching → washing with water → fixing →
A small amount of water washing→Water washing→Stabilization (13) Color development→Stop→Bleaching→Small amount of water washing→Fixing→'A small amount of water washing→Water washing→Stabilization Among these steps, steps (4) and (5) are particularly preferably used.

Another preferred embodiment of the processing method of the present invention is a method in which part or all of the overflow solution of the color developing solution according to the present invention is allowed to flow into the subsequent bleaching solution or bleach-fixing solution. This is because when the color developing solution according to the present invention is allowed to flow into the bleach or bleach-fix solution at a constant rate, the generation of sludge in the bleach or bleach-fix solution is suppressed, and surprisingly, the generation of sludge from the bleach-fix solution is suppressed. This is because silver recovery efficiency 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 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 can contain, for example, a non-diffusive color coupler, generally a phenolic or alpha-naphthol based coupler, which produces a cyan partial color image. The green-sensitive layer may contain at least one non-diffusive color coupler, usually a 5-pyrazolone color coupler, and a birazolotriazole, producing a magenta partial color combination, for example. The blue-sensitive layer can contain, for example, at least one non-diffusive color coupler that produces a yellow color image, generally a color coupler having open-chain ketomethylene groups. Color couplers can be, for example, 6-14- or 2-equivalent couplers.

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

Suitable couplers are disclosed, for example, in the following publications:
Abfu's research report (M itteilungln a
Usden Forschungslaborator
ien der Aofa), Leverkusen/Munich
en), Vol. IIl, p, 111 (19
61) “Color Coupler J” by Naka W. Berb (W, Pe1z)
): K. Venkatar
alan), “Chemistry Op Synthesis Dice J (The Cheg+1rsry of
5ynthetic Dyes), Vol.
, 4.341-387, Academic Press (A
(1971)
:T.H.James
, r+f-setrio7-zapaphotographic・
Process J
tographtc process), 4th edition, 35
Pages 3-362; and the magazine Research Disc 0-Sure (Research D 1sclosure) N
o, 17843, Section ■.

According to one particularly preferred embodiment, a color coupler is used which couples well even without the normally added benzyl alcohol. Benzyl alcohol is commonly used as a phase transfer agent to enable the coupling between the oxidized color developer and coupler to proceed at the desired rate to form an image dye. However, in practical use, benzyl alcohol is always a source of troubles as mentioned above, especially problems due to the formation of tar. Suitable couplers which can be used without benzyl alcohol are described in German Patent Application No. 3,209,710;
No. 2,441,779, No. 2.640.601@ and European Patent Application No. 0067689.

Preferred yellow couplers have a structure corresponding to the following formula.Magenta couplers have a structure corresponding to the following formula.M-5Cyan couplers have a particularly preferred structure.

C2H.

Among the above-mentioned yellow couplers, when a fast-reacting yellow coupler is used in particular, color development during short-time processing is improved, and staining in the lowest density area is also improved. Preferably used.

The fast-reactive yellow coupler used in the blue-sensitive silver halide emulsion layer according to the present invention is a yellow coupler with a relative coupling reaction rate of 0.3 or more, preferably a relative coupling reaction rate of 0.5 or more. It is a yellow coupler.

The coupling reaction rate of the couplers is determined by the rate of the coupling reaction of the two couplers M and N, which give different dyes that can be clearly separated from each other, in the color image obtained by mixing the mixture and adding it to a silver halide emulsion for color development. It can be determined as a relative value by measuring the amount of pigment.

If we express the maximum concentration (DM) wax of coupler M, the color development of the concentration DM in the middle stage, and the color development of coupler N (DN)■ ax1DN, then the ratio of the reaction activity of the double force puller RM/ RN is expressed by the following formula.

That is, in a silver halide emulsion containing mixed couplers,
The value of the coupling activity ratio RM/RN can be determined from the slope of the straight line obtained by plotting several pairs of DM and DN obtained by applying various stages of exposure and color development on two orthogonal axes. .

By using a fixed coupler N and determining the value of RM/RN for various couplers as described above, a relative value of the coupling reaction rate, that is, a relative coupling reaction rate value can be determined.

In the present invention, it refers to the RM/RN value when the following coupler is used as the above coupler N.

The amount of the fast-reacting yellow coupler of the present invention is not limited, but is preferably from 2X10-3 to 5X10" mole, more preferably from 1X10-2 to 5X10" mole per mole of silver in the blue-sensitive silver halide emulsion layer. 5×101 moles.

Specific examples of the fast-reacting yellow coupler of the present invention are listed below, but the invention is not limited thereto.

[Exemplary compounds]

(Y'-1+ (Y'-2) (Y'-3) (Y'-4) (Y'-5) (Y'-6) (Y'-7) (Y'-8) (RM/ RN=0.65 ) (Y'-9) (Y'-10) (Y'-11) (Y'-1l1.6 (AM/RN=1.27) (RM/RN=0.96) ( Y'-171.6 (RM/RN=0.88) (Y'-21) .6 (Y'-22) ○ (Y'-30) Ct H (Y'-35) (Y'-36) (RM/RN=0.80! (Y'-37) (Y'-38) (RM/RN=0.6) (Y'-39) (RM/RN=0.9) In the present invention, As the magenta coupler, a pyrazolotriazole magenta coupler is more preferably used than the above-mentioned pyrazolone magenta coupler.This is useful when bleaching or bleach-fixing is performed immediately after color development using a high silver chloride light-sensitive material. However, when a pyrazolotriazole magenta coupler is used as the magenta coupler, this disadvantage is not only improved, but also the magenta dye density in the highest density area during short processing times is also better. Among the pyrazolotriazole couplers, couplers represented by the following general formula [M-II] are particularly preferably used.

In the magenta coupler represented by the general formula [M-II, 2 represents a group of nonmetallic atoms necessary to form a nitrogen-containing heterocycle, and the ring formed by Z may have a substituent.

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 typically includes alkyl, aryl, anilino, acylamino, sulfonamide, alkylthio, allylthio, alkenyl,
Examples include cycloalkyl and the like, but in addition, halogen atoms, cyphalkenyl, alkynyl, heterocycle, sulfonyl, rufinyl, phosphonyl, acyl, carbamoy, sulfamoyl, cyano, alkoxy, allyloxy, heterocycleoxy, siloxy, and acyluo.

xy, carbamoyloxy, amino, alkylamino,
imide, ureido, sulf7moylamino, alkoxycarbonylamino, aryloxycarbonylamino,
Also included are alkoxycarbonyl, aryloxycarbonyl, heterocyclic thio groups, 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 1 l, 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.
1 liter, especially 5 to 7 is 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. Niacyl groups include alkylcarbonyl groups, arylcarbonyl groups, etc.; carbamoyl groups include alkylcarbamoyl groups, arylcarbamoyl groups, etc.; sulfamoyl groups include alkylsulfamoyl groups,
Niacyloxy groups such as arylsulfamoyl groups include alkylcarbonyloxy groups, arylcarbonyloxy groups, etc.; carbamoyloxy groups include alkylcarbamoyloxy groups, arylcarbamoyloxy groups, etc.; ureido groups include alkylureido groups, arylureido groups, etc. ; As the sulf7moylamino group, an alkylsulfamoylamino group, an arylsulfamoylamino group, etc.; As the heterocyclic group, a 5- to 7-membered one is preferable, and specifically, a 2-furyl group, a 2-chenyl group, 2-pyrimidinyl group, 2-benzothiazolyl group, etc. - The heterocyclic oxy group preferably has a 5- to 7-membered heterocycle, for example 3
．． 4.5.6-tetrahydropyranyl-2-oxy group,
1-phenyltetrazole-5-oxy group, etc.; As the heterocyclic thio group, a 5- to 7-membered heterocyclic thio group is preferable, such as 2-pyridylthio group, 2-benzothiazolylthio group, 2.4-diphenoxy- 1,3.5-triazole-6 monothio group, etc.: Siloxy group includes trimethylsiloxy group, triethylsiloxy group, dimethylbutylsiloxy group, etc. Imide group includes succinimide group, 3-heptadecylsuccinimide group, Nispiro compound residues such as phthalimide group and glutarimide group include Spi0 [3.31 hebutane-
1-yl, etc.; As a bridged hydrocarbon compound residue, PisicO[2.

2,1]hebutan-1-yl, tricyclo[3.

3, 1.13) 7]decane-1-yl, 7.7-dimethyl-bicyclo[2.2.11hebutan-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 Bonylamino, carboxyl, (R1' has the same meaning as R above, 2' has the same meaning as 2 above, R2' and R3' represent a hydrogen atom, an aryl group, an alkyl group, or a heterocyclic group), etc. Although various groups may be mentioned, a halogen atom, particularly a chlorine atom is preferred.

Examples of the nitrogen-containing heterocycle formed by 2 or 2' include a pyrazole ring, an imidazole ring, a triazole ring, or a tetrazole ring, and examples of the substituents that the ring may have include those described for R above. can be mentioned.

More specifically, what is represented by the general formula CM-I] is represented by, for example, the following general formulas [M-I[1 to [M-■]].

[M-III [M-1 [[] [M-IV] [M-Vl [M-Vl] ' General formula [M-■] In the general formulas [M-I[] to [M-■], R1 -R
8 and x have the same meanings as R and X above.

Also, preferred among the general formulas [M-IF] are those represented by the following general formula [M-■].

General formula [M-■] In the formula, R1. X and Z+ have the same meanings as R, X and Z in the general formula [M-11].

Among the magenta couplers represented by the general formulas [M-II] to [M-Vl], magenta couplers represented by the general formula [M-I[] are particularly preferred.

The ring formed by 2 in general formula [M- -rXl is preferred.

General formula [M-rXl -R'-SO2-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 it is straight chain or branched.

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

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

General formula [M-Xl Rho C- In the direct formula, Rg, R1o and Rtl each have the same meaning as R above.

Also, two of the above Rs, R1o and Rt+, for example, R9
and Rao may be bonded to form a saturated or unsaturated ring (e.g., cycloalkane, cycloalkene, heterocycle), and Ra1 may be bonded to the group ring to form a bridged hydrocarbon compound residue. Good too.

Among the general formula [M-Xl, preferred are <f)Rs
When at least two of ~R11 are alkyl groups, (
This is the case when one of Rs to R11, for example, R1+, is a hydrogen atom, and the other two, R9 and Rlo, combine to form a cycloalkyl together with the root carbon atom.

Furthermore, it is preferable among (i) that two of R9 to Eh+ 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 is most preferably represented by the following general formula [M-X
II.

General formula [M-XII R1l-CH2- In the formula, R1l has the same meaning as R above.

Preferred as R11 is a hydrogen atom or an alkyl group.

Typical specific examples of the compounds according to the present invention are shown below.

Atmosphere CH.

CI2M! s In addition to the above representative examples of compounds according to the present invention, specific examples of compounds according to the present invention include Japanese Patent Application No. 61-9791.
Among the compounds described on pages 66 to 1l2 of Book No. M, N011-4.6.8-17゜19-24.2
6-43.45-59.61-104, 106-1l
1. 1l3~162. Compounds represented by 164 to 223 can be mentioned.

Also, the coupler is described in the Journal of the Chemical
Society (Journal of the Chei)
ical Soc+ety), Perki
n) 1 (1977), 2047-2052, U.S. Patent No. 3.725.067, JP-A-59-99437
No. 58-42045, No. 59-162548,
No. 59-171956, No. 6G-33552, No. 6
No. 0-43659, No. 6G-172982 and No. 60
It can be synthesized by referring to No.-190779 and the like.

The couplers of the invention are usually 1X1 per mole of silver halide.
0-3 mol to 1 mol, preferably lX10-2 mol-8
It can be used in the range of X1G'' moles.

Further, the magenta coupler according to the present invention can be used in combination with other types of magenta couplers.

In the present invention, among the cyan couplers, a cyan coupler represented by the following general formula [C-II or [C-[1] is preferably used. When bleach-fixing is performed, stains tend to occur in unexposed areas, but when using a specific cyan coupler represented by the following general formula [C-11 or [C-I] as a cyan coupler, This is because not only this drawback is improved, but also the silver bleaching performance of the photosensitive material is improved.

General formula [C-II General formula [C-! I] In the formula, R1, R7 and R4 each represent an aliphatic group, an aryl group or a heterocyclic group which may have a substituent, and R1 and R6 each represent a hydrogen atom, a halogen atom, or a substituent. Represents an optional aliphatic group, aryl group or acylamino group.

However, R5 may form a ring with R2, R5 represents an alkyl group which may have a substituent, and Z.

Each of the above Z2 represents a hydrogen atom or a group that can be separated by reaction with an oxidized product of a color developing agent.

Logic represents 0 or 1.

Next, according to the present invention, the general formula [C-II or [C-
The cyan coupler shown in [II] will be described in detail.

R, , R, and R1 are aliphatic groups, preferably having 1 carbon number
~32 aliphatic groups (e.g., methyl, butyl, tridecyl, cyclohexyl, allyl, etc.), aryl groups (e.g., phenyl, naphthyl, etc.), or hetero-II (e.g., 2-virunyl groups) , 2-imidazolyl group, 2-furyl group, 6-quinolyl group, etc.); , aryloxy group (e.g., 2,4-not-7 milphenoxy group, 2-chloro7eth/oxy group, 4-cyanophenoxy group, etc.), fulkenyloxy group (e.g.,
2-propenyloxy group, etc.), acyl group (e.g., acetyl group, benzoyl group, etc.), ester group (e.g.,
butoxycarbonyl group, phenoxycarbonyl group, acetoxy group, benzoyloxy group, butoxysulfonyl group, toluenesulfonyloxy group), 7mido group (for example, acetylamide 7 group, ethylcarbamoyl group, dimethylcarbamoyl group, methanesulfonamide group, butylsulfamoyl group), sulfamide group (e.g., dipropylsul7amoylami7 group, etc.), imide group (e.g., succinimide group, hydantoinyl group, etc.), ureido group (e.g., phenylureido group, dimethylureido group, etc.) , aliphatic or aromatic sulfonyl group (e.g., methanesulfonyl group, phenylsulfonyl group, etc.), aliphatic or aromatic thio group (e.g., ethylthio group, phenylthio group, etc.), hydroquine group, cyan group,
It may be substituted with a group selected from a carboxy group, a nitro group, a sulfo group, a halogen atom, etc.

R1 and R@ are water 1! Each halogen atom represents an aliphatic group, an aryl group, or an acylamino group which may have a substituent, provided that R3 may form a ring with R2, where the group which may have the above substituent Examples of the substituent include the groups mentioned above for R1, R2 and R1.

In the general formula [C-IF, n represents 0 or 1.

In the general formula [C-I[], R3 represents an alkyl group which may have a substituent, preferably a furkyl group which may have a substituent having a total carbon number of 2 or more (for example, an ethyl group, Propyl group, butyl group, pentadenyl group, t-butyl group, cyclohexyl group, cyclohexylmethyl group, phenylthiomethyl group, dodecyl oxene 7ethiomethyl group, butanamidomethyl group, methoxymethyl group, etc.).

General formula [C-IF rising general formula [C-III,
Zl and 2. each represents a hydrogen atom or a group capable of leaving by reaction with an oxidized product of a color developing agent.
fluorine atom, chlorine atom, bromine atom, etc.), alkoxy groups (e.g., ethoxy group, dodecyloxy group, nodoxyethylcarbamoylmethoxy group, carboxypro-ruoxy group, methylsulfonylethoxy group, etc.), aryloxy group (e.g., 4 -chlorophenoxy group, α-methoxyphenoxy group, 4-carboxyphenoxy group, etc.),
Alkoxy groups (e.g., acetoxy, tetrazocallyloxy, benzoyloxy, etc.), sulfonyloxy groups (e.g., methanesulfonylamino, toluenesulfonyloxy, etc.), amide groups (e.g., dichloroacetyl 7-mino group), , 7 heptafluorobutylamide groups,
methanesulfonylamino group, toluenesulfonyl 7mino group, etc.), phenoxycarbonyloxy group (e.g., ethoxycarbonyloxy group, pencyloxycarbonyloxy group, etc.), 7lyloxycarbonyloxy group (
(e.g., phenoxycarbonyloxy group, etc.), aliphatic or aromatic thio group (e.g., ethylthio group, phenylthio group, tetrazolylthio group, etc.), imide group (e.g., succinimide group, hydantoinyl group, etc.), aromatic azo group (e.g., , phenylazo group, etc.)
These miscellaneous groups may include photographically useful groups.

In the general formula [C-11, R, which is also preferred, is an aryl group or a heterocyclic group, such as a halogen atom, an alkyl group, an alkoxy group, an aryloxy group, an acylamino group, an acyl group, a carbamoyl group, a sulfonamide group, or a sulfonamide group. More preferably, it is an aryl group substituted with a sulfonyl group, a sulfamide group, an oxycarbonyl group, or a cyano group.

In the general formula [C-11, when R3 and R; do not form a ring, Rt is preferably a substituted or substituted alkyl group, or a 7-aryl group, particularly preferably a substituted aryloxy-substituted alkyl group, , R5 is preferably a hydrogen atom.

In the general formula IC-l1l, R4 is preferably a substituted or unsubstituted alkyl group or aryl group, and particularly preferably a substituted monoloxy-substituted furkyl group.

In the general formula [C-III, R1 is preferably an alkyl group having 2 to 15 carbon atoms and a methyl group having a substituent having 1 or more carbon atoms, and examples of the substituents include a 7-lylthio group, an alkylthio group, and an acyl 7-methyl-7 group. , 7-aryloxy group, and alkyloxy group are preferred.

In the general formula [C-l1l, R3 is more preferably a furkyl group having 2 to 15 carbon atoms, and particularly preferably an alkyl group having 2 to .mu. carbon atoms.

In the general formula [C-[1], R6 is preferably a hydrogen atom or a halogen atom, with a chlorine atom and a 7-wire atom being particularly preferred.

Preferred % in general formula [C-II and [C-[1]
ZI and Z are each a hydrogen atom, a halogen atom, a flukoxy group, a 7-aryloxy group, an acyloxy group, and a sulfone 7-mido group.

In the general formula [C-l1l, Z is preferably a halogen atom, and particularly preferably a chlorine atom or a fluorine atom.

When n=o in the general formula [C-II, Z2 is more preferably a halogen atom, and particularly preferably a chlorine atom or a 7-group atom.

Cyan dye-forming couplers of the general formula [C-11 or [C-111] are commonly used in silver halide emulsion layers (particularly for red-sensitive emulsions). The amount added is preferably 2X10'' to 5X10' mole, more preferably 1X102 to 3X101, per mole of silver halide.
Used in moles.

Furthermore, methods for synthesizing cyan couplers represented by the general formulas [C-II and [C-II] are described in U.S. Patent No. 3,772.002, U.S. Pat.
It can be easily synthesized based on the method described in specifications such as No. 4,427,767.

Specific compounds represented by the general formulas [C-11 and [C-11] are listed below, but the present invention is not limited thereto.

The cyan coupler according to the present invention usually has IX 10-3 to 1 mole per mole of silver halide, preferably IX
A range of 10-2 moles to 8 x 10'' moles can be used.

In the present invention, when a nitrogen-containing heterocyclic mercapto compound is used in combination with the high silver chloride light-sensitive material of the present invention, not only the desired effects of the present invention can be favorably achieved, but also a bleach-fixing solution can be added to the color developer. In the present invention, it can be cited as a more preferred embodiment because it has the additional effect of minimizing the influence on photographic performance that occurs when mixed with.

The nitrogen-containing heterocyclic mercapto compound according to the present invention includes an imidaline ring, an imidazole ring, an imidasilone ring, a pyrazoline ring, a pyrazole ring, a pyrazolone ring,
Oxazoline ring, oxazole ring, oxacilone ring, thiazoline ring, thiazole ring, thiazolone ring, selenazole ring, selenazole ring, selenazolone ring, oxadiazole ring, thiadiazole ring, triazole ring, tetrazole ring, benzimidazole ring, benztriazole ring, indazole ring, benzoxazole ring, benzthiazole ring, benzimidazole ring, pyrazine ring, and rimidine ring, pyridazine ring, triazine ring, oxazine ring,
Thiazine ring, tetrazine ring, quinazoline ring, phthalazine ring, polyazaindene ring (e.g. triazaindene ring,
Tetrazaindene ring, pentazaindene ring, etc.). Among these, particularly preferred nitrogen-containing heterocyclic mercapto compounds include oxazole ring, oxacyazole ring, thiadiazole ring, triazole ring,
These are a tetrazole ring, a benzimidazole ring, a benzimidazole ring, a pyrimidine ring, a triazine ring, and a polyazaindene ring.

Specific examples of mercapto compounds useful in the present invention are listed below.

E'-13I'-14 Knee 15 I'-16I'-2
6 I'-28 C* Hs C 1'-39 I'-41 1'-43 I'-45 I'-46 I'-50 I'-51 1'-52 1'-53 1'-54 1'+ 55 ■-56 Summer-57 Yen□N 1'-59 1'-60 1'JI ■-62 ■-63 1'-64 To□To 1'J6 1'-671'
J8 1'-69■-72 1p-731'-74 1'+75 I
'-76■-fu g l
'-801-811'-82 ■-83 C (Jul-1) The above compound was published in the Journal of the Chemical Society (J, Chew, soc, ) 49.1748.
1927, Journal of Organic Chemistry (J, Org, Chew, ) 39.246
9.1965, JP-A-50-89034, JP-A No. 55-7
No. 9436, No. 51-102639, No. 55-5946
No. 3, Annaren Hemi (Ann, Chia+
.

), 44-3.1954, Special Publication No. 40-28496,
Chemical Berichte (Chew, Ber, ) 20
．． 231.1887, USP No. 3,259,976, Chemical and Pharmaceut.
ical Bulletin) (Tokyo) 26
Volume, 314 (1978),
Richte bar Deutseben Chemi
schen Ge5ellsdraft) 8L1l1
(1948), U.S. Patent No. 2,843,491, U.S. Patent No. 3,017,270, British Patent No. 940,169,
It can be synthesized by referring to the method described in Journal of the American Chemical Society, 44.1502-1510, etc.

The nitrogen-containing heterocyclic mercapto compound (hereinafter simply referred to as a norcapto compound) is, for example, JP-A No. 51-1071l.
No. 9, No. 48-102621, No. 55-594463
No. 59-114333.

In the present invention, the mercapto compound is preferably added to two or more plural photographic constituent layers.

The total amount of mercapto compounds used varies widely depending on the layer structure of the silver halide photographic light-sensitive material, the type of mercapto compound, the amount of silver halide, processing conditions, etc., and is generally 101 mol per 1-2. mole, preferably 107
Although it is in the range of -105 moles, the present invention is not limited to the total amount itself, but is determined by the degree of anti-capri in each emulsion layer and the magnitude of the effect of the mercapto compound between each layer.

The silver halide grains used in the silver halide emulsion layer of the present invention contain at least 70 mol% of silver chloride, and the remainder may contain bromide and iodide, but it is preferable that they are substantially silver chloride, and bromide , iodide is preferably present in a very small amount. In a special case, it is also a preferred embodiment that the blue-sensitive layer is silver halide containing 30 mol% of bromide, and the other two layers, for example, the green-sensitive layer and the red-sensitive layer, contain about 99% chloride. It is. The silver halide is preferably a core-shell particle and has a double layer structure.

-g, the grains consist of at least two regions with different halide compositions, e.g. one core and at least one shell, and at least one region B contains at least 10 mol % silver bromide, preferably at least 25
Contains mole % silver bromide, but not more than 50 mole % 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 bromide of at least 10 mole percent and no bromide-rich zone ZBr on the surface of the silver halide grains.

The silver bromide rich zone ZBr in these grains can be present 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). Particularly preferred is the preparation method by the double-inflow method with adjustment of DAQ;
17643, Sections E 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, such as tin compounds as described in Belgian Patent Nos. 493.464 and 568.687, and as described in Belgian Patent No. 547, for example.
, 323, or aminomethylsulfinic acid derivatives. Money,
Noble metals and precious metal compounds such as platinum, palladium, iridium, ruthenium or rhodium are also suitable sensitizers. This chemical sensitization method was developed by the Zeitschrift Fair Bitsenschaft Photography (Z, W
iss, Photo, ) 46.65~72 (19
51) Earl Koslovsky (R, K oslov)
sky); and the above research.
Disclosure No. 17643, Section■
See also:

The emulsions can be sensitized using optically known methods, for example using common polymethine dyes such as neutrocyanines, basic or acidic carbocyanines, rhodacyanines, hemicyanines, styryl dyes, oxonols and the like: F.M.Ha■er
)'s "The Cyanine Dyes and Related Hunbounds"
(19)
64) Ullmanns Enzyklpadie d
er technischenchemie) 4th edition, volume 18, page 431 and the following, and Research Disclosure No. 17643, supra, section 2.

Conventional antifoggants and stabilizers can be used.

Azaindenes are particularly suitable stabilizers, with tetra- and penta-azaindenes being preferred, especially those substituted with hydroxyl or amino groups. Compounds of this kind are described, for example, in the article by Bier (3irr), Zeitschrift Ver Bissenschaftliche Fotograf (Z, Wiss, Photo, ) 47
．． 1952, 1), 2-58, and the above-mentioned Research Disclosure No. 0.17643, Section ■.

The components of the photographic material can be combined by conventional known methods, e.g. U.S. Pat. No. 2,322,027, U.S. Pat. See No. 3,785,897. Components of photographic materials, such as couplers and U.sub.2 absorbers, can also be combined in the form of charged latexes: see German Patent Application No. 2,541,274 and European Patent Application No. 14,921. The components can also be fixed in the material as polymers: for example German Patent Application No. 2,044,992, US Pat. No. 3.37
See No. 0,952 and No. 4,080,211.

Customary layer supports can be used for the materials, such as 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, especially polyethylene or polypropylene: see in this regard Research Disclosure No. 17643, Section X■, supra.

Customary hydrophilic film-forming agents can be used as protective colloids or binders for the layers of the recording material, such as proteins, especially gelatin, alginic acid or its derivatives such as esters, amides or salts, carboxymethylcellulose and cellulose sulfates. Reference may also be made to the binders set out in Research Disclosure 17643, Section 2, supra.

The layers of photographic material can be hardened using conventional methods such as epoxides, heterocyclic ethyleneimines or acryloyl type hardeners. Furthermore, the layers can be cured by a method according to German Patent Application No. 2,218,009 to produce a color photographic material suitable for high temperature operation.

The photographic layers or color photographic multilayer materials can also be hardened with diazine, triazine or 1,2-dihydroquinoline type hardeners or vinyl sulfone type hardeners.

Other suitable curing agents are German Patent Application No. 2.43.
No. 9,551, No. 2,225,230 and No. 2,31
No. 7,672 and the above Research Disclosure 1
No. 7643, Section XI.

[Specific Effects of the Invention] As explained above, the present invention eliminates the need for additional means such as recycling of the color developing source, making it economically inexpensive, and without deteriorating photographic performance. It has been possible to provide a method for processing a silver halide color photographic light-sensitive material, which can consistently provide stable photographic performance of images even if the number of replenishers is significantly reduced.

[Specific Examples of the Invention] Hereinafter, the present invention will be specifically explained using Examples, but the embodiments of the present invention are not limited thereto.

Example-1 An experiment was conducted using the following color paper, treatment liquid, and treatment process.

[Color Paper] The following layers were sequentially coated on a polyethylene coated paper support from the support side to prepare a photosensitive material.

In addition, as polystyrene coated paper, the average molecular weight is 1
00,000, 200 parts by weight of polyethylene with a density of 0.95 and 1 l. 6.8% by weight of anatase-type titanium oxide was added to a mixture of 20 parts by weight of polyethylene with a density of 0680, and the extrusion coating method was used to coat the surface of high-quality paper with a weight of 17G (1/f) with a thickness of 0.0
A coating layer of 35 m5+ was formed, and a coating layer of 0.04 m1 in thickness was provided on the back side using only polyethylene. The polyethylene-coated surface of this support was pretreated by corona discharge, and then each layer was sequentially applied.

No. 1111: A blue-sensitive silver halide emulsion layer consisting of a silver halide emulsion having the silver halide composition shown in Table 1, the emulsion containing 350 g of gelatin per mol of silver halide,
Sensitized using 2.5X1G-4 moles of sensitizing dye of the following structure per mole (using isopropyl alcohol as solvent) and dissolved and dispersed in dibutyl phthalate 2,5
-di-t-butylhydroquinone 2001G/x”
and exemplified yellow coupler Y- as a yellow coupler.
5 halogenated - containing 2X1G-1 mole per mole of silver,
It is coated with silver of 130Gio/f.

2nd layer G dissolved and dispersed in dibutyl phthalate, 1 octylhydroquinone 300110/f 1 UV absorber, 2-(2'-hydroxy-3',5'-di-t-butylphenyl)benzotriazole, 2 − (
2'-hydroxy-5'-1-butylphenyl)benzotriazole, 2-(2'-hydroxy-3'-1
-butyl-5'-methylphenyl)-5-chlorobenzotriazole and 2-(2-hydroxy-3',5
A gelatin layer containing a mixture of '-di-t-butylphenyl)-5-riO-benzotriazole 20010/f is coated to give a gelatin weight of 1900 IQ/f.

No. 31i: A green-sensitive silver halide emulsion layer consisting of a silver halide emulsion having the silver halide composition shown in Table 1, the emulsion containing 450 g of gelatin per mol of silver halide, and containing 1 mol of silver halide.
Exemplary magenta coupler M-5 was used as a magenta coupler sensitized using 2.5X 10 moles of a sensitizing dye having the following structure per mole, and dissolved and dispersed in a solvent containing a 2:1 mixture of dibutyl phthalate and tricrenyl phosphate. V) per mole of silver halide 1.5x 1G-1 mo)
Contains Lt gold and is coated at 11 m 280 mg/f. In addition, 0.3 mol of 2.2.4-trimethyl-6-lauryloxy-7-[-octylchroman was contained per 1 mol of coupler as an antioxidant.

Fourth layer Di[-octylhydroquinone 30 mQ/f dissolved and dispersed in dioctyl phthalate and 2-(2'-hydroxy-3') as a UV absorber.

5'-di-t-butylphenyl)benzotriazole,
2-(2'-hydroxy-5'-t-butylphenyl)
Benzotriazole, 2-(2'-hydroxy-3
'-t-butyl-5'-methylphenyl)-5'-chlorobenzotriazole and 2-(2'-hydroxy-3',5'-t-butylphenyl)-5-chloro-
Mixture of benzotriazole (2: 1.5: 1
．． 5: Zelag containing 2) 5001I1g/f
The gelatin layer was coated to have a thickness of 19Q Ong/i''.

Fifth layer: A red-sensitive silver halide emulsion layer consisting of a silver halide emulsion having the silver halide composition shown in Table 1, the emulsion containing gelatin soog per mole of silver halide,
2,5-di-t-butylhydroquinone isomq sensitized using 2.5X1 G' moles of sensitizing dye of the following structure per mole and dissolved and dispersed in dibutyl phthalate.
/1j and cyan coupler and exemplary cyan coupler C'-
2 per mole of silver halide, and the silver amount was 280111 (J/f).

6th layer: Gelatin layer coated so that the amount of gelatin is 90001111/f.

The silver halide emulsions used in each light-sensitive emulsion layer (layers 1, 3, and 5) were prepared by the method described in Japanese Patent Publication No. 7772/1983, and were prepared using sodium thiosulfate pentahydrate. Chemically sensitized and stabilized with 4-hydroxy-6-
It contained methyl-1,3,3a,7-tetrazaindene, bis(vinylsulfonylmethyl)ether as a hardening agent, and saponin as a coating aid.

The above light-sensitive material (silver halide composition changed) was subjected to stepwise exposure and processed with the following processing steps and processing solution (the preservative of the color developing solution was changed, the comparison was without preservative). The maximum concentration of yellow pigment was measured and the ratio of the comparison without preservative was calculated. The results are shown in Table'-1.

Standard processing steps [1-layer color development 38°C 1 minute (2) Bleach fixing 38°C 1 minute [3] Water washing 25-35°C
1 minute [4] Drying 75 to 100°C for about 2 minutes Processing solution composition: Color developing tank solution> Bleach-fixing tank solution> As is clear from Table 1, in the case of an emulsion containing 70 mol% or more of silver chloride, It can be seen that the use of the hydroxylamine derivative according to the present invention as a preservative for a color developing solution is very preferable because the maximum density does not decrease.

Example 2 Each of the color developing solutions added with the preservatives listed in Table 2 used in Example 1 was stored for 10 days, and the color developing solution without preservative immediately after preparation was used as a comparison. As in Example 1, after the development process, the gamma value of the yellow dye (a value between 11 degrees and 0.8 to density 1.8) was determined, and the ratio was calculated by comparing the result with no preservative immediately after preparation. The results are shown in Table-2.

As is clear from Table 2, in the case of an emulsion containing 70% or more silver chloride, the use of the hydroxylamine derivative according to the present invention as a preservative means that the gamma value does not change even when the color developer is stored. It turns out to be very favorable.

Example (3) Emulsions No. and E used in Example (1) were used as silver halide emulsions, and Y-5, M-5 and Vc'-2 used in Example were used as couplers.
) The photosensitive material used in Example (1) was used except that the coupler was changed to the coupler shown in Example (1).

The color developing solution used was Example (1) in which a color developing solution containing VEI-IA (e.g. Compound (+-1)) as a preservative was used.
).

After processing, the maximum and minimum reflection densities of yellow, magenta and cyan dyes were measured using Sakura Photoden Density PDA-65 (
Konishiroku Photo Industry Co., Ltd.! It was measured by The result is decline (3)
are summarized in

From Table (3), it is clear that the fast-reactive yellow couplers (sensitive materials No. 2 to No. 6), the general formula [M-Il
Magenta coupler indicated by (Sensitive material No. 7 to 13)
By using the cyan coupler (sensitive material No. 14 to 26) represented by the general formula [C-11 and/or [C-III], both the maximum color density and the minimum density are improved, and in the present invention. It turns out that it is a preferable coupler.

In particular, a fast-reacting yellow coupler, with the general formula [M-
Magenta coupler represented by 11 and general formula [C-II
It turns out that it is particularly preferable to use cyan couplers represented by C-ml or C-ml in combination.

Example (4) As a silver halide emulsion, emulsion Nos. and E used in Example (1) and organic inhibitors (1, 3,
(added to each layer in step 5), and the color developing solution is D as a preservative.
Using EHA, 0.5xl of the bleach-fix solution used in Example (1) was added per 11 color developing solutions, and the development was carried out in the same manner as in Example (1). The slope value between . The results are as follows: (4) As is clear from Table (4), by using the specific heterocyclic mercapto compound according to the present invention, even if the bleach-fix solution is mixed into the color developing solution, the relative It can be seen that the gamma value does not change much, indicating stable photographic characteristics.

Example-5 In Example-1, the concentration of potassium sulfite in the color developer was changed as shown in Table-5, and the experiment was the same as in Example-1, with no preservative and potassium sulfite 1g/2 compared. After processing, the maximum density of yellow dye was measured, and potassium sulfite H1# was applied without preservative! Maximum concentration of 100
The ratio was calculated. The results are shown in Table-5.

From Table 5, in the present invention, especially potassium sulfite is added to the color developing solution at 1. Examples where Oo/ffi or less is preferable (
6) Color developing solutions Nos. 1 to 22 having the following compositions were prepared.

(Color developing solution) Next, use the color developing solution described in Attenuation (6) at an aperture ratio of 100 cz"
/1 (air contact area is 100 for 11 color developing solution)
cm'') was stored in a container at 38° C. for 2 weeks, and the tar property of the color developer was evaluated.

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

++ 10 A large amount of tar generated 10 Tar attached to the wall (black) + Slight tar generated on the surface - No tar generated Table (6) As is clear from decay (6), the preservative (I-1) of the present invention Sulfur as a metal compoundff! By adding cerium and manganese sulfate, polyhydroxy compounds according to the present invention (color developer No. 4.5), minoboricarboxylic acid (color developer No. 6 to 8), flukanolamine [(No. 9
．． 10), when polyalkylimine (11) and the above compounds were added together (No. 1L to 17), the tar property was improved, and when used together, it was even better! [It can be seen that there is a significant improvement effect. It can be seen that the above-mentioned improvement effect can be obtained even if the preservative is replaced with the preservative (No. 18 to 22) according to the present invention.

Example (7) The color developing solution (No. 1 to 22) described in Example (6) was added to 5
The sample was stored in a sealed glass bottle at 0°C for 5 days, and the same treatment and evaluation as in Example (4) were performed.

The results are summarized in (7).

As is clear from Table (7) Decay (7), when the bleach-fix solution is stored with a very small amount of contamination (model running condition fi), the preservative (1-1) of the present invention contains sulfur as a metal compound. l! ! ! Adding cerium and manganese sulfate,
Polyhydroxy compound according to the present invention (color developer No.
4', 5') Hon R (coloring ILff) on Amitsuborica
lflNo, 6' to 8'), 7Al/-luamines (No, 9', 10'), polyalkylimine (11') and the above compound used in combination (No, 1l'
~17') When added, fluctuations in photographic properties after storage were improved, and when used in combination, it was found that there was an even more pronounced improvement effect. It can be seen that this improvement effect can be obtained even if the preservative is replaced with the preservative (No. 18' to 22') according to the present invention.

[Example 8] Color developing agent (A-1) in the color developer used in Example 1
) was changed to (B-1> or (B-2) below) and a similar experiment was conducted, but the magentastin in the unexposed area deteriorated by 0.03 in both cases.

Similarly, the color developing crude drug (A-1) of Example 1,
When the same experiment as in Example 1 was carried out by changing the exemplified compounds (A-2), (A-4) and (8-15),
Similar results were obtained.

(B-1) (B-2) N.H.

Example (9) The fluorescent whitening agent (exemplified compound (A'-4)) in the color developer used in Example (1) was changed as shown in Table (8) below, and Example (1) The development process was carried out according to the following. Check the yellow stain in the unexposed area after processing with Sakura Photodensitometer PD
Measurement was performed using A-65 (manufactured by Konishiroku Photo Industry Co., Ltd.).

The results are summarized in Table (8).

Table (8) CF-1) (Fluorescent Brightener) (F-2) (Fluorescent Brightener) From Attenuation (8), the triazylstilbene fluorescent brightener represented by the general formula [11] is used in the present invention. It can be seen that yellow stain is further improved by using it in combination with the above treatment method.

Example 10 A silver halide photosensitive material (
Emulsions No., G, HSI and J) were prepared.

Layer 1: 1.20 Mf gelatin, 0.40 Mf (in terms of silver, the same applies hereinafter) blue-sensitive silver halide emulsion, and 0.
1 dissolved in dioctyl phthalate of S5Q/-t'
Layer containing yellow coupler (Y-5) with 0x1 G' molar Q/f.

Layer 2 - Intermediate layer consisting of gelatin of -0,70111/f.

B3...1.20 (J/l' gelatin, 0.22a
/f green-sensitive silver halide emulsion and 0.30Q/f
A layer containing 1,0×10′ mole g/v of magenta coupler (M-5) dissolved in dioctyl phthalate.

Layer 4: Intermediate layer consisting of 0.700/l'' gelatin.

Layer 5: 1,75 X 10-3-E dissolved in 1.200/V gelatin, 0.28 Mv red-sensitive silver halide emulsion and 0.25 Q/f dibutyl phthalate.
) I,, (J /f (1) Cyan coupler (C'-2
).

Layer 6-1. A layer containing 0132 (1/i2) Tinupin 328 (UV absorber manufactured by Ciba Geigy) dissolved in h /f gelatin and 0.25 M t' dioctyl phthalate.

Layer 7: A layer containing gelatin of 0.481)/f.

In addition, as a hardening agent, 2,4-dichloro-6-hydroxy-8-triazine sodium was added in layers 2, 4 and 7.
Each was added in an amount of 0.017a per 1g of gelatin.

The average silver halide composition in the silver halide emulsion is shown in Table 4.

The thus prepared color vapor sample was photoprinted and then subjected to running processing using an automatic developing machine 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℃ 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 developer tank solution] [Color developer replenisher] [Bleach-fix tank solution] [Bleach-fix replenisher] [Water-washing alternative fast-setting tank solution and replenisher] For running processing, add the above color developer tank solution, Fill the bleach-fixing tank liquid and the stabilizing tank liquid, and replenish the above-mentioned color developing replenisher, bleach-fixing replenisher, and washing substitute stable replenisher through a metering pump every 3 minutes while processing the color vapor sample. Ta.

The amount of replenishment to the color developing tank is listed in Table 4, but the amount of replenishment to the bleach-fixing tank is 220 bleach-fixing replenisher per 1f of color vapor, and the amount of replenishing to the stabilization tank is 2501J2 of washing substitute stabilizing replenisher. did.

The stabilization processing baths of the automatic processor are the first to third tanks in the direction of the flow of the photosensitive material, and the final tank is refilled, and the overflow liquid is transferred from the final tank to the previous tank. This overflow liquid was then flowed into the preceding tank to create a multi-tank countercurrent system.

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 a 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. Table 4 shows the results.
It was shown to.

From the above results, it is clear that the silver halide composition is outside the scope of the present invention (emulsion N
o, G) and comparative examples in which the silver halide composition is within the scope of the present invention but the chloride concentration in the tank liquid is less than 2XIO'mol/, the photographic density can be improved by lowering the replenishment amount. However, if the silver halide composition and the chloride concentration in the tank liquid are both within the range of the present invention, even if the replenishment amount is reduced, the photographic density will not decrease and extremely good running performance can be obtained. I know what I can do.

Example (11) The silver halide color light-sensitive material described in Example (10) was used except that Emulsion No. used in Example (10) was used as the silver halide emulsion, and the color development replenisher and tank liquid were The halide concentration (ax/1) of K B
Color development replenishment using r/K Cl = 0.0059/ Q, 054? 1! Using a color developing solution, a bleach-fix solution, and a stabilizing solution, which were run at a volume of 100xl/x'', the pH of the bleach-fix solution was changed to attenuation (10),
It was processed in the same processing steps as in Example (10), and the lowest grade of yellow dye was evaluated for density and desilvering property.

Note that the minimum reflection density was measured using PDA-65 (manufactured by Konishiroku Photo Industry Co., Ltd.), and the desilvering property was measured by the fluorescence Xa method.

Decay (10) Decay As is clear from (10), when the pH of the bleach-fix solution increases, both the minimum reflection density and the desilvering performance deteriorate, and when the pH is too low (bleach-fix solution No. 1), the minimum reflection density becomes high. (Become.

The pH of the bleach-fix solution is 4.5-6.8 (No, 2-6
) has good minimum reflection density and good desilvering properties, and can be said to be a preferable embodiment for the present invention.

Example (1l) As the silver halide composition, emulsion No. (
The color light-sensitive material of Example (10) was used except that F) was used, and the color developing solution had a halide concentration of 0.0017 mol 10 with the replenisher and tank solution KBr/KCl 11 degrees.
．． 054 mol, and the amount of replenisher for the color developer was 200 mol.
When the xl/z2 color development temperature was set to 38° C. and the color development processing time was set to attenuation (11), running processing was performed in the same manner as in Example (10).

The running process was performed until the amount of the color developer replenisher replenished into the color developer tank solution became twice the amount of the tank solution.

Note that the running processing amount is shown in (11).

The evaluation method was the same as in Example (10).

The results are shown in Table (11).

Table (11) K-round is the ratio of the amount of replenisher refilled to the tank capacity.

As is clear from Table (11), when the processing time for color development is short, especially when the processing time is 45 seconds or less, the variation in photographic density becomes large depending on the amount of running per day.
When the processing time is 30 minutes or more, especially 3 minutes or more, the photographic density exhibits stable photographic characteristics with little variation.

Example 13 Preparation of emulsion - 0.3N NaCffi and 0.3N NaCffi were added to a 2.6% gelatin solution.
A silver chloride emulsion was prepared by a simultaneous mixing method while controlling the 3NA (1 NO3 solution) AIJ. Based on this emulsion, further 2NNaCj was added while keeping I)A(+ at 6.8
! Its size was increased to 40 times the volume by adding 2NAgNO3 and 2NAgNO3 solutions.

This AOCj! KBr containing 40 mol% bromide in particles
The AQ Br /A11l C1 shell was applied by a simultaneous mixing method of /Na Cfl solution and AONO3 solution.

The resulting grains are monodisperse emulsions with an average of 0.58μ, but AgC4! The m content was 96 mol % based on the total silver halide, and the A(l Sr content was 4 mol %).

Adjusting photographic materials Emulsion K was used to prepare photographic materials shown in the following table.

Table-1l Emulsion 1, support polyethylene coated paper 2, blue photosensitive layer coupler Y-5 (DBP dispersion) 3, intermediate layer 4, green photosensitive 1m cuff 5-M-5 (DOP dispersion) 5,
Intermediate layer 6, red photosensitive layer coupler C-7 (DOP dispersion) 7, protective layer a, UV agent gold-containing layer hardener and UV absorber Treatment process bath Temperature Time developing bath 35°C 50'' bleach-fixing bath
35℃ 50" stable 30℃
50" developer bath has the following composition: [Tank solution] The developer bath was processed with the following replenisher solution at a rate of 80 x Q/f: [Replenisher solution] E-Tank solution] Bleach-fix bath replenishment To make the liquid, the liquid in the tank was simply made ao o mf.

[Stabilizer] (1) For comparison, the same photographic material was developed using a conventional developer using a conventional processing method.

Developer, Tank Solution The developer was replenished using the following replenisher solution at a rate of 801117f: Replenisher Solution The bleach-fix bath was as described above.

The maximum color density of the sample developed after adjusting the developing solution and the photographic material was processed after 2000f processing over 30 days, and the maximum color density was measured. There was almost no change in each developer. Furthermore, it was found that there was almost no overflow, and that economical processing could be carried out in an extremely stable manner. Also, as a matter of course, since it did not contain benzyl alcohol, no tar formation was observed in the developing tank. on the other hand,
In a comparative experiment, immediately after preparing the developer, a significant decrease in color density was observed due to the presence of hydroxylamine, and thereafter the density changed significantly, making stable processing impossible. Also, significant tar formation was observed due to benzyl alcohol.

Example 14 As an additional experiment, silver halide photographic materials containing silver bromide in various ranges were processed with the color developing solution of the present invention. When the bromide content was less than 10 mol %, no elution of bromide into the developer was observed even when the development reaction was carried out to the maximum. This was confirmed by quantifying bromide in actual running fluid.

4.1m white simple attack 1 time 1 U Honda 68 months 1 Ni Naro Halloween 4 colors 1 true impression 19. Outline the schematic diagram.

Claims (6)

[Claims] (1) After imagewise exposing a silver halide color photographic light-sensitive material having at least one silver halide emulsion layer on a support, it is developed with a color developing solution containing at least a p-phelenediamine color developing agent. , in a method of processing a silver halide color photographic light-sensitive material, in which the color developing solution is continuously processed while replenishing a replenishing solution, the silver halide emulsion layer comprises silver halide grains containing at least 70 mol % of silver chloride. The color developing solution has the following general formula [I]
1. A method for processing a silver halide color photographic material, which comprises the compound represented by the following formula and at least 2×10^-^2 mol of chloride per liter of color developing solution. General formula [I] ▲There are numerical formulas, chemical formulas, tables, etc.▼ In the formula, R_1 and R_2 each represent an alkyl group or a hydrogen atom. However, both R_1 and R_2 are not hydrogen atoms at the same time. Further, R_1 and R_2 may form a ring. (2) A method for processing a silver halide color photographic light-sensitive material according to claim (1), wherein the silver halide grains are silver halide grains containing at least 90 mol % of silver chloride. . (3) The halogenated compound according to claim (1) or (2), wherein the color developer contains at least 3 x 10^-^2 moles of chloride per liter of the color developer. Processing method for silver color photographic materials. (4) Claim (1) characterized in that the color developing solution does not substantially contain benzyl alcohol;
The method for processing a silver halide color photographic light-sensitive material as described in (2) or (3). (5) Claims (1), (2), (3), or (4), characterized in that the color developing solution does not overflow even when processed continuously while being replenished with a replenisher. A method for processing the silver halide color photographic light-sensitive material described above. (6) Claims (1) and (1) above, characterized in that the replenisher is supplied so as to keep the liquid level of the developer bath constant.
2), (3), (4) or (5), the method for processing a silver halide color photographic material;