JPH02191950A - Processing method for silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To prevent fogging by processing a sensitive material having at least one silver chloride-rich silver halide emulsion layer with a developing soln. contg. specified amts. of chloride ions and bromide ions and further contg. a compd. represented by a specified formula. CONSTITUTION:A developing soln. contg. a compd. represented by formula I is used. In the formula, each of R<1> and R<2> is H, optionally substd. alkyl, alkenyl, aryl or a hetero-arom. group, R<1> and R<2> are not simultaneously H and may bond to each other to form a hetero ring together with N and the hetero ring is a 5- or 6-membered satd. or unsatd. ring having C, H, halogen, O, N, S, etc., as the constituent atoms. The color developing soln. further contains 3.5X10<-2>-1.5X10<-1>mol/l chloride ions and 3.0X10<-5>-1.0X10<-3>mol/l bro mide ions.

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, and more specifically, it relates to a method for processing a silver halide color photographic light-sensitive material, and more specifically, to a method for processing a silver halide color photographic light-sensitive material. Concerning an excellent development processing method.

(Prior Art) In recent years, in the photographic processing of color photographic 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.

(In the formula, R1 and R1 are hydrogen atoms, and the common methods for shortening the time of non-substitution or each treatment step include increasing the temperature and increasing the amount of replenishment, but there are other methods such as strengthening stirring. Many methods have been proposed for adding various promoters.

In particular, for the purpose of speeding up color development and/or reducing the amount of replenishment, color photographic materials containing silver chloride emulsions instead of conventionally widely used silver bromide emulsions or silver iodide emulsions are processed. For example, it is known how to
International Publication No. WO 37-04534 describes a method for rapidly processing a high silver chloride silver halide color photographic light-sensitive material with a color developer substantially free of sulfite ions and benzyl alcohol.

However, it has been found that when development is performed using an automatic processor based on the above method, streaky fogging occurs. This is thought to be a so-called submerged pressure sensitizing stripe, which occurs when the photosensitive material comes into contact with a roller or the like in the developing tank of an automatic processor, causing scratches and pressure sensitization, resulting in striped fog. Ru.

Furthermore, it has been found that there is a problem in that the photographic characteristics (particularly the gradation and maximum density of the cyan coloring layer) fluctuate during continuous processing.

As described above, rapid processing using high silver chloride color photographic materials has serious problems such as pressure sensitization fog in the liquid and fluctuations in photographic properties, and a solution to these problems has been strongly desired.

In addition, in a rapid processing method using high silver chloride color photographic light-sensitive materials, Japanese Patent Application Laid-Open No. 58-953 describes a method for reducing fluctuations in photographic properties (fogging) caused by continuous processing.
45, JP-A-59-232342 discloses the use of organic antifoggants. However, its anti-fogging ability is not sufficient to prevent the generation of pressure-sensitizing streaks in the liquid, and when used in large quantities, it has been found that the maximum density decreases and development is delayed, and it is not possible to solve the above problems. There wasn't.

In addition, JP-A-61-70552 discloses a method for reducing replenishment of the developer by using a high chloride silver halide color photographic light-sensitive material and adding a replenishment amount in an amount that does not cause overflow into the developer bath during development. A method is described in JP-A-63-106655, in which a silver halide color photographic material whose silver halide emulsion layer has a high silver chloride content is treated with a hydroxylamine compound for the purpose of stabilizing the processing. A method of developing with a color developing solution containing chloride at a predetermined concentration or higher is disclosed.

However, with these methods, pressure sensitizing streaks that occur during the development process using the automatic developing machine described above and variations in photographic characteristics during continuous processing (particularly gradation changes and maximum density changes in the cyan coloring layer) are observed. However, the above problems were not solved.

(Problems to be Solved by the Invention) Therefore, the first object of the present invention is to provide a rapid processing method that uses a high silver chloride photosensitive material and prevents the occurrence of streaky fog. .

A second object of the present invention is to have excellent photographic properties such as high maximum density and low minimum density in rapid development processing using high silver chloride color photographic light-sensitive materials, and to improve the photographic properties associated with continuous processing. It is an object of the present invention to provide a development processing method in which fluctuations (particularly changes in gradation and maximum density of a cyan coloring layer) are significantly suppressed.

(Means for Solving the Problems) An object of the present invention is to provide a silver halide color photographic material,
A silver halide color containing at least one layer of a high silver chloride silver halide emulsion comprising 80 mol% or more of silver chloride in a method of processing with a color developer containing at least one aromatic primary amine color developing agent. The photosensitive material has 3.5 chloride ions and 3.5 bromide ions, respectively.
XIO-5~1.5X10-'-[-/L, /7! ,3
．． Achieved by a method for processing a silver halide color photographic light-sensitive material, which is characterized by processing with a color developer containing QXIQ-5 to 1 and QX10 mol/l and a compound represented by general formula (I). It was done.

-Spelling Allowance (1) % Formula % In the formula, R1 and R2 are a hydrogen atom, an unsubstituted or substituted alkyl group, an unsubstituted or substituted alkenyl group, an unsubstituted or substituted teryl group, or a heteroaromatic group RI and R, which represent hydrogen atoms, do not become hydrogen atoms at the same time, but may be linked to each other to form a heterocycle together with a nitrogen atom. The ring structure of the heterocycle is a 5- to 6-membered ring, and includes a carbon atom, a hydrogen atom, a halogen atom, an oxygen atom, a nitrogen atom,
It is composed of sulfur atoms, etc., and may be saturated or unsaturated.

Chloride ions are well known as one of the antifogging agents, but their effect is small, and even when used in large amounts, it is difficult to completely prevent streaky fog that occurs when processed with an automatic processor. On the contrary, this had the adverse effect of delaying development and lowering the maximum density.

Bromide ion is also known as an antifoggant, and depending on the amount added, it can prevent the generation of streaky pressure blur, but it also suppresses development and lowers the maximum density and sensitivity, making it impractical for practical use. It was unbearable.

The compound represented by the general formula (1) is International Publication W○8T-
04534 Koyori, a preservative for developing agents described in JP-A No. 63-106655, etc. It has excellent preservative properties and has a high maximum density when processing poor high-silver chloride photographic materials. It is known that there is little color alienation. However, the poor stability of the compound itself and the fact that it has development activity, although its activity is low, are one of the major causes of fluctuations in photographic properties (particularly changes in gradation and maximum density of the cyan coloring layer) during continuous processing. It turned out to be one.

As a result of various studies, the present inventors have determined that a high silver chloride color light-sensitive material containing a high silver chloride emulsion with a silver chloride content of 80 mol% or more has a chloride ion concentration and a bromide ion concentration of 3. .5X10-5 to 1.5X10"'mol/l
, 3.0.times.10.sup.-5 to 1.0.times.0.times.10.sup.-' mol/l, it has been found that rapid processing in which the above-mentioned pressure fog is prevented is possible. Furthermore, it has been found that the effect of preventing pressure blurring is further enhanced by combined use with the compound (1).

Furthermore, it has been found that the fluctuations in photographic properties due to continuous processing due to the compound of binding margin (1) are significantly reduced by the combined use of the concentrations of chloride ions and bromide ions of the present invention. .

Thus, the effect of the combination of a relatively large amount of chloride ions, a very small amount of bromide ions, and the compound of -Tsuzuriyo (1) has not been known until now, and the details of the effect are unknown. However, future research will clarify this.

JP-A No. 63-106655 discloses that a silver chloride photosensitive material containing 70 mol% or more is mixed with chloride of 2×10-" mol or more and the general formula (
A method of processing using a developer containing the compound shown in 1) is described. However, the concentration of bromide ions in the developer is a treatment outside the scope of the present invention, and furthermore, there is no description of the specific effects of the combination of appropriate amounts of bromide ions and chloride ions according to the present invention. There is no description of the problem to be solved, and the present invention is not inferred.

The present invention will be explained in detail below.

The silver halide emulsion of the present invention consists essentially of silver chloride.

Here, "substantially" means that the content of silver chloride based on the total halogenated 11I is 80 mol% or more, preferably 95 mol% or more, and more preferably 98 mol% or more. From the viewpoint of rapidity, the higher the silver chloride content, the more preferable.

The amount of silver coated in the silver halide photosensitive material of the present invention is 0.80 g.
/nf or more is preferable from the viewpoints of rapidity, desilvering properties, and prevention of pressure-sensitizing muscles.This is thought to be due to the effect of reducing the film thickness in addition to simply reducing the amount of silver. Coated silver amount 0
．． More preferably, it is 75 g/m or less, and the coating silver amount is 0.65. It is particularly preferable that it is less than g/i. Further, from the viewpoint of image density, etc., 0.3 g/n or more is preferable.

In the present invention, 3.5 chloride ions are added to the color developer.
X10-5 to 1.5X10-'mol/I! , it is necessary to contain. Preferably 5 X 10-5 to lXl
0-'mol/l. Chlorine ion concentration is 1.5X10
If it is more than -' mol/l, it has the disadvantage of retarding development and does not achieve the object of the present invention of rapid development and high maximum density. Furthermore, if it is less than 3.5 x 10 = mol/l, it is not possible to prevent streaky pressure fog, and furthermore, photographic property fluctuations (especially changes in the maximum density and gradation of the cyan coloring layer) due to continuous processing cannot be prevented. ), and the object of the present invention cannot be achieved.

In the present invention, 3.0% bromine ion is added to the color developer.
X10-' mol/l-1, 0X10-'5, 0X10-
S mol-5×10-′ mol/l, more preferably 1.0×10-5 to 3×10-′ mol/l. Bromine ion concentration is lXl0-'mol/! If more than 3.0X10-
If it is less than 'mol/l, it is not possible to prevent streak-like pressure blurring, and furthermore, it is impossible to prevent fluctuations in photographic properties (especially maximum density and gradation changes of the cyan coloring layer) due to continuous processing. Therefore, the purpose of the present invention cannot be achieved.

Here, chlorine ions and bromine ions may be directly added to the developer, or may be eluted from the photosensitive material in the developer.

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 potassium chloride.

It may also be supplied in the form of a countersalt of the fluorescent brightener added to the developer.

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

When eluting from the photosensitive material in the developer, both chlorine ions and bromine ions may be supplied from the emulsion or may be supplied from a source other than the emulsion.

The compound represented by general formula (I) will be explained in detail.

General formula (1) % Formula % In the formula, R1 and R1 represent a hydrogen atom, an unsubstituted or substituted alkyl group, an unsubstituted or substituted alkenyl group, an unsubstituted or substituted aryl group, or a heteroaromatic group. R. and R. cannot be hydrogen atoms at the same time, and may be linked to each other to form a petero ring together with a nitrogen atom. The ring structure of the Peter ring is a 5- to 6-membered ring composed of carbon atoms, hydrogen atoms, halogen atoms, oxygen atoms, nitrogen atoms, sulfur atoms, etc., and may be saturated or unsaturated.

It is preferable that R' and R2 are an alkyl group or an alkenyl group, and the number of carbon atoms is preferably 1 to 10, particularly 1 to 5.
is preferred. Examples of the nitrogen-containing heterocycle formed by connecting Ro and R2 include a piperidyl group, pyrrolysilyl group, N-alkylpiperazyl group, morpholyl group, indolinyl group,
Examples include benztriazole group.

Among the compounds represented by the general formula (1), the compound represented by the following general formula (1-a) is useful for preventing fluctuations in photographic properties and
It is particularly preferred in terms of preventing the streaky fog mentioned above.

General formula (1-a) -A Ho->< In the formula, L represents an optionally substituted alkylene group, and A represents a carboxyl group, a sulfo group, a phosphono group, or a phosphine group.
i group, 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; R is a hydrogen atom, a substituted represents an optional alkyl group.

General formula (1-a) will be explained in detail below.

In the formula, L represents a linear or branched alkylene group having 1 to 10 carbon atoms, which may be substituted, and preferably has 1 to 5 carbon atoms. Specifically, methylene, ethylene, trimethylene,
Propylene is mentioned as a preferred example. Examples of the substituent include a carboxy group, a sulfo group, a phosphono group, a phosphinic acid residue, a hydroxy group, and an alkyl-substituted ammonio group, and preferred examples include a carboxy group, a sulfo group, a phosphono group, and a hydroxy group. . 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 (preferably 1 to 5 carbon atoms), a carbamoyl group which may be substituted with alkyl (preferably 1 to 5 carbon atoms), and a carbamoyl group which may be substituted with alkyl (preferably 1 to 5 carbon atoms). Represents a good sulfamoyl group,
Carboxy group, sulfo group, hydroxy group, phosphono group,
Preferred examples include carbamoyl groups 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. Particularly preferred examples include a carboxyethyl group, a sulfoethyl group, a sulfopropyl group, a phosphonomethyl group, and a phosphonoethyl group. R represents a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms, which may be substituted, and preferably has 1 to 5 carbon atoms. Examples of substituents include 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, and an alkyl group. Represents an optionally substituted sulfamoyl group. There may be two or more substituents. R is a hydrogen atom, a carboxymethyl group,
Preferable examples include carboxyethyl group, carboxypropyl group, sulfoethyl group, sulfopropyl group, sulfobutyl group, phosphonomethyl group, phosphonoethyl group, and hydroxyethyl group, and hydrogen atom, carboxymethyl group, carboxyethyl group, sulfoethyl group, Particularly preferred examples include a sulfopropyl group, a phosphonomethyl group, and a phosphonoethyl group.

I4 and R may be linked to form a ring.

Specific examples of the compound of general formula (1) in the present invention are listed below, but the present invention is not limited thereto.

In addition, the amount of the following compounds added to the color developing solution is 0.00
It is desirable to add it at a concentration of 5 mol/l to 0.5 mol/l, preferably 0.03 mol/l to 0.1 mol/l.

Compound example CZH5-N-C2H5 C) 130cJ, -N-CZH, -0CHffH +-j CzHsOCJn-N-CHi-C) I=CHzNII
OI! ■ C1H5-N)! H ■-10 CH OCJ, -NH H ■-13 Ha lh ■ H H ■-19 ■-20 ■-21 tHs Js ■-15 C4H? C, H9 ■ C) 13 CH.

■-17 ! -22 CH3 Hs ■ ■-24 ■ ■ ■-27 Φ H ■-29 [0-NH-CHICo□H ■-30 IO-Nll-CHIC)lICo! H■-31 HO-NH-CI-CO*H Hs 80-NH-CI-Co□H C1)Is ■-33 HO-N)I-CH-Go! H 4H9 ! -45 HO-NH-Ch-POtHz ■ 80-N)l-CI-Ct(z-Co□HL ■-35 10-NH-C1h-CH-CO2H C.I.

■-36 IO-NH-CHICHIS (hH ■-37 80-Nu-CHzCHClbSOiHH )10-NH-(cuz)3SO2H ! HO-NH-(CTo)asOJ ■-40 HO-NH-CHgPOJz ■-41 110-NH-CH-P(hH! CH3 !-42 )to-N)I-C1lzC)lzPOJz■-43 IO-NH- CHzCHzOH [-44 HO-NH-(Cth)sOH ■ ■-56 )1ONtlcthcH(POsHz) t■-64 80-NHCHzCHzC-N)IC(CHI) zc
Hz-S(hH) The compound represented by the general formula (+) is obtained by alkylating commercially available hydroxylamines (
It can be synthesized by nucleophilic substitution reaction, addition reaction, Mannich reaction). West German patent 115963
Publication No. 4, “Inorganic Power/Chemical Power/Actor J (
rnorganica Chiiiica Acta)+
93+ (1984) 101-108, etc., and a specific method is described below.

Synthesis of Exemplified Compound (7) 11.5 g of sodium hydroxide and 96 g of sodium chloroethanesulfonate were added to 200 d of an aqueous solution of 20 g of hydroxylamine hydrochloride, and the mixture was kept at 60'C and 40 d of an aqueous solution of 23 g of sodium hydroxide was added over 1 hour. I added it slowly. Further, the temperature was kept at 60°C for 3 hours, and the reaction solution was cooled under reduced pressure.
After condensing, 200ml of concentrated hydrochloric acid was added and heated to 50°C. Eliminate insoluble matter! Add 500ml of methanol to the filtrate to obtain the desired product (
Exemplary compound (7)) was obtained as monosodium salt crystals.

41g (yield 53%) Synthesis of Exemplary Compound (21) Hydroxylamine hydrochloride 7.2g and phosphorous acid 18.0g
32.6 g of formalin was added to the aqueous hydrochloric acid solution and heated under reflux for 2 hours. The resulting crystals were recrystallized from water and methanol to obtain 9.2 g (42%) of Exemplified Compound (11).

In the present invention, from the viewpoint of processing stability during continuous processing and prevention of streaky pressure fog, it is preferable that the color developer does not substantially contain sulfite ions.

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.

D-IN, N-diethyl-p-phenylenediamine D-22-amino-5-diethylaminotoluene D-32-amino-5-(N-ethyl-N-laurylamino)toluene D-44-(N-ethyl- N-(β-hydroxyethyl)aminocoaniline D-52-methyl-4-[N-ethyl-N=(β-hydroxyethyl)aminocoaniline D-64-amino-3-methyl-N-ethyl-N −(β
-(methanesulfonamide)ethylcouaniline D-7N-(2-amino-5-diethylaminophenylethyl)methanesulfonamide D-8N, N-dimethyl-p-phenylenediamine D-94-amino-3-methyl-N -ethyl-N-methoxyethylaniline D-104-amino-3-methyl-N-ethyl-N-β
-Ethoxychethylaniline D-114-amino-3-methyl-N-ethyl-N-β
-Ethoxyethylaniline Among the above-mentioned -phenylenediamine derivatives, 4-amino-3-methyl-N-ethyl-N-[β-(
methanesulfonamido)ethyl]-aniline (exemplified compound D-6) and 2-methyl-4-[N-ethyl-N-
(β-hydroxyethyl)aminocoaniline (exemplified compound D-5).

Further, these p-phenylenediamine derivatives may be salts such as sulfate, hydrochloride, sulfite, and p-)luenesulfonate. The concentration is preferably from about 0.1 to about 20 g, more preferably from about 0.5 g to about 15 g.

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

- Tsuzuri allowance (A) (wherein, RlJ is a hydroxyalkyl group having 2 to 6 carbon atoms, R1□ and RlJ are each a hydrogen atom, and 1 to 6 carbon atoms)
an alkyl group, a hydroxyalkyl group having 2 to 6 carbon atoms,
It represents a benzyl group or the formula -CaH2+a -N, where n is an integer of 1 to 6,
X' X and X' each represent 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 above-mentioned - binding allowance (A) are as follows.

(A-1) Ethanolamine, (A-2) Jetanolamine, (A-3)) Jetanolamine, (A-4) Di-isopropanolamine, (A-5) 2
-Methylaminoethanol, (A-6) 2-ethylaminoethanol, (A-7) 2-dimethylaminoethanol, (A-8) 2-diethylaminoethanol, (A
-9) 1-diethylamino-2-propatool, (A-10) 3-diethylamino-1-propatool, (A-11) 3-dimethylamino-1-propatool, (A-12) Isopropylaminoethanol, (A-1
3) 3-amino-1-propatol, (A-14)
2-Amino-2-methyl-1,3-propanediol, (A-15) Ethylenediaminetetraisopropanol, (A-16) Benzyljetanolamine, (A-17)
) 2-amino-2-(hydroxymethyl)-1,3-
Propanediol.

(A-18) 1,3-diaminopropanol (A-19
)1.3-bis(2-hydroxyethylmethylamino)
-Proper Tools These compounds represented by the above-mentioned binding allowance (A) have an effect point of 3 g to 100 per 11 color developing solution.
It is preferably used in the range of 6g to 5g, more preferably 6g to 5g.
It is used in the range of 0g.

The color developing solution according to the present invention is suitable for the following - Binding margin CB-■] and (B-
A compound represented by I[) is more preferably used.

General formula [B-1] I General formula (B-I[) i In the formula, R14, Rt5, R1 & and RCt are each a hydrogen atom, a halogen atom, a sulfonic acid group, and a carbon atom number of 1
~7 alkyl group, -OR, , also represents R11
1, Rt9, Rto and Rit each represent a hydrogen atom or an alkyl group having 1 to 1 carbon atoms. However, R
When t5 represents -OH or a hydrogen atom, Rt4 represents a halogen atom, a sulfonic acid group, an alkyl group having 1 to 7 carbon atoms, OR+m.

The alkyl groups represented by RI4, RIB, Ro and R1'l include those having substituents, such as methyl group, ethyl group, 1so-propyl group, n-propyl group, L-butyl group, n-butyl group, Examples include a hydroxymethyl group, a hydroxyethyl group, a methylcarboxylic acid group, a benzyl group, etc., and the alkyl group represented by RCt, Rt9, Rt, and R21 has the same meaning as above, and further examples include an octyl group. .

Further, examples of the phenyl group represented by Rt4, RIS, Rlh, and R17 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-1-2) 1.2-dihydroxybenzene-3,5-disulfonic acid (B-I-3) 1.2.3- Trihydroxybenzene-5-carboxylic acid (B-1-4) 1.2.3-trihydroxybenzene-5-carboxymethyl ester (B-1-5) 1.2.3-1-dihydroxybenzene-5- hydroxybenzene-3,4,6-trisulfonic acid (B-n-1) 2.3-dihydroxynaphthalene-6-sulfonic acid (B-It-2) 2.3.8-trihydroxynaphthalene-6-sulfonic acid (B-I[-3) 2. 3-dihydroxynaphthalene-6-carboxylic acid (B-n-4) 2.3-dihydroxy-8-isopropyl-naphthalene (B-n-5) 2.3-dihydroxy-8-chloro-naphthalene-6-
Among the above sulfonic acid compounds, compounds particularly preferably used in the present invention include 1,2-dihydroxybenzene-3,
Examples include 5-disulfonic acid, and it can also be used as alkali metal salts such as sodium salts and potassium salts. (Specific exemplary compound (B-1-2)).

In the present invention, the binding allowance (B-13 and (B-11)
) is 5 to 15 per 12 color developing solution.
It can be used in the range of 15 to 1 g, preferably 15 to 1
It is desirable to use the amount in the range of 0g/1, more preferably 25~7g.

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 buffers. Buffers include sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate, sodium borate, potassium borate,
Sodium tetraborate (borax), potassium tetraborate, 0
-Sodium hydroxybenzoate (sodium salicylate), potassium 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 mol/l.
It is preferably 0.1 mol/l to 0.1 mol/l or more.
Particularly preferred is 4 mol/Il.

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, ethylenediaminetetraacetic acid, triethylenetetraminehexaacetic acid,
nitriloN,N,N-)lis(methylenephosphonic acid),
Ethylenediamine-N,N,N',N'-tetrakis (methylenephosphonic acid), 1,3-diamino-2-propatoltetraacetic acid, transcyclohexanediaminetetraacetic acid, nitrilotripropionic acid, 1,2-diaminopropanetetraacetic acid Acetic acid, hydroxyethyliminodiacetic acid, glycol ether diamine tetraacetic acid, hydroxyethylene diamine triacetic acid, ethylene diamine orthohydroxyphenylacetic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, 1-hydroxyethylidene-1,1-diphosphonic acid,
N,N'-bis(2-hydroxybenzyl)ethylenediamine-N,N'-diacetic acid, catechol-3,4,6
-trisulfonic acid, catechol-3,5-disulfonic acid, 5-sulfosalicylic acid, 4-sulfosalicylic acid.

Among these chelating agents, preferably ethylenediaminetetraacetic acid, ethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, 1. 3-diaminopropanol tetrahedral acid, ethylenediamine-N, N, N', N'
-Tetrakis (methylenephosphonic acid) and hydroxyethyliminodiacetic acid are good.

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

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

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

As a development accelerator, Japanese Patent Publication No. 37-16088 and No. 3
No. 7-5987, No. 3B-7826, No. 44-123
No. 80, No. 45-9019 and U.S. Patent No. 3,813
, p-phenylenediamine compounds shown in JP-A-52-49829 and JP-A-50-15554, JP-A-Sho 50
-137726, Japanese Patent Publication No. 44-30074, Japanese Patent Publication No. 56-156826 and Japanese Patent Publication No. 52-43429, etc., and the quaternary ammonium salts disclosed in US Pat. 6
No. 10,122 and p described in No. 4,119゜462
-Aminophenols, U.S. Patent No. 2,494,903
No. 3,128,182, No. 4,230,796, No. 3.253919, Special Publication No. 41-11431,
U.S. Patent Nos. 2,482,546 and 2,596,92
Amine compounds described in No. 6 and No. 3,582,346, etc., Japanese Patent Publication No. 37-16088, No. 42-2520
No. 1, U.S. Patent No. 3,128,183, Special Publication No. 1973-
11431, 42-23883, and U.S. Pat. No. 3,532,501, and other 1-phenyl-3-pyrazolidones,
hydrazines, mesoionic compounds, ionic compounds,
Imidazole, 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.
．． 0d or less, more preferably all (not contained).

When it is not substantially contained, fluctuations in photographic properties during continuous processing, particularly increases in staining, are smaller, and more favorable results can be obtained.

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-
Nidropenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole, 2-
Representative examples include nitrogen-containing heterocyclic compounds such as thiazolyl-benzimidazole, 2-thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolizine, and adenine.

The color developer used in the present invention preferably contains a fluorescent whitening agent.
Diamino-2,2'-disulfostilbene compounds are preferred, and the amount added is 0 to 10 g/(, preferably 0.1
~6g/f.

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

The processing time of the color developer of the present invention is 10 seconds to 120 seconds,
Preferably, the effect of the present invention is significant in 20 seconds to 60 seconds. Further, the effects of the present invention are particularly remarkable when the treatment temperature is 33 to 45°C, preferably 36 to 40°C.

The amount of replenishment of color developer during continuous processing is 20 to 220 #d per liter of photosensitive material! , preferably from 25 to 160, particularly preferably from 30d to 110d, since the effects of the present invention can be effectively exhibited.

In addition, the color developer of the present invention has relatively superior performance in its liquid aperture ratio (air contact area (rrf)/liquid volume (cTl)) than combinations other than those of the present invention under any conditions. From the viewpoint of the stability of the developer, the liquid aperture ratio is preferably 0 to 0.1c+a-', and in continuous processing, it is practically 0.001cm-5 to 0.05CI+-'.
The range is preferably 0.002CII, more preferably 0.002CII
+-' ~0. 03cm-'.

Generally, when hydroxylamine etc. are used as a preservative, even if the aperture ratio of the color developer is reduced,
It is widely known that decomposition occurs due to heat or trace metals. 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 or used for a long period of time. Therefore, in this case, the smaller the liquid aperture ratio is, the more preferable it is, and the most preferable is 0 to 0.002 cm-'.

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

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

The bleach or bleach-fix solution 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 iodide (
For example, a rehalogenating agent such as ammonium iodide) may be included.

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, and water-soluble thioureas. These silver halide solubilizers can be used alone or in combination of two or more. It is also possible to use a special bleach-fix solution made of a combination of a fixing agent and a large amount of a halide such as potassium iodide as described in JP-A-55-155354. In the present invention, it is preferable to use thiosulfate, especially ammonium thiosulfate. The amount of fixing agent per IIl is preferably in the range of 0.3 to 2 mol, more preferably in the range of 0.5 to 1.0 mol. be.

The pH range of the bleach-fix solution or fixer solution in the present invention is as follows:
3 to 8 are preferred, and 4 to 7 are particularly preferred. p
If H is lower than this, the desilvering property will be improved, but the deterioration of the solution and the leucoization of the cyan dye will be promoted. On the other hand, if the pH is higher than this, 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.

The bleach-fix solution may also contain various other fluorescent brighteners, antifoaming agents, surfactants, and organic solvents such as polyvinylpyrrolidone and methanol.

The bleach-fix solution and fixer used in the present invention contain sulfites (e.g., sodium sulfite, potassium sulfite, ammonium sulfite, etc.) and bisulfites (e.g., ammonium bisulfite, sodium bisulfite, bisulfite, etc.) as preservatives. (e.g., potassium metabisulfite, etc.), metabisulfites (e.g., potassium metabisulfite, sodium metabisulfite, ammonium metabisulfite, etc.). These compounds are approximately 0 in terms of sulfite ion.
．． It is preferable to contain 02 to 0.50 mol/2,
More preferably, it is 0.04 to 0.40 mol/J2. 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 agent 5. A fluorescent brightener, chelating agent, antifungal agent, etc. may be added as necessary.

The bleach-fix solution 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 1M of photosensitive material.
30-250-1, preferably 40-150 d. Generally, an increase in staining and poor desilvering tend to occur as the amount of replenishment is reduced, but according to the present invention, the amount of replenishment of the bleach-fix solution can be reduced without causing such problems. Can be done.

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 varies widely depending 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 (number of stages), the replenishment method such as free flow or down flow, and various other conditions. Can be set to . 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 (J
our own of the 5ociety of
Motion Picture and Television
ion Engineers) Volume 64, p. 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. The problem arises. 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, cyabendazoles, and chlorinated sodium isocyanurate described in JP-A No. 57-8542, and other benzotriazoles, as well as ``Chemistry of antibacterial and antifungal agents'' by Hiroshi Horiguchi, are also available. ”,
It is also possible to use the disinfectants described in the Hygiene Technology Extra Section "Sterilization, Disinfection, and Antifungal Technology of Microorganisms" and the Japan Antibacterial and Antifungal Society's "Encyclopedia of Antibacterial and Antifungal Agents."

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 2 minutes.
A range of 30 seconds to 1 minute and 30 seconds at 40°C is selected.

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 5B-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-2-methyl-4
A stabilizing bath containing -isothiazolin-3-one, a bismuth compound, an ammonium compound, etc. is 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 leaves the final bath (generally water washing or stabilization tower).
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 above order, but they may be applied in a different order. Furthermore, an infrared-sensitive silver halide emulsion layer can be used in place of at least one of the above-mentioned emulsion layers. These photosensitive emulsion layers contain 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.

The halogen composition of the emulsion may be different or the same among the grains, but if an emulsion having the same halogen composition among the grains is used, it is easy to make the properties of each grain uniform. In addition, regarding the halogen composition distribution inside silver halide emulsion grains, there are grains with a so-called uniform structure in which the composition is the same in every part of the silver halide grain, and grains with a core inside the silver halide grain and a shell surrounding it. (Shell) [-layer or multiple layers] A particle with a so-called layered structure in which the halogen composition is different, or a structure having a non-layered portion with a different halogen composition inside or on the surface of the particle (if it is on the surface of the particle, the edge of the particle , a structure in which portions of different compositions are joined on a corner or surface) can be appropriately selected and used.

In order to obtain high sensitivity, it is more advantageous to use one of the latter than particles with a uniform structure, and it is also preferable from the viewpoint of pressure resistance. When silver halide grains have the above-mentioned structure, even if the boundaries between parts with different halogen compositions are clear boundaries, the boundaries may be unclear due to the formation of mixed crystals due to compositional differences. It is also possible to actively have continuous structural changes.

In high silver chloride emulsions, the silver bromide localized layer is formed in a layered or non-layered manner inside silver halide grains and/or in a layered or non-layered manner as described above.
Alternatively, those having a structure on the surface are preferable. The halogen composition of the localized layer is at least 1 in terms of silver bromide content.
It is preferably 0 mol%, and more preferably more than 20 mol%.

These localized layers can be located inside the grains or on the edges, corners, or surfaces of the grain surfaces, and one preferred example is one in which they are epitaxially grown on a part of the corner of the grains.

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

Furthermore, it is also effective to further increase the silver chloride content of the silver halide emulsion for the purpose of reducing the amount of replenishment of the 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 0.1μ to 2μ.

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, the above monodisperse emulsion may be blended in the same layer for the purpose of obtaining a wide latitude, or heavy N coating may be used. Preferably done.

The shape of silver halide grains contained in photographic emulsions is regular (cubic, tetradecahedral, or octahedral).
lar) those with crystal shapes, those with irregular crystal shapes such as spherical, plate-like, etc.
Alternatively, a composite form of these can be used. In the present invention, particles having the above-mentioned regular crystal form account for at least 50%, preferably at least 70%, and more preferably at least 70%. The content is 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 Pho by es
tographque (PaulMan Le 1
Publishing, 1967), Photo-gfaph! by G. F. Duffin. c Ea+ulsion C
he+n1sLry (published by Focal Press,
(1966), V. L., Zelikman eL.
by HakIng andCoaLing Photo
ograph<Emuldion (Focal P
It can be prepared using the method described in (Published by Res Inc., 1964). That is, any of the acidic method, neutral method, ammonia method, etc. may be used, and the method for reacting the soluble root salt with the soluble halogen salt may be any method such as one-sided mixing method, simultaneous mixing method, or a combination thereof. It is also possible to use a method (so-called back mixing method) in which zero particles that may be used are formed in an atmosphere containing excessive negative ions. As one form of the simultaneous mixing method, a method in which the pHg in the liquid phase in which silver halide is produced can be kept constant, that is, the so-called Chondrald double jet 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,
Ruthenium: Examples include salts or complex salts of 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 widely depending on the purpose, but is preferably 101 to 104 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 enhancement method, sulfur sensitization typified by the addition of unstable sulfur compounds, noble metal sensitization typified by gold sensitization, or reduction enhancement 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.
The one described on the 22nd right upper surface is preferably used.

Spectral enhancement 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.6 In the present invention, light in a wavelength range corresponding to the desired spectral sensitivity is absorbed. It is preferable to add a spectral sensitizing dye to achieve the desired color formation. Examples of spectral sensitizing dyes used in this case include 1e (by F. M. Harmer).
terocyclic compounds-Cyan
ine dies and related comp
ounds (John Wiley & 5ons (
Published by New York, London, 1964
2013). Examples of specific compounds and spectral enhancement methods are described in the above-mentioned Japanese Patent Application Laid-Open No. 6
2-215272 Publication Specification, page 22, upper right corner - 3rd page
The one described on page 8 is 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 light-sensitive material, the color light-sensitive material contains a yellow coupler, a magenta coupler, and a cyan coupler, which form yellow, magenta, and cyan colors, respectively, by camplisolysis with an oxidized product of an aromatic amine color developer. Usually used.

In the present invention, the following formulas (c-B, (
C-11), (M-1), (M-■) and (Y), the mechanism of action is unknown, but a certain amount of Bre, Cj! as mentioned above is used. When color development is performed using a color developer containing θ and further containing a compound of general formula (■) (preferably general formula (+-a)), the above-mentioned fluctuations in photographic properties can be further reduced.

- Formula (C-1) ll - Formula (C-I[) General formula (Y) H General formula (M-1) 1 Mathematical formula CM-I[) In general formulas (C-1) and (C-11) ,R8,
R1 and R4 represent a substituted or unsubstituted aliphatic, aromatic or heterocyclic group, R3, Rs and R6 represent a hydrogen atom, halogen atom, aliphatic group, aromatic group or acylamino group, R3 together with R2 -L may represent a group of nonmetallic atoms forming a nitrogen-containing 5- or 6-membered ring,
Yz represents a hydrogen atom or a group capable of leaving during a coupling reaction with an oxidized form of a developing agent, and n represents 0 or l.

RS in general formula (C-m) is preferably an aliphatic group, such as a methyl group, ethyl group, propyl group, butyl group, pentadecyl group, L-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 formula (C-1) or (c-n) 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 formula (C-1), when R3 and R2 do not form a ring, R2 is preferably a substituted or unsubstituted alkyl group, or an alkyl group, and particularly preferably a substituted aryloxy-substituted alkyl group. , R1 is preferably a hydrogen atom.

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

In formula 14 (C-II), R3 preferably has 2 to 2 carbon atoms.
It is a methyl group having 15 alkyl groups 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 formula (C-n), R3 is more preferably an alkyl group having 2 to 15 carbon atoms, particularly preferably an alkyl group having 2 to 4 carbon atoms.

- In the formula (C-n), hydrogen atoms and halogen atoms are preferred, with chlorine atoms and fluorine atoms being particularly preferred - In the formulas (C-I) and (C-n), preferred Y+ and Y2 are hydrogen atoms, respectively. atoms, halogen atoms, alkoxy groups, aryloxy groups, acyloxy groups, and sulfonamide groups.

In general formula (M-1), R1 and R9 represent an aryl group, R3 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.

Aryl group (preferably phenyl group) of R1 and R,
The substituents allowed for are the same as the substituents allowed for the substituent R, and two or more! When the iA group is present, it may be the same or different. Rw is preferably a hydrogen atom, a fatty acyl group, or a sulfonyl group, and particularly preferably a hydrogen atom.

Preferred Y is of the type Φ which leaves off with either a sulfur, oxygen or nitrogen atom, e.g. U.S. Pat.
．． Particularly preferred are sulfur atom dissociative types as described in No. 3SL892 and International Publication No. W088104795.

In the general formula (M-I[), R1° represents a hydrogen atom or a substituent, Y4 represents a hydrogen atom or a leaving group,
Particularly preferred are halogen atoms and arylthio groups, Za
SZb and Zc are methine, substituted methine, =N- or -
N) represents I-, 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, including when it is part of an aromatic ring* RIG or Y4
When forming a dimer or more multimer, Za, Zb
Alternatively, when Zc is a substituted methine, this also includes the case where the substituted methine forms a dimer or more multimer.

Among the pyrazoloazole couplers represented by the general formula (M-n), imidazo (1, 2-b) Preferred are pyrazoles,
U.S. Patent Section 4.540. Pyrazolo described in '654 (
1,5-b).(1,2,4))reazole is 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, European Patent Publication No. 226, It is preferred to use pyrazolotriazole couplers having an alkoxy group or an alkoxy group at the 6-position as described in No. 849, No. 294, and No. 785.

In the general formula (Y), R11 represents a halogen atom, an alkoxy group, a trifluoromethyl group, or an aryl group, R1< represents a hydrogen atom, a halogen atom, or an alkoxy group, A is -N) ICORI: l, (C -1), where RI3 and R14 each represent an alkyl group, an aryl group, or an acyl group eYs represents a leaving group The leaving group Y is preferably of the type that leaves off at either an oxygen atom or a nitrogen atom, and the leaving group Y leaves at a nitrogen atom is particularly preferred.

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

(C-4) H C4)! 9 (C-7) (C-S) (C-13) (C-14) (C-15) (C-16) zHs (C-9) (C-12) (C-17) (C- 18) (C-19) I (C-20) (C-21) (C-22) (M-4) (M-6) (M-1) (M-2) (M-3) (M -7) (M-8) I l H3 (Y-1) (Y-2-) (Y-3) υ■ (Y-4) (Y-7) (Y-8) (Y-5) ( Y-6) (Y-9) The couplers represented by the above formats (C-1) to (Y) are:
The amount of silver halide emulsion constituting the photosensitive layer 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, any number of known techniques can be used.Usually, the coupler can be added by an oil-in-water dispersion method known as the oil protection method9. After dissolving in a solvent, 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 distillation, noodle washing, ultrafiltration, or the like, and then mixed with the photographic emulsion.

The dispersion medium for such a coupler has a dielectric constant (25"C
) 2 to 20 and a high boiling point organic solvent and/or a water-insoluble polymer compound having a refractive index (25° C.) of 1.5 to 1.7.

As the high boiling point organic solvent, preferably the following general formula (A) ~
A high boiling point organic solvent represented by (E) is used. especially,
General formulas (C-1), (C■), (M-I), (M
Particular preference is given to couplers represented by -■) and (Y).

-Format (A) w.

Wffi-o-p=.

General formula (B) W+-Coo-Wz General formula (E) W+-0-11z (wherein, W, , W, and W are each substituted or unsubstituted alkyl group, cycloalkyl group, alkenyl group, aryl represents a group or a heterocyclic group, W4 is W,
represents OW or S-W, n is an integer from 1 to 5, and when n is 2 or more, W4 may be the same or different from each other; - In format (E), W and W2 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 other than formula (A) or E).
It can be used as long as it is a compound that is immiscible with water at temperatures above °C and is a good solvent for the coupler. The melting point of the high boiling point 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.
C or higher.

For details on these high boiling point organic solvents, please refer to JP-A-62
-215272 Publication Specification, page 137, lower right column ~ 14
It is written in the upper right column of page 4.

These couplers can also be synthesized with rhodapul latex polymers (
For example, the emulsion can be dispersed in an aqueous solution of a hydrophilic colloid by impregnating it with a polymer (eg, US Pat. No. 4,203,716) or by dissolving it in a water-insoluble but organic solvent-soluble polymer.

Homopolymers or copolymers described on pages 12 to 30 of International Publication No. WO 3 B100723 are preferably used, and acrylamide polymers are 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 antifoggant.

Various anti-fading agents can be used in the photosensitive material of the present invention. That is, hydroquinones, 6
-Hydroxychromans, 5-hydroxycoumarans,
Spirochromans, p-alkoxyphenols, hindered phenols centered on bisphenols, gallic acid derivatives, methylenedioxybenzenes, aminophenols, hindered amines, and silylation and alkylation of the phenolic hydroxyl groups of these compounds. Typical examples include ether or ester derivatives. Also, (bissalicylaldoximado)nickel complex and (bis-N,N dialkyldithiocarbamado)
Metal complexes such as nickel complexes can also be used.

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

Hydroquinones are disclosed in U.S. Patent 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. 3.982944, No. 4,430,42
No. 5, British Patent No. 1,363,921, U.S. Patent No. 2
, 710.801, 2.816,028, etc., and 6-hydroxychromans, 5-hydroxycoumarans, and spirochromans are disclosed in U.S. Patent No. 3.432.300.
No. 3,573,050, No. 3,574,62
No. 7, No. 3,698,909, No. 3,764,3
No. 37, JP-A No. 52-152225, spiroindanes are described in U.S. Patent No. 4,360,589, and p-alkoxyphenols are described in U.S. Patent No. 2,735,765.
No., British Patent No. 2,066.975, Japanese Unexamined Patent Publication No. 1983-1
No. 0539, Japanese Patent Publication No. 57-19765, etc., and hindered phenols are disclosed in U.S. Pat.
JP 52-72224, U.S. Patent No. 4,228,23
No. 5, U.S. Pat.
No. 32.886, Japanese Patent Publication No. 56-21144, etc., and hindered amines are disclosed in U.S. Patent No. 3,336,135,
No. 4,268,593, British patent cylinder 1.326,8
No. 89, No. 1,354,313, No. 1.410,
No. 846, JP 51-1420, JP 58-11
No. 4036, No. 59-53846, No. 59-78
No. 344, etc., and metal complexes are disclosed in U.S. Pat. No. 4,050,9.
No. 38, No. 4.241,155, British patent cylinder 2.0
27.731 (A), etc., respectively. The desired properties of these compounds can be achieved by co-emulsifying them with the corresponding color couplers and adding them to the photosensitive layer, usually in an amount of 5 to 100% by weight. In order to prevent the cyan dye image from deteriorating 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 ultraviolet absorbers, aryl group-substituted benzo) IJ azole compounds (e.g., U.S. Pat. No. 3,533
, 794), 4-thiazolidone compounds (
For example, U.S. Patent Nos. 3,314°794 and 3,35
2,681), benzophenone compounds (
For example, those described in JP-A-46-2784), cinnamate ester compounds (for example, U.S. Pat. No. 3,705.80)
No. 5, U.S. Pat. No. 3,707,395), butadiene compounds (as described in U.S. Pat. No. 4,045,229), or benzoxidole compounds (e.g., U.S. Pat. No. 3,406,070). No. 3,677.672
No. 4,271,307) can be used. An ultraviolet absorbing coupler (for example, an α-naphthol cyan dye-forming coupler) or an ultraviolet absorbing polymer may be used. These ultraviolet absorbers may be mordanted in specific layers.

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

In addition to the above-mentioned couplers, it is particularly preferable to use the following compounds. Particularly preferred is the combination with a pyrazoloazole coupler.

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

A preferred compound (F) has a second-order reaction rate constant Kg (in trioctyl phosphate at 80°C) with p-anisidine of 1. Oj2/mols e c ~I
It is a compound that reacts in the range of X 10-'j2/mol sec. Incidentally, the second-order reaction rate constant can be measured by the method described in JP-A-63-158545.

K! When is larger than this range, the compound itself becomes unstable and may react with gelatin or water and decompose. On the other hand, if K2 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 format (Fl) or (Flu).

General formula (FI) R, -(A) , l -X General formula (FII) Rt -C=Y In the formula, Rt and Rz each represent an aliphatic group, an aromatic group, or a heterocyclic group. n represents 1 or O. A represents a group that reacts with the aromatic amine developer to form a chemical bond, and X represents a group that reacts with the aromatic amine developer and leaves. B represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an acyl group, or a sulfonyl group, and Y promotes the addition of an aromatic amine developing agent to the compound of general formula (Fn). represents a group that Here, R3 and X, Y and Rt, or B may be bonded to each other to form a cyclic structure.

Among the methods of chemically bonding with the residual aromatic amine developing agent, the typical ones are substitution reaction and addition reaction.

For specific examples of compounds represented by general formulas (Fl) and (FIG), see JP-A-63-158545 and JP-A-62-
283338, European Patent Publication No. 298321, European Patent Publication No. 27
Those described in specifications such as No. 7589 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 -format (Gl ).

General formula (G-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 a photosensitive material to release a nucleophilic group. Compounds represented by the -form (Gl), which represent a group, have Z as Pearson's nucleophilicity "CIl, I value (R, G,
Am.

CheIl, Soc, 90. 319 (196
B)) is preferably a group having 5 or more, or a group derived therefrom.

Specific examples of compounds represented by the general formula (C,I) are disclosed in European Patent Publication No. 255722 and Japanese Patent Application Laid-Open No. 1986-14
No. 3048, No. 62-229145, Patent Application No. 1983-1
Those described in European Patent Publication No. 36724, European Patent Publication No. 62-214681, European Patent Publication No. 298321, European Patent Publication 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 a hydrophilic dye or a dye that becomes water-soluble through photographic processing as a filter dye in the hydrophilic colloid layer or for various purposes such as preventing irradiation or halation. You can leave it there. Such dyes include oxonol dyes, hemioxonol 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 The Macromolecular Chemistry of Gelatin, written by Arthur Weiss. Press, published in 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 materials, and reflective supports can be used. For purposes of the present invention, the use of reflective supports is more preferred.

The ``reflective support j'' used in the present invention refers to one that enhances the reflectivity and makes the dye image formed in the silver halide emulsion layer clear. Examples include 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 metal may be aluminum, tin, silver, magnesium, or an alloy thereof, and 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 the metal onto another substrate. Preferably, a layer of water-resistant resin, particularly thermoplastic resin, is provided on the metal surface. It is preferable to provide an antistatic layer on the side of the support of the present invention opposite to the side having the metal surface. For details of such a support, 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 calculated by dividing the observed area into adjoining unit areas of 68 m x 6 μm, and dividing the area of fine particles projected onto that unit area. It can be determined by measuring the occupied area ratio (%) (Ri). The coefficient of variation of the occupied area ratio (%) can be determined by the ratio s/R of the standard deviation S of Ri to the average value (R) of Ri. The number (n) of target unit areas is preferably 6 or more. Therefore, the coefficient of variation s/R can be found as follows.

In the present invention, the coefficient of variation of the occupied area ratio (%) of the pigment fine particles is preferably 0.15 or less, particularly 0.12 or less. If it is 0.08 or less, the dispersibility of the particles can be said to be "substantially uniform."

(Example) Examples of the present invention will be specifically shown below, but the present invention is not limited thereto.

Example 1 A multilayer color photographic paper having the following N configuration was produced on a paper support laminated on both sides with polyethylene. 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 antifading agent (Cpd-1), 150 cc of ethyl acetate, 1.0 cc of solvent (Solv-3), and 1.0 cc of solvent (Solv-3).
4) Add and dissolve 3.0 cc, add this solution to 450 cc of a 10% aqueous gelatin solution containing sodium dodecylbenzenesulfonate, and disperse with an ultrasonic homogenizer. A first layer coating solution was prepared by mixing and melting the mixture into 420 g of a silver chlorobromide emulsion (silver bromide 0.7 mol %) containing a silver bromide. The coating solutions for the second to seventh layers were also made of steel in the same manner as the coating solution for the first layer.

1,2-bis(vinylsulfonyl)ethane was used as the gelatin hardening agent for each layer.

The following spectral sensitizing dyes were used in each layer.

Blue-sensitive emulsion layer; anhydro-5-5°-chloro-3,3
'-Disulfoethylthiacyanine hydroxide green malignant emulsion layer; anhydro-9-ethyl-5,5'-diphenyl-3,3'-disul,foethyloxacarpocyanine hydroxide red malignant emulsion layer; 3,3'- diethyl-5-methoxy-9
, 9'-(2,2'-dimethyl-1,3-propano)thiatribocyanine yossite.The following substances were also used as stabilizers for each emulsion layer.

was used.

[3-carboxy-5-hydroxy-4-(3(3-carboxy-5-oxo-1-(25-disulfonatophenyl)-2-pyrazolin-4-ylidene)-1-propenyl)-1- pyrazolyl]benzene-2,5-disulfonate disodium salt N,N'-(4,8-dihydroxy-9,10-dioxo-3,7-cissulfonato anthracene-1,5-diyl)bis(aminomethanesulfonate) nate)-tetrasodium salt [3-cyano-5-hydroxy-4-(3-(3-cyano-5-oxo-1-(4-sulfona, tophenyl)-
2-pyrazolin-4-ylidene)-1-pentanyl)-
X-pyrazolyl] Hensen-4-sulfonato sodium salt and the following as anti-irradiation dye (layer structure) The composition of each layer is shown below. The numbers represent the coating amount (g/n()).The silver halide emulsion represents the coating amount in terms of silver.

Support Paper support laminated on both sides with polyethylene First layer (blue sensitive layer) Silver halide emulsion (AgBr: 0.7 mol% cubic, average grain size 0.9μ) Gelatin yellow coupler (ExY) Antifading agent (Cpd- 1) Capacity (SOIV 3) 7 Volume (SOIV 4) Ol 29 Second layer (color mixing prevention layer) Gelatin 0, 80 Color mixing prevention agent (Cpd-2) Capacity (Solv 1) Solvent (3o1v 2) 0. 055 0, 03 0.015 Tertiary N (green sensitive layer) Silver halide emulsion (AgBr: 017 mol% cubic grain size 0545μ) Gelatin magenta coupler (ExM) Antifading agent (Cpd-3) Antifading agent (Cpd- 4) Solvent (Solv-1) Solvent (3o1v 2) 0, 28 Fourth N (color mixing prevention N) Gelatin color mixing prevention agent (Cpd-2) Ultraviolet absorber (UV-1) Ultraviolet absorber (UV-2) Capacity (Solv-1) 0,05 1 volume (SOIV-2) 0,05 Seventh layer (protective layer) Gelatin 1,07 Fifth layer (red-sensitive layer) Silver halide emulsion (AgBr: 2 mol% Cubic , particle size 0.5μ) Gelatin cyan coupler (ExC-1) Cyan coupler (ExC-2) Antifading agent (Cpd-1) ) Capacity (Solv-1) Solv. 1 medium (Solv-2) 0, 19 Sixth N (Ultraviolet absorption N) Gelatin ultraviolet absorber (UV-1) Ultraviolet absorber (UV-2) Capacity (Solv-1) Capacity (Solv-2) (Ex x Y) Yellow coupler α-pivalyl α -(3-benzyl-1-hydantoynyl)-2-chloro-5[β-dodecylsulfonyl)-butyramido]acetanilide (ExM) magenta coupler 1-(2,4,6-drichlorophenyl-3[2-chloro- 5(3-octadecenylsuccinimide)anilino]-5-pyrazolone (ExC-1) Cyan coupler 2-pentafluorobenzamide-4-chloro-5[2
-(2,4-di-tert-amylphenoxy)-3-
Methylbutyramidophenol (ExC-2) Cyan coupler 2,4-dichloro-3-methyl-6-[α-(2,4-
Di-tert-amylphenoxy)butylamide] phenol (Cpd-1) Anti-fade agent 2.5-Di-tert-amylphenyl-3+5-di-tert-butylhydroxybenzoate (Cpd-2) Color mixing inhibitor 2.5-di-tert- Octylhydroquinone (Cpd-3) Anti-fade agent 1.4-Di-tart-ami7L/-2,5-dioctyloxybenzene (Cpd-4) Anti-fade agent 2.2'-Methylenebis(4-methyl-6-Lert −
butylphenol) (Cpd-5) 1)-(p-)luenesulfonamide)-phenyl-dodecane (Solv-3) Solvent di(i-nonyl)phthalate (3o1v 4) Solvent N,N-diethylcarbonamidomethoxy-2゜4-di-t-amylbenzene (UV-1) UV absorber 2-(2-hydroxy-3,5-di-tert-amylphenyl)benzotriazole (UV-2) UV absorber 2-(2-hydroxy -3,5-di-tert-butylphenyl)benzotriazole (Solv-1) Solvent di(2-ethylhexyl) phthalate (Solv-2) Solvent dibutyl phthalate The sample obtained as above was used as A. Sample A
Samples B-H were prepared in the same manner as above except that the halogen composition of the emulsion was changed as shown in Table 1.

Table 1 In order to investigate the photographic properties of these coated samples, the following experiments were conducted.

First, using a sensitometer (FWH model manufactured by Fuji Photo Film Co., Ltd., color temperature of light source 3200K) on the coated sample,
Provided gradation exposure for sensitometry. The exposure at this time was carried out at an exposure time of 1/10 seconds and an exposure amount of 250 CMS.

The coating sample was subjected to the following treatment process and the following treatment composition,
Processed using an automatic developing machine. However, the composition of the color developer was changed as shown in Table 2.

Body”Lnmata color development Bleach fixing 3 Rinse ■ 3 Rinse ■ 3 Rinse ■ 3 Drying 7 Single dish once 38℃ 45 seconds 0-36℃ 45 seconds 0-37℃ 30 seconds 0-37℃ 30 seconds 0~37℃　　30 seconds 0~80℃ 60 seconds The composition of each treatment liquid is as follows.

Left I Eriri Statue Gyokusui 80
0 m j! Ethylenediamine-N,N.

N,N-tetramethylenephosphonic acid 3.0g Organic preservative A
(1-1) 0. 03 mol Sodium chloride See Table 2 Potassium bromide
See Table 2 Potassium carbonate
25g N-ethyl-N-(β-mecnsulfonamidoethyl)-3-methyl-4-aminoaniline sulfate 5.0g triethanolamine 10.0g Fluorescent brightener (4,4'
- Diaminostilbene type) Add 2.0g water to 1000mj! pH (25℃)
10.05j-Wataru 13L night water Ammonium thiosulfate (70%) Sodium sulfite Iron ethylenediaminetetraacetate (I [I) Ammonium Ethylenediaminetetraacetic acid disodium Ammonium Bromide Glacial acetic acid water was added to pH (25°C) 4 0 0 mj! 100mj! 7g 5g g 0g g 1 0 0 0ml t 5,40 u''≦(Ion exchange water (calcium, magnesium each 31)E
) m or less) The maximum densities (Dmax) of blue (B), green (G), and red (R) in the above sensitometry were measured using a Macbeth densitometer, and the results are shown in Table 2.

Furthermore, using a photosensitive needle (FW manufactured by Fuji Photo Film Co., Ltd.) (color temperature of mold and light source 3200K),
Uniform exposure to gray light was applied, and processing was performed in the same manner as the sensitometry described above to evaluate sensitized muscles. Evaluation criteria is 4
The stages are shown below.

Sensitized muscle evaluation sample L O0c11! Number of sensitizing muscles in (10cm x 10C11) As can be seen from ■ to ■, the maximum concentration is high and the generation of sensitized muscles is prevented.

In processing steps ■, @~O, the generation of sensitizing muscles is prevented, but the maximum density is low and the purpose of the present invention, which is rapid development processing, cannot be achieved. Processing steps ■, ■, [phase] ,
In case (2), although the maximum concentration is high, sensitizing muscles occur and the object of the present invention cannot be achieved.

As shown in processing steps Φ~■, ■, and ■, when a high silver chloride photosensitive material is used and the processing solution of the present invention is used, an effect of preventing the generation of sensitizing muscles is observed, but in processing steps 0~ As shown in Figure O, when a photosensitive material with a silver chloride content lower than 80 mol% is used, no effect of preventing the development of sensitizing streaks is observed even when the developer of the present invention is used. This shows that the combination of bromide ion concentration and chloride ion concentration specifically prevents sensitizing streaks in high silver chloride light-sensitive materials.

Example 2 A multilayer color photographic paper having the layer structure shown below was prepared on a paper support laminated on both sides with polyethylene. The coating solution was prepared as follows.

Preparation of No.-N Coating Solution Yellow coupler (ExY) 19.1 g, color image stabilizer (Cpd-1) 4.4 g and color image stabilizer (Cpd-1)
7) Add 27.2 cc of ethyl acetate and solvent (S
Add and dissolve 8.2g of olv-3), and
was emulsified and dispersed in 185 cc of 10% dodecylbenzenesulfone. On the other hand, a silver chlorobromide emulsion (cubic with a cubic average grain size of 0.85μ and a grain size distribution coefficient of variation of 0.07; containing 1.0 mol% of silver bromide locally on a part of the grain surface) was prepared as follows. Each of the two venetral aggravating pigments shown in Fig. A sample was prepared in which sulfur sensitization was performed after adding OXlo-' moles. The above emulsified dispersion and this emulsion were mixed and dissolved to prepare a first layer coating solution having the composition shown below. Coating solutions for the second to seventh layers were also prepared in the same manner as the coating solution for the first layer.

The gelatin hardening agent for each layer is 1-oxy-3゜5-
Dichloro-5-1-riazine sodium salt was used.

The following spectral sensitizing dyes were used in each layer.

Blue-sensitive emulsion layer Green-sensitive emulsion layer (4.0 x 10-' mol per 1 mol of halogenated i)
and (halogenated! per II mole?, 0X10-' mole)
Red-sensitive emulsion layer 5 (hSOsH-N(Ctlls)* (2.0XI of each of the above two types per mol of silver halide)
O-' mole) (1.2X10-' mole per mole of S halide)
For the red-sensitive emulsion layer, halogenate the following compounds!
2.6×10 −″ moles were added per mole of ffl.

and also 1-(5-methylureidophenyl)5-mercaptotetrazole per mole of silver halide for the blue-sensitive emulsion layer, green-sensitive emulsion layer, and red-sensitive emulsion layer, respectively.
5X10-'mol, 7.7xto-'mol, 2.5X1
0-'mol was added.

The following dyes are added to the emulsion layer to prevent irradiation.
Added.

(Layer structure) The composition of each layer is shown below. The numbers are coating ffi (g/n (
) represents the silver halide emulsion coating amount in terms of silver.

Support Polyethylene laminate paper [The polyethylene on the first layer side contains a white pigment (TiOz) and a blue dye (ulmarine blue)] Layer - (blue sensitive layer) The above-mentioned silver chlorobromide emulsion gelatin yellow coupler (ExY) 0 , 30 1, 86 0, 82 Color image stabilizer (Cpd-1) Color image stabilizer (Cpd-7) Capacity (Solv-3) Second layer (color mixing prevention layer) Gelatin color mixing prevention agent (Cpd-5) Solvent (3o1v-1) Solvent (Solv-4) Tertiary N (green sensitive layer) Silver chlorobromide emulsion (grain size 0.40μ, cubic with coefficient of variation 0.09, 1 mol% of silver bromide applied to the grain surface) gelatin magenta coupler (xM) color image stabilizer (Cpd-3) color image stabilizer (Cpd-4) color image stabilizer (Cpd-8) 0,19 solvent ( SolV-2) 0, 03 0, 35 Fourth layer (ultraviolet absorption layer) Gelatin ultraviolet absorber (UV-1) Color mixing inhibitor (Cpd-5) Solvent (Solv-5) 0, 36 Fifth layer (red sensitivity N) Silver chlorobromide emulsion (cubic grain size 0.36μ, coefficient of variation 0.11, containing 1.6 mol% silver bromide locally on a part of the grain surface) Gelatin cyan coupler (ExC ) Color image stabilizer (Cpd-6) Color image stabilizer (Cpd-7) Color image stabilizer (Cpd-9) Solvent (Solv-6) Sixth calendar (ultraviolet absorbing layer) Gelatin ultraviolet absorber (UV-1 ) Color mixing inhibitor (Cpd-5) Solvent (Solv-5) (ExM) Magenta coupler seventh layer (protective layer) Acrylic modified copolymer of gelatin polyvinyl alcohol (denaturation degree 17%) Liquid paraffin (Ex x Y) Yellow coupler l.

Ol (Ex
:6 Mixture (weight ratio) (cpa ■) Color image stabilizer (Cpd-3) Color image stabilizer (Cpd-4) Color image stabilizer (Cpd Color mixture prevention agent (Cpd) Color image stabilizer (UV-1) Ultraviolet light 4:2:4 mixture (weight ratio) of absorbent (3o1v1) solvent (cpa 2:4;4 mixture (weight ratio) of color image stabilizer) (Cpd color image stabilizer 1 ← HI -CH- 1 CON HCaH*(t) Average molecular weight (Cpd-8) Color image stabilizer H3 CH Co(3o1v-2) 1:1 mixture (volume ratio) of 8 solvents (Solv-3) Solvent (3o1v-4) Solvent (Solv -5) Solvent COOCeH+q (CHz)*COOCeHlt The sample obtained as above was designated as F.

After the sample F was imagewise exposed, continuous processing (running test) was performed using an automatic paper processing machine using the following processing steps and processing composition until twice the tank capacity for color development was replenished.

The composition of the color developer was changed as shown in Table 3.

Toyoda and Inu 1゛" color development 36℃ 45 seconds 109mjl! 4I
2 Bleach fixing 30-36℃ 45 seconds 215mj2
46 Stable ■ 30~37℃ 20 seconds
212 Stable■ 30~37℃ 20 seconds
21 Stable■ 30~37℃ 20 seconds 364mj!
21 Drying 70-85° C. 60 seconds * Replenishment amount per 1 M of irradiating material (3 tank countercurrent method was used to stabilize ■-■.) The composition of each treatment solution is as follows.

Water 800mj! 800mj! Ethylenediaminetetraacetic acid 5.6-cyhydroxybenzene-1.2.4 Trisulfonic acid Triethanolamine Sodium chloride Potassium bromide Potassium carbonate N-ethyl-N-(β-methanesulfonamidoethyl)-3-methyl-4- Aminoaniline sulfate organic preservative A (see Table 3) Sodium sulfite fluorescent brightener (Sumitomo Chemical HrTEX-4) Add water to pH (25°C) 5.0 g 5.0 g 0.3 g 0.3 g 8.0 g 8.0 g See Table 3 See Table 3 25 g 25 g 5.0 g 9.5 g 0.03o+ol 0.05mo10.1g
0.2g 1.0g2.5g 1000ml Look i! 10.05
10.60 Water
400s+j! Ammonium thiosulfate (70%) 100mA Sodium sulfite 17g Iron ethylenediaminetetraacetate (I[l) Ammonium 55g Disodium ethylenediaminetetraacetate 5g Glacial acetic acid 9g Add water
1000m12pH (25℃)
5.40 Fixed decoy (tank liquid and auxiliary liquid are the same) Formalin (37%) Formalin-sulfite adduct 5-chloro-2-methyl-4-isothiazolin-3-one 2-methyl-4-isothiaprisole 3 -on copper sulfate 0.1g 0.7g 0.02g 0.01g 0. 005g ammonia water (28%) Add 2.0g water to 1000mlIlp100O
C) 4.0 Note that the replenisher concentration was set so that the chlorine ion concentration and bromide ion concentration of the developer solution were maintained at the tank solution concentration from the start to the end of the running process.

Using a sensitometer (FWH model manufactured by Fuji Photo Film Co., Ltd., color temperature of light source 3200K), 2 m1 (s light) was applied to the coated sample for sensitometry.The exposure at this time was 1/lO. The exposure time was 250 CMS and the exposure amount was 250 CMS.

The sensitometry is processed at the start and end of the running test, and the red color at the start of the run (
The maximum density change (ΔD max) of RL) and the amount of change in gradation (density difference from the point representing density 1.5 to the density point on the high exposure side of 0°3 in AogE) were measured using a Macbeth densitometer. The results are shown in Table 3.

Furthermore, at the end of the run, the muscle aggravation was evaluated in the same manner as in Example-1 using the above-mentioned Fufu sample. The evaluation criteria are in four stages and are shown below.

Evaluation of sensitized muscles Sample 100ctA (10cmx Number of aggravated muscles in 10cm) 0 pieces 1-2 bottles 3-5 pieces 6 or more The evaluation results are shown in Table 3.

According to Table 3, the processing step ■ processed with the developer of the present invention
As shown in ~ ■, the maximum density of the cyan coloring layer (RL) is high, the maximum density and gradation change due to running are small, and the effect of preventing the development of sensitized muscles is high, resulting in good results. Obtained.

As shown in Processing Process ■, when bromide ions and chloride ions are in the concentration range of the present invention and no preservative is added to the developing agent, the maximum density is high, but the maximum density gradation decreases significantly due to running. Also, the pressure aggravating muscles are significantly worse after running. It is clear that a preservative for the developing agent is required.

As shown in processing steps ■ to ■, even if the bromide ion and chloride ion concentration is within the concentration range of the present invention, if the preservative for the developing agent is a compound other than the present invention, the maximum concentration will be low and it will be difficult to run. The accompanying maximum density change and gradation change are significant, and furthermore, the effect of preventing muscle aggravation is low, and the object of the present invention cannot be achieved.

As shown in treatment steps O to 0, when the concentration of chloride ions or bromide ions is higher than the concentration of the present invention, sensitized muscle generation is almost suppressed, but the maximum concentration is reduced. Furthermore, a new fact has been discovered that when the bromide ion concentration is high, the cyan coloring layer (RL) becomes darker with running, and the object of the present invention cannot be achieved.

Example 3 A multilayer color photographic paper having the layer structure shown below was prepared on a paper support laminated on both sides with polyethylene. The coating solution was prepared as follows.

No.-N Coating Solution Preparation Yellow coupler (ExY) 19.1g, color image stabilizer (Cpd-1) 4.4g and color image stabilizer (Cpd-7)
) to 0.7 g of ethyl acetate and solvent (So
l v-3) 8.2g was added and dissolved, and this solution was diluted to 10%
The mixture was emulsified and dispersed in 185 cc of a 10% gelatin aqueous solution containing 1 cc of sodium dodecylbenzenesulfonate. On the other hand, bulk silver bromide emulsion (cubic average grain size 0.88μ
, grain size distribution coefficient of variation 0.08, containing 0.2 mol% silver bromide on the grain surface) were added with 2.0 x 10-' mol of each of the following blue-sensitive sensitizing dyes per mol of silver, and then sulfur-sensitized. A textured product was prepared. The above emulsified dispersion and this preparation were mixed and dissolved to prepare a first layer coating solution having the composition 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. The gelatin hardening agent for each layer is 1-oxy-3,5-dichloro-5
- Triazine sodium salt was used.

The following spectral sensitizing dyes were used in each layer.

Blue-sensitive emulsion layer Green-sensitive emulsion layer (halogenated! 4.0 x 10-' mol per 1 mol)
and 5O:+H-N(Cdls)s (7.0X10-' mol per 1 mol of halogenated oct)
Red-sensitive emulsion layer 5OJ-N(C2Hs)s (0.9X10-' mol per 1 mol of halogenated i)
(2.0 x 10 mol each per mol of silver halide)
For the red-sensitive emulsion layer, the following compounds were added at 2.6 x 10-' moles per mole of halo and silvergenide.

Further, for the blue-sensitive emulsion layer, the green-sensitive emulsion layer, and the red-sensitive emulsion layer, 1-(5-methylureidophenyl)-5-mercaptotetrazole was added at 8.5 x 10-' mol per mol of halogenated i, and 7. 7XIO-'mol, 2.5
X10-' moles were added.

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

50gK (layer structure) The composition of each layer is shown below. Paint the numbers! (g/rrf
) represents. The silver halide emulsion represents the coated amount in terms of silver.

Support polyethylene laminate paper [The polyethylene on the first layer side contains a white pigment (TiOz) and a bluish dye (ulmarine blue)] Part-F! (Blue-sensitive layer) Silver chlorobromide emulsion 0.30 Gelatin 1.86 Yellow coupler (ExY) 0.82 Color image stabilizer (Cpd-
1) 0.19 solvent (Solv-3) Color image stabilizer (Cpd-7) Second N (color mixing prevention layer) Gelatin color mixing prevention agent (Cpd-5) Capacity (Solv-1) Solvent (Solv-4) Third N (green sensitive layer) Silver chlorobromide emulsion (1:3 mixture (Ag mole ratio) of one with a cubic average grain size of 0.55μ and one with a cubic average grain size of 0.39μ).

Coefficient of variation of particle size distribution 0.10, 0.08° AgBr O, 8 mol% grains localized on the surface of the child.

gelatin Magenta coupler (ExM) Color image stabilizer (Cpd-3) Color image stabilizer (Cpd-8) 0, 35 0,06 0, 12 Color image stabilizer (Cpd-9) Solvent (Solv 2) Fourth N (ultraviolet absorption layer) gelatin Ultraviolet absorber (UV-1) Color mixing inhibitor (Cpd-5) Solvent (3o1v 5) Fifth layer (red sensitive layer) Silver chlorobromide emulsion (cubic average grain One with a size of 0.58μ, 1 = 4 mixture of 0.45μ (Ag molar ratio).

Coefficient of variation of particle size distribution 0.09.0.11゜ Granules containing 0.6 mol% of AgBr localized on a part of the child's surface Ta.

gelatin Cyan coupler (E x C) Color image stabilizer (Cpd-6) 0,03 0,54 0, 23 1, 34 0, 32 0, 17 Color image stabilizer (Cpd-10) Oo color image stabilizer (Cpd-7) 0° Solvent (3o1v-6) 0° sixth layer (UV absorption layer) gelatin 0, 53 UV absorber (tJV-1) 0° Color mixing inhibitor (Cpd-5) 0° Solvent (Solv-5) 0° Seventh layer (protective layer) gelatin 1, polyvinyl alcohol acrylic 0° modified copolymer (denaturation degree 17%) liquid paraffin 0° (E x Y) yellow coupler (Cpd-1) Color image stabilizer (Cpd-3) color image stabilizer (Cpd-5> Color mixing prevention agent H (ExM) magenta coupler (ExC) cyan coupler C! R=　CzHs Ca Hq CI! .

2:4:4 mixture (Cpd-6) 2:4:4 mixture (weight ratio) of color image stabilizer (Cpd-7) Color image stabilizer -← HZ -CH-Masushita CON) (CaH9 (Ni) Average molecular weight 60° (Cpd-8) Color image stabilizer (Cpd) Color image stabilizer (Solv-1) solvent (Cpd 10) 2:1 mixture of color image stabilizer (Solv-2) solvent ( Capacity ratio) (Solv-3>Solvent (UV-1) Ultraviolet absorber (3o1v-4) solvent: 2:4 mixture (weight ratio) (Solv 5) Solvent C00CaH+t (CHz)s 000CIIH1? (5o1v-6) Solvent The sample obtained in the above manner is set to 0th order as G, and trial 1
Same as 4G, except that each emulsion layer is coated i&1fi.
Samples G to K were prepared by changing t as shown in Table 4.

Table 4 After imagewise exposure of the above sample G-K, continuous processing (running test) was carried out using a paper processing machine in the following processing steps until twice the tank capacity of the color developer was replenished.

Mutual cooperation once! Plate and left 11'' Publisher 1 color development 38'C 45 seconds See Table 5, B bleach fixing 3
0~36°C 45 seconds 61m7!41Wash ■ 30
～37℃ 30 seconds 21Wash■ 30～
37℃ 30 seconds 21Wash ■ 30-3
7℃ 30 seconds 364mA 24 Dry 70
~85° C. 60 seconds *Amount of replenishment per 1 d of irradiating material The composition of each treatment solution is as follows.

Sadan Erli Yingketsu [tank liquid] Water 80
0mj! Ethylenediamine-N, N, 3.
ogN',N''-tetramethidinephosphonic acid triethanolamine sodium chloride potassium bromide potassium carbonate N-ethyl-N-(β-methanesulfonamidoethyl)-3-methyl-4-aminoaniline sulfate organic preservative A (1-1) Fluorescent brightener (Sumitomo Chemical Weak 1117EX-4') Add water 1) H (25°C) 8.0 g See Table 5 See Table 5 5 g 5.0 g 0.03 mo1 1.0g 1 0 0 0nA 10.05 4 liters 1 basket [tank liquid] Water 40
0+wj! Thioroffi lit ammonium (70%
) 1001m! ammonium sulfite
38g Iron ethylenediaminetetraacetate (f[[) Ammonium 55g Disodium ethylenediaminetetraacetate 5g Glacial acetic acid
Add 9g water
10100O! 1) H (25℃>
5.40 [Replenishment solution] 2.5 times concentrated solution of tank solution Washing solution (tank solution and replenishment solution are the same) Ion exchange water (calcium and magnesium are 3p each)
pm or less) In addition, for color developing solution, bleach-fixing solution, and washing solution,
Distilled water was added in the amount of evaporated water, and continuous processing was performed while correcting for evaporation concentration.

Using a sensitometer (FWH model manufactured by Fuji Photo Film Co., Ltd., color temperature of light source 3200 K) on the school cloth sample,
Provided gradation exposure for sensitometry. The exposure at this time was carried out at an exposure time of 1/10 seconds and an exposure amount of 250 CMS.

The sensitometry is processed at the start and end of the running test, and the red color at the start of the run (
RL) maximum density change (ΔDmax) and gradation (density 1
．． The amount of change in the density difference (from the point representing 5 to the density point on the high exposure side of 0.3 in logE) was measured using a Macbeth densitometer, and the results are shown in Table 5.

Furthermore, at the end of the run, the aggravated muscles were evaluated in the same manner as in Example 1 using the above applied sample. The evaluation criteria are in four stages and are shown below.

Evaluation of aggravated muscles Sample 100c+++ (10cmX
Number of aggravated muscles in 10 cm) 0 0 △ 1-2 × 3-5 × × 6 or more The evaluation results are shown in Table 5.

According to Table 5, as shown in processing steps ■ to ■, when processed with the developer of the present invention (■ to
L) had a high maximum density, little change in maximum density and gradation due to running, and was furthermore highly effective in preventing the development of sensitized muscles, giving good results. Processing step (2) has a lower concentration of chloride ions and bromide ions than the present invention, and compared to processing step (2) of the present invention, the generation of sensitized muscles is significant, so it is not possible to achieve the purpose of the present invention. Recognize. Processing process■
, ■ has a higher concentration of chloride ions and bromide ions than the present invention, and compared to the treatment process ■ of the present invention, the cyan color development J
It can be seen that the maximum density of ffl(RL) is low, and the maximum density and gradation change due to running are significant, so that the object of the present invention is not achieved.

Furthermore, according to the processing steps (1) to (2), the chloride ion concentration in the developer and the bromide ion Q7j1.
The degree is 4 X I O-5 to I X 10-' respectively.
More favorable results were obtained in terms of maximum density and gradation change accompanying running when mol/β was 5 x 10 - 5 x 10 -' mol/l.

Furthermore, according to processing step (1) and [phase] to @, in the present invention, when the coating silver amount of the photosensitive material is 0.8 g/rrr or less, the maximum density and gradation changes due to running are ,
It can be seen that it is preferable to prevent the generation of sensitized muscles, and it is particularly preferable that the amount is 0.05g10f or less.

Example-4 Same as Example-3, except that in the treatment step (■),
I-2, 1-3, ■- in place of I-1 of organic preservative A
When using 12, ■-17, ■-36, l-53,
Good results were obtained in the same manner.

Example 5 A running test was conducted in the same manner as in Example 3, except that the developer was changed in the processing step (①) as follows.

The results are shown in Table 6.

Processing process 1 time Plate color development 39°C 45 seconds Bleach fixing 30-36°C 45 seconds stable ■ 30-37'C 20 seconds stable ■ 30-37°C 20 seconds stable ■ 30-37'C 20 seconds drying 70-85° C60 seconds* Replenishment amount per photosensitive material (3 tank countercurrent system from stable ■ to ■) The composition of each processing solution is as follows.

1-stroke 'JL' 4 convex IJL 35d 4j2 215d 4f 364d 242 Water ethylenediaminetetraacetic acid 5.6-cyhydroxybenzene-1.2.4-trisulfonic acid Triethanolamine Sodium chloride Potassium bromide 00m 00d 5.0g 5 .0g 0.6g 0.6g 11.0 g 11.0 g See Table 6 See Table 6 Potassium carbonate N-ethyl-N-(β methanesulfonamidoethyl)-3-methyl-4-aminoaniline sulfate Organic preservative A (see Table 6) Sodium sulfite fluorescent brightener (WRITEX-4 manufactured by Sumitomo Chemical) 1.0 g
Add 5.5 g water and 10
00I111000dpH (25°C)
10.05 10.90 The bleach-fix solution, the tank solution for the washing solution, and the replenisher were the same as in Example-3.

0.07+no! 0.04mol 5g 0.2g 15.0g 5g 5.0g 0.1g According to Table 6, when processed with the developer of the present invention, the maximum density of the cyan coloring layer (RL) is high and Good results were obtained, with little change in maximum density and gradation, and a high effect of preventing the development of sensitized muscles.

In the present invention, when the preservative is a compound represented by the general formula (I-a) (processing steps ① to ②), it is found that the change in photographic properties due to running is particularly small, which is more preferable.

Example-6 Same as treatment step ① of Example-5, but l-12
Instead of ■-13, ■-21, ■-30, ■-41,
Similar good results were obtained using ①-54.

Claims (1)

[Scope of Claim] A method of processing a silver halide color photographic light-sensitive material with a color developer containing at least one aromatic primary amine color developing agent, comprising a highly chlorinated material containing 80 mol% or more of silver chloride. A silver halide color light-sensitive material containing a silver silver halide emulsion in at least one layer is treated with chloride ions and bromide ions of 3.5 x 10^-^5 to 3.5 x 10, respectively.
1.5×10^-^1 mol/l, 3.0×10^-^5
Contains ~1.0×10^-^3 mol/l and has the general formula (
A method for processing a silver halide color photographic light-sensitive material, which comprises processing with a color developer containing a compound represented by I). General formula (I) ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ (In the formula, R^1 and R^2 are hydrogen atoms, unsubstituted or substituted alkyl groups, unsubstituted or substituted alkenyl groups, unsubstituted or substituted aryl group or a heteroaromatic group.R_1 and R_2 cannot be hydrogen atoms at the same time, and may be linked to each other to form a heterocycle with a nitrogen atom.The ring structure of the heterocycle is 5 ~6-membered ring, carbon atom, hydrogen atom, halogen atom, oxygen atom,
It is composed of nitrogen atoms, sulfur atoms, etc., and may be saturated or unsaturated. )