JPS62257157A - Processing method for silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve the shelf life of a color developing soln. by incorporating a specific magenta coupler into a silver halide emulsion layer and incorporating a specific compd. and manganese salt and cerium salt into the color developing soln. CONSTITUTION:This photosensitve material contains the magenta coupler expressed by the formula I in at least one silver halide emulsion layer. The color developing soln. to be used in a color developing stage contains the compd. expressed by the formula II and at least one of the compd. selected from the manganese salt and cerium salt. In the formula I, Ar denotes a phenyl group, substd. Y is the group to be desorbed when a dye is formed by coupling with the oxidant of an N-hydroxylalkyl substd.-p-phenylenediamine deriv. color developing agent. R denotes an acylamino group, anilino group or ureide group. In the formula II, R1, R2 denote an alkyl group or hydrogen atom, and both of R1 and R2 are not a hydrogen atom.

Description

Detailed Description of the Invention [Industrial Application Field] The present invention relates to a method for processing silver halide color photographic materials, and more specifically, to processing silver halide color photographic materials using a stable color developing solution with improved storage stability. The present invention relates to a method for processing JY color photographic materials.

[Background of the Invention] Generally, after exposure, silver halide color photographic materials are processed with a color developing solution containing a color developing agent. Aromatic primary amines are usually used as color developing agents, but aromatic primary amine color developing agents are generally very easily oxidized and are exposed to oxygen in the air in highly alkaline solutions such as color developing solutions. easily oxidized by

Therefore, sulfites are generally used to preserve the shape of aromatic primary amine color developing agents. Sulfite MW is a compound commonly used as a preservative for developing agents in black and white developers, generally in the form of sulfites or bisulfites of alkaline compounds such as sodium or potassium. but,
In color developing solutions, their use is severely limited. In other words, sulfites sulfonate the oxide of the color developing agent generated during the color development reaction process, and therefore inhibit the coupling reaction between the oxide of the color developing agent and the coupler, making it especially difficult to use couplers with slow coupling reactions. This reduces the color density of the silver halide emulsion layer. Therefore, the sulfite concentration in the color developer is usually kept low. At low concentrations of sulfite, the color developing agent will gradually oxidize even in the presence of sulfite; these problems can be overcome by using hydroxylamine as described in U.S. Pat. No. 3,746.544. Improved with use.

On the other hand, in color photographic processing, processing is normally carried out continuously using an automatic development system while replenishing replenisher according to the amount of photosensitive material processed, but replenishing the replenisher inevitably causes a large amount of overflow. Due to the waste generated and disposed of, this method poses a major economic and pollution problem. Therefore, in recent years, in order to reduce the overflow, a so-called concentrated low replenishment process in which the amount of replenisher is reduced and a small amount of concentrated replenisher is replenished has become popular. In such a processing method, the residence time of the color developing solution in the processing tank of the automatic processing machine is improved, so that the oxidation of the color developing agent progresses more. Although this tendency can be improved by increasing the sulfite concentration in the color developer, the darkening method results in a significant decrease in dye concentration as described above. Furthermore, as mentioned above, hydroxylamine effectively suppresses the progress of oxidation of the color developing agent that occurs when the sulfite concentration is low, but hydroxylamine! ! When the acid salt is used up, it is rapidly oxidized, so increasing the amount of hydroxylamine has little effect, and has the disadvantage that the ammonia produced by the decomposition of hydroxylamine causes fog on the photosensitive material. Furthermore, the generated ammonia is dispersed into the air, which causes a phenomenon in which l)H in the color developing solution decreases, which also affects photographic properties.

As a technique to improve these drawbacks, a patent application filed in 1986-10
No. 3839 and patent application No. 59-6437i % T: 9
1. A technique has been known to improve the preservability by further using a cerium salt or a manganese salt in the above-mentioned conventional system using Faite salt and hydroxylamine as a preservative, as shown in the figure. In recent years, there has been a trend toward lower replenishment of color developers for economic and pollution reasons, and as a result, the residence time of the developer is becoming longer and longer, and the developer is often subject to more severe air oxidation. This is becoming increasingly difficult to compensate for with conventional technology. Furthermore, with the reduction in replenishment, the amount of photosensitive materials processed per unit volume increases, and as a result, the amount of metal salts such as calcium and magnesium that are eluted and accumulated from the photosensitive materials also increases. The actual situation is that the amount of contaminated bleach-fix solutions that use iron complex salts as bleaching agents is increasing.

Furthermore, with the speeding up of processing, 30% of the photographic material
Processing is now being carried out at high temperatures of 0.degree. In addition, the conveyance speed of automatic processors has become slower due to the development of compact laboratories in recent years, resulting in a longer transit time for the photosensitive material to exit the color developing solution and enter the next process of bleaching solution or bleach-fixing solution. There is a tendency to

Under these circumstances, when the above-mentioned cerium salt or manganese salt technology is used in a color developing solution, the oxidation of the developing solution progresses due to air during this transit time, and under this condition color development occurs. It has been found that when a photographic material after development enters a bleaching solution or a bleach-fixing solution, magentastin occurs in the photographic material.

[Object of the Invention] Therefore, the first object of the present invention is to provide a method for processing a silver halide color photographic light-sensitive material that provides stable photographic properties even when a color developing solution is replenished at low levels. A second object is to provide a method for processing silver halide color photographic materials in which magentastin generated in a bleach solution or a bleach-fix solution in a low-speed automatic processor is improved.

Other objects of the invention will become apparent in the following.

[Structure of the Invention] As a result of various studies by the present inventors, the object of the present invention is to
After imagewise exposing a silver halide color photographic material having at least one silver halide emulsion layer on a support,
In a method for processing a silver halide color photographic light-sensitive material which is subjected to processing including at least a color development step, at least one of the silver halide emulsion layers contains a magenta coupler represented by the following general formula [M], and the color development step The present invention has been achieved by discovering that this can be achieved when the color developing solution used in the solution contains a compound represented by the following general formula [1] and at least one compound selected from manganese salts and cerium salts. be.

General Formula [I] (In the formula, R1 and R2 each represent an alkyl group or a hydrogen atom, and R1 and R2 are not both hydrogen atoms. Furthermore, R1 and R2 may form a ring. ) General formula [M] (In the formula, Ar is a phenyl group and includes a substituted phenyl group. Y is an N-hydroxyalkyl substituted p-phenylenediamine derivative that is coupled with an oxidized form of a coloring agent to form a dye. It represents a group that leaves when formed.R represents an acylamimuL anilino group or a ureido group.

) Among the compounds represented by the general formula [I] of the present invention, for example, N,N-diethylhydroxylamine can be used as a preservative for a black and white developing agent in a color developing solution containing a black and white developing agent. It has been known.

Hydroquinone, hydroquinone monosulfonic acid, phenidone, para-aminophenol, etc., which are usually black and white developing agents, are relatively stable when used as black and white developing agents in a black and white developer, and sulfites are used as a preservative. However, when added to a color developing solution, a cross-oxidation reaction occurs with the color developing agent, and its storage stability is known to be extremely poor. The shape retention of the black and white developing agent added to the color developing solution is
Hydroxylamine has little effect.

An example of using N,N-diethylhydroxylamine as a preservative for a black and white developing agent added to a color developer is when a color photographic material is developed by a reversal method using a color developer containing a coupler. It is known to be used together with phenidone in the so-called external color development method. The role of phenidone in this case is to increase the development speed of external photosensitive materials with poor developability and to increase the density of dye images.

In a magenta color developing solution that does not contain phenidone, N,N-diethylhydroxylamine is
It is known that it actually has an adverse effect on the storage stability of external color developing solutions by destroying couplers (see Japanese Patent Publication No. 45-22198).

Another example of using a compound of the present invention, such as N,N-diethylhydroxylamine, as a preservative for a black and white developing agent added to a color developer is as follows: Techniques for retaining the shape of added phenidone derivatives (see JP-A No. 53-32035) and techniques for retaining the shape of phenidone derivatives together with hydroquinones (see JP-A-52-153437) can be mentioned. .

As mentioned above, the compound of the present invention has been known to be used as a preservative for black and white developing agents added to color developing solutions. It is not known as a constant agent.

In recent years, there has been a desire in the industry for a technology that allows rapid processing of silver halide color photographic materials and that also provides stable photographic properties due to concerns about processing stability.
In particular, a method for processing silver halide color photographic materials that can be processed quickly is desired.

In other words, silver halide color photographic materials are subjected to running processing in automatic processing machines installed in each laboratory, but as part of an effort to improve service to users, processing is carried out on the same day that processing is received. WAit! In recent years, there has been a demand for returns within a few hours of receipt, and there is an urgent need to develop technology that can handle the process even more quickly.

Looking at the conventional technologies for rapid processing of silver halide color photographic light-sensitive materials, there are: [1] technology based on improvements in silver halide color photographic light-sensitive materials, [2] technology using physical means during development processing, and [3] development processing. Technology based on improving the composition of the processing liquid used for processing.

Among the rapid processing techniques in [I] above, techniques using silver halide photographic materials containing silver halide grains made of high concentration silver chloride (for example, Japanese Patent Application Laid-Open No. 58-95345)
No., JP-A-60-19140, JP-A-58-9573
(described in Publication No. 6, etc.) provides particularly excellent speed-up performance. However, when such photosensitive materials containing high silver chloride are used, hydroxylamine, which is normally used as a preservative for coloring agents in color developing solutions, causes a silver development reaction due to its reducing power, resulting in insufficient dye density. There is a drawback that it becomes a thing. However, when hydroxylamine is not used, the storage stability of the color developing solution deteriorates significantly. It's really a trade-off relationship. In addition, cerium salts and manganese salts significantly retain the color developing agent while hydroxylamine is present, but they also accelerate the decomposition speed of hydroxylamine itself.
It has been found that when the hydroxylamine is depleted, the retention property deteriorates rapidly. The inventors of the present invention have conducted various studies and found that the above-mentioned problems can be solved simultaneously when monoalkylhydroxylamine or dialkylhydroxylamine is used in combination with cerium salt and/or manganese salt. We found that it is possible to improve the Therefore, another object of the present invention is to increase the period of maintaining stability, and further,
A color developer and transfer agent for silver halide color photographic light-sensitive materials that improves magentastin, improves preservability, prevents silver development reactions from occurring in high-silver chloride light-sensitive materials, and enables rapid processing. An object of the present invention is to provide a method for processing silver halide color photographic materials.

Next, the general formula [I] will be explained in detail.

R1 and R2 each represent an alkyl group or a hydrogen atom that is not a hydrogen atom, but 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, such as , methyl group, ethyl group, n-propyl group, 1so-propyl group, and the like.

The alkyl groups of R1 and R2 include those having a substituent, and examples of the substituent include an amino group, an alkoxy group (for example, a methoxy group, etc.), a sulfonic acid group, a carbon'M group, a hydroxyl group, etc. For example, U.S. Pat.
, 287.125, 3,293.034, 3,287,124, and the like.

Further, R1 and R2 may be combined to form a ring, for example, a heterocycle such as piperidine or morpholine.

Preferred specific exemplary compounds represented by the general formula [I] are shown below.

(I-1) C21-! 5 -OH 2H5 (I-2) (I-3) (I-4)
(1-5) (I-〇)
, (I-7) (I-8)
(I-9) (I-1o) (I
-11) (l-12) (l-
13) (I-14) (I-
15) (I-16) (I-1
7) (l-1s) (l-19
) These compounds of the present invention may be used in the form of salts such as hydrochloride, sulfate, p-toluenesulfonate, oxalate, phosphate, and acetate.

Among the compounds represented by the above general formula [I], (I-1) and (I-2) are particularly preferably used from the viewpoint of the desired effects of the present invention.

The concentration of the compound of the present invention in the color development liquid is about the same concentration as hydroxylamine commonly used as a preservative, for example, 0.1 fJ#! ~50 g/ffi is preferably used, more preferably 11 J/ffi ~30 g#! and more preferably 3 g/ffi to 20 g/ll
It is.

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

Manganese chloride @ acid manganese sulfite manganese bromide phosphate manganese nitrate manganese permanganate potassium acetate manganese oxalate manganese citrate manganese ethylene diamine tetraacetate manganese sulfate cerium nitrate cerium chloride cerium carbonate cerium phosphate cerium acetate cerium citrate Cerium Acid These manganese salts and cerium salts are each in the form of ions (manganese ions and cerium ions) in an amount of 0.00% per liter of color developer. It is preferable to use it in the range of Bag to 100mQ, more preferably 0,3n+g to 2
0Il1g, especially 0.51QfJ~1
0 mg is particularly preferably used from the viewpoint of the desired effect of the present invention.

Normally, a preservative is added to the color developer. ii! IPl
i salt s x 10-3 mol/2~4X10-2 mol/
Although used within the range of y, in the color developing solution according to the present invention,
When the sulfite concentration is 4 x 10-3 mol or less per 11 parts of the color developing solution, it is possible to suppress the decrease in color density that is thought to be caused by the dissolution physical phenomenon of high silver chloride-containing photosensitive materials, and also to improve storage stability. Since the deterioration in printing ability is extremely slight, it is possible to provide a processing method for silver halide color photographs using a color developing solution or transfer, which enables rapid processing using photosensitive materials containing high silver chloride. The sulfite concentration in the color developer is 4 x 10-3 mol/
2 or less is preferably used. Furthermore, this effect is better exhibited at 0 to 2 x 10-3 mol/l.

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

As the color developing agent used in the color developer 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 paraphenylenediamine compounds that do not have water-soluble groups such as N,N-diethyl-p-phenylenediamine,
Not only does it have the advantage of not causing contamination of photosensitive materials and 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)
n -CH20H1-(CH2), -NH8O2-(C
H2),, CHa, -(CH2)m O-(CH2)1
1-CH3, -(CH20H20)n CCl1lH2
+1 (m and n each represent an integer of 0 or more.

), -COOHJJ, -8O3H! 1st prize is preferred. It is mentioned as a good thing.

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

More than 100 Child 1 Exemplary color development agent (A-1) Hs C2C2H4N HS O2CHs (A-2) H, C2C, H40H (A-3) HIO2CtH,OH (A-4) HIC2C2H-OCHs (A-5) Hs　C2C3Hs　S　O3H (A-6) H, CC, H40H (A-7) HOH, C2C2H, OH (A-8) HIC, C, H, 5O3H (A-9) HIC<　C5HsSOsH H2 (A-10) (A-11) (A-12) (A-13) (A-14) Hs　C<ノCH,CH,OiC,H.

(A-15) Hs C2Cx H-N HSO* CHa(A-1
6) H, C, C2H4OH Among the color developing agents exemplified above, exemplification No. and (A-
1), (A-2), (A-3), (A-4>, (A-6
>, (A-7) and (A-15), with (A-1) being particularly preferred.

The above color developing agents are usually hydrochloride, TiAPa salt, D-
It is used in the form of a salt such as toluenesulfone Fl salt.

The color developing agent having a water-soluble group used in the present invention is
Usually 1X10' to 2X10- per 12 color developer
It is preferable to use the amount in the range of 1 mol, but from the viewpoint of rapid processing, it is used in an amount of 1.5 x 10-2 per color developer.
A range of X10-1 mol 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 and No. 58-24137 are used, and specifically, for example, 2',4'-bismethanesulfonamide-4-diethylaminodiphenylamine, 2'-methanesulfonamide-4' −(2
,4,6-1-lyinpropyl)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-doliisobrobyl)benzenesulfonamide diphenylamine, 2,4'-bismethanesulfonamide-4-N, N-diethylaminodiphenylamine, 4-n-hexyloxy-2'-methanesulfonamide-4'-(2,4,6-doliisobrobyl)benzenesulfonamide diphenylamine,
4-methoxy-2'-methanesulfonamide-4' -
(2,4,6-)-lyinpropyl)benzenesulfonamide diphenylamine, 4-diethylamino-4'
-(2,4,6-dolyisobrobylbenzenesulfonamido)diphenylamine, 4-n-hexyloxy-3
7-Methyl-4'-(2,4,6-dolyisobrobylbenzenesulfonamido)diphenylamine, 4-N.

N-diethylamino-4'-(2,4,6-doliisobrobylbenzenesulfonamido)diphenylamine,
Examples include 4-N,N-dimethylamino-2-phenylsulfonyl-4' = (2,4,6-doliisobrobylbenzenesulfonamide) diphenylamine.

The amount a of the dye precursor added to the photosensitive material is preferably 05 to 22 mo, more preferably 4 to 12 mo per 100 c1z of the photosensitive material.

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

General formula [D] (In the formula, R2+ 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 benzyl 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 [D] are as follows.

(+)-1) Ethanolamine, (D-2) Jetanolamine, (D-3) 1-jetanolamine, (D-4) Di-isopropanolamine, (D-5) 2
-Methylamino 1knol, (1)-6>2-di[thylaminoethanol, (t)-7>2-dimethylaminoethanol, (D-8) 2-diethylaminoethanol,
(D-9>1-diethylamine-2-11]panol, (D-10) 3-diethylamino-1-propatool, (D-11) 3-dimethylamino-1-bu[]panol, (D-12 ) isopropylamine ethanol, (D-
13>3-amino-1-propertool, (D-14)2
-amino-2-methyl-1,3-71copanediol, (D-15) ebulene diamine deI-light [1
Panol, (D-16)benzyljetanolamine, <D-1
7) 2-amino-2-(hydroxymethyl)-1,3-
Propanediol.

These compounds represented by the general formula [[)] have an effect of 3 g to 1 ffi of the color developer.
It is preferably used within the range of 100g, more preferably 6
It is used in the range of g to 50a.

The color developer according to the present invention has the following general formula [8-IF
When containing the compounds represented by [B-IV] to [B-IV], the objective effects of the present invention can be better achieved, and the bleaching edge blur that occurs when bleaching or bleach-fixing is performed immediately after color development is also improved. Since the present invention has the effect of
3 is more preferably used.

General formula [B-IF General formula [8-111 In the formula, R++, R+2, R+3 and RN are each a hydrogen atom, a halogen atom, a sulfonic acid group, or a carbon atom number of 1 to
7 alkyl group, -OR+s, I7 -C00R+s, -CON or phenyl group R
+.

represents. Also, R+s, R+s, Roj5 and R+a
each represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms. However, when R12 represents a hydrogen atom or a hydrogen atom, R++ represents a halogen atom, a sulfonic acid group, an alkyl group having 1 to 7 carbon atoms, or a phenyl group.

-propyl group, n-propyl group, t-butyl group, lobethyl group, hydroxymethyl group, hydroxyethyl group, methylcarboxylic group, and the alkyl group represented by R+5, R+s, R17 and R+a are as defined above, Further examples include octyl group.

In addition, the phenyl group represented by R++, R+2, R+3 and R is a phenyl group, a 2-hydroxyphenyl group,
Examples include 4-aminophenyl group.

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

(B-I-1) 4-isopropyl-1,2-dihydroxybenzene (8-I-2) 1,2-dihydroxybenzene-3,5-disulfonic acid (B-I-3) 1,2.3 -t-dihydroxybenzene-5-carboxylic acid (B-I-4) 1,2,3-1-lihydroxybenzene-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-1) 2,3-dihydroxynaphthalene-6-sulfonic acid (B -I-2) 2,3,8-trihydroxynaphthalene-6-sulfonic acid (B-II-3) 2,3-dihydroxynaphthalene-6-carboxylic acid (B-IF-4) 2,3-dihydroxy- 8-Isopropyl-naphthalene (B-II-5) 2,3-dihydroxy-8-riOronaphthalene-6-
Among the above-mentioned sulfonic acid compounds, 1,2-dihydroxybenzene-3.
Examples include 5-disulfonic acid, which can also be used as alkali gold B salts such as sodium salts and potassium salts.

In the present invention, the general formulas [B-11 and [B-II
The compound represented by I is 5 ma to 20 ma per 11 color developing solution.
9, preferably 10II1
Good results are obtained by adding between g and 10 g, more preferably between 20 m and 3 g.

The following margin general formula [B-1[[] General formula [B-IV] (In the general formula [B-1[1]eyohi[8-IV], L G
．． tAlkylene group, cycloalkylene group, phenylene group, -La -0-La -0-La- or -Ls
Represents Z-Lq-. Here, Z is, L12-R
41 L12-R to 1 to L+a each do not represent an alkylene group.

R33 to R43 each represent a hydrogen atom, a hydroxyl group, a carboxylic acid group (including its salts), or a phosphone MW (including its salts). However, at least two of R33 to R3B are carboxylic acid groups (including salts thereof) or phosphonic acid groups (including salts thereof), and at least two of R37 to R39 are carboxylic acid groups (including salts thereof). (contains salt)
or a phosphonic acid group (including its salts). ) In the general formula [B-I[[] and [B-rV], L
The alkylene group, cycloalkylene group, and phenylene group represented by these, and the alkylene groups represented by L1 to LI3 include those having substituents.

Next, these general formulas [B-I[1] and CB-IV
Preferred specific examples of the compound represented by are listed below.

[Exemplary Compounds] [B-1[[-1] Ethylenediaminetetraacetic acid [B-I[[-21 Diethylenetriaminepentaacetic acid [B-I[[-31 Ethylenediamine-N-(β-hydroxyethyl')-]
N,N',N'-Triacetic acid [B-I[[-4] Propylenediaminetetraacetic acid [8-III-5] Triethylenetetraminehexaacetic acid [B-111-6] Cyclohexanediaminetetraacetic acid [8-11] [-7] 1.2-Diaminopropane-tetraacetic acid [8-1[1-8] 1.3-diaminopropan-2-ol-tetraacetic acid [B-I[[-9] Ethyl ether diaminete 1-U Acetic acid [B-1 [[-10] Glycol ether diamine tetraacetic acid [B-III-
11] Ethylenediaminetetrapropionic acid [B-III-12] Phenyldiaminetetraacetic acid [8-Ill-13] Ethylenediaminetetraacetic acid disodium salt CB-I [
[-14] Ethylenediaminetetraacetic acid tetra(trimethylammonium) salt [B-III-151 Ethylenediaminetetraacetic acid tetrasodium salt [B-I[[-16] Diethylenetriaminepentaacetic acid pentasodium salt [B-III-17] Ethylenediamine-N -(β-hydroxyethyl)-N
, N' , N' -Sodium triacetate CB-I[[-18] Propylenediaminetetraacetic acid sodium salt [B-I[
[-191 Ethylenediaminetetramethylenephosphonic acid [B-II
I-201 Cyclohexanediaminetetraacetic acid sodium salt [8-1 [[-21] Diethylenetriaminepentamethylenephosphonic acid [B-1-22] Cyclohexanediaminetetramethylenephosphonic acid [B-rV-1 is trilotriacetic acid [B -IV - 2] Iminodiacetic acid [B-IV-3] Nitrilotripropionic acid [B-rV-4] Nitrilotrimethylenephosphonic acid [B-TV-5] Iminodimethylenephosphonic acid [B-rV-6] Nitrilotriacetic acid trisodium salt These Among the compounds represented by the general formula [B-III] or [B-IV], compounds particularly preferably used in the present invention include [B-I[[-1], []B-I
II-2] [B-I[1-5], [B-1-8], [8
-III-19], [8-IV-11 and H[8-IV-
4]. Furthermore, these general formulas [B-1[]
The compound represented by [B-IV] is preferably used in an amount of 0.1 to 20 g per 12 of the 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-IF to [B-IV] may be used alone or in combination. In addition, other chelating agents such as oxycarboxylic acids such as citric acid or gluconic acid, phosphonocarboxylic acids such as 2-phosbobutane-1,2,4-tricarboxylic acid, and polyphosphoric acids such as tripolyphosphoric acid or hexametaphosphoric acid. They may be used in combination.

In the present invention, it is preferable to use a triazylstilbene fluorescent brightener represented by the following general formula [11] in the color developing solution according to the present invention because fogging will be less likely to occur.

General formula [1[[] In the formula, X+, X2, Y+ and Y2 are each a hydroxyl group, a halogen atom such as chlorine or bromine, a morpholim L alkoxy group (e.g. methoxy, methoxy, methoxyethoxy, phenoxy, p-sulfonate). phenoxy, etc.), alkyl groups (e.g. methyl, ethyl, etc.), aryl groups (e.g. phenyl, methoxyphenyl, etc.), amine groups, alkylamino groups (e.g. methylamino, ethylamino, butylamino, dimethylamino, cyclohexylamino, β-hydroxyethylamino, di(β-hydroxyethyl)amino, β-sulfoethylamino, N-(β-sulfoethyl)-N'-methylamino, N-(β-hydroxyethyl-N'-methylamino, etc.) , arylamino group (e.g. anilino, 0-, 1-, p-sulfoanilino, 〇-,
m-, p-chloroanilino, 0-, m-, D-)-luidino, 0-, l-, p-carboxyanilino, o-, m
-, p-hydroxyanilino, sulfonaphthylamino,
0-, a+++, p-aminoanilino, 0-, m-, p
- Anilino, etc.). M is a hydrogen atom, sodium,
Represents potassium, ammonium or lithium.

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

= =, +
8 ->

The triazylstilbene-based brightener represented by the formula [I[1] is, for example, the Chemical Industry Association sr optical brightener J (
It can be synthesized by the usual method described on page 8 of [Published in August 2013].

These triazylstilbene type brighteners are preferably used in an amount of 0.2 to 6 g, particularly preferably 0.4 to 3 g, per 11 of the color developing solution used in the present invention.

The color developing solution of the present invention can contain the following developing solution components in addition to the above components.

Examples of alkaline agents other than the above carbonates include sodium hydroxide, potassium hydroxide, silicates, sodium metaborate, potassium metaborate, trisodium phosphorus PIi,
Tripotassium phosphate, borax, etc. alone or in combination,
They can be used in combination as long as the above-mentioned effects of the present invention, that is, no precipitation occurs and l) the H stabilizing effect is maintained. In addition, due to pharmaceutical needs or for the purpose of increasing ionic strength, dibasic sodium phosphate, dihydrogen phosphate, etc.
Various salts can be used, such as potassium, sodium bicarbonate, potassium bicarbonate, borates, and the like.

Additionally, inorganic and organic antifoggants can be added as necessary.

Further, a development accelerator can also be used if necessary.

As a development accelerator, U.S. Pat. No. 2.648.604,
Various pyridinium compounds as typified by Patent Publication No. 3,671,247 and Japanese Patent Publication No. 44-9503M, cationic compounds thereof, cationic pigments such as phenosafranin, neutral salts such as thallium nitrate, the United States Patent No. 2, 5
No. 33,990, No. 2,531,832, No. 2.
950.970, 2.577, 127, and Japanese Patent Publication No. 44-9504, nonionic compounds such as polyethylene glycol, derivatives thereof, and polythioethers are included. Also, U.S. Patent No. 2.304.92
In addition to benzyl alcohol and phenethyl alcohol described in No. 5, acetylene glycol,
Examples include methyl ethyl ketone, cyclohexanone, thioethers, pyridine, ammonia, hydrazine, and amines.

In the above, when using a poorly soluble organic solvent such as benzyl alcohol, tar is likely to be generated due to long-term use of the color developing solution, especially during running processing in a low replenishment system. Proximity to the paper sensitive material to be processed may even lead to serious malfunctions that significantly impair its commercial value.

In addition, since poorly soluble solvents have poor solubility in water, they not only require a stirring device to prepare the color developing solution itself, but also the use of such a stirring device can reduce the dissolution rate. Due to its poor performance, there is a limit to its development accelerating effect.

Furthermore, poorly soluble organic solvents reduce the biochemical oxygen demand ff
The pollution load value such as i (BOD) is large, and it is impossible to dispose of it in sewers or rivers, etc., and treatment of the waste liquid requires a large amount of labor and cost. It is preferable to reduce or eliminate its use as much as possible.

Furthermore, the color developing solution of the present invention may contain ethylene glycol, methyl cellosolve, methanol, acetone, dimethylformamide, β-cyclodextrin, and others as required.
The compounds described in each publication can be used as a purulent agent to increase the solubility of a developing agent.

Furthermore, auxiliary developers can also be used with the developing agents. These auxiliary developers include, for example, N-methyl-p-aminophenol hexulfate (methol).
, phenidone, N,N'-diethyl-p-aminophenol salt M salt, N,N.

N',N'-tetramethyl-p-phenylenediamine hydrochloride is known, and its addition is usually 0.
．． 01! J~1.0 (1/ffi is preferred. In addition, if necessary, competitive couplers, fogging agents, colored couplers, development inhibitor releasing couplers (so-called DI
R coupler) or a development inhibitor-releasing compound can also be added.

Furthermore, other anti-stain agents, anti-sludge agents,
Various additives such as a multilayer effect accelerator can be used.

Each component of the above color developing solution can be sequentially added to a certain amount of water and stirred. In this case, the component with low solubility in water can be added by mixing with the above-mentioned organic solvent such as triethanolamine. More generally, the color developing solution of the present invention is prepared by adding a concentrated aqueous solution or a solid state of a plurality of components that can coexist stably in a small container into water and stirring. Obtainable.

In the present invention, the above color developing solution can be used in any pH range, but from the viewpoint of rapid processing, the pH is 9.5 to 13.0.
pH is preferably 9.8 to 1, more preferably pH 9.8 to 1.
Used in 3.0.

In the present invention, the processing temperature for color development is 30
C. or more and 50.degree. C. or less, the higher the temperature, the faster the treatment is possible, which is preferable, but from the viewpoint of storage stability, it is better not to be too high, and it is preferable to process at 33.degree. C. or more and 45.degree. C. or less.

The color development time is generally about 3 minutes and 30 seconds, but from the viewpoint of speeding up, it is preferably within 2 minutes, and more preferably within a range of 30 seconds to 1 minute and 30 seconds.

The color developing solution according to the present invention can be applied to various processing methods such as a spray set in which the processing solution is atomized, a web method using contact with a carrier impregnated with the processing solution, or a developing method using a viscous processing solution. Can be done. Preferred processing steps include color development, bleach-fixing, and water washing (or stabilization), and in the bleach-fixing step, the bleaching agent and the fixing step can be provided separately, and the bleaching agent is a metal complex salt of an organic acid. The complex salt is one in which a metal ion such as iron, cobalt or copper is coordinated with an aminopolycarboxylic acid or an aged acid such as oxalic acid or citric acid. The most preferred organic acid used to form such a metal salt of an ionic acid is a polycarboxylic acid. These polycarboxylic acids or aminopolycarboxylic acids may be alkali metal salts, ammonium salts or water-soluble amine salts. Specific examples of these include the following.

[1] Ethylenediaminetetraacetic acid [2] Diethylenetriaminepentaacetic acid [3] Ethylenediamine-N-(β-oxyethyl)-N, N', N
' -Triacetic acid [4] Propylenediaminetetraacetic acid [5] Nitri-O-triacetic acid [6] Cyclohexanediaminetetraacetic acid [7] Iminodiacetic acid [8] Dihydroxyethyl glycine citric acid or tartaric acid) [9] Ethyl ether diamine tetraacetic acid [10] Glycol ether di7minetetraacetic acid [11] Ethylenediaminetetrabrobionic acid [12]
Phenylenediaminetetraacetic acid [13] Ethylenediaminetetraacetic acid disodium salt [14] Ethylenediaminetetraacetic acid tetra(trimethylammonium) salt [15] Ethylenediaminetetraacetic acid tetrasodium salt [16] Diethylenetriaminepentaacetic acid pentasodium salt [173 Ethylenediamine-N- (β-oxyethyl)
-N,N',N'-Triacetic acid sodium salt [18] Propylene diamine tetraacetic acid sodium salt [19 Conitriloacetic acid sodium salt [20] Cyclohexanediamine tetraacetic acid sodium salt These bleaches are preferably 5 to 450 g/fl, more preferably is used at 20 to 250 Q/l. The bleach-fixing solution contains a silver halide fixing agent in addition to the above-mentioned bleaching agent, and if necessary, a sulfite 1'ili salt as a preservative. In addition, iron ethylenediaminetetraacetate (I
[[] A bleach-fixing solution consisting of a complex salt bleach and a small amount of a halide such as ammonium bromide other than the silver halide fixing agent mentioned above, or conversely a composition containing a large amount of a halide such as ammonium bromide. Further, a special bleach-fix solution having a composition consisting of a combination of an ethylenediaminetetraacetic acid iron(III) complex salt bleaching agent and a large amount of a halide such as ammonium bromide can also be used. As the halides, hydrochloric acid, hydrobromic acid, lithium bromide, sodium bromide, potassium bromide, sodium iodide, potassium iodide, ammonium iodide, etc. can also be used in addition to ammonium bromide. can.

The silver halide fixing agent contained in the bleach-fixing solution is a compound that reacts with silver halide to form a water-soluble complex salt, such as thioVA, which is used in ordinary fixing processing.
Potassium acid, thiotii! [a Sodium, thio such as ammonium thiosulfate [? salt, potassium thiocyanate,
Typical examples include thiocyanate Fa salts such as sodium thiocyanate and ammonium thiocyanate, thiourea, and thioether. These fixatives are used at a concentration of 5g/2 or more in a range that can be dissolved, but generally 2'O
(Use at 1 to 250 g/liter.

The bleach-fix solution contains boric acid, borax, sodium hydroxide,
Various pH slowing agents such as potassium hydroxide, sodium carbonate, potassium charcoal, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, and ammonium hydroxide may be contained alone or in combination of two or more. The powder may also contain various optical brighteners, antifoaming agents, or surfactants. In addition, preservatives such as hydroxylamine, hydrazine, and bisulfite adducts of aldehyde compounds, organic chelating agents such as aminopolycarboxylic acids, and stabilizers such as nitroalcohols and nitrates,
Organic solvents such as methanol, dimethylsulfamide, dimethylsulfoxide, etc. can be appropriately contained.

The bleach-fix solution used in the present invention includes JP-A No. 46-280, JP-B No. 45-8506, JP-B No. 46-556, Belgian Patent No. 770,910, JP-B No. 45-8836,
Various bleach accelerators described in JP-A-53-9854, JP-A-54-71634 and JP-A-49-42349 can be added.

Bleach-fix solution 1))-1 is used on 4.0 varnish, but generally it is used at I)H5.0 or more and pH 9.5 or less, preferably pl-16.0 or more and pi-19.5 or less. The more preferred p l-I used in 6.
Processed at 5 or more and 8.5 or less. The processing temperature is 80°C or less, which is 3°C or more, preferably 5°C or more lower than the temperature of the processing solution in the color developing tank, but preferably 55°C.
Use the following methods to prevent evaporation, etc.

The halide grains used in the silver halide color photographic light-sensitive material applied to the present invention include silver chloride, silver bromide, silver iodide,
Any of silver chlorobromide, silver chloroiodide, silver iodobromide, silver chloroiodobromide, and mixtures thereof can be used, but those used are particularly preferred from the viewpoint of rapid processability. , silver halide grains containing at least 80 mol% of silver chloride, preferably 90 mol% or more, more preferably 95 mol% or more.

In a silver halide color photographic light-sensitive material made of a silver halide emulsion containing such silver halide grains, the color development liquid of the present invention is particularly advantageously applied because the dye density decreases significantly due to hydroxylamine. .

The silver halide emulsion containing silver halide grains consisting of 80 mol% or more of silver chloride may contain silver bromide and/or silver iodide as a silver halide composition in addition to silver chloride,
In this case, silver bromide is at most 20 mol%, preferably at most 10 mol%, more preferably at most 5 mol%, and when silver iodide is present, it is at most 1 mol%, preferably 0.5 mol%. It is as follows. Such silver halide grains substantially consisting of silver chloride according to the present invention contain 80% or more by weight of all the silver halide grains in the silver halide emulsion layer containing the silver halide grains. It is preferably 100%, and more preferably 100%.

The crystals of the silver halide grains used in the present invention may be normal crystals, twin crystals, or other crystals, and have [1001 planes and [111
] Any aspect ratio can be used.

Further, the crystal structure of these silver halide grains may be uniform from the inside to the outside, or may have a layered structure (core-shell type) in which the inside and outside are different. Further, these silver halides may be of a type that forms a latent image mainly on the surface or of a type that forms a latent image inside the grain. Further, tabular silver halide grains (JP-A-58-
No. 113934 and Japanese Patent Application No. 170070/1983) may also be used.

The silver halide grains used in the present invention may be obtained by any of the acidic method, neutral method, and ammonia method.

Alternatively, for example, seed particles may be produced using an acidic method, and then grown using an ammonia method, which has a high growth rate, to grow to a predetermined size. When growing silver halide grains, the I)Hll)A(1) in the reaction vessel is controlled to match the growth rate of silver halide grains as described in JP-A-54-48521, for example. It is preferable to implant and mix five silver ions and five halide ions simultaneously.

Preferably, the silver halide grains according to the present invention are prepared as described above. A composition containing the silver halide grains is referred to as a silver halide emulsion in this Specification 4.

These silver halide emulsions contain activated gelatin; sulfur sensitizers such as allylthiocarbamide, thiourea, cystine; selenium sensitizers; reduction sensitizers such as stannous salts, thiourea dioxide, Polyamines, etc.; noble metal sensitizers, such as gold sensitizers, specifically potassium aurithiocyanate, potassium chloroaurate, 2-aurothiol-3-
Sensitizers such as methylbenzothiazolium chloride or water-soluble salts such as ruthenium, palladium, platinum, rhodium, iridium, etc., specifically ammonium chlorovaladate, potassium chloroaurate and sodium chloroparadate (these Depending on the size of the group, these substances act as sensitizers or fog suppressants. It may also be chemically sensitized (for example, in combination with a sensitizer).

The silver halide emulsion according to the present invention is subjected to chemical ripening by adding a sulfur-containing metal substance, and before, during, or after this chemical ripening, a nitrogen-containing emulsion having at least one kind of hydroxytetrazaindene and a mercapto group is produced. It may contain at least one type of heterocyclic compound.

The silver halide used in the present invention is mixed with an appropriate sensitizing dye in an amount of 5 x 10-8 to 3
Optical sensitization may be achieved by adding 3 moles. Various sensitizing dyes can be used, and each sensitizing dye can be used alone or in combination of two or more. Examples of sensitizing dyes that can be advantageously used in the present invention include the following.

That is, as sensitizing dyes used in blue-sensitive silver halide emulsions, for example, West German Patent No. 929.080, US Pat. No. 2,231,658, US Pat.
Same No. 2,503,776, Same No. 2,519,001, Same No. 2,912゜329, Same No. 3.656.959
No. 3,672.897, No. 3,694,21
No. 7, No. 4,025,349, No. 4.046, 5
No. 72, British Patent No. 1.242.588, Special Publication No. 1972
Examples include those described in No. 14030, No. 52-24844, and the like. Examples of sensitizing dyes used in green-sensitive silver halide emulsions include U.S. Pat. No. 1,939,201, U.S. Pat. .763,
Typical examples include cyanine dyes, merocyanine dyes, and composite cyanine dyes as described in British Patent No. 505.979. Further, as sensitizing dyes used in red-sensitive silver halide emulsions, for example, U.S. Pat.
270゜378, same No. 2.442.710, same No. 2
．． Typical examples thereof include cyanine dyes, merocyanine dyes, and composite cyanine dyes as described in Japanese Patent No. 454.629 and No. 2,776.280.

Furthermore, U.S. Patent No. 2,213,995, U.S. Patent No. 2.4
No. 93.748, German Patent No. 2.519.001, West German Patent No. 929.080, etc., cyanine dyes, merocyanine dyes or composite cyanine dyes are used as green-sensitive silver halide emulsions or red-sensitive silver halide emulsions. It can be advantageously used in emulsions.

These sensitizing dyes may be used alone or in combination.

The photographic material of the present invention may be optically sensitized in a desired wavelength range by a spectral sensitization method using cyanine or merocyanine dyes alone or in combination, if necessary.

As a particularly preferred spectral sensitization method, a typical one is, for example, a method using PA for a combination of benzimidazolocarbocyanine and benzoxazolocarbocyanine.
No. 36, No. 43-22884, No. 45-18433, No. 47-37443, No. 48-28293, No. 4
No. 9-6209, No. 53-12375, Japanese Unexamined Patent Publication No. 1983-
No. 23931, No. 52-51932, No. 54-801
No. 18, No. 58-153926, No. 59-11664
64, No. 59-116647, and the like.

Further, regarding the combination of carbocyanine having a benzimidazole nucleus with other cyanine or merocyanine, for example, Japanese Patent Publication Nos. 45-25831 and 47-11
No. 114, No. 47-25379, No. 48-38406
No. 48-38407, No. 54-34535, No. 55-1569, JP-A-50-33220, No. 50
-38526, 51-107127, 51-
No. 115820, No. 51-135528, No. 52-1
No. 04916, No. 52-104917, and the like.

Furthermore, regarding combinations of benzoxazolocarbocyanine (oxa-carbocyanine) and other carbocyanines, for example, Japanese Patent Publication Nos. 44-32753 and 46
-11627, JP-A No. 57-1483, and regarding merocyanine, for example, Japanese Patent Publication No. 4B-38408.
No. 48-41204, 5o-4ose2@, JP-A-56-25728, 58-10753@, 5
No. 8-91445, No. 59-116645, No. 50-
No. 33828 etc. are mentioned.

Regarding combinations of thiacarbocyanin and other carbocyanins, for example, Japanese Patent Publication Nos. 43-4932, 43-4933, 45-26470, 4
No. 6-18107, No. 47-8741, JP-A-59-
No. 114533, etc., and the method described in Japanese Patent Publication No. 114533 using zeromethine, monomethine or dimethine merocyanine, monomethine or trimethine cyanine and methylyl dye can be advantageously used.

In order to add these sensitizing dyes to the silver halide emulsion according to the present invention, a dye solution such as methyl alcohol, ethyl alcohol, acetone, dimethylformamide, or fluorinated alcohol described in Japanese Patent Publication No. 40659/1984 is used in advance. It is used by dissolving it in a hydrophilic organic solvent.

The addition may be made at any time such as at the start of chemical ripening of the silver halide emulsion, during ripening, or at the end of ripening, and in some cases, it may be added at a step immediately before coating the emulsion.

The photographic constituent layer of the silver halide color photographic light-sensitive material of the present invention may contain a water-soluble dye or a dye (AI dye) that can be decolored with a color developing solution. Examples of the AI dye include oxonol dye, hemioxonol dye, Dyes, merocyanine dyes and azo dyes are included. Among them, oxonol dyes, hemioxonol dyes, merocyanine dyes, and the like are useful.

Examples of AI dyes that can be used include British Patent No. 584.6
No. 09, No. 1,277.429, Japanese Unexamined Patent Publication No. 1985-85
No. 130, No. 49-99620, No. 49-114
No. 420, No. 49-129537, No. 52-10
No. 8115, No. 59-25845, No. 59-11
1G40, No. 59-111641, U.S. Patent No. 2
, No. 274.782, fA 2,533. -172, 2.95G, 079, 3.125.448
No. 3゜148. il'17, 3.177
, No. 078, No. 3,247.127, No. 3.2G
O.

No. 601, No. 3.540.887, No. 3.575
．． 704@, same No. 3.653.905, same No. 3,71
No. 8,472, No. 4.071.312@, No. 4.0
Examples include those described in No. 70,352.

These AI dyes are generally used at a concentration of 2 per mole of dye in the emulsion layer.
It is preferable to use X 10-3 to 5 X 10-1 mol, more preferably 1 X 10-2 to 1 x 10-
Use 1 mole.

The McGinck coupler represented by the general formula [M] will be described in detail below.

The magenta dye-forming coupler used in the present invention can be represented by the following general formula CM.

General formula [M] Ar: A phenyl group, especially a substituted phenyl group.

Examples of substituents include halogen atoms, alkyl groups, alkoxy groups, aryloxy groups, alkoxycarbonylmoyl groups, sulfonyl groups, sulfonamide groups, and acylamino groups, and the phenyl group represented by Ar has two or more substituents. It's okay.

Specific examples of substituents are listed below.

Halogen atoms: chlorine, bromine, fluorine Alkyl groups: methyl group, ethyl group, iso-propyl group, butyl group, [-butyl group, t-pendel group, etc., but especially alkyl groups having 1 to 5 carbon atoms preferable.

Alkoxy group: methoxy group, ethoxy group, butoxy group,
Examples include sec-butoxy group, iso-pentyloxy group, and particularly preferred is an alkoxy group having 1 to 5 carbon atoms.

Aryloxy group: phenoxy group, β-naphthoxy group, etc., but this aryl moiety may further have the same substituents as listed for the phenyl group represented by Ar.

Alkoxycarbonyl group: The above-mentioned carbonyl group with an alkoxy group attached thereto, and those in which the alkyl moiety has 1 to 5 carbon atoms, such as a methoxycarbonyl group and a pentyloxycarbonyl group, are preferable.

Alkylcarbamoyl groups such as carbamoylurbamoyl groups Sulfamoyl groups: Alkylsulfamoyl groups such as sulfamoyl groups, methylsulfamoyl groups, dimethylsulfamoyl groups, ethylsulfamoyl groups Sulfonyl groups: methanesulfonyl groups, ethanesulfonyl groups , an alkylsulfonyl group such as a butanesulfonyl group, an arylsulfonyl group Sulfonamide group: an alkylsulfonamide group such as a methanesulfonamide group or a toluenesulfonamide group, an arylsulfonamide mW Acylamino group: an acetamino group, a pivaloylamino group, a benzamide group, etc. are particularly preferred. is a halogen atom, of which chlorine is most preferred.

Y2N-Hydroxyalkyl substituted m-p-phenylenediamine derivative represents a group that leaves when a dye is formed by coupling with an oxidized product of a color developing agent.

Specifically, for example, a halogen atom, an alkoxy group, an aryloxy group, an acyloxy group, an arylthio group, an alkylthio group, -(to)2 (Z is selected from a nitrogen atom and a carbon atom, an oxygen atom, a nitrogen atom, a sulfur atom) (Represents a group of atoms required to form a 5- or 6-membered ring with an atom.) Specific examples are given below.

Halogen atom: chlorine, bromine, fluorine Alkoxy group: ethoxy group, benzyloxy group, methoxyethylcarbamoylmethoxy group, tetradecylcarbamoylmethoxy group, etc. Aryloxy group: phenoxy group, 4-methoxyphenoxy group, 4-nitrophenoxy group, etc. Acyloxy group Groups: acetoxy group, myristoyloxy group, benzoyloxy group, etc. Arylthio group: phenylthio group, 2-butoxy-5-
Alkylthio groups such as octylphenylthio group, 2.5-dihexyloxyphenylthio group: methylthio group, octylthio group, hexadecylthio group, benzylthio group, 2-(diethylamino)ethylthio group, ethoxycarbonylmethylthio group,
phenoxyethylthio group, etc. -r'q z: birazolyl group, imidazolyl group, triazole group, tetrazolyl group, etc. R: When R is an acylamino group, examples thereof include acetamido group, isobutylamino group, benzamide group, 3-[
α-(2,4-di-tert-amylphenoxy)butyramide]benzamide group, 3-[α-(2,4-di-tert-amylphenoxy)acetamido]benzamide group, 3-[α-(3-pentadecylphenoxy) ) butylamide]benzamide group, α-(2,4-dite
rt-amylphenoxy)butyramide group, α-(3-
Examples include a pentadecylphenoxy)butyramide group, a hexadecaneamide group, an isostearoylamino group, a 3-(3-octadecenylsuccinimide)benzamide group, or a pivaloylamino group. When R is an anilino group, examples thereof include an anilino group. , 2-chloroanilino group, 2.
4-dichloroanilino group, 2.5-dichloroanilino group, 2.4.5-trichloroanilino group, 2-chloro-5
-tetradecanamide anilino group, 2-chloro-5-(
3-octadecenylsuccinimide) anilino group, 2-
Chloro-5-[α-(3-tert-butyl-4-hydroxy)tetradecanamido)anilim L2-chloro-5-tetradecyloxylponylanilino group, 2-chloro-5-(N-tetradecylsulf7moyl) Anilim L2.4-dichloro-5-tetradecyloxyanilino group, 2-chloro-5-(tetradecyloxycarbonylaminoanilino group, 2-chloro-5-octadecylthioanilino group or 2-chloro-5-( N-tetradecylcarbamoyl)anilino group, etc. When R is a ureido group, examples include 3-((2,4-di-tert-aminophenoxy)acetamido)phenylureido group,
phenylureido group, methylureido group, octadecylureido group, 3-teradecanamide phenylureido group or N. There are N-dioctylureido groups and the like. Among the compounds represented by general formula [1], particularly preferred compounds are represented by general formula [I].

General formula [I[] r In the formula, Y and A" represent the same meanings as in general formula [I].

X: represents a halogen atom, an alkoxy group, or an alkyl atom.

Specific examples are listed below.

Halogen atoms: chlorine, bromine, fluorine alkoxy groups: methoxy group, ethoxy group, butoxy group,
Alkoxy groups having 1 to 5 carbon atoms such as sec-butoxy group and iso-bentyloxy group are preferred.

Alkyl group: An alkyl group having 1 to 5 carbon atoms, such as medyl group, edyl group, 1so-propyl group, butyl group, t-butyl group, and t-pentyl group, is preferable. Particularly preferred is a halogen atom, with chlorine being particularly preferred.

R1: represents a group that can be substituted on the benzene ring, and 11 does not represent 1 or 2. When n is 2, R1 may be the same or different. As a group that can be substituted on the benzene ring represented by R1, a halogen atom, rt'n, 'R+, Rn, and Rnr may each be the same or n, and a hydrogen atom or each may have a substituent. 7. Represents an alkyl group, alkenyl group or aryl group. Among these, preferred are:
Specific examples of magenta couplers are shown below, but the invention is not limited thereto.

Examples of B in the above formula include the following.

M-1-Nl-ICOCl, 1112. M-2-
NIICOC,,H,.

Cttl'lts C8゜l-12゜Σ ≧ M-42 These magenta couplers of the present invention are disclosed in JP-A-56-380.
No. 43, No. 57-14837, No. 57-20403
It can be easily synthesized according to the method described in No. 6, No. 58-14833, etc.

The addition n of the magenta coupler of the present invention is preferably o, oos to 2 mol, more preferably 0.01 to 1 mol, per mol of silver halide.

In the present invention, in addition to the magenta coupler represented by the general formula [M], the following photographic couplers can be used.

Cyan couplers include common phenolic compounds and naphthol compounds, such as U.S. Pat. No. 2,369,929.
No. 2,434,272, No. 2,474,293, No. 2.895,826, No. 3.253.924, No. 3,034,892, No. 3.311.476, 3.386.301, 3,419,390,
Those described in 3.458.315, 3.476, 563, 3.531.383, etc. can be used.

The same publication also describes methods for synthesizing these compounds.

Examples of photographic magenta couplers include compounds such as pyrazolone, pyrazolotriazole, pyrazolinobenzimidazole, and indasilone, which can be used in combination with the magenta coupler of the present invention. As a pyrazolone magenta coupler, U.S. Patent No. 2,600
．． No. 788, No. 3,062.653, No. 3,127
, No. 269, No. 3,311,476, No. 3, 419
．． No. 391, No. 3,519,429, No. 3,55
No. 8,318, No. 3,684,514, No. 3.888
．． No. 680, JP-A-49-29639, JP-A No. 49-1
No. 11631, No. 49-129538, No. 50-1
No. 3041, Special Publication No. 53-47167, No. 54-10
Compounds described in No. 491 and No. 55-30615: As pyrazolotriazole magenta couplers, U.S. Patent No. 1.247,493 and Belgian Patent No. 792
．． As the diffusion-resistant colored magenta coupler, compounds in which the coupling position of the colorless magenta coupler is substituted with arylazo are generally used.
No. 71, No. 2.983.608, No. 3,005,
No. 712, No. 3,684.514, British Patent No. 937
, No. 621, JP-A-49-123625, JP-A No. 49-3
Examples include compounds described in No. 1448.

Furthermore, a colored magenta coupler of the type described in US Pat. No. 3,419,391, in which the dye flows out into the processing solution by reaction with an oxidized product of a developing agent, can also be used.

As photographic yellow couplers, open-chain ketomethylene compounds have conventionally been used, and generally widely used benzoylacetanilide type yellow couplers and pivaloylacetanilide type yellow couplers can be used. Further, 2-detached yellow couplers in which the carbon atom at the coupling position is substituted with a substituent that can be removed during the coupling reaction are also advantageously used.

Examples of these are U.S. Pat. No. 2,875,057, 3.2
No. 65.506, No. 3,664,841, No. 3,
No. 408,194, No. 3,277.155, No. 3
, No. 447,928, No. 3.415.652, Japanese Patent Publication No. 49-13576, Japanese Patent Publication No. 29432-1983, No. 48-68834, No. 49-10736, No. 49-
No. 122335, No. 50-28834, No. 50-13
2926@ etc. together with the synthesis method.

The use of the above-mentioned diffusion-resistant couplers a in the present invention is generally carried out in amounts of 0.000.
05 to 2.0 mol.

In the present invention, DIR compounds are preferably used in addition to the above-mentioned diffusion-resistant couplers.

Furthermore, in addition to DIR compounds, compounds that release development inhibitors during development are also included in the present invention, such as those disclosed in U.S. Pat. No. 3,297,445, U.S. Pat. , 417,914, JP-A No. 52-15271, JP-A No. 53-9116, JP-A No. 53-9116,
Examples include those described in No. 59-123838 and No. 59-127038.

The DIR compound used in the present invention is a compound capable of reacting with an oxidized form of a color developing agent to release a development inhibitor.

A typical example of such an IR compound is a DIR coupler in which a group capable of forming a compound having a development inhibiting effect when separated from the active site is introduced into the active site of the coupler. 454, U.S. Patent No. 3.227.554, U.S. Patent No. 4,095,984,
It is described in No. 4.149.886, etc.

When the above DIR coupler undergoes a coupling reaction with an oxidized color developing agent, the coupler core forms a dye,
On the other hand, it has the property of releasing a development inhibitor. Further, in the present invention, U.S. Pat.
No. 41, No. 3.958.993, No. 3.961.95
No. 9, No. 4,052,213, JP-A-53-1105
No. 29, No. 54-13333, No. 55-161237
When it undergoes a coupling reaction with the oxidized form of a color developing agent as described in
Also included are compounds that do not form pigments.

Zaranimata, JP-A-54-145135, JP-A No. 56-1
Upon reaction with oxidized color developing agents such as those described in No. 14946 and No. 57-154234, the mother nucleus forms a dye or colorless compound, while the 1lili eliminated timing group undergoes intramolecular nucleophilic substitution. The present invention also includes so-called timing DIR compounds, which are compounds that release a development inhibitor by reaction or elimination reaction.

Also, JP-A No. 58-160954, No. 58-16294
Timing DI, in which a timing group as described above is bonded to the coupler core, produces a completely diffusible dye when reacted with an oxidized form of a color developing agent described in No. 9.
It also includes R compounds.

The base of the DIR compound contained in the light-sensitive material is preferably used in a range of 1.times.10@-4 mol to 10.times.10@-1 mol per 1 mol of silver.

The silver halide color photographic light-sensitive material used in the present invention may contain various other photographic additives. For example, Research Disclosure Magazine 17643
Antifoggants, stabilizers, ultraviolet absorbers, color stain inhibitors, optical brighteners, color image @thigh color inhibitors, antistatic agents, hardeners, surfactants, plasticizers, Wetting agents and the like can be used.

In the silver halide color photographic light-sensitive material used in the present invention, the hydrophilic colloids used to prepare the emulsion include gelatin, derivative gelatin, graft polymers of gelatin and other polymers, and proteins such as albumin and casein. , cellulose derivatives such as hydroxyethyl cellulose derivatives and carboxymethyl cellulose, starch derivatives, single or copolymer synthetic hydrophilic polymers such as polyvinyl alcohol, polyvinylimidazole, and polyacrylamide.

Examples of the support for the silver halide color photographic light-sensitive material used in the present invention include baryta paper, polyethylene-coated paper, polypropylene synthetic paper, a transparent support provided with a reflective layer or a reflective material, such as a glass plate, Examples include polyester films such as cellulose acetate, cellulose thiolate, and polyethylene terephthalate, polyamide films, polycarbonate films, and polystyrene films, and other common transparent supports may also be used. These supports are appropriately selected depending on the intended use of the photosensitive material.

Various coating methods such as dipping coating, air doctor coating, curtain coating, and hopper coating can be used to coat the silver halide emulsion layer and other photographic constituent layers used in the present invention. Also, U.S. Patent No. 2.713
It is also possible to use a simultaneous coating method of two or more layers by the method described in No. 1, No. 791 and No. 2,941,898.

In the present invention, the coating position of each emulsion layer can be determined arbitrarily. For example, the full color mark II! ! In the case of a photosensitive material for i-paper, it is preferable to arrange a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a red-sensitive silver halide emulsion layer in this order from the support side. Each of these photosensitive silver halide emulsion layers may consist of two or more layers.

In the photosensitive material of the present invention, it is optional to provide an intermediate layer with an appropriate thickness depending on the purpose, and a filter layer,
Various layers such as an anti-curl layer, a retention layer, and an antihalation layer can be used in appropriate combinations as constituent layers.

Hydrophilic colloids that can be used in the emulsion layers as described above can be used as binders in these constituent layers, and various types of colloids that can be contained in the emulsion layers as described above can be used in these layers. Photographic additives may be included.

In the method for processing a silver halide color photographic light-sensitive material of the present invention, if the silver halide color photographic light-sensitive material is a light-sensitive material that is processed by a so-called internal development method in which a coupler is contained in the photosensitive U El, color It can be applied to any silver halide color photographic material such as paper, color negative film, color positive film, color reversal film for slides, color reversal film for movies, color reversal film for TV, and reversal color vapor.

[Specific Effects of the Present Invention] As explained above, the present invention provides a color developing solution that has excellent storage stability and provides stable photographic properties even during low replenishment processing and rapid processing. A method for processing silver halide color photographic materials using the present invention could be provided.

More specifically, the present invention provides a method for processing a silver halide color photographic material in which magentastin generated in a bleaching solution or a bleach-fixing solution is reduced in, for example, a low-speed automatic developer.

[Specific Examples of the Invention] The present invention will be specifically explained below with reference to Examples, but the embodiments of the present invention are not limited to these.

[Example 1] On a paper support laminated with polyethylene, the following layers were sequentially coated from the support side to prepare a comparative photosensitive material sample.

Layer 1...1.3 (1/i' gelatin, 0.340/
Blue-sensitive silver chlorobromide emulsion (A
(97 mol% as JC) and 0. (i41J/i”
A layer containing 0/12 of 1°QXlo-3 moles of the following yellow coupler (Y-1) dissolved in dioctyl phthalate.

Layer 2: Intermediate layer consisting of 0.51 Mf gelatin.

Layer 3...1.3 (1/l' gelatin, 0.220/
m' green-sensitive silver chlorobromide emulsion (98 mol % as 800ffi) and 1,3X10-3 mol IJ/n' of the following magenta coupler ( M′-1).

Layer 4: Intermediate layer made of gelatin of 1.2Q/n'.

Layer 5: Gelatin of 1.20/n2, 0.21(1/
i' red-sensitive silver chlorobromide emulsion (98 mol% as silver chloride)
and 1,2X10-3 mol g/f of the following cyan coupler (
A layer containing C-1).

Layer 6...1.1 (1/i' gelatin and 0.28 (
0,340 dissolved in 1/n2 dioctyl phthalate
/i' layer containing Tinuvin 328 (ultraviolet absorber manufactured by Ciba Geigy).

Layer 7: o, a layer containing 45Mf gelatin.

As a hardening agent, 2.4-dichloro-6-hydroxy-8-triazine sodium was added in layers 2.4 and 7 at 0.013 gg% per 1 g of gelatin, respectively. M-1! Color paper for comparison was prepared in the manner described above. In the same manner, the magenta coupler (~1'-1) was changed to a magenta coupler as shown in Table 1 below to prepare and use experimental samples as samples of the present invention and comparative samples.

Next, these samples were subjected to wedge-shaped exposure using a conventional method, and then subjected to the following development treatment.

Treatment process Treatment temperature Treatment time [1] Color development! ! ! 38℃ 45 seconds [2] Bleach 38℃ 45 seconds [3]
Washing with water 30℃ 100 seconds [4]
Drying: 60-80°C for 10 seconds The following color developing solution and bleach-fixing solution were used.

[Color developer] Potassium chloride 2.0 jl Potassium sulfite 0.29 Hydroxylamines (Listed in Table 1) Metal j!
(Listed in Table 1) Chelating agent (Illustrative compound example (B-I-2)) 0.5 a
Color developing agent (Illustrated compound example (A-1)) 5.3g Potassium carbonate 30 Q Add water to make 1, and add potassium hydroxide and 50% sulfuric acid to pl-110
, Is.

[Bleach-fix solution] Ethylenediaminetetraacetic acid ferric ammonium dihydrate, eo, o g ethylenediaminetetraacetic acid M 3.0 (1 dio I
AII! Ammonium (70% solution) 100.01
1 Sub-FaR7 ammonium (40961M) 27.
Add 5n12 water to bring the total volume to 12, and adjust to I) l-17,20 with potassium carbonate or glacial acetic acid.

The above color developing solution was heated to 38°C and the aperture ratio was 140C1.
” (Air contact area is 140 for 11 color developing solution.
cf), stored for 3 weeks, and developed using a color developer after storage.

However, the color vapor sample was developed in a transit time of 8 seconds after the color development process until entering the bleach-fix solution.

Transfer the sample after development to the Kura photodensitometer PD-65 (
The magenta density (sudden) of the unexposed area and the yellow density of the highest density area where the developability is the slowest were measured using a photo camera (manufactured by Roku Konishi Photo Industry ■).

The results are summarized in Table 1.

As is clear from Table 1 above, the compound represented by the general formula [I] and the metal salts (manganese salt and/or
or cerium salt) in the color developing solution, and when using the mabinta coupler represented by the general formula [M] in the photosensitive material, the generation of magentastin is small,
It is also seen that sufficient yellow density can be obtained despite the short color development time of 45 seconds.

However, if any one of these elements is missing, the effect of any one of them will be insufficient. Similarly, unsatisfactory results are obtained when metal salts other than those of the invention are used.

[Example 2] Color developing agent (Δ-1
) was changed to (B-1) or (B-2) below and a similar experiment was conducted, and the magentastin in the unexposed area deteriorated by 0.02 in both cases.

Similarly, the same experiment as in Example 1 was carried out by changing the color developing crude drug (A-1) of Example 1 to exemplified compounds (A-2), (A-4), and (Δ-15), respectively. I was surprised to see similar results.

(B-1) (B-1) [Example 31 Example 1. The same experiment was carried out in the same manner as in Example '1, except that the silver halide composition of the blue-sensitive layer in the silver halide color photosensitive material used in Experiment No. 11 was changed as shown in Table 2 below. Ta. The results are summarized in Table 2.

Table 2 As is clear from Table 3, when the silver halide composition of the silver halide color photographic light-sensitive material contains silver chloride of 80 mol% or more, the yellow dye concentration becomes almost sufficient, but below this level, the silver chloride concentration is almost sufficient. It can be seen that sufficient dye density cannot be obtained when the content is low.

Furthermore, it can be seen that when the content is 90 mol% or more, better dye density is obtained, and when it is 95 mol% or more, the density is particularly good. This effect was obtained by similarly changing the silver halide composition of the red-sensitive layer and the green-sensitive layer, and the same results were obtained for the cyan dye density and magenta dye density. Toriwa 1pu,
It has been found that when the silver chloride content of all silver halide emulsion layers is 80 mol % or more, especially 90 mol % or more, especially 95 mol % or more, all the layers give a preferable dye density and give a complete black color. .

[Example 4] Exemplary compound (A'-2) was added to the color developer used in Example 1.
, (A'-4) and (A'-9) (all triadylstilbene fluorescent brighteners) at 2 g/! When the experiment was carried out in the same manner as in Example 1, the occurrence of magentastin was between 0.01 and 0.02.
In other words, it decreased by 20% to 40%.

[Example 5] Exemplary compounds (D-3) and (D-7) were added to the coloring phenomenon liquid used in Experiment No. 11 of Example 1 at a concentration of 12 [] /
When ffi was added and the same experiment as in Example 1 was conducted, the degree of coloring of the color developing solution was further improved, and magentastin was further reduced by about 0.01.

[Example 6] The same experiment as in Example 1 was conducted except that 1 ppm of copper ions and 0.3 nQ/l of bleach-fix solution were mixed into the color developing solution used in Experiment No. 11 of Example 1. Ta.

However, in the color developing solution, exemplified compounds (B-I-2), (B-I-3)<B-III-2 are used as clearing agents.
), (B-IV-1> and for comparison, 2-phosphonobutane-1,2,4-1-ricarboxylic acid and tetrapolyphosphoric acid were each added at 10/ffi lζ.

First, the appearance (yellow coloring degree) of the color developer was observed, and the results are listed in Table 3. The appearance of the IC stock was evaluated on the following four levels.

10-T+ Significant yellow coloring-1・-1-Yellow coloring+Slightly yellow coloring-Yellow: VJ No color Table 3 As is clear from Table 3 above, general formula (B-I) ~ (13
-IV) is combined with the developer of the present invention.
When used in a color developing solution, heavy metal ions may be mixed in (4) Even under extremely harsh conditions, the amount of decomposition in the color developer is small;
It can be seen that the degree of coloration is also further improved. Furthermore,
It is also effective against M stain when heavy metal ions are mixed. However, this effect is hardly obtained with chelating agents other than those of general formula (B-I) ((3-IV).

[Example 7] Using the color paper sample prepared in Example 1, the concentration of potassium chloride in the color developer used in Experiment No. 11 of Example 1 before storage is shown in Table 4 below. A phenomenon treatment was carried out according to the treatment steps of Example 1. The yellow dye density (highest density part) of the sample after treatment was measured.

Table 4 As is clear from Table 4 above, the degree of sulfite M salt m in the color developer according to the present invention is 1. Sufficient yellow density is obtained when GXlo-2 mol/liter or less, especially when 4X10-
3 moles/! Particularly good -r yellow color density 1q can be obtained in the following cases, and ff11 is suitable for rapid processing.

[Example 8] Color developing solution No. 11L used in Example 1 The grade of cerium ions added was 0 to 4 as shown in Table 5 below.
The same experiment as in Example 1 was carried out with V varying in the range 00 m<1/l.

Show the results! Uni J: Stop and show me.

Table 5 From Table 5 above, when the metal salt according to the present invention is present in the form of ions at 0.1 to 100 ma/Q, the decomposition of the color developer and the degree of coloring (tarring) are good, and the magenta tin is also good. It turns out that.

It can be seen that it is particularly good when the amount is 0.3 to 20 mo/l, and particularly good when it is 0.5 to 10 mo/ffi.

Patent applicant Konishiroku Photo Industry Co., Ltd. procedure? tn orthographic device method) August 8, 1985

Claims (1)

[Claims] After imagewise exposing a silver halide color photographic light-sensitive material having at least one silver halide emulsion layer on a support,
In a method for processing a silver halide color photographic light-sensitive material which is subjected to processing including at least a color development step, at least one of the silver halide emulsion layers contains a magenta coupler represented by the following general formula [M], and the color development step A method for processing a silver halide color photographic material, characterized in that the color developing solution used in the step contains a compound represented by the following general formula [I] and at least one compound selected from manganese salts and cerium salts. . General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R_1 and R_2 each represent an alkyl group or a hydrogen atom, and both R_1 and R_2 are not hydrogen atoms. Also, R_1 and R_2 may form a ring.) General formula [M] ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, Ar is a phenyl group and includes a substituted phenyl group. Y is N-hydroxy Alkyl-substituted p-phenylenediamine derivative represents a group that leaves when a dye is formed by coupling with an oxidized form of a coloring agent.R represents an acylamino group, anilino group, or ureido group.)