JPH0387825A - Method for processing silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve color developability in spite of rapid processing and to drastically suppress the fluctuation in the sensitivity at the time of continuous processing by subjecting a silver halide color photographic sensitive material to development processing for 10 to 40 seconds with a color developing soln. contg. specific compds. CONSTITUTION:The silver halide color photographic sensitive material provided with >=1 layers of emulsion layers contg. emulsions substantially consisting of a silver chloride is subjected to development processing for 10 to 40 seconds with the color developing soln. contg. one kind of the compds. expressed by formula I. (In the formula, L denotes an alkylene group which may be substd.; A denotes a carboxy group, sulfo group, phosphono group, residual phosphinic acid group, hydroxy group, amino group which may be substd., with alkyl, ammonio group which may be substd. with alkyl, carbamoyl group which may be substd. with alkyl, sulfamoyl group which may be substd. with alkyl, alkyl sulfonyl group which may be substd.; R denotes a hydrogen atom, alkyl group which may be substd.)

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a method for processing a silver halide color photographic light-sensitive material. The present invention relates to a processing method that can provide stable photographic performance even at times.

(Prior Art) In recent years, in the photographic processing of color photosensitive materials, it has been desired to shorten the processing time due to the shortening of the finishing delivery time and the reduction of laboratory work. Increasing the temperature and increasing the amount of replenishment are common methods to shorten the time of each processing step, but many other methods have been proposed, such as increasing stirring or adding various accelerators. .

In particular, for the purpose of speeding up color development and/or reducing the amount of replenishment, color photographic materials containing silver chloride emulsions are processed in place of conventionally widely used silver bromide emulsions or silver iodobromide emulsions. For example, it is known how to
International Publication No. WO 37-04534 describes a method for rapidly processing a high silver chloride color photographic material with a color developer substantially free of sulfite ions and benzyl alcohol. However, even in the above method, it has been found that if further rapid processing, for example, color development is performed in 40 seconds or less, stable photographic performance cannot be obtained, and in particular, sufficient maximum color density cannot be obtained. Furthermore, even when continuous processing is carried out at a processing time of 45 seconds based on the above method, stable photographic performance is still not obtained, and in particular, the maximum color density and sensitivity fog vary depending on the difference in processing amount. Studies by the present inventors have revealed that in continuous processing using rapid color development, the photographic performance fluctuates so much that it cannot be used. As a treatment method using hydroxylamines as a preservative,
JP-A-61-106655 discloses a technique of processing in 45 to 60 seconds using a color developing solution containing a hydroxyl pentane having an alkyl group or an alkoxyalkyl group as a substituent. At present, if these compounds were used to speed up the process, photographic properties such as sensitivity fluctuations would occur, resulting in failure.

In addition, from the viewpoint of promoting color development, we have investigated the use of benzyl alcohol, which has been known in the past, in combination, but it has been found that this has disadvantages such as lowering the solubility of the liquid and increasing staining after treatment. Furthermore, from the viewpoint of promoting silver development,
-144547 No. 5 B-50532, No. 58-
No. 115438, No. 60-158444, No. 60-1
As described in No. 58445 and No. 60-165651, a method of incorporating a 1-phenyl-3-pyrazolidone derivative into a silver halide color photographic light-sensitive material was also investigated; In light-sensitive materials, the effect was completely insufficient.

Furthermore, when high-silver chloride color photographic materials are used for rapid processing and low replenishment, there is a serious problem of fluctuations in photographic properties, and a solution to this problem has been strongly desired. Changes in photographic properties (especially fog) using organic antifoggants
Japanese Patent Application Laid-open Nos. 58-95345 and 59-232342 are known as methods for reducing this. However, this antifoggant did not have a sufficient effect, and when used in large amounts, it was found that the maximum density decreased and development was delayed, and the above problems could not be solved.

(Problems to be Solved by the Invention) Therefore, the first object of the present invention is to provide a processing method for high-silver chloride color light-sensitive materials that provides excellent color development even when rapid processing is performed. be. A second object of the present invention is to provide a processing method that exhibits stable performance with little variation in photographic performance even when the above-mentioned light-sensitive material is continuously processed.

A third object of the present invention is to provide a processing method that has stable performance with less fluctuation in sensitivity, fog, etc. and less fluctuation in photographic performance even when low replenishment is performed.

(Means to solve the problem) The object of the present invention was distantly achieved by the following method.

That is, a silver halide color photographic light-sensitive material provided with at least one emulsion layer having an emulsion consisting essentially of silver chloride is processed using a color developer containing at least one compound represented by the following general formula (1). , 10
1. A method for processing a silver halide color photographic material, which is characterized in that development is performed in seconds to 40 seconds.

(In the formula, L represents an optionally substituted alkylene group, and A
is a carboxy group, a sulfo group, a phosphono group, a phosphinic acid residue, a hydroxy group, an a) group which may be substituted with alkyl, an ammonio group which may be substituted with alkyl, a carbamoyl group which may be substituted with alkyl, an alkyl i! (represents a sulfamoyl group which may be ffi or an alkylsulfonyl group which may be substituted, R is a hydrogen atom or an alkyl group which may be substituted).

Here, "substantially silver chloride" means that the content of silver chloride relative to the total amount of silver halide is 90 mol% or more, preferably 95 mol% or more, and more preferably 98 mol% or more. From the viewpoint of speed, the higher the content of silver chloride, the more preferable;
The high silver chloride composition of the present invention may contain a small amount of silver bromide or silver iodide. Alternatively, it may have many useful benefits, such as weakening the desensitization caused by spectral sensitizing dyes.

Further, the emulsion layer containing the emulsion made of silver chloride is preferably all layers including a blue-sensitive layer, a green-sensitive layer and a red-sensitive layer. Furthermore, in the present invention, the effect becomes more pronounced by reducing the amount of coated silver.

Therefore, hydroxylamines having a hydrophilic group of the general formula (1) are capable of speeding up color development in comparison with diethylhydroxylamine, which is conventionally used for processing light-sensitive materials with high silver chloride threads. The reason is,
The conversion rate of dye to the amount of developed silver in color development is
This seems to be because it is superior in the former system, and as a result,
It is thought that it provides efficient coloring even in a short period of time.

However, in photosensitive materials made of high silver chloride,
According to the research of the present inventors, there is no big difference in development for longer than 40 seconds depending on whether the hydroxylamine has a hydrophilic group or not, but that the difference becomes noticeable in development for less than 40 seconds. This is noteworthy.

Next, general formula (1) will be explained in detail.

(In the formula, L represents a linear or branched optionally substituted alkylene group having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, and specifically, methylene, ethylene, trimethylene, and propylene are preferable. Examples of direct substituent groups include carboxy groups, sulfo groups, phosphono groups, phosphinic acid residues, hydroxy groups, and ammonio groups which may be substituted with alkyl; A is given as a preferable example.
is a carboxy group, sulfo group, phosphono group, phosphinic acid residue, hydroxy group, alkylrI! #! ! ! aξ) group which may be substituted with alkyl, an ammonio group which may be substituted with alkyl, a carbamoyl group which may be substituted with alkyl, a sulfamoyl group which may be substituted with alkyl, an alkylsulfonyl group which may be substituted with carboxy, Preferred examples include a sulfo group, a hydroxy group, a phospho/M group, and a carbamoyl group which may be substituted with alkyl. Preferred examples of -LA include carboxymethyl group, carboxyethyl group, carboxypropyl group, sulfoethyl group, sulfopropyl group, sulfobutyl group, phosphonomethyl group, phosphonoethyl group, and hydroxyethyl group. group, carboxyethyl group, sulfoethyl group, sulfopropyl group, phosphonomethyl group,
A particularly preferred example is a phosphonoethyl group.

R represents a hydrogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, and examples of the substituent include a carboxy group, a sulfo group, a phosphono group, and a phosphine group. Acid residue, hydroxy group, amino group which may be substituted with alkyl, ammonio group which may be substituted with alkyl, carbamoyl group which may be substituted with alkyl, sulfamoyl group which may be substituted with alkyl, alkylsulfonyl which may be substituted with alkyl group, azilamino group, alkylsulfonylamino group, arylsulfonylamino group, alkoxycarbonyl group, amino group which may be substituted with alkyl,
Represents an arylsulfonyl group, nitro group, cyano group, halogen atom, there may be two or more substituents, R is a hydrogen atom, methyl group, ethyl group, propyl group, carboxymethyl group, carboxyethyl group, carboxypropyl Preferred examples include a sulfoethyl group, a sulfopropyl group, a sulfobutyl group, a phosphonomethyl group, a phosphonoethyl group, and a hydroxyethyl group. , a phosphonoethyl group can be mentioned as a particularly preferred example. (L and R may be linked to form a ring.) Next, specific compounds of the present invention will be described, but are not limited to these.

(3) CH.

CH.

(4) (5) (6) 8 H3 4 H9 CH.

CH.

Shir1 snow Shir1! Ichishi U3 (8) (12) H H CH.

Hs (19) HO-NH-CH.

COL (20) HO-NH-CHI CHl O8 (21) 0-NH CH-Cot CH.

(22) 0-NH CH-Cot C! H2 (23) HO-NH-CM-Co□ 4 H9 (24) HO-NH-CH-CHl COt CH.

(25) HO-NH-CH.

-CH-Cot CHl (26) HO-NH-CT-1m CHl SOW (27) HO-NH-CHI CHCH* 13O1 CH (28) (29) (30) (31) HONH(CHl)s 50s HONH-(CHx)4 50s HO-NH-CI (yo PO, H.

HONHCHPOsHx Hs (32) (33) (34) (35) HONHCHm CHl PO3 H0-NH-CHI CHl 0HHO-NH-(
CH), 0H HO-NH-CH, -PO! Hx z (46) HONHCHffi CH (POs 8 )2 \ CHxCHxCNH-C(CHs) x-Cut-5O
J1 (54) 80-NHCH*C1bC-NHC(CH3) xcH
g-3OJ1 The amount of the compound of general formula (1) added is preferably 0.1 g to 50 g, more preferably 0.2 g to 20 g per liter of color ring image liquid.

The compound represented by the general formula (1) can be obtained by converting commercially available hydroxylamines into alkylation reactions (nucleophilic substitution reactions,
addition reaction, Mannich reaction). West German Patent No. 1159634, "Inorganic force, force acta
ica Chimlca Acta) + 93, (1
984) 101-108, etc., and the specific method is described below.

Synthesis of Compound Exemplary Compound (7) 11.5 g of sodium hydroxide and 96 g of sodium chloroethanesulfonate were added to an aqueous solution (200-) of 20 g of hydroxylamine hydrochloride, kept at 60°C, and 40 d of an aqueous solution of 23 g of sodium hydroxide was added to 1 The mixture was added slowly over a period of time.Furthermore, the temperature was maintained at 60°C for 3 hours, the reaction solution was concentrated under reduced pressure, and salt preparation #200M1 was added and heated to 50°C. (Exemplified Compound (7)) was obtained as monosodium salt crystals. 41 g (yield 53%) Synthesis of Exemplified Compound O The resulting mixture was heated under reflux for 2 hours. The resulting crystals were recrystallized from water and methanol to obtain 009.2 g (42%) of the exemplary compound.

In the present invention, in place of hydroxylamine and sulfite ion, which are generally used as preservatives for the developing agent in the color developer, the following organic preservatives can be used in addition to the compound represented by (1).

Here, the term "organic preservative" refers to any organic compound that reduces the rate of deterioration of aromatic primary amine color developing agents when added to the processing solution for color photographic light-sensitive materials, such as air in color developing agents. Organic compounds that have the function of preventing oxidation caused by , diamines, polyamines, quaternary ammonium salts, nitroxy radicals,
Particularly effective organic preservatives include alcohols, oximes, diamide compounds, and fused ring amines. These are Japanese Patent Application No. 61-147823 and Japanese Patent Application No. 61-1735.
No. 95, No. 61-165621, No. 61-18861
No. 9, No. 61-197760, No. 61-186561
No. 61-198987, No. 61-201861, No. 61-186559, No. 61-170756,
No. 61-188742, No. 61-188741, U.S. Pat. No. 3,615,503, U.S. Pat.
etc. are disclosed.

The color developer used in the present invention contains a known aromatic primary amine color developing agent.

Preferred examples are p-phenylenediamine derivatives, representative examples of which are shown below, but are not limited thereto.

-1 D-2 -3 -4 -5 -6- 7- -9 N,N-diethyl-p-phenylenediamine 2-amino-5-diethylaminotoluene 2-amino-5-(N-ethyl-N-lauryl amino)
Toluene 4-[N-ethyl-N-(β-hydroxyethyl)aminocoaniline 2-methyl-4-[N-ethyl-N-(β-hydroxyethyl)aminocoaniline 4-amino-3-methyl-N -Ethyl-N-(β-(methanesulfonamido)ethyl]-aniline N-(2-amino-5-dinithylaminophenylethyl)methanesulfonamide N,N-dimethyl-p-phenylenediaene 4-amino -3-Methyl-N-ethyl-N-methoxyethylaniline D-10 4-amino-3-methyl-N-ethyl-N
-β-ethoxyethylaniline D-11 4-amino-3-methyl-N-ethyl-N
-β-Butoxyethylaniline Among the above P-phenylenediamine derivatives, 4-amino-3-methyl-N-ethyl[β-(methanesulfonate)ethyl)-aniline (exemplified compound D-
6) and 2-methyl-4-[N-ethyl-(β-hydroxyethyl)aminocoaniline (Exemplary Compound D-5)
It is.

Further, these p-phenylenediamine derivatives may be salts such as sulfate, hydrochloride, sulfite, and p-)luenesulfonate. The amount of the aromatic-grade amine developing agent used is preferably about 0.1 g to about 20 g per 12 developing solutions.
More preferably about 0.

Concentrations range from 5g to about 15g.

In the color developing solution according to the present invention, a compound represented by the following general formula (A) is more preferably used in order to improve the effects of the present invention.

(In the formula, R. is a hydroxyalkyl group having 2 to 6 carbon atoms,
R1! and Ro each represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a hydroxyalkyl group having 2 to 6 carbon atoms, a benzyl group, or a formula CnHzn-N), where n is an integer of 1 to 6, χ and (X' each represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a hydroxyalkyl group having 2 to 6 carbon atoms) Preferred specific examples of the compound represented by the general formula (A) are as follows.

(A-1) Ethanol ξ, (A-2) Jetanolamine, (A-3) Triethanol ξ, (A-41
Di-isopropanol ξane, (A-5) 2
-Methylacugetanol, (A-6) 2-ethylaminoethanol, (A-7) (A-8) (A-9) (A-10) (A-11) (A-12) (A-13 ) (A-14) (A-15) (A-16) (A-17) (A-18) (A-19) 2-dimethylaminoethanol, 2-diethylaminoethanol, l-diethylamino-2-propanol Tool, 3-diethylamino-1-propatol, 3-dimethylamino-1-propatol, isopropylaminoethanol, 3-amino-1-propatol, 2-amino-2-methyl-1.3 propanediol, ethylenethia ξNtetraisopropanol Benzyljetanolamine, 2-amino-2-(hydroxymethyl)-1,3-propanediol, 1,3-cyanobrobanol, 1,3-bis(2-hydroxyethylmethylaξ) ) - Propatool, the desired effect of the present invention is from 3g per ij2 color developer
It is preferably used within the range of 100g, more preferably 6
It is used in the range of g to 50 g.

The color developing solution according to the present invention has the following general formulas (B-I) and (B-
Compounds represented by n) are more preferably used.

General formula CB-1) H General formula CB-It) In the formula, Ro, Rlss Rl&, and RI'l are each a hydrogen atom, a halogen atom, a sulfonic acid group, an alkyl group having 1 to 7 carbon atoms, -0R4, C0ORr *, Ro
, R1? , Ri, and Ro each represent a hydrogen atom or an alkyl group having 1 to 18 carbon atoms.

However, when Rts represents 10) I or a hydrogen atom, R14 is a halogen atom, a sulfonic acid group, or a carbon atom number l.
~7 alkyl group, -0R4, C0OR+ 9, the above R
The alkyl groups represented by 14, R4, R1 & and R17 include those having substituents, such as methyl group, ethyl group,
1so-propyl group, n-propyl group, t-butyl group,
Examples include n-butyl group, hydroxymethyl group, hydroxyethyl group, methylcarboxylic acid group, benzyl group, and R4, R1? , Rt.

The alkyl group represented by R□ has the same meaning as above, and further includes an octyl group.

Also Ro, R4, Ro and R1? Examples of the phenyl group represented by include a phenyl group, a 2-hydroxyphenyl group, and a 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-1-1) 4-isopropyl-1,2-dihydroxybenzene (B-I-2) 1.2-dihydroxybenzene-3,5-disulfonic acid (B-1-3) 1.2.3- 1-lihydroxybenzene-5 carboxylic acid (B-1-4) 1.2.3-) dihydroxybenzene-5-carboxymethyl ester (B-1-5) L,2.3-) dihydroxybenzene-5 -Carboxy-n-butyl ester (B-1-6) 5-butyl-1,2,3-trihydroxybenzene (B-1-7) 1,2-dihydroxybenzene-3,4゜6-trisulfone Acid (B-I[-1) 2.3-dihydroxynaphthalene-6-sulfonic acid (B-11-2) 2.3.8-trihydroxynaphthalene-6-sulfonic acid (B-11-3) 2. 3-dihydroxynaphthalene-6-carboxylic acid (B-1f-4) 2.3-dihydroxy-8-isopropyl-naphthalene (B-11-5) 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
, 5-disulfonic acid, and can also be used as alkali metal salts such as sodium salts and potassium salts ((B-1-2) of specific exemplified compounds).

In the present invention, the general formulas CB-1) and (B-4)
The compound represented by is 5~15g per 12 color developer
It can be used in the range of 15 to 10, preferably 15 to 10.
It is desirable to use the amount in an amount of 25 to 7 g.

The color developer used in the present invention preferably has a pH of 9
-12, more preferably 9-11.0, and the color developer may contain other known developer component compounds.

In order to maintain the above pH, it is preferable to use various buffering agents. As the buffering agents, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, triphosphate Sodium, dipotassium phosphate, sodium borate, potassium borate,
Sodium tetraborate (borax), potassium tetraborate, 0
-Sodium hydroxybenzoate (sodium salicylate), potassium o-hydroxybenzoate, 5-sulfo-
Examples include sodium 2-hydroxybenzoate (sodium 5-sulfosalicylate) and potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate).

The amount of the buffer added to the color developer is 0. 1 mole/
I1 or more is preferable, especially 0. 1 mol/E
~0.4 mol/j! It is particularly preferable that

In addition, various chelating agents can be used in the color developer as an anti-settling agent for calcium or magnesium or to improve the stability of the color developer.

Specific examples are shown below, but are not limited to, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, ethylenethiacarotetraacetic acid, triethylenetetraminewood acetic acid,
Nitrilo-N,N,N-)lis(methylenephosphonic acid)
, ethylenediamine-N,N,N',N'-tetrakis (methylenephosphone M), 1,3-diamino-2-propatoltetraacetic acid, transcyclohexanediaminetetraacetic acid, nitrilotripropionic acid, l,2-diaminopropane Tetraacetic acid, hydroxyethyliminodiacetic acid, glycol ether diamine tetraacetic acid, hydroxyethylene diamine triacetic acid, ethylene diamine orthohydroxyphenylacetic acid, 2-phosphonobutane-1,2,4-)licarboxylic acid, l-hydroxyethylidene-1,1-diphosphone acid, N,N'bis(2-hydroxybenzyl)ethylenediamine-N,N'-diacetic acid, catechol-3,4,6-
trisulfonic acid, catechol-3,5-disulfonic acid,
5-sulfosalicylic acid, 4-sulfosalicylic acid.

Among these chelating agents, preferred are ethylenethiatintetraacetic acid, ethylenetriaminepentaacetic acid, triethylenetetraminewood acetic acid, l3-diaminopropanoltetraacetic acid, and ethylenediamine-N.

N, N', N'-tetrakis (methylenephosphonic acid)
, hydroxyethyliminodiacetic acid is good.

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

The amount of these chelating agents added should be sufficient to sequester metal ions in the color developer. For example, 11
It is about 0.1g to Log per unit.

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

As a development accelerator, Japanese Patent Publication No. 37-16088 and No. 3
No. 7-5987, No. 3B-7826, No. 44-123
No. 80, No. 45-9019 and U.S. Patent No. 3,813
, p-phenylenediamine compounds shown in JP-A-52-49829 and JP-A-50-15554;
Quaternary ammonium salts shown in Japanese Patent Publication No. 0-137726, Japanese Patent Publication No. 44-30074, Japanese Patent Application Publication No. 56-156826 and Japanese Patent Publication No. 52-43429, etc., U.S. Patent No. 2,6
No. 10,122 and p described in No. 4,119゜462
-Aminophenols, U.S. Specialty Kitsuki 2,494,903
No. 3,128.182, No. 4,230.796, No. 3,253゜919, Special Publication No. 11431/1973, U.S. Special Publication No. 2,482.546, No. 2,596.9
26 and 3,582,346, etc., Japanese Patent Publication Nos. 37-16088 and 42-252
No. 01, U.S. Special Publication No. 3.128.183, Special Publication No. 1973
-11431, No. 42-23883, and U.S. Special Kitsuki No. 3,532,501, etc., polyalkylene oxides, other 1-phenyl-3-pyrazolidones, hydrazines, meso-ionic compounds, ionic compounds, imidazoles, etc. can be added as necessary.

Preferably, the color developer contains substantially no benzyl alcohol, by substantially 2 to 12 parts of the color developer.
．． 0M1 or less, more preferably no content at all. Substantially no content results in smaller fluctuations in photographic properties, especially increases in staining during continuous processing, and more favorable effects can be obtained.

When processing a color light-sensitive material made of a high silver chloride emulsion at an ultra-quick time of 40 seconds or less, various methods such as increasing the processing temperature can be considered in order to obtain satisfactory photographic properties.
As disclosed in Japanese Unexamined Patent Publication No. 63-106655, even if a method of containing chlorine ions at a specific concentration is used, photographic fluctuations such as increased fogging occur.

However, it was unexpected that these problems could be effectively solved by using a certain amount of bromine ions together with chlorine ions as described below.

Therefore, in the present invention, preferably 3.5X10-2 to 1°5X10-' chlorine ions are contained in the color developing solution.
Mol/11 more preferably 4X10-' to lX10-'
Contains mol/i. The amount of bromine ion in the color developer is preferably 3.0 x 10-' mol/j! -1,0xl
O-'mol/j! contains.

More preferably 9.0 x 10-' to 5 x 10-' mol/2, still more preferably 1.0 x 10-' to 3
10-'mol/2. Here, the chloride ion concentration is 1
．． More than 5×10 −′ mol/l has the disadvantage of retarding development. If the amount of bromine ion is less than 3.5 x 10-''mol 72, it is not possible to prevent staining, and furthermore, there is a large variation in photographic properties (especially minimum density) due to continuous processing, and the purpose of the present invention cannot be achieved. The concentration is lXl
If it is more than 0-' mol/l, development will be delayed, resulting in a decrease in maximum density and sensitivity fluctuation; if it is less than 3.0 x 10-' mol/l, staining cannot be prevented and furthermore, continuous The photographic properties change greatly due to processing, and the object of the present invention cannot be achieved.

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

When added directly to a color developer, chloride ion supplying substances include sodium chloride, potassium chloride, ammonium chloride, nickel chloride, magnesium chloride, manganese chloride, calcium chloride, and cadmium chloride.
Among them, preferred are sodium chloride and chloride.

In addition, sodium bromide, potassium bromide, ammonium bromide, lithium bromide, Calcium, magnesium bromide, manganese bromide, nickel bromide, cadmium bromide, cerium bromide,
Examples include thallium bromide, of which potassium bromide and sodium bromide are preferred.

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

In the present invention, in addition to chlorine ions and bromide ions, any antifoggant can be added as necessary. As antifoggants, alkali metal halides such as potassium iodide and organic antifoggants can be used. Examples of organic antifoggants include benzotriazole, 6-
Nitrobenzimidazole, 5-nitroisoindazole, 5methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole, 2-thiazolyl-benzimidazole, 2-thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolizine, adenine Typical examples include nitrogen-containing heterocyclic compounds such as:

The color developer used in the present invention preferably contains an optical brightener. As an optical brightener, 4,4'-
Diamino-2,2'-disulfostilbene compounds are preferred, and the amount added is 0 to 10 g/I! , preferably 0.1
~6g/l.

Furthermore, various surfactants such as alkylsulfonic acids, arylphosphonic acids, aliphatic carboxylic acids, and aromatic carboxylic acids may be added as necessary.

The effects of the present invention are most noticeable when the color developer of the present invention is processed for 10 seconds to 40 seconds, preferably 20 seconds to 35 seconds. In addition, the treatment temperature is 33 to 60°C, preferably 3
The effect of the present invention is particularly remarkable at 6 to 50°C.

The replenishment amount of the color developer during continuous processing is preferably 20 to 220 d, preferably 25 to 16 OI, particularly preferably 30 M to 110 d per photosensitive material, since the effects of the present invention can be effectively exhibited. The color developer of the invention has a liquid aperture ratio (air contact area (e)/liquid volume (C1l)
')) has relatively better performance than combinations outside the present invention under any conditions, but from the viewpoint of stability of the color developer, O-0,1CI-' is preferable as the liquid opening ratio. In the process, 0. 001cm-
The range is preferably from ' to 0.05 CI-', more preferably from 0.0020-1 to 0.03 cm-'.

It is generally known that when hydroxylamine is used as a preservative, decomposition occurs due to heat or trace metals even if the aperture ratio of the color developer is reduced. However, in the color developer of the present invention, these decompositions are extremely small and the color developer can be sufficiently put to practical use even when the color developer is stored for a long time or used as a replenisher for a long time. Therefore, in this case, it is preferable that the liquid aperture ratio is small, from O to 0.002C.
II-' is most preferred.

On the other hand, there are cases where processing is performed with a wide aperture ratio under the condition that a certain amount of processing is processed and then discarded, but even in such a processing method, if the structure of the present invention is followed, excellent performance can be achieved. I can do it.

Further, from the viewpoint of accelerating development, a method of incorporating a 1-phenyl-3-pyrazolidone derivative into the light-sensitive material can be used in combination as long as the effects of the present invention are not impaired.

In the present invention, desilvering treatment is performed after color development. The desilvering step generally consists of a bleaching step and a fixing step, but it is particularly preferable that they are carried out simultaneously.

The bleach or bleach-fix solutions used in the present invention may contain bromides (e.g., potassium bromide, sodium bromide, ammonium bromide), or chlorides (e.g., potassium chloride, sodium chloride, ammonium chloride), or iodides. (eg, ammonium iodide).

If necessary, one or more inorganic substances having pH buffering ability such as boric acid, borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate, citric acid, sodium citrate, tartaric acid, etc. Acids, organic acids and alkali metal or ammonium salts thereof, or corrosion inhibitors such as ammonium nitrate, guanidine, etc. can be added.

The fixing agent used in the bleach-fixing solution or fixing solution according to the present invention is a known fixing agent, namely sodium thiosulfate,
Thiosulfates such as ammonium thiosulfate; thiocyanates such as sodium thiocyanate and ammonium thiocyanate; thioether compounds such as ethylene bisthioglycolic acid and 3,6-cythio-1,8-octanediol; These are halogenated II solubilizers, and these can be used alone or in combination of two or more. In addition, a special bleach-fixing solution consisting of a combination of a fixing agent described in JP-A-55-155354 and a large amount of a halide such as potassium iodide can also be used.In the present invention, thiosulfate The amount of fixing agent per 11 is preferably from 0.3 to 2 mol, more preferably from 0.5 to 1.0 mol.

The pH range of the bleach-fix solution or fixer solution in the present invention is as follows:
3 to 8 is preferable, and 4 to 7.6 (particularly preferable. If the pH is lower than this, the desilvering property is improved, but the deterioration of the solution and the leucoization of the cyan dye are accelerated. If it is higher, desilvering is delayed and staining is more likely to occur.

In order to adjust the pH, hydrochloric acid, sulfuric acid, nitric acid, acetic acid, bicarbonate, ammonia, caustic potash, caustic soda, sodium carbonate, potassium carbonate, etc. can be added as necessary.

Further, the bleach-fix solution may contain various other optical brighteners, antifoaming agents, surfactants, and organic solvents such as polyvinylpyrrolidone and methanol.

The bleach-fix solution and fixer solution used in the present invention contain sulfites (e.g., sodium sulfite, potassium sulfite,
ammonium sulfite, etc.), bisulfites (e.g. ammonium bisulfite, sodium bisulfite, potassium bisulfite, etc.), metabisulfites (e.g. potassium metabisulfite, sodium metabisulfite, ammonium metabisulfite, etc.) ) and other sulfite ion-releasing compounds. These compounds are approximately 0.0 in terms of sulfite ion.
The content is preferably 2 to 0.50 mol/l, more preferably 0.04 to 0.40 mol/l. Particularly preferred is the addition of ammonium sulfite.

Sulfites are commonly added as preservatives, but other preservatives include ascorbic acid, carbonyl bisulfite adducts,
Sulfinic acids, carbonyl compounds, sulfinic acids, etc. may be added.

Furthermore, buffering agents, optical brighteners, chelating agents, antifungal agents, etc. may be added as necessary.

The bleach-fixing agent of the present invention has a processing time of 10 seconds to 120 seconds, preferably 20 seconds to 60 seconds. Also, the replenishment amount is 1r of photosensitive material.
30-250-1 preferably 40M1-15 per rf
(ld).As the replenishment amount decreases, -M tends to increase staining and desilvering failure, but according to the present invention,
The amount of replenishment of the bleach-fix solution can be reduced without causing such problems.

The silver halide color photographic light-sensitive material of the present invention is generally subjected to a water washing and/or stabilization process after fixing or desilvering treatment such as bleach-fixing.

The amount of water used in the washing process depends on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), the application, the temperature of the washing water, the number of washing tanks (the number of stages), the replenishment method such as countercurrent or forward flow, and various other conditions. Can be set over a wide range. this house,
The relationship between the number of flushing tanks and the amount of water in the multistage countercurrent method is described in the Journal of the Society of Motion.
Picture and Television Engineers (
Journal of the 5ociety of
Motion Picture and Te1evi
sion Engineers) Volume 64, 9.248
-253 (May 1955 issue).

According to the multi-stage countercurrent method described in the above-mentioned literature, the amount of water used for washing can be significantly reduced, but due to the increase in the residence time of water in the tank, bacteria will breed, and the generated suspended matter will adhere to the photosensitive material. In the processing of the color photosensitive material of the present invention, as a solution to such problems,
The method for reducing calcium and magnesium described in Japanese Patent Application No. 61-131632 can be used very effectively. In addition, chlorine-based disinfectants such as isothiazolone compounds, cyabendazole, chlorinated sodium isocyanurate, and other benzotriazoles described in JP-A No. 57-8542, "Chemistry of Antibacterial and Antifungal Agents" by Hiroshi Horiguchi It is also possible to use the disinfectants described in ``Microorganism Sterilization, Disinfection, and Anti-Mold Techniques'', a complete collection of sanitary techniques, and ``Encyclopedia of Anti-Bacterial and Anti-Mold Agents'' edited by the Japanese Society of Anti-Bacterial and Anti-Mold.

The pH of the washing water in the processing of the photosensitive material of the present invention is 4 to 9.
and preferably 5 to 8. The washing water temperature and washing time can also be set variously depending on the characteristics of the photosensitive material, its use, etc., but generally it is 20 seconds to 2 minutes at 15 to 45°C, preferably 25 to 45°C.
A range of 30 seconds to 1 minute and 30 seconds is selected at 0'C.

Even in such short-time water washing, according to the present invention, there is no increase in staining and good photographic characteristics can be obtained.

Furthermore, the photosensitive material of the present invention can also be directly processed with a stabilizing solution instead of washing with water. In such stabilization treatment, Japanese Patent Application Laid-open Nos. 57-8543 and 58-1
No. 4834, No. 59-184343, No. 60-220
No. 345, No. 60-238832, No. 60-2397
No. 84, No. 60239749, No. 61-4054,
All known methods described in Japanese Patent No. 61-118749 and the like can be used. Especially 1-hydroxyethylidene-1,1-diphosphonic acid, 5-chloro-2methyl-4-
Stabilizing baths containing isothiazolin-3-one, bismuth compounds, ammonium compounds, etc. are preferably used.

Further, following the water washing process, a further stabilization process may be performed, such as a stabilizing bath containing formalin and a surfactant, which is used as a final bath for color photosensitive materials for photography. .

The processing time of the present invention is defined as the time from when the photosensitive material comes into contact with the color developer until it exits the final bath (generally water washing or stabilization bath).
The effects of the present invention can be significantly exhibited in a rapid treatment process in which the processing time is 30 seconds or less, preferably 3 minutes or less.

The color photographic light-sensitive material of the present invention can be constructed by coating at least one blue-sensitive silver halide emulsion layer, one green-sensitive silver halide emulsion layer, and one red-sensitive silver halide emulsion layer on a support. In general color photographic paper, the layers are usually coated on the support in the order listed above, but they may be coated in a different order. It can be used in place of at least one of the emulsion layers described above. These photosensitive emulsion layers contain a silver halide emulsion sensitive to each wavelength range, and dyes that are complementary colors to the sensitizing light - yellow for blue, magenta for green, and cyan for red.
By containing a so-called color coupler that forms a color, subtractive color reproduction can be performed. However, the coloring hues of the photosensitive layer and the coupler may not correspond as described above.

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

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

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

Such a high silver chloride emulsion preferably has a structure in which the localized silver bromide layer is provided inside and/or on the surface of the silver halide grains in a layered or non-layered manner as described above. The halogen composition of the localized layer is preferably at least 10 mol% in terms of silver bromide content, and more preferably more than 20 mol%. , a corner or a surface, and one preferable example is one in which the grain is epitaxially grown on a part of the corner of the grain.

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

It is also effective to further increase the silver chloride content of the silver halide emulsion in order to reduce the amount of replenishment of the development processing solution.

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

Average grain size of the silver halide grains contained in the silver halide emulsion used in the present invention (the grain size is defined as the diameter of a circle equivalent to the projected area of the grain, and the number average thereof is taken)
is preferably 0.1 μ to 2 μ.

In addition, their particle size distribution has a coefficient of variation (standard deviation of particle size distribution divided by average particle size) of 20%.
Hereinafter, a so-called monodisperse emulsion of 15% or less is preferable. In this case, it is also preferable to blend the above monodisperse emulsion in the same layer or to apply multilayer coating in order to obtain a wide latitude. .

The shape of silver halide grains contained in photographic emulsions is regular (cubic, tetradecahedral, or octahedral).
It is possible to use a material having an irregular crystal shape, a material having an irregular crystal shape such as a sphere, a shape, a plate shape, etc., or a material having a composite shape thereof. In addition, it may be made of a mixture of particles having various crystal forms.In the present invention, among these particles, 50% or more of particles having the above-mentioned regular crystal form,
The content is preferably 70% or more, more preferably 90% or more.

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

The silver chlorobromide emulsion used in the present invention is P, Glafkid
Chimie et Ph1sique by es
Photographique (Pau1Mon
te1, 1967), G, F, DuLfl
nRP Photo-graphic Elpulsion
Chemistry (Focal Press, 1966), V, L, Zelik+wana
Making and Coating Ph
otographic Emulsion (Foca
1 Press, 1964). i.e. acid method,
Any of the neutral method, ammonia method, etc. is acceptable <1. In addition, the format for reacting soluble root salts with soluble halogen salts is as follows:
Any method such as one-sided mixing method, simultaneous mixing method, or a combination thereof may be used. A method in which zero particles are formed in an atmosphere containing excess silver ions (so-called back mixing method)
You can also use As one form of the simultaneous mixing method, a method in which the pAg in the liquid phase in which silver halide is produced can be kept constant, that is, the so-called Chondrod double agent method can also be used. According to this method, a silver halide emulsion having a regular crystal shape and a nearly uniform grain size can be obtained.

Various polyvalent metal ion impurities can be introduced into the silver halide emulsion used in the present invention during the process of emulsion grain formation or physical ripening.

Examples of compounds used include cadmium, zinc, lead,
Salts such as copper and thallium, or iron, which is a group II element,
Examples include salts or complex salts of ruthenium, rhodium, palladium, osmium, iridium, platinum, and the like. In particular, the above-mentioned Group Ⅰ elements can be preferably used. The amount of these compounds added varies over a wide range depending on the purpose, but is preferably from 10'9 to 100 moles relative to silver halide.

The silver halide emulsion used in the present invention is usually subjected to chemical sensitization and spectral sensitization.

Regarding the chemical sensitization method, sulfur sensitization typified by the addition of unstable sulfur compounds, noble metal sensitization typified by gold sensitization, or reduction sensitization can be used alone or in combination. Regarding compounds used for chemical sensitization, see the lower right column on page 18 of the specification of JP-A-62-215272.
Those described in the upper right column of page 22 are preferably used.

Spectral sensitization is performed for the purpose of imparting spectral sensitivity in a desired light wavelength range to the emulsion of each layer in the light-sensitive material of the present invention. It is preferable to add an absorbing dye-spectral sensitizing dye. Examples of the spectral sensitizing dye used in this case include FoM, Hets by Harmer.
rocyclic compounds-Cyania
e dies and related co.
mpounds (John Wiley i 5on
Published by NeHYork, London, 196
4) can be mentioned. As specific examples of compounds and spectral sensitization methods, those described in the above-mentioned JP-A-62-215272 specification, page 22, upper right column to page 38, are preferably used.

The silver halide emulsion used in the present invention has the following properties:
Alternatively, various compounds or their precursors can be added for the purpose of stabilizing photographic performance. As specific examples of these compounds, those described on pages 39 to 72 of the specification of JP-A-62-215272 mentioned above are preferably used.

The emulsion used in the present invention may be either a so-called surface latent image type emulsion in which a latent image is mainly formed on the grain surface or a so-called internal latent image type emulsion in which a latent image is mainly formed inside the grain. Also good.

When the present invention is applied to a color photosensitive material, the color photosensitive material includes a yellow coupler, a magenta coupler, and a cyan coupler that form yellow, magenta, and cyan colors respectively by coupling with an oxidized product of an aromatic amine color developer. is usually used.

Cyan couplers, magenta couplers and yellow couplers preferably used in the present invention have the following general formulas (C-I), (C-If), (M-1), (M-11).
and (Y).

General formula (C-1) 0 ■ General formula (C-U) H Y.

General formula (M-1) General formula (M-11) General formula (Y) In general formula (C-summer) and (C-n), R, %R
t and R1 represent a substituted or unsubstituted aliphatic, aromatic, or heterocyclic group, R1, g, and R6 represent a hydrogen atom, a halogen atom, an aliphatic group, an aromatic group, or an acylamino group, and R3 represents R3 'l may also represent a group of nonmetallic atoms forming a nitrogen-containing 5R ring or 6-membered ring together with 'l
1 and Y* represent a hydrogen atom or a group capable of leaving during a coupling reaction with an oxidized form of a developing agent, and n represents O or 1.

R in general formula (C-II) is preferably an aliphatic group, such as a methyl group, ethyl group, propyl group, butyl group, pentadecyl group, Lert-butyl group, cyclohexyl group, cyclohexylmethyl group, Examples include phenylthiomethyl group, dodecyloxyphenylthiomethyl group, butanamidomethyl group, and methoxymethyl group.

Preferred examples of the cyan coupler represented by the general formula (C-1) or (C-I[) are as follows.

In general formula (C-1), preferable R is an aryl group,
A heterocyclic group, such as a halogen atom, an alkyl group, an alkoxy group, an aryloxy group, an acylamino group, an acyl group,
More preferably, it is an aryl group substituted with a carbamoyl group, a sulfonamide group, a sulfamoyl group, a sulfonyl group, a sulfamide group, an oxycarbonyl group, or a cyano group.

In general formula (C-1), when R1 and R8 do not form a ring, R8 is preferably a substituted or unsubstituted alkyl group or aryl group, particularly preferably a substituted aryloxy-substituted alkyl group, R3 is preferably a hydrogen atom.

In general formula (C-U), R4 is preferably a substituted or unsubstituted alkyl group or aryl group, and particularly preferably a substituted aryloxy-substituted alkyl group.

In the general formula (c-n), is preferably has 2 to 1 carbon atoms.
It is a methyl group having an alkyl group of 5 and a substituent having 1 or more carbon atoms, and the substituent is preferably an arylthio group, an alkylthio group, an acylamino group, an aryloxy group, or an alkyloxy group.

In the general formula (C-n), Rs is more preferably an alkyl group having 2 to 15 carbon atoms, particularly preferably an alkyl group having 2 to 4 carbon atoms.

In general formula (C-■), R4 is preferably a hydrogen atom or a halogen atom, and chlorine atom and fluorine atom are particularly preferable. In general formulas (C-I) and (C-n), preferable Y and Y are each , hydrogen atom, halogen atom, alkoxy group, aryloxy group, acyloxy group, and sulfonate group.

In general formula (M-1), R1 and R9 represent an aryl group, R1 represents a hydrogen atom, an aliphatic or aromatic acyl group, an aliphatic or aromatic sulfonyl group,
Y represents a hydrogen atom or a leaving group.

The substituents allowed for the aryl group (preferably the phenyl group) of h and R9 are the same as the substituents allowed for the substituent R1, and when there are two or more substituents, they may be the same or different. R is preferably a hydrogen atom,
It is an aliphatic acyl group or a sulfonyl group, and particularly preferably a hydrogen atom.

Preferably, Y is of the type that leaves off with either sulfur, oxygen or nitrogen atoms, such as the US Special Kitsuki 4.3
Particularly preferred are sulfur atom dissociative types as described in No. 51,897 and International Publication No. W088104795.

In the general formula CM-ff), R1° represents a hydrogen atom or a substituent; eY4 represents a hydrogen atom or a leaving group; a halogen atom or an arylthio group is particularly preferred;
Zb and Zc represent methine, substituted methine, 5ll- or -Nt, one of the Za-Zb bond and the Zb-Zc bond is a double bond, and the other is a single bond.

When the Zb-Zc bond is a carbon-carbon double bond, eRI includes the case where it is part of an aromatic ring. Or, when Y4 forms a dimer or more multimer, or when Za, zb or Zc is a substituted methine, it includes the case where a dimer or more multimer is formed with the substituted methine.

Among the pyrazoloazole couplers represented by the -M formula (M-1t), imidazo (1, 2-b) Preferred are pyrazoles,
Pyrazolo(1,5-b)(1,2,4) triazoles described in US Pat. No. 4,540,654 are particularly preferred.

In addition, a branched alkyl group as described in JP-A No. 61-65245 is directly connected to the 2.3 or 6-position of the pyrazolotriazole ring to create a pyrazolotriazole coupler, which is described in JP-A No. 61-65246. pyrazoloazole couplers containing a sulfonamide group in the molecule, pyrazoloazole couplers having an alkoxyphenylsulfonamide ballast group as described in JP-A-61-147254, and European Patent Publication No. 226. It is preferred to use pyrazolotriazole couplers having an alkoxy or aryloxy group in the 6-position, such as those described in No. 849 and No. 294.785.

In the general formula (Y), R11 represents a halogen atom, an alkoxy group, a trifluoromethyl group, or an aryl group, Rlt represents a hydrogen atom, a halogen atom, or an alkoxy group, A represents -NHCORl3, provided that L
s and Ro each represent an alkyl group, aryl group or acyl group, Y represents a leaving group, Lx and Rlt, R
The substituents for lt are the same as the substituents allowed for R1, and the leaving group is preferably of the type that leaves at either an oxygen atom or a nitrogen atom, with the nitrogen leaving type being particularly preferred. preferable.

General formula (C-1), (C-11), (M-1), (M-
Specific examples of couplers represented by II) and (Y) are listed below.

(C-1) (C-2) (C-3) (C-4) H (C-6) C! Ha (C-7) (C-8) tHs (C-9) (C-10) (C-12) H (C-13) (C-14) (C-15) (C-17) (C -18) (C-19) (C-20) (C-21) (C-22) Sushi I'+3 (M-1) CI (M-2) CI (M-3) (M-4) ( M-6) Hff (M-7) (M-8) (Y-1) (Y-2) (Y-3) (Y-4) (Y-5) (Y-6) (Y-7) (Y-8) (Y-9) The couplers represented by the above general formulas (C-1) to (Y) are:
In the silver halide emulsion layer constituting the photosensitive layer, there is usually 0.1 to 1.0 mol per mol of silver halide, preferably 0.
．． It is contained in an amount of 1 to 0.5 mol.

In the present invention, in order to add the coupler to the photosensitive layer, various known techniques can be used.1 Usually, the coupler can be added by an oil-in-water dispersion method known as the oil protection method. After dissolving, it is emulsified and dispersed in an aqueous gelatin solution containing a surfactant. Alternatively, water or an aqueous gelatin solution may be added to a coupler solution containing a surfactant to form an oil-in-water droplet dispersion with phase inversion.

Alkali-soluble couplers can also be dispersed by the so-called Fischer dispersion method. From the coupler dispersion,
The low-boiling organic solvent may be removed by M distillation, noodle washing, ultrafiltration, or the like, and then mixed with the photographic emulsion.

As a dispersion medium for such a coupler, the dielectric constant (25℃)
It is preferable to use a high boiling point a solvent and/or a water-insoluble polymer compound having a refractive index (25"C) of 1.5 to 1.7.

As a high boiling point solvent, Preferably the following general formula %formula%() A high boiling point Ia solvent represented by is used. It will be done.

General formula (B) t+, -coo- quality.

General formula (E) W+ O'IJt (wherein -1, 6 and ka each represent a substituted or unsubstituted alkyl group, cycloalkyl group, alkenyl group, aryl group or heterocyclic group, -4 is W ,, OW
, or S-8, where n is an integer from H to 5, and when n is 2 or more, ``H8'' and ``H8'' may be the same or different from each other, and in -a formula (E), -5 and H8 may form a fused ring).

The high boiling point organic solvent that can be used in the present invention also has a melting point of 100°C or less and a boiling point of 140°C or less, even if it is not the general formula (A) or ε,
Compounds that are immiscible with water at temperatures above ℃ and can be used as long as they are good solvents for couplers. The melting point of the high-boiling organic solvent is preferably 80°C or lower. The boiling point of the high boiling point organic solvent is preferably 160°C or higher, more preferably 170°C or higher.

For details of these high boiling point III solvents, see the lower right column on page 137 of the specification of JP-A No. 62-215272.
It is written in the upper right column of page 144.

These couplers can also be synthesized with rhodapul latex polymers (
For example, it can be emulsified and dispersed in an aqueous hydrophilic colloid solution by impregnating it into a polymer (US Pat. No. 4.203.716) or by dissolving it in a water-insoluble but Ia-solvent soluble polymer.

Preferably, the homopolymers or copolymers described on pages 12 to 30 of International Publication No. W088100723 are used, and the use of acrylamide-based polymers is particularly preferred from the viewpoint of color image stabilization.

The light-sensitive material produced using the present invention may contain a hydroquinone derivative, an aminophenol derivative, a gallic acid derivative, an ascorbic acid derivative, etc. as a color anti-capri agent.

Various anti-fading agents can be used in the photosensitive material of the present invention. B. Organic anti-fading agents for cyan, magenta and/or yellow images include hydroquinones, 6
-Hydroxychromans, 5-hydroxycoumarans,
Spirochromans, p-alkoxyphenols, hindered phenols centered on bisphenols, gallic acid derivatives, methylene dioxybenzenes, aminophenols, hindered amines, and the phenolic hydroxyl groups of these compounds are silylated and alkylated. A typical example is an ether or ester conductor. Further, metal complexes such as (bissalicylaldoximado)nickel complex and (bis-N,N-dialkyldithiocarbamado)nickel complex can also be used.

Specific examples of organic antifade agents are described in the following patent specifications:

Hydroquinones are US Special Kitsuki No. 2.360.290,
2.418.613, 2.700.453, 2,701.197, 2.728.659
No. 2.732.300, No. 2.735.76
No. 5, No. 3.982,944, No. 4.430.4
25, UK Toku Kitsuki No. 1.363.921, US Toku Kitsuki No. 2.710.801, No. 2.816.028, etc., 6-hydroxychromans, 5-hydroxycoumarans, and spirochromans are U.S. Special Kitsuki 3,432.30
No. 0, No. 3.573.050, No. 3.574.6
No. 27, No. 3.698°909, No. 3.764.
337, JP-A-52-152225, etc., and spiroindans are described in U.S. Patent No. 4.360.589, p-
Alkoxyphenols are U.S. Patent No. 2,735,76
No. 5, British Special Kitsuki No. 2.066.975, Japanese Patent Publication No. 1983-
10539, Japanese Patent Publication No. 57-19765, etc., and hindered phenols are disclosed in U.S. Pat.
Gallic acid derivatives, methylenedioxybenzenes, and aminophenols are disclosed in U.S. Patent Publication No. 3.457.079 and U.S. Patent Publication No. 4.
332,886, Special Publication No. 56-21144, etc.
Hinder door fruits are US special Kitsuki No. 3.336.135, same No. 4.268.593, UK special Kitsuki 1.326,
No. 889, No. 1.354,313, No. 1.410
, No. 846, Japanese Patent Publication No. 51-1420, Japanese Patent Publication No. 58-1
No. 14036, No. 59-53846, No. 59-7
No. 8344, etc., and metal complexes are listed in the US Special Kitsuki 4.050.
No. 938, No. 4.241゜155, British Special Kitsuki 2.
027.731 (^) etc. These compounds can be used to achieve the desired purpose by co-emulsifying the corresponding color coupler with the coupler and adding it to the photosensitive layer in an amount of usually 5 to 100% by weight. In order to prevent deterioration of the cyan dye image due to heat and especially light, it is more effective to introduce an ultraviolet absorber into the cyan coloring layer and the layers on both sides adjacent to it.

As the ultraviolet absorber, a benzotriazole compound substituted with an aryl group (for example, U.S. Specialty Kitsuki 3.533.7
94), 4-thiazolidone compounds (for example, U.S. Tok. Kitsuki No. 3.314,794, U.S. Patent No. 3.352.
681), benzophenone compounds (for example, those described in JP-A-46-2784), cinnamic acid ester compounds (for example, those described in U.S. Pat. ), bucdiene compounds (as described in U.S. Pat. No. 4,045,229), or benzoxidol compounds (for example, as described in U.S. Pat. No. 3.406.070, No. 3.677, 672 and No. 4. 271.307) can be used. UV-absorbing couplers (for example, α-naphthol-based cyan dye-forming couplers) and UV-absorbing polymers may also be used. ! The absorbent may be mordanted in a particular layer.

Among these, benzotriazole compounds substituted with the aforementioned aryl group are preferred.

In addition, it is particularly preferable to use the following compounds together with the couplers described above, particularly in combination with pyrazoloazole couplers.

That is, a compound (F) that chemically bonds with the aromatic amine developing agent remaining after color development processing to produce a chemically inert and substantially colorless compound and/or an aroma remaining after color development processing. For example, after treatment, compound 15(G), which chemically combines with the oxidized form of a color developing agent to form a chemically inert and substantially colorless compound, may be used simultaneously or alone. This is preferable in order to prevent the occurrence of staining and other side effects due to the formation of coloring dyes due to the reaction between the color developing agent remaining in the film or its oxidized product and the coupler during storage.

A preferred compound (F) has a second-order reaction rate constant kg (in trioctyl phosphate at 80°C) with p-aningine of 1. Oj! /mol-see 41
X10-'j! It is a compound that reacts in the range of /s+ol·sec.

Incidentally, the second-order reaction rate constant can be measured by the method described in JP-A-63-158545.

When k is larger than this range, the compound itself becomes unstable and may react with gelatin or water and decompose. On the other hand, if kl is smaller than this range, the reaction with the remaining aromatic amine developing agent will be slow, and as a result, side effects of the remaining aromatic amine developing agent may not be prevented.

A more preferable compound (F) can be represented by the following general formula (Fl) or (Fn).

General formula (Fl) R1-(^), -X General formula (Fn) R, -C-Y In the formula, R8 and R8 each represent an aliphatic group, an aromatic group, or a heterocyclic group, and n is Represents 1 or O.

A represents a group that reacts with an aromatic amine developer to form a chemical bond, X represents a group that reacts with an aromatic amine developer and leaves the group, B represents a hydrogen atom, an aliphatic group , represents an aromatic group, a heterocyclic group, an acyl group, or a sulfonyl group, and Y represents a group that promotes addition of an aromatic amine developing agent to the compound of general formula (Fn), where R
1 and X, Y and R8 or B may be bonded to each other to form a cyclic structure.

What is the typical method of chemically bonding with residual aromatic amine developing agents? & conversion reaction and addition reaction.

For specific examples of compounds represented by general formulas (Fl) and (Fn), see JP-A-63-158545 and JP-A-62-2.
83338, European Patent Publication No. 298321, European Patent Publication No. 277
Those described in specifications such as No. 589 are preferred.

On the other hand, a more preferable compound (G) that chemically bonds with the oxidized aromatic amine developing agent remaining after color development processing to produce a chemically inactive and colorless compound is the following general formula (Gl ) can be expressed as

General formula (CI) -Z In the formula, R represents an aliphatic group, an aromatic group or a heterocyclic group, and Z is a nucleophilic group or a nucleophilic group that is decomposed in the photosensitive material to release a nucleophilic group. In the compound represented by the general formula (Of), which represents a group, Z has Pearson's nucleophilicity "C11sl value (R, G, Pearson* et al., J.
As.

Ch@-, Soc,, Tsuru, 319 (196B))
is preferably 5 or more, or a group derived from it.

For specific examples of compounds represented by the general formula (Gl), see European Patent Publication No. 255722, Japanese Patent Application Laid-Open No. 1430-1980
No. 48, No. 62-229145, patent application No. 63-136
No. 724, No. 62-214681, European Patent Publication 29
Those described in No. 8321, No. 277589, etc. are preferred.

Further, details of the combination of the above-mentioned compound (G) and compound (F) are described in European Patent Publication No. 277589.

The photosensitive material produced using the present invention contains water-soluble dyes or dyes that become water-soluble through photographic processing as filter dyes in the hydrophilic colloid layer, or for various purposes such as preventing radiation and haley silanes. Such dyes which may be used include oxonol dyes, hexoxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Among them, oxonol dyes, hemioxonol dyes and merocyanine dyes are useful.

As the binder or protective colloid that can be used in the emulsion layer of the light-sensitive material of the present invention, it is advantageous to use gelatin, but other hydrophilic colloids can be used alone or together with gelatin.

In the present invention, the gelatin may be either lime-treated or acid-treated. Details of the gelatin manufacturing method can be found in Arthur Vuis' book, The Macromolecule Chemistry of Gelatin ( Published by Academic Press, 1964).

As the support used in the present invention, transparent films such as cellulose nitrate film and polyethylene terephthalate, which are usually used in photographic light-sensitive materials, and reflective supports can be used. For the purpose of the present invention, reflective supports are used. is more preferable.

The "reflective support" used in the present invention is one that enhances the reflectivity and makes the dye image formed in the silver halide emulsion layer clearer. Includes those coated with a hydrophobic resin containing a dispersed light-reflecting substance such as titanium oxide, zinc oxide, calcium carbonate, and calcium sulfate, and those using a hydrophobic resin containing a dispersed light-reflecting substance as a support. For example, baryta paper, polyethylene-coated paper, polypropylene synthetic paper, transparent supports with a reflective layer or a reflective material, such as glass plates, polyester films such as polyethylene terephthalate, cellulose triacetate or cellulose nitrate, polyamide film, polycarbonate film,
Examples include polystyrene film and vinyl chloride resin.

As other reflective supports, supports having a specular reflective or second type diffuse reflective metal surface can be used. The metal surface has a spectral reflectance of 0.5 in the visible wavelength range.
The above is preferable, and it is also preferable to roughen the metal surface or use metal powder to make it diffusely reflective. The surface may be a surface of a metal plate, metal foil, or thin metal layer obtained by rolling, vapor deposition, plating, or the like.

Among these, it is preferable to obtain the metal by vapor-depositing it on another substrate.It is preferable to provide a layer of water-resistant resin, especially a thermoplastic resin, on the metal surface. For details of such a support, which is preferably provided with an antistatic layer on the opposite side, see, for example, JP-A-61-210.
No. 346, No. 63-24247, No. 63-24251
No. 63-24255, etc.

These supports can be appropriately selected depending on the purpose of use.

As a light-reflecting substance, it is best to thoroughly knead a white pigment in the presence of a surfactant, and also coat the surface of the pigment particles with
It is preferable to use one treated with a tetrahydric alcohol.

The occupied area ratio (%) of white pigment fine particles per defined unit area is most typically calculated by dividing the observed area into 6-×6- adjacent unit areas and projecting them onto that unit area. It can be determined by measuring the occupied area ratio (%) (RL) of the fine particles. The coefficient of variation of the occupied area ratio (%) is the ratio s of the standard deviation S of R& to the average value (R) of RL.
/R. The number of target unit areas (n) is preferably 6 or more, so the coefficient of variation is 87.
The page can be found by

In the present invention, the coefficient of variation of the occupied area ratio (%) of pigment fine particles is preferably 0.15 or less, particularly 0.12 or less. When O,OS or less, the dispersibility of the particles is substantially "uniform". It can be said that.

Example 1 A multilayer color photographic paper having the following layers was prepared on a paper support laminated on both sides with polyethylene. 1! Make the cloth liquid as follows! li&IL, ta.

19.1 g of yellow coupler (ExY), 4.4 g of color image stabilizer (Cpd-1) and color image stabilizer (Cp
d-7) Add and dissolve 27.2 cc of ethyl acetate and 8.2 g of solvent (Solv-1) to 0.7 g, and dissolve this solution in 8 cc of 10% sodium dodecylbenzenesulfonate.
The mixture was emulsified and dispersed in 185 cc of a 10% aqueous gelatin solution. On the other hand, chlorobromide emulsion (cubic, average grain size 0.8
The coefficient of variation of the particle size distribution of a 3-near mixture (molar ratio) of 8- and 0.70- is 0.08 and 0.1
0.0, each emulsion contains 0.2 mol % of silver bromide locally on the grain surface), and the following blue-sensitive sensitizing dyes are added per mol of silver to 2.0 x 10-' mol for large-sized emulsions, respectively. In addition, for small size emulsions, 2.5X1
After adding 0''' mole, sulfur sensitization was performed to prepare iPl.

The above-mentioned emulsified dispersion and this emulsion were mixed and dissolved to prepare a first coating solution as shown below.

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

The following spectral sensitizing dyes were used in each layer.

Blue-sensitive emulsion layer (2.0X10-' mole each for large size emulsions and 2.5X10-' mole each for small size emulsion per mole of halogen i!) Green-sensitive emulsion layer (halogen i! For each mole, 4.0 x 10-' moles for large size emulsions and 5 x 10-' moles for small size emulsions.
．． 6 x 10' moles) and (per mole of silver halide, for large size emulsions 0 x 10 -' moles and for small size emulsions 1
．． OX 10-S mole) red-sensitive emulsion layer (per mole of silver halide, 0.9X10-' mole for large size emulsions and 1 x 10-' mole for small size emulsions)
．． To the red-sensitive emulsion layer, the following compound was added in an amount of 2.6 x 10-'' mole per mole of silver halide.

In addition, 1-(5-methylureidophenyl)-5-mercaptotetrazole was added to the blue-sensitive emulsion layer, green-sensitive emulsion layer, and red-sensitive emulsion layer at a concentration of 8% per mole of silver halide, respectively.
．． 5X10-' moles, ? , 7X10-'mol, 2.5X
lO-' moles were added.

In addition, for the blue-sensitive emulsion layer and the green-sensitive emulsion layer, 4-hydroxy-6-methyl-1,3,3a,'/-tetrazaindene was added per mole of the halogenated i.
0-' moles and 2X10-' moles were added.

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

and (layer structure fi) The composition of each layer is shown below.

The number is the coating amount (g/bo) The silver halide emulsion represents the coating amount in terms of primate.

Support polyethylene laminate paper [The polyethylene on the first layer side contains a white pigment (Ti(h) and a blue dye (ulmarine)]) -th layer (blue-sensitive layer) The above-mentioned silver chlorobromide emulsion 0.30 gelatin 1. 86 Yellow Kabra, -(ExY) 0.82 Color image stabilizer (Cpd-1) 0.19 Solvent (Solv-1) 0.3
Five-color image stabilizer (Cpd-7) 0
．． 06 Second layer (color mixing prevention layer) Gelatin 0.99 Color mixing prevention agent (Cpd-5) 0.08
Solvent (Solv-1) 0.
16 solvent (Solv-4)
0.08 Third layer (green sensitive layer) Silver chlorobromide emulsion (cubic, 1:3 mixture of one with an average grain size of 0.551M and one with an average grain size of 0.39-(Ag molar ratio) 0 grain size distribution The coefficient of variation is 0.1O and 0.08
, each emulsion contained 8 mol% of AgBr O locally on the grain surface) 0.12 Gelatin
1.24 magenta coupler (Ex
M) 0.20 color image stabilizer (Cpd-
2) 0.03 color image stabilizer (Cp
d-3) 0.15 color image stabilizer (
CPd-4) 0.02 Color image stabilizer (Cpd, 9) 0.02 Solvent (Solv-2) 0.4
0 Fourth layer (UV absorption N) Gelatin 1.58 Ultraviolet absorber (UV-1) 0.47 Color mixing prevention agent (Cpd-5) 0.05
Solvent (Solv-5) 0.
24 Fifth layer (red-sensitive layer) Silver chlorobromide emulsion (cubic, 1:4 mixture (46 molar ratio) of average grain size of 0.58 m and 0.45 m) 0 Coefficient of variation of grain size distribution are 0.09 and 0.11,
(Each emulsion contained AgBrO, 6 mol% locally on a part of the grain surface) 0.23 Gelatin
1.34 cyan coupler (ExC)
0.32 color image stabilizer (Cpd-6
) 0.17 color image stabilizer (Cpd
-7) 0.40 color image stabilizer (C
pd-8) 0.04 solvent (SO
IV-6) 0.15 6th layer (ultraviolet absorption layer) Gelatin 0.53 ultraviolet &
! Absorber (UV-1) 0.16 Color mixture prevention agent (Cpd-5) 0.0
2 Solvent (Solv-5) ゛0.08 Seventh layer (protective layer) Gelatin 1.33 Acrylic modified copolymer of polyvinyl alcohol (denaturation degree 17%)
) 0.17 liquid paraffin 0.03 (ExY) l: 1 mixture (molar ratio) with yellow coupler (ExM) 1: 1 mixture (molar ratio) of magenta coupler (ExC) Cyan coupler R=Ct) Is and C4L and 0)1 in a ratio of 2:4:4 by weight (Cpd-1) Color image stabilizer (Cpd-2) Color image stabilizer (Cpd-3) Color image stabilizer (Cpd-4) Color image stabilizer (CPd-5) Color mixing inhibitor (Cpd-6) 2:41 mixture (weight ratio) of color image stabilizer (Cpd-7) Color image stabilizer → CH, -CH)r- C0NHCJ*(t) Average molecular i160,000 (Cpd-8) Color image stabilizer H (Cpd-9) Color image stabilizer (UV4) 4:2:4 mixture (weight ratio) of ultraviolet absorber (Solv-1) Solvent (Solv- 2) 2:1 mixture of solvents (volume ratio) (Solv-4) Solvent (Sol-5) Solvent C00CIHI? (C)I,).

C00CIHI? (Solv-6) Solvent The steps and composition of the processing liquid for processing the multilayer color photographic paper obtained above are as follows.

Processing and Benefits and Plate Color Development See Table 1 Bleaching Window Coating See Table 1
Rinse at 35”C for 45 seconds■ Rinse at 35℃ for 20 seconds■ Rinse at 35℃ for 20 seconds■
Dry at 35℃ for 20 seconds 8
0°C for 60 seconds Next, the following treatment solution was prepared.

That's right.

Ethylenediamine - N, N, N' N-tetrakis (methylene phosphonic acid) Potassium bromide Potassium chloride Triethanolamine The following QOid 2, 0g See Table 1 See Table 1 10 .0g Potassium carbonate optical brightener (WHITEX-4, manufactured by Sumitomo Chemical) Additives (see Table 1) N-ethyl ~ N-(β-methanesulfonamidoethyl)-3 Add monomethyl-4-acunoaniline water pH (25°C) 7g 1.0g 0.05mol 0 000d 10.50 Reduction 4 Ammonium thiosulfate (700g/42) Sodium sulfite ethylenecyamine iron tetranolate (I [[) Ammonium ethylenecyamine Aminetetraacetic acid disodium trilam 00d 00d 7g 5g g Add ammonium water to 1000d pH (25℃) 6.0 1]S (moxibustion ion exchange water (calcium, magnesium 3pp each)
- Below) Next, the coated sample was subjected to gradation exposure for sensitometry using a photosensitive needle (Model FWH manufactured by Fuji Photo Film Co., Ltd., color temperature of light source 3200@K). The exposure at this time was carried out at an exposure time of 1/10 second and an exposure amount of 250 CMS.

The sensitometry was performed using the above processing steps, and the maximum magenta density (Dsax) was measured using a Macbeth densitometer. Furthermore, each developer was left for 4 weeks at 35°C in a beaker (liquid opening ratio: 0.02 CI-'). This aged solution was subjected to sensitometry in the same manner, and the minimum magenta density (Dmin) and the change in cyan sensitivity (ΔS) between immediately after preparation and the aged solution were determined. Sensitivity indicates the logH value at a point 0.2 higher in sensitivity than the minimum concentration.

As is clear from Table 1, when conventional diethylhydroxylamine is used as an additive, when the conventional processing time is shortened to 35 seconds or less, magenta D■a decreases and cyan sensitivity changes. becomes larger (NIll~3
), it can be seen that if the compound of the present invention is used, sufficient color development is achieved even if the time is shortened to 35 seconds or 20 seconds, and the change in sensitivity is small. (NCL4.5.7.8.1O111,13,
14,16,17,19,20), when the concentration of chloride ions is 3 x 10-' mol/L 2 x 10-' mol/l, and when the concentration of bromide ions is 4 x 10-' mol/l,
At 2X10-'' mol/l, the photographic performance changes slightly (Stones 26-33); chloride ions and bromide ions range from 3.5xlO-2 to 1.5X10-''mol/1..3.
Ox 10-' ~1. OX 10-'mol/
It can be seen that a range of l gives better photographic performance.

Example 2 The photosensitive material prepared in Example 1 was subjected to imagewise exposure, and was continuously processed in the following processing steps using an automatic color paper processing machine until twice the capacity of the color development tank was refilled ( A running test was conducted. Also, a separate example-
Exposure was applied using the method described in 1 above, and processing was performed before and after the running test.

Color development 2 tables 2 tables 109d Bleach fixing 35℃ 45 seconds 215d Rinse ■ 35℃ 20 seconds Rinse ■ 35℃ 20 seconds Rinse ■ 35°C 20 seconds 250- Drying 80℃ 60 seconds The replenishment amount is the value per photosensitive material. 3-tank countercurrent method for rinsing ■→■ %formula% tank liquid water 00jd 0.0IC1-' 0.0IC1-' 0.0IC1-' 0.01C11-' 0.01cm-' replenisher 700- Ethylenecyan N, N.

N',N''-tetrakis (methylenephosphonic acid) 3.0g potassium bromide
0.015 g potassium chloride
5g Triethanolamine 10g Potassium carbonate 25g Fluorescent brightener (k) IITEX-41, 0g manufactured by Sumitomo Chemical) Additive (see Table 2) 50mMN-Methyl-
N(β-methanesulfonagodoethyl)-3-methyl-4-aminoaniline, 5 Add water to 1000ml tp100O
℃) 10.053.3g 0g 0g 2g 5g 3.58 70a+M, 5 000d 10.55 Yingzu fixed spring release (tank solution and replenishment solution are the same) Ammonium thiosulfate (700g/l) Sodium sulfite 00m 00d 7g Ethylenediamine tetra Iron acetate (1) Ammonium 55g Ethylenediaminetetraacetic acid disodium 5g Add water 1o00dpH (25°C)
5.40U um direct (tank fluid and refill fluid are the same) Ion exchange water (calcium, magnesium 3pp each
- below) The color paper described above was exposed through an optical wedge and processed before and after each successive process.

Magenta sensitivity change (ΔS) is a photographic characteristic after continuous processing.
) and the maximum magenta density after continuous processing (Ds+ax
) was evaluated. However, the sensitivity is the same as in Example 1.

As is clear from Table 2, when conventional diethylhydroxylamine is used as an additive, when the conventional processing time is shortened to 35 seconds or less, magenta D-a decreases and magenta sensitivity changes significantly. Naruga (Kan 34.3
5) It can be seen that when the compound of the present invention is used, even if the time is shortened to 35 seconds or 20 seconds, sufficient color is developed and the change in sensitivity is small (N(136-59)).

Example 3 A multilayer color photographic paper having the layer structure shown below was prepared on a paper support which was laminated on both sides with polyethylene and whose surface was subjected to corona discharge treatment. The coating solution was prepared as follows.

Preparation of coating solution for the first layer: 60.0 g of yellow coupler (ExY) and 28.0 g of anti-fading agent (Cpd-1), 150 cc of ethyl acetate, 1.0 cc of solvent (So 1v-3),
Iv-4) 3.0 cc was added and dissolved, and this solution was added to 450 cc of a 10% gelatin aqueous solution containing sodium dodecylbenzenesulfonate, and then dispersed using an ultrasonic homogenizer. Silver chlorobromide emulsion containing sensitizing dye (silver bromide 0.7 mol%) 420
g to prepare a first layer coating solution.

The coating solutions for the second to seventh layers were also prepared in the same manner as the coating solution for the first layer. The gelatin hardening agent for each layer is 1,2-
Bis(vinylsulfonyl)ethane was used.

The following spectral sensitizing dyes were used in each layer.

Blue-sensitive emulsion layer; anhydro-5,5'-dichloro-3,
3'-disulfoethyl thiacyanine hydroxide green-sensitive emulsion layer; anhydro-9-ethyl-5,5'-diphenyl-3,3'-disulfoethyl oxacarbocyanine hydroxide red-sensitive emulsion layer; 3,3' -diethyl-5-methoxy-9
, 11-neopentylthiazidylupocyanine iodide The following substances were used as stabilizers for each emulsion layer.

The following dyes were used as anti-irradiation dyes.

[3-carboxy-5-hydroxy-4-(3-(3-
Carboxy-5-oxo-1-(2,5-bisulfonatophenyl)-2-pyrazolin-4ylidene)-1-propenyl)-1-pyrazolyl]benzene-2,5-disulfonate-disodium salt N,N' - (4,8-dihydroxy-9,10dioxo-3,7-cissulfonatoanthracene-1,5-diyl)bis(methanesulfonate)-tetrasodium salt [3-cyano-5-hydroxy-4- (3-(3-cyano-5-oxo-1-(4-sulfonatophenyl)-
2-pyrazolin-4-ylidene)-1-pentanyl)-
1-pyrazolyl]benzene-4-sulfonate-sodium salt (layer structure) The composition of each layer is shown below. The numbers represent the coating amount (g/po). Silver halide emulsions represent the coating amount in terms of silver.

Paper support laminated on both sides with polyethylene and corona discharge treated on the surface.

-th layer (blue-sensitive layer) The above-mentioned silver chlorobromide emulsion (AgBr O, 7 mol %, cubic, average grain size 0.9 μm) 0.29 Gelatin t, SO yellow coupler (ExY) 0.60 Anti-fading Agent (Cpd
-1) 0.28 solvent (Solv-3)
0.01 solvent (Solv-4)
0.03 Second layer (color mixing prevention agent) Gelatin 0.80 Color mixing prevention agent (Cpd-2) 0.055 Solvent (Solv
-1) 0.03 Solv W (Solv-2)
0.15 Third layer (green-sensitive layer) Above-mentioned silver chlorobromide emulsion (AgBr 0.7 mol%, cubic, average grain size 0.45 μm) 0.18 Gelatin 1.86 Magenta coupler (ExM) 0. 27 Anti-fading agent (Cp
d-3) 0.17 anti-fading agent (Cpd-4
) 0.10 solvent (Solv-1)
0.2 solvent (Solv-2)
0.03 Fourth layer (color mixing prevention layer) Gelatin 1.70 Color mixing prevention agent (Cpd-2) 0.065 Ultraviolet absorber (
UV-1) 0.45 Ultraviolet absorber (UV-1)
2) 0.23 solvent (Solv-1)
0.05 solvent (So 1 v-2)
0. 05 Fifth layer (red-sensitive layer) Above-mentioned silver chlorobromide emulsion (AgBr 4 mol%, cubic, average grain size 0.5 μm) 0.21 Gelatin 1. 80 cyan coupler (ExC-1) 0.26 cyan coupler (E
xC-2) 0.12 anti-fading agent (Cpd-1
) 0.20 Solvent (Solv-1)
0.16 solvent (Solv-2)
0.09 Color development accelerator (Cpd-5) 0.
15 Sixth layer (ultraviolet absorption layer) Gelatin 0.70 ultraviolet absorber (UV-1) 0.26 ultraviolet absorber (
UV-2) 0.07 Solvent (Solv-1)
0.30 solvent (Solv-2)
0.09 Seventh layer (protective layer) Gelatin 1.07 (ExY
) Yellow coupler α-pivalyl α-(3-benzyl-1-hydantoynyl)-2-chloro-5-[β-(dodecylsulfonyl)
butyramide] acetanilide (ExM) magenta coupler 7-chloro-6-itubroby-3- (3-[(2-
Butoxy-5tert-octyl)benzenesulfonyl]propyl)-IH-virasoro[5°1-dan)-1,2
, 4-triazole (ExC-1) cyan coupler 2-pentafluorobenza 4-triazole (ExC-1).

-5(2-(2,4-di-tert-aruphenoxy)-3-methylbutyramidophenol (ExC-2)
Cyan coupler 2,4-dichloro-3-methyl-6-[α-(2,4-
Tert-amylphenoxy)butyarmide]phenol (Cpd-1) anti-fade agent-(-Cut-CI+T- CONHCJw(n) Average molecular weight 80.000(
Cpd-2) Color mixing inhibitor 2.5-di-tert-octylhydroquinone (Cp
d-3) Anti-fade agent 7.7'-dihydroxy-4,4,4',4'-tetramethyl-2,2'-spirochroman (Cpd-4) Anti-fade agent N-(4-dodecyloxyphenyl) -Morpholine (Cpd-5) Color accelerator p-(p-toluenesulfonamide) phenyl-dodecane (Solv-1) Solvent Di(2-ethylhexyl) phthalate (Solv-2) Solvent Dibutyl phthalate (Solv-3) Solvent (l-nonyl)phthalate (Solv-4) solvent N,N-diethylcarbonamido-methoxy-2,4-
Di-t-amylbenzene (UV-1) UV absorber 2-(2-hydroxy-3,5-di-tert-amylphenyl)benzotriazole (TJV-2) UV absorber 2-(2-hydroxy-3 , 5-di-tert-butylphenyl)benzotriazole A cleaning test similar to that in Example 2 was conducted using the above-mentioned sensitive material. In addition, exposure was applied by the method separately described in Example-1, and treatments were performed before and after each successive treatment.

Magenta gradation change (Δγ) is a photographic characteristic after continuous processing.
) and the maximum magenta density (Dmax) after continuous processing
The 0 gradation evaluated was expressed as a density change from a point representing a density of 0.5 to a density point on the high exposure side of 0.3 at 1 ogE. The results are shown in Table 3.

As is clear from Table 3, when conventional diethyl hydroxyl chloride is used as an additive, when the conventional processing time is shortened to 35 seconds or less, the magenta Dmax decreases and the magenta gradation changes significantly. Naruga (Nn60.
61), it can be seen that when the compound of the present invention is used, even if the time is shortened to 35 seconds or 20 seconds, sufficient color is developed and the change in sensitivity is small (Hiroshi 62-85).

Example 4 The photosensitive material prepared in Example 1 was subjected to imagewise exposure, and the following processing steps were carried out using an automatic color paper processing machine until the tank capacity for color development was refilled twice. Processing (running test) was performed. Also, a separate example-
Exposure was applied using the method described in 1 above, and processing was performed before and after the running test.

Bleach fixing 35℃ 45 seconds 215d l? ! !
.

Rinse■ 35℃ 20 seconds 10i rinse■ 35℃ 20 seconds 101 rinse■
35°C 20 seconds 250d 10 ffi drying 80°C 60 seconds 0 Replenishment amount per 1 td of photosensitive material.

A three-tank countercurrent flow system was used for rinsing from ■ to ■.

Further, the liquid aperture ratio of the color developer is 0.005 cm-' on average for both of the above.

The m precepts for each treatment solution are as follows.

Bleach-fix solution (tank solution and replenisher are the same) Ammonium thiosulfate (70%) Sodium sulfite Iron ethylenediaminetetraacetate (I 25℃) 100 (ld 5, 40 1Z release (tank fluid and refill fluid are the same) Ion exchange water (calcium, magnesium, 3 ppm or less).

The maximum density (Dmax) of yellow, magenta, and cyan after the end of the running test was measured, and the sensitivity change (ΔS) of cyan after the end of the running with respect to the cyan at the start of the running test was calculated.

However, the sensitivity is the same as in Example 2.

As is clear from Table 4, when conventional diethylhydroxylamine is used as an additive, the conventional processing time is shortened to 35 seconds, and when the replenishment amount is reduced, the Dmax of yellow, magenta, and cyan decreases. However, if the compound of the present invention is used, even if the time is shortened to 35 seconds and the amount of replenishment is reduced, each color will be sufficiently colored and the sensitivity change will be small. Recognize(
Nllk89-115).

Example 5 Using the photosensitive material prepared in Example 1, the same treatments as in Example 1 were performed under the conditions shown in Table 5.

Comparative Compound 1 Comparative Compound 2 Comparative Compound 3 Comparative Compound 4 As is clear from Table 5, the compounds with poor hydrophilicity (comparative compounds 1 to 4) as described above and the compounds listed in general formula (1) of the present invention A comparison shows that good photographic properties can be obtained using the compounds of the present invention. (N1116~
127.130.135) In particular, when the concentration of bromide ions is between 3.0X10-' and 1.0
It can be seen that good photographic properties can be obtained in the case of In addition, even in continuous processing involving elution from photosensitive materials, fluctuations in photographic performance, particularly fluctuations in sensitivity, can be largely suppressed.

Furthermore, sensitivity fluctuations that tend to occur when the amount of color developer replenishment is reduced can be largely suppressed.

These effects are particularly remarkable when color development is performed in a state containing chlorine ions and bromine ions at the concentrations described above.

Claims (2)

[Claims] (1) A silver halide color photographic light-sensitive material provided with at least one emulsion layer having an emulsion consisting essentially of silver chloride is subjected to color development containing at least one compound represented by the following general formula (I). Depending on the liquid, 10
1. A method for processing a silver halide color photographic material, which is characterized in that development is performed in seconds to 40 seconds. General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, L represents an alkylene group that may be substituted, and A
is a carboxy group, a sulfo group, a phosphono group, a phosphinic acid residue, a hydroxy group, an amino group which may be substituted with alkyl, an ammonio group which may be substituted with alkyl, a carbamoyl group which may be substituted with alkyl, a carbamoyl group which may be substituted with alkyl, R represents a hydrogen atom or an optionally substituted alkyl group. ) (2) Chloride ion and bromide ion are each 3.5
×10^-^2 to 1.5 ×10^-^1 mol/l, 3.
The processing method according to claim 1, which comprises processing with the above color developer containing 0x10^-^5 to 1.0x10^-^3 mol/l.