JPH01304461A - Method of processing silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To decrease the replenishing amt. of a developing soln. and to lessen the fluctuation in photographic characteristics without impairing rapidness by processing a photosensitive material contg. a prescribed ratio of a high silver chloride emulsion and prescribed gelatin with the prescribed developing soln. CONSTITUTION:The silver halide color photographic sensitive material which contains the high silver chloride emulsion consisting of >=80mol% silver chloride in one layer and in which >=10wt.% of the total amt. of the coated gelatin is acid-treated gelatin is processed with the developing soln. contg. at least one kind of arom. primary amine color developing agents and the replenishing amt. of the developing soln. is specified to 20-120ml per 1m<2> photosensitive material. The content of the acid-treated gelatin is >=10wt.%, more preferably 15-100wt.% of the total amt. of the coated gelatin. The isoelectric point of the acid-treated gelatin is 6-9.5, more preferably 7-9.5. The total amt. of the coated gelatin is 1-30g, more preferably 2-20g per 1m<2> photosensitive material.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a method for processing silver halide color light-sensitive materials, and in particular to a method for processing silver halide color light-sensitive materials in which the amount of replenishment of color developer is significantly reduced. Regarding.

(Prior art) The processing of halogenated one-dimensional color photographic materials basically consists of two steps: color development (in the case of color reversal materials, the first monochrome development before that) and desilvering. Silver consists of a bleach and fix process or a single bath bleach-fix process used in combination or alone. If necessary, additional treatment steps such as water washing, stopping treatment, stabilization treatment, and pretreatment for accelerating development may be added.

In color development, the exposed silver halide is reduced to silver, and at the same time, the oxidized aromatic primary amine developing agent reacts with the coupler to form a dye. During this process, halogen ions generated by decomposition of silver halide are eluted into the developer and accumulated. On the other hand, the color developing agent is consumed by reaction with the coupler mentioned above. Furthermore, other components are retained in the photographic light-sensitive material and taken out, and the concentration of the components in the developer decreases. Therefore, in a development method in which a large amount of silver halide photographic light-sensitive material is continuously processed using an automatic processor, etc., the components of the color developer are kept within a constant concentration range in order to avoid changes in development finish characteristics due to changes in component concentration. We need a means to do so.

For example, consumable components such as developing agents and preservatives are generally kept at a high concentration in the replenisher when the effect of concentration is small.

In addition, eluates such as halogens that have the effect of inhibiting development are
In some cases, its concentration in the replenisher may be reduced or it may not be included. Furthermore, it is possible that certain compounds may be included in the replenisher to eliminate the effects of eluates. Also pl
In some cases, the concentration of r, alkali, or chelating agent may be adjusted. As such a method, a method of replenishing a replenisher for supplementing the missing components and diluting the increasing components is usually used. This replenishment inevitably generates a large amount of overflow fluid, which poses a major economic and pollution problem.

In recent years, there has been a strong desire to reduce the amount of color developer replenishment for the purpose of speeding up the development process, saving resources, and reducing pollution. However, simply reducing the amount of color developer replenishment results in
Accumulation of eluates from light-sensitive materials, particularly bromine ions, which are strong development inhibitors, and various organic compounds, causes problems in that development activity is reduced and speed is impaired.

As a means to solve this problem, a development acceleration technique is required, and many speed-up techniques for reducing the amount of developer replenishment are being studied. For example, one known method is to accelerate development by increasing the pH and processing temperature of the color developer. However, this method causes serious problems such as high fog, poor stability of the developer, and increased fluctuations in photographic properties during continuous processing. Further, as another acceleration technique, a method of adding various development accelerators has been described, but the accelerating effect thereof is insufficient and unsatisfactory.

For the purpose of reducing the accumulation of bromide ions, which are strong inhibitors of development, and speeding up the development, the silver chloride content was disclosed in Japanese Patent Application Laid-open No. 58-95345, No. 59-232342, No. 61-70552, and International Publication Patent No. WO 8-104534. A method using a silver halide photosensitive material with a high oxidation rate has been disclosed and is considered to be an effective means for reducing the amount of developer replenishment without impairing speed. However, when we actually performed continuous processing with a reduced amount of developer replenishment, although the speed was not compromised,
Photographic properties, especially minimum density, maximum density, and gradation, change significantly due to continuous processing, and image storage stability after processing changes significantly.
In particular, a new problem was discovered in which the stain significantly increases over time.

Currently, the amount of replenishment of color developer varies somewhat depending on the photosensitive material to be processed, but it is 1 ml per bottle of Miyako material to be processed.
Generally, about 80 to 1000 d is required. This is because, as mentioned above, if the replenishment amount is further reduced without sacrificing speed, photographic characteristics will greatly fluctuate during continuous processing as described above, and image storage stability after processing will increase, especially staining, which is an extremely serious problem. occurs, and no technology has been found that can fundamentally solve these problems.

(Problems to be Solved by the Invention) Therefore, the first object of the present invention is to maintain photographic properties, especially maximum density, in continuous processing without impairing speed even when the amount of color developer replenishment is significantly reduced. It is an object of the present invention to provide a developing processing method with small variations in minimum density and gradation. A second object of the present invention is to provide a processing method that improves image storage stability after processing, particularly preventing an increase in staining over time, even when the amount of color developer replenishment is significantly reduced.

(Means for Solving the Problem) As a result of various studies, the present inventors were able to achieve the above object by the method described below.

In a method of continuously processing a silver halide color photographic light-sensitive material with a color developer containing at least one aromatic primary amine color developing agent, a high silver chloride emulsion containing 80 mol% or more of silver chloride is formed in at least one layer. and a silver halide color photographic light-sensitive material in which 10 wL% or more of the total applied gelatin arsenic is acid-treated gelatin, and the replenishment amount of the color developer is 20 to 20 per bottle of the silver halide photographic light-sensitive material.
120rR1, a method for processing a silver halide color photographic material.

The acid-treated gelatin used in the present invention is gelatin molded by treatment with hydrochloric acid or the like during the production process from collagen, and is different from alkali-treated gelatin which is usually used in the photographic industry and involves treatment with lime or the like. For details on the production and properties of these gelatins, see Arthur Vei.
Author: The Macromolecular Che
mistry of Ge1atin JAcadem
ic Press, pp. 187-217 (1964
However, the biggest difference is the isoelectric point (
The acid-treated gelatin has a PI of 6.0 to 9.5, while the alkali-treated gelatin has a PI of 4.5 to 5.
．． 3.

The use of acid-treated gelatin in color photographic light-sensitive materials is described in Japanese Patent Publication No. 51-43777, Japanese Patent Application Publication No. 51-8938, Japanese Patent Application Publication No. 53-5624, etc., but these all involve reticulation of the film surface. It's about improvement,
It was an entirely unexpected fact that the use of acid-treated gelatin would improve the photographic properties of color light-sensitive materials during continuous processing and the image storage stability after processing.

The content of acid-treated gelatin in the color light-sensitive material used in the present invention is 10-t% or more based on the total amount of coated gelatin,
Preferably it is 5 wt% or more.

Moreover, the upper limit is 100%.

The acid-treated gelatin used in the present invention has an isoelectric point of 6 to 9.
5, preferably 7 to 9.5.

The molecular weight of the acid-treated gelatin used in the present invention is not particularly limited, but is preferably 10,000 to 200,000.

Examples of gelatin that can be used in combination with acid-treated gelatin include gelatin described below as a binder.

In the present invention, the "total coated gelatin amount" refers to the gelatin on both sides of the support, but preferably refers to the gelatin amount on the side of the support on which the silver halide emulsion layer is present.

Here, the "total amount of applied gelatin" is preferably 1 to 30 g, more preferably 2 to 20 g per rrr of photosensitive material.
It is g.

In the present invention, the amount of acid-treated gelatin is 1 Qwt % or more, but if it is less than 10%, it is difficult to sufficiently develop the gelatin to be effective, especially to prevent thermal staining.

The method of the present invention is most effective when applied to continuous processing. Here, the term "continuous processing" refers to continuous processing in which processability is maintained constant by using means such as adding a replenisher to reduce exhaustion of the processing solution due to development processing.

The color developer used in the present invention will be explained in detail.

The range of replenishment amount of the color developer in the present invention, which is 20 to 120 tn1 per 1 d of silver halide photosensitive material, will be explained. Due to the above-mentioned problems, it is impractical in the prior art to reduce the replenishment amount of the developer to less than 120 -, but this has been made possible for the first time by the present invention. Refill amount 120
d/Photosensitive material 1. (is a value located on the boundary between the range made possible by the present invention for the first time and the range made possible by a combination of conventional techniques other than the present invention.Also, although it varies somewhat depending on the photosensitive material, the replenishment of the developer The amount is 20me/
If the photosensitive material is less than l11, the amount of processing liquid taken out by the photosensitive material exceeds the amount of replenishment, the processing liquid decreases, and continuous processing becomes practically impossible.

The replenishment amount 2 (1+j/photosensitive material 1.) differs somewhat depending on the photosensitive material, but indicates the amount at which the amount of processing liquid taken out by the photosensitive material and the replenishment amount are approximately equal.

The developer used in the present invention preferably does not substantially contain benzyl alcohol in order to reduce fluctuations in photographic properties during continuous processing. Here, "substantially free" means preferably 2 ml/1 or less, more preferably Q, 5+nff1/j! The benzyl alcohol concentration is as follows, most preferably all (no) benzyl alcohol.

It is more preferable that the developer used in the present invention does not substantially contain sulfite ions. Sulfite ion functions as a preservative for the developing agent, and at the same time acts as a silver halide solubilizer and as a developing agent. It reacts with the Jl compound and has the effect of reducing the dye formation efficiency.

Such an effect is presumed to be one of the causes of increased fluctuations in photographic characteristics that occur when the amount of color developer replenishment is reduced. Here, "substantially not containing" preferably means 5
．． The sulfite ion concentration is OX 10-3 mol/1 or less, and most preferably no sulfite ion is contained at all. However, in the present invention, a very small amount of sulfite ions used to prevent oxidation of the processing agent kit, which is reduced in developer strength <'+□ before being mixed into a solution for use, is excluded.

The developer used in the present invention preferably does not substantially contain sulfite ions, and more preferably does not substantially contain hydroxylamine. This is because hydroxylamine functions as a preservative in the developer. At the same time, it has silver developing activity itself, and it is thought that fluctuations in the concentration of hydroxylamine greatly affect photographic properties.

Here, "not containing substantially hydroxylamine" preferably means 5. A hydroxylamine concentration of less than OX 10-'' mole/1, and most preferably no hydroxylamine at all.

The developer used in the present invention preferably contains an organic preservative in place of the hydroxylamine and sulfite ions, from the viewpoint of stability of photographic properties during continuous processing and image storage stability after processing.

The term "organic preservative" as used herein refers to any organic compound that reduces the rate of deterioration of an aromatic primary amine color developing agent when added to a processing solution for a color photographic light-sensitive material. That is, they are organic compounds that have the function of preventing color developing agents from being oxidized by air, among others, hydroxylamines (excluding hydroxylamine), hydroxamic acids, hydrazines, hydrazides, phenols, α- Hydroxyketones, α-aminoketones, t, I! Particularly active organic preservatives include monoamines, diamines, polyamines, quaternary ammonium salts, nitroxy radicals, alcohols, oximes, diamide compounds, and fused amines. These are patent applications filed in 1986-147.
No. 823, No. 61-173595, No. 61-1656
No. 21, No. 61-188619, No. 61-], 97
No. 760, No. 61-186561, No. 61-1989
No. 87, No. 61-201861, No. 61-18655
No. 9, No. 6], -] No. 170756, No. 61-18
No. 8742, 6l-18874L U.S. Patent No. 3615
No. 503, No. 2494903, JP-A-52-1430
20, Japanese Patent Publication No. 4B-30496, etc.

Regarding the preferred organic preservatives, their formulas and specific compounds 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
5 mol, /1 to 0.5 mol/I, preferably 0.03
It is preferable to add it to a concentration of mol/1 to 0.1 mol/l.

As the hydroxyamines, the following are preferred.

The best formula (■) R eye-N-RI! (2) H In the formula, R11 and Rf2 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. R11 and Rf2 do not become hydrogen atoms at the same time, and may be linked to each other to form a heterocycle between the nitrogen atom and Rf.

The ring structure of the heterocycle is a 5- to 6-membered ring, composed of carbon atoms, hydrogen atoms, halogen atoms, nitrogen atoms, sulfur atoms, etc., and may be saturated or unsaturated.

It is preferable that the R eyes and Rf2 are an alkyl group or an alkenyl group, and the number of carbon atoms is preferably 1 to 10, particularly preferably 1 to 5. The nitrogen-containing heterocycle formed by connecting R11 and R+z is a piperidyl group, Pyrrolysilyl group, N-
Examples include an althylbiperazyl group, a morpholyl group, an indolinyl group, and a benztriazole group.

Preferred substituents for R11 and R1'' are a hydroxy group, an alkoxy group, an alkyl or arylsulfonyl group, an amide group, a carboxy group, a cyano group, a sulfo group, a nitro group and an amino group.

Compound example) Fu-I C2) 1s-N CtHsOH ~i-2C) I30CzHa N CJa 0C
HzOf( ■-3CJsOCJi N CHz C) I field C
H.

O1! OHOH As the hydroxams HH, the following are preferred.

General formula <IX) Al1-X2l-N-0-Y2' zI In the formula, A2I is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, the substitution is also l, (
is an unsubstituted amino group, a substituted or unsubstituted beterocyclic group, a substituted or unsubstituted alkoxy group, a monosubstituted or unsubstituted aryloxy group, a substituted or unsubstituted carbamoyl group, a substituted or unsubstituted sulfamoyl group , represents an acyl group, a carboxy group, a hydroxyamino group, or a hydroxyaminocarbonyl group. Examples of the substituent include a halogen atom, an atomyl group, an alkyl group, an alkoxy group, and the like.

Preferably A! + represents a substituted or unsubstituted alkyl group, aryl group, amino group, alkoxy group, or aryloxy group. Particularly preferred examples include substitution or fE
A-substituted amino group, alkoxy group, and aryloxy group. The number of carbon atoms is preferably 1 to 10.

Represents 180-. Preferably, X21 is -C- and B21 is a hydrogen atom, a substituted or unsubstituted alkyl group'
, represents a substituted or unsubstituted aryl group.

At this time, A'' and R21 may be connected to form a ring structure, and the substituent is the same as the substituent listed for A21. Preferably, R1+ is a hydrogen atom.

Y! I represents a hydrogen atom or a group that can become a hydrogen atom through a hydrolysis reaction.

Compound example CI(:+-C-N)l-Of(C,H,0-C-N)l-OH 1X-5 CHI CH,-C-N-OH ■ Hydrazines and hydrazides include the following. Preferably.

General formula (X) In the formula, Rffl, R32, and R3ff represent a hydrogen atom, a substituted or unsubstituted alkyl group, an aryl group, or a heterocyclic group, and R34 is a hydroxy group, a hydroxyamino group, or a substituted or unsubstituted represents an alkyl group, aryl group, heterocyclic group, alkoxy group, monoloxy group, carbamoyl group, or amino group. The heterocyclic group is a 5- to 6-membered ring, composed of C, H, O2N, S, and halogen atoms, and may be saturated or unsaturated. X31 is -CO-1-S
OZ-1H represents a divalent group selected from -0-, and n is 0 or 1. In particular, when n=o, Ria represents a group selected from an alkyl group, an aryl group, and a heterocyclic group, and R3j and R34 may jointly form a heterocyclic group.

In general formula (X), Ral, R3! , R) ff is preferably a hydrogen atom or a C1-C1° alkyl group,
In particular, it is most preferable that R3' and R3Z are hydrogen atoms.

-S In formula (X), R34 is preferably an alkyl group, an aryl group, an alkoxy group, a carbamoyl group, or an amine group, and particularly preferably an alkyl group or a substituted alkyl group. Preferred substituents for the alkyl group here include a carboxyl group, a sulfo group, a nitro group, an amino group, a phosphono group, and the like. χ3' is preferably -CO- or -8O2-, most preferably -○○-.

N) 12NHcOcl13 NLNHCONL NH! NH30J Nl+ NHzN)ICMHz NHzNHCOCONHNHz NH! NHCIbC)12C)I! SOJN)I! N.H.
CHCOO)l cJHl(n) NHJHC)IzCHzCOO)l The following are preferred as the phenols.

-Formula (X[) In the formula, R41 is a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, a carboxyl group, a sulfo group, a carbamoyl group, a sulfamoyl group, an amide group, a sulfonamide group. group, ureido group, alkylthio group, arylti, nitro group, cyano group, amino group, formyl group, acyl group, sulfonyl group, alkoxycarbonyl group, aryloxycarbonyl group, alkoxysulfonyl group, and aryloxysulfonyl group represents. When R'' is further substituted, examples of the substituent include a halogen atom, an alkyl group, an aryl group, a hydroxyl group, an alkoxy group, etc. In addition, when there are two or more R41s, the f! Even if the class is the same °
They may be different, and when they are adjacent, they may be bonded to each other to form a ring. The ring structure is 5~
It is a 6-membered ring, composed of carbon atoms, hydrogen atoms, halogen atoms, oxygen atoms, nitrogen atoms, sulfur atoms, etc., and may be saturated or unsaturated.

R42 represents a hydrogen atom or a hydrolyzable group, and m and n are each an integer from 1 to 5.

-m In formula (XI), R4' is preferably an alkyl group, a halogen group, an alkoxy group, an alkylthio group, a carboxyl group, a sulfo group, a carbamoyl group, a sulfamoyl group, an amino group, an amide group, a sulfonamido group, a nitro group, and a cyano group. Among these, an alkoxy group, an alkylthio group, an amino group, and a nitro group are particularly preferred, and these are more preferably located at the ortho or para position of the (OR") group, and the number of carbon atoms in R41 is preferably from 1 to 10. , 1 to 6 are particularly preferred.

Preferred R42 is a hydrogen atom or a hydrolyzable group having 1 to 5 carbon atoms. Also, (OR”)
When there are two or more groups, it is more preferable that they are located at ortho or para positions with respect to each other.

XI-1 H TS XI-5 XI-6 XI-7 H ゝOH XI-9 H 蒐□ SO, Na Xl-10 0H ■ SO, H The following are preferred.

General formula (η) R5I Rsz represents a hydrogen atom, a substituted or unsubstituted alkyl group, or an aryl group, and R5I and R5
Z may jointly form a carbocycle or a heterocycle R5
I represents a hydroxyl group or a substituted or unsubstituted amino group.

-i In formula (XI), R5I is preferably a hydrogen atom, an alkyl group, an aryl group, or an alkoxy group;
5t is preferably a hydrogen atom or an alkyl group.

XI-1 CHsCCHzOH XI-2 0H CHiCCOCH2 XI-4 irises CHzCCHzNIICzHs XI-5 ■ HC-cozo.

XI-6 XI-8 0H Xl CH30C-C)lcz)Is X! -10 Sugars are also preferred organic preservatives.

Sugars (also called carbohydrates) consist of monosaccharides and polysaccharides.
Many have the general formula c,,H! -0-e too. Car I, Ii
The group generally refers to aldehydes or ketones of polyhydric alcohols (called aldoses and ketoses, respectively), their reduced derivatives, oxidized derivatives, dehydrated derivatives, and a wider range of derivatives such as amino acids and thiols. Moreover, polysaccharide refers to a product obtained by dehydration condensation of two or more of the above-mentioned monosaccharides.

More preferable among these PRs are aldoses having a reducing aldehyde group and derivatives thereof, and particularly preferable ones among these are those corresponding to katsai tang.

XI-I D-Oxylose Xl-2L-Arabinose Xl-3D-Ribose ■-4D-Deoxyribose ■-5D-Glyose Xl-6D-Galactose ■-7D-Mannose]-8 Glucosamine ■-9L-Sorbose Xl-10D- Sorbitol monoamines include the following:

General formula (separate) R'+! R'1-N-R'3 In the formula, Rl, R'tZ, and R'tgo represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an aralkyl group, or a heterocyclic group, where R7I and R 'rt.

R? l and R12 or R72 and R? 3 may be connected to form a nitrogen-containing heterocycle.

Here, R1, RIZ, and R73 may have a substituent. As l, Rff2, and Bqs, hydrogen atoms and alkyl groups are particularly preferred. Further, examples of the substituent include a hydroxyl group, a sulfone group, a carboxyl group, a halogen atom, a nitro group, an amino group, and the like.

Cumulative I N+GHzC)IzOH) Z Cumulative-2L
NCToCLOH m3HN+CHzCHzOH)zH CIHIsN+cHzcHcHzOH).

Bullet-6 N-8 (HOCH, CH, ÷ JCHtCHzS02cHz child-
11 HN+CHtCOOH)z ■-12 ) 100CCHzCHzcHcOOH 硼1Hz Cu-13 HzNCllrCHzSOzNHz HzN Shield C+GHzOH)-15 HOC)lzcHcOOH N H.

N-19 The following diamines are preferred.

General Formula (XV) In the formula, R1, R#2, R1, and 8 units represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an aralkyl group, or a heterocyclic group.

Ras represents a divalent radical, specifically an alkylene group, an arylene group, an aralkylene group, an alkenylene group, or a heterocyclic group.

R1, Rs! , Ro, and Ro4 are particularly preferably a hydrogen atom or an alkyl group, and R1'5 is particularly preferably an alkylene group.

Stand-1 XI'-3 0H)1. NCHICII□N+CHzGHzOH) zH
zNCHzCHCHzNlh HV-9 HV-10 As the polyamines, the following are preferred.

General formula <'a> In the formula, R4+, R92, R91 and R09' represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an aralkyl group or a heterocyclic group.

RlS, R9k, and R9? represents a divalent organic group,
Specifically, it has the same meaning as R'' in the general formula (Xv) above.
e Xv1 and X9! is -N-1-〇-1-S-2-CO-
1-SO, -1-S〇= or a linking group composed of a combination of these linking groups, and RQa is R1, R9!
, R93 and R94 have the same meaning. 0m represents O or an integer of 1 or more.

(The upper limit of m is not particularly limited, and as long as the core compound is water-soluble, it may have a high molecular weight, but usually m is preferably in the range of 1 to 3.) 'XXA-1 H3 HzNCHzCHzNCHzCHzNHz8-2 (HOCHzCHz+ zNcHzcHzOc)
HJ+CtbCHzOH) z Shuichi 4 Seedling-5 'AA-6 O) 1 0H As the quaternary ammonium salt, the following are preferable.

General formula (A1) (wherein, R101 represents an n-valent organic group, R102, R
'03 and RQa4 represent a monovalent organic group. The organic group here represents a group having 1 or more carbon atoms, and specifically represents an alkyl group, an aryl group, a heterocyclic group, etc.
, R"3 and R1°' may be combined to form a heterocycle containing a quaternary ammonium atom. n is an integer of 1 or more, and Xθ represents a counter anion. , )RI02, R+oz and R104, a particularly preferred monovalent group is a substituted or unsubstituted alkyl group, and when at least one of RIG!, RI03 and RIoa is a hydroxyalkyl group, an alkoxyalkyl group or a carboxyalkyl group is most preferred.

n is preferably an integer of 1 to 3, more preferably 1 or 2
It is.

CtHs -N + (:zH40H) 3.1/2S
Oa'-Wall-3 N+CJaOH)t, Br-Bulk-4 (C1Hs÷J+CzHtOH)z, C1" Bulk-
5 OO- Js bulk-9 CH co CH conitroxy radicals are preferably the following.

General formula (m) R111 and R112 are each a hydrogen atom, an alkyl group,
Represents an aryl group or a heterocyclic group. Further, these alkyl groups, aryl groups or heterocyclic groups may have a substituent jA group. Examples of such substituents include a hydroxy group, an oxo group, a carbamoyl group, an alkoxy group, a sulfamoyl group, a carboxy group, and a sulfo group. Examples of the heterocyclic group include a pyridyl group and a piperidyl group.

Preferably R111, R11! is a substituted or unsubstituted aryl group or tertiary alkyl group (eg, 1-butyl group).

(Compound example) M! -2 Jun-3 Jun-4 The following alcohols are preferred.

-Formula RIzI RI2t CX121 In the formula, RIzI represents a hydroxy-substituted alkyl group, and RIzI represents an unsubstituted alkyl group or a group similar to RIzI. R123 represents a hydrogen atom or a group similar to R10. X l 21 represents a hydroxy group, a carboxyl group, a sulfo group, a nitro group, an unsubstituted or hydroxy-substituted alkyl group, an unsubstituted or substituted amide group, or a sulfonamido group.

- In the S formula (e), XI! + is preferably a hydroxy group, carboxyl group, or hydroxyalkyl group.

Cave-I CH, CH3 ++ HO-C-C-0)I ++ CH, CH.

! -2CH.

CL C1+.

■-3 +10- CH-CI -0)1 CI (3CL Hiroshi-4 HO-GO+ GHzOH)! ■-5 (HO-CH2÷,Coo)I Separate-6 C+CHzOH+a )[-7 (HOCIl,÷)CGHz Original-8 ()IOCH2÷sc N)ICOCHz()IOC
Hz+zCSOJ CI! 3 Double-10 80-C)I CHzC)lzOH H20H The following alcohols are preferred.

-Format (Xx) R"' -C1+CHCHt O1+, lR""R1
! 3 where RI31. R1co2 and R12co each represent a hydrogen atom or an alkyl group, and n represents a positive integer up to 500.

The alkyl group represented by R131, R122, and R133 preferably has 5 or less carbon atoms, more preferably 2 or less carbon atoms. R111, R1:14, R13
3 is very preferably a hydrogen atom or a methyl group, most preferably a hydrogen atom.

n is preferably a positive integer of 3 or more and 100 or less, more preferably 3 or more and 30 or less.

Twin-1 HO+C)Iz(JIzO÷tOH Sou-2 CI’lsO+CLC)IzO÷308CH3 Souzu HOCHzCI(zOcHs Xx-7 80-(-C1l, C1l, 0÷7H Average molecular weight: approx. 300 X-8 HO+ CHzCHzO÷llH Average molecular weight: Approximately 800 Sou-9 )10+c)12G)120÷. H Average molecular weight: approx. 3000 Sou-10 1(0(-C)ItCH20÷1H Average molecular weight: Approximately 8000 As the oximes, the following are preferred.

-Formula 1) %Formula% In the formula, R"' and RI42 are each a hydrogen atom,
A substituted or unsubstituted alkyl group, and a substituted or unsubstituted 4 represent an unsubstituted aryl group. Also, R141 and R
142 may be the same or different, and these groups may be connected.

-S In formula (A), preferred as RI41 and R11 are alkyl groups substituted with halogen groups, hydroxyl groups, alkoxyl groups, amino groups, carboxyl groups, sulfo groups, phosphonic acid groups, and nitro groups, and unsubstituted alkyl groups. It is an alkyl group.

Further, the total number of carbon atoms in the general formula (separate) is preferably 30 or less, and more preferably 20 or less.

Double-1 -OH CH, -C-C-CL -OH Separate-2 N-0) I HO+ CHz+ yCC+ C1lO÷30H-OH Separate-4 N-0)1 Separate-5 1-OH HChCCHzCHtC-CCHxCHzCOOHN-
0)1 The following polyamines are preferred.

General formula (following) In the formula, X''1 and Xl52 are -C0-2 or SO
t-, RI51, R15t, RIS3
, R"', R"' and Ru5h represent a hydrogen atom, an unsubstituted or substituted alkyl group, and RIS? represents an unsubstituted or substituted alkylene group, an unsubstituted or substituted arylene group, and an unsubstituted or substituted aralkylene group,
m', m'' and n represent O or l.

Shoulder-・1 HJCNHCNHz chicken-2 )12NcllHNHcNH! ■-3 )IZN-C-C-NH! Contempt-4 HzNCNHCHHzCHzNHCNHzTobi-5 Chicken-G HzNSOJI (SChNHz As the condensed cyclic amines, the following are preferred.

General formula 01XI11) In the formula, X represents a trivalent atomic group necessary to complete the condensed ring, and RI and Rt are an alkylene group, an arylene group,
Represents an alkenylene group or an aralkylene group.

Here, R1 and R1 may be the same or different from each other.

Among the general 2〇tXI[[), particularly preferred are compounds represented by the general formulas (1-a) and (1-b).

In the formula, XI is -E? R1 representing N or “IEcH,
ヰ1l Rz is defined in the same way as in the general formula (Xill),
R3 represents a group similar to R', R'', or -CH, C-.

In the general formula (1-a), XI is preferably miN. The number of carbon atoms in R1, R1, and R3 is preferably 6 or less, more preferably 3 or less, and most preferably 2. preferable.

R1, R1, and R3 are preferably an alkylene group or an arylene group, and most preferably an alkylene group.

In the fl river formula, R1 and Bx are defined in the same way as in general formula (1).

In general formula (1-b), the number of carbon atoms in R' and R'' is preferably 6 or less. R1 and R2 are preferably an alkylene group or an arylene group, and most preferably an alkylene group.

-Among the compounds of formulas (1-a) and (techniques - b), especially -
Compounds represented by the format (1-a) are preferred.

Twin m-4 Twin m-6 Twin m-7 Twin m-B Double I[1-9 Double ■-10 Double ■-12 XX] If-16 Of the general formula (V[lI) to (XXIn) according to the present invention Many compounds are commercially available and can be easily prepared manually.

Two or more of the above-mentioned hammer preservatives may be used in combination. A preferred combination is at least one compound of the general formulas (Vlll) to (XI![) and at least one compound among (XIV) and (XXIII).

A more preferable combination is at least one of the general formulas (■) and (XV) and at least one of the general formulas (XVI) and (X X II+ ).

The color developer used in the present invention will be explained below.

The color developer (& liquid used in the present invention includes a known
Contains an aromatic primary amine color developing agent. A preferred example is p-phenylenediamine, and representative examples are shown below, but the invention is not limited thereto.

D-IN, N-diethyl-p-phenylenediamine D-24-(N-ethyl-N-(β-hydroxyethyl)aminocoaniline D-32-methyl-4-[N-ethyl-N-(β- hydroxyethyl) aminocoaniline D-44-amino-3-methyl-N-ethyl-N-(β
The use of (methanesulfonamidoethyl)-aniline, especially D-4, is preferred.

Additionally, these p-phenylenediamine derivatives may be salts such as sulfates, hydrochlorides, p-)luenesulfonates, and the like. The amount of aromatic-grade amine developing agent used is preferably in a concentration of about 0.1 g to about 20 g, more preferably about 0.5 g to about 10 g per developer solution.

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

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

The amount of the M street agent added to the color developer is 0.1 mol/β
It is preferably at least 0.1 mol/71! ~
Particularly preferred is 0.4 mol/l.

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,
N,N,N-)rimethylenephosphonic acid, ethylenediamine-N,N,N'.

N'-tetramethylenephosphonic acid, 1,3-diamino-
2-propatoltetraacetic acid, Trauss cyclohexanediaminetetraacetic acid, nitrilotripropionic acid, 1,2-diaminopropanetetraacetic acid, hydroxyethyliminodiacetic acid, glycol etheraminetetraacetic acid, hydroxyethylenediaminetriacetic acid, ethylenediamine orthohydroxyphenyl Acetic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, N,N'-bis(2-hydroxybenzyl)ζ
Ethylenediamine-N,N'-diacetic acid 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, 1ρ
It is about 0.1g to Log per unit.

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

As a development accelerator, Japanese Patent Publication No. 37-16088 and No. 3
No. 7-5987, No. 38-7826, No. 44-123
No. 80, No. 45-9019 and U.S. Patent No. 3,813
, p-funynylene diamine compounds shown in JP-A-52-49829 and JP-A-50-155-4, JP-A-52-49829 and JP-A-50-155-4.
No. 137726, Japanese Patent Publication No. 44-30074, Japanese Patent Publication No. 1977
Quaternary ammonium salts represented by No. 6-156826 and No. 52-43429, etc., U.S. Patent No. 2.610
, 122 and 4,119.462; U.S. Pat. No. 2, '494.903;
No. 3,128,182, No. 4,230,796, No. 3,253,919, Japanese Patent Publication No. 11431/1973, U.S. Patent No. 2゜482.546, No. 2,596,926
and amine compounds described in Japanese Patent Publication No. 3,582,346, etc., Japanese Patent Publication No. 1983, No. 6088, No. 42-252.
No. 01, U.S. Patent No. 3,128,183, Special Publication No. 1973
-11431, 42-23883, and U.S. Patent No. 3,532,501, and other 1-phenyl-3-pyrazolidones,
hydrazines, mesoionic compounds, ionic compounds,
Imidazole, etc. can be added as necessary.

Any antifoggant can be added to the color developer used in the present invention, if necessary.

As anti-capri agents, alkali metal halides such as sodium chloride, potassium bromide, potassium iodide and organic anti-capri agents can be used. Examples of organic antifoggants include benzotriazole ζ 6-nidropenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole,
5-'7t) Typical examples include nitrogen-containing heterocyclic compounds such as rhobenzotriazole, 2-thiazolylpenzimidazole, 2-thiazolylmethylpenzimidazole, indazole, hydroxyazaindolizine, and adenine. I can give it to you.

The color developer used in the present invention preferably contains an optical brightener. As an optical brightener, 4,4'-
Diamino-2,2'-disulfostylhene compounds are preferred. Addition amount is 0-5g/β, preferably 0.1-4g
/l.

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

The processing temperature of the color developer of the present invention is 20 to 50°C, preferably 30 to 40°C. The treatment time is 20 seconds to 5 minutes, preferably 30 seconds to 2 minutes.

The replenishment amount of the color developer of the present invention is 2.
0-120-1, preferably 30-100d.

The replenishment amount here refers to the amount of so-called color developer replenisher to be replenished, and the amount of additives and the like for correcting deterioration over time and concentration is outside the replenishment amount of the present invention.

The additives mentioned here include, for example, water for diluting the concentrate, preservatives that tend to deteriorate over time, or alkaline agents that increase the pH.

After color development, the photographic emulsion layer is usually bleached.

The bleaching process may be carried out simultaneously with the fixing process (bleach-fixing process) or separately. Furthermore, in order to speed up the processing, it is possible to use a processing method in which bleaching is followed by bleach-fixing, furthermore, processing in two consecutive bleach-fixing baths, fixing before bleach-fixing, or bleach-fixing. A post-bleaching treatment can also be optionally carried out depending on the purpose. As a bleaching agent, for example, iron <m>, cobalt (II)
Compounds of polyvalent metals such as +), chromium (■), and copper (II), peracids, quinones, nitro compounds, and the like are used.

Typical bleaching agents include ferricyanide; dichromate; organic complex salts of iron (I) or cobalt (III), such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1.3 -Aminopolycarboxylic acids such as diaminopropanetetraacetic acid and glycol ether diaminetetraacetic acid, or complex salts of citric acid, tartaric acid, malic acid, etc.;
Persulfates; bromates; permanganates; nitrobenzenes and the like can be used. Among these, aminopolycarboxylic acid iron (III) complex salts and persulfates, including ethylenediaminetetraacetic acid iron (I [[) Complex salts are particularly useful in both bleach and bleach-fix solutions. The pH of bleaching solutions or bleach-fixing solutions using these aminopolycarboxylic acid iron (I[[) complex salts is usually 5.5 to 8, but in order to speed up the processing, the pH may be lowered. You can also do it.

A bleach accelerator may be used in the bleaching solution, bleach-fixing solution, and their prebaths, if necessary.

Specific examples of useful bleach accelerators are described in U.S. Pat. No. 3,893,858;
, No. 290,812, JP-A-53-95.630, Research Disclosure Fish No. 17.129 (197
Compounds having a mercapto bond or a disulfide group as described in JP-A-50-140,129; U.S. Patent No. 3,706;
Thiourea derivatives described in No. 561; JP-A-58-16.
Iodide salt described in No. 235; West Germany Kitsuki 2°748.4
Polyoxyethylene compounds described in No. 30;
Polyamine compound 7 bromide ion described in No. 5-8836 can be used. Among these, compounds having a mercapto group or a disulfide group are preferred from the viewpoint of a large promoting effect, and are particularly described in U.S. Time Kitsuki No. 3,893,858, West German Patent Kitsuki No. 1゜290.812, and Japanese Patent Application Laid-open No. 1983-95,630. Preference is given to the compounds described in U.S. Pat. No. 4,555.
The compound described in No. 2.834 is also preferred, and it can be determined by the method described in May 2005 issue). J According to the multi-stage countercurrent method described in the above-mentioned document, the amount of water used for washing can be significantly reduced, but the increased residence time of water in the tank causes bacteria to propagate and the generated suspended matter to adhere to the photosensitive material. Problems such as this arise. In the processing of the color photosensitive material of the present invention, as a solution to such problems,
The method for reducing calcium ions and magnesium ions described in Japanese Patent Application No. 61-131.632 can be used very effectively. Also, JP-A-57-8,542
Chlorinated disinfectants such as isothiazolone compounds, cyabendazole, chlorinated sodium isocyanurate, and other benzotriazoles listed in the issue, "Chemistry of antibacterial and fungicidal agents" written by Hiroshi Horiguchi, "Microbial It is also possible to use the contagious agents described in ``Sterilization, Disinfection, and Anti-Mildew Techniques'' and ``Encyclopedia of Antibacterial and Antifungal Agents'' edited by the Japanese Society of Antibacterial and Antifungal Agents.

The pH of the washing water in the processing of the photosensitive material of the present invention is 4-
9, preferably 5-8. 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 10 minutes at 15-45°C, preferably 20 minutes.
A range of 30 seconds to 5 minutes at 5-40°C is selected. 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 No. 57-8: 543, 5B-14
All known methods described in No. 834, No. 60-220,345 can be used.

Further, following the water washing treatment, a further stabilization treatment may be carried out, and an example thereof is a stabilizing bath containing a formali and a surfactant, which is used as a final bath for color photosensitive materials for photography. can.

Various chelating agents and antifungal agents can also be added to this stabilizing bath.

The overflow liquid resulting from the water washing and/or replenishment of the stabilizing liquid can also be reused in processes such as the desilvering process.

The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and speeding up processing. In order to incorporate a color developing agent, it is preferable to use various breaker of the color developing agent. For example, U.S. Patent No. 3,342,59
Indoaniline compounds described in No. 7, No. 3,342.
No. 599, Research Disclosure 14.850
Schiff base-type compounds described in No. 15.159 and aldol compounds described in No. 13.924, U.S. Patent No. 3
, 719.492, JP-A-53-i
Examples include urethane compounds described in No. 35,628.

The silver halide color light-sensitive material of the present invention may optionally contain various 1-phenyl-3
- Typical compounds that may contain birapritons are JP-A-56-64,339 and JP-A-57-144.547.
No. 5, No. 115,438, etc.

The various processing solutions used in the present invention are used at a temperature of 10°C to 50°C. Normally, the temperature is 33°C to 38°C, but higher temperatures may be used to accelerate the processing and shorten the processing time, or vice versa. It is possible to achieve improved image quality and stability of the processing solution by lowering the temperature. Further, in order to save silver on the photosensitive material, a treatment using cobalt intensification or hydrogen peroxide intensification as described in Tori Tokutoku Kitsuki No. 2.226.770 or US Pat. No. 3,674.499 may be performed.

The method of the present invention can be applied to processing color paper, color reversal paper, color direct positive paper, etc.

Next, details of the silver halide color photographic material used in the present invention will be explained.

The silver halide emulsion of the present invention has a silver chloride content of 80 mol% or more, preferably 95 mol% or more, more preferably 9
It is 8 mol% or more. From the viewpoint of rapidity, the higher the silver chloride content, the more preferable. Furthermore, the high silver chloride composition of the present invention may contain a small amount of silver bromide or silver iodide. In some cases, there are many useful points, such as reducing desensitization caused by spectral sensitizing dyes. Preferably, the halogen composition of the silver halide in all the photosensitive emulsion layers is 80 mol % or more.

Are the interior and surface layers of the silver halide grains used in the present invention different? ! ! (core/shell particles), a multiphase structure such as a bonded structure, or the entire particle may consist of a uniform phase. Moreover, they may be mixed.

Average grain size of silver halide grains used in the present invention (
In the case of spherical or nearly spherical particles, the particle diameter is taken as the particle size, and in the case of cubic particles, the particle size is taken as the particle size, and it is the average based on the projected area.

The average particle is also expressed in sphere terms. ) is preferably 2 μm or less and 0.1 μm or more, particularly preferably 1.5
It is not more than 0.15 μm. The grain size distribution may be narrow or wide, but the value obtained by dividing the standard deviation value of the grain size distribution curve of the silver halide emulsion by the average grain size (variation rate) is within 20%, particularly preferably 15%. %
So-called monodispersed silver halide emulsions within the following are preferably used in the present invention. In addition, in order to satisfy the target gradation of a light-sensitive material, two or more types of monodisperse silver halide emulsions with different grain sizes are used in an emulsion layer having substantially the same color sensitivity. (preferably those having the above-mentioned fluctuation rate) can be mixed in the same layer or coated with heavy N in a separate layer. Furthermore, two or more types of polydisperse silver halide emulsions or a combination of a monodisperse emulsion and a polydisperse emulsion may be mixed or layered for use.

The shape of the silver halide grains used in the present invention is regular (cubic, octahedral, rhombidodecahedral, dodecahedral, etc.).
r) crystals or coexistence of these crystals, or irregular (irregular) crystals such as spherical
It may have a crystalline form (ular), or it may have a composite form of these crystalline forms.

Tabular grains may also be used, especially when the length/thickness ratio is 5.
In particular, tabular grains with a particle size of 8 or more account for 5% of the total projected area of the grain.
An emulsion containing 0% or more may be used, an emulsion consisting of a mixture of these various crystal forms may be used, and these various emulsions may be of a surface latent image type in which a latent image is mainly formed on the surface;
Any type of internal latent image formed inside the particles may be used.

The amount of silver coated in the silver halide emulsion of the photosensitive material used in the method of the present invention is generally 1.5 g/Ii.
! - not more than 0.8g/but preferably not more than 0.3g
/n (or more. The amount of coated silver is 0.8 g/M or less, which is very preferable in terms of rapidity, processing stability, and post-processing image storage stability (especially suppression of yellow stain).

The photographic emulsion used in the present invention is described in Research Disclosure (RD) vol, 176Tteml.
Section 7643 (I, II, ■) (December 1978)
It can be prepared using the method described in .

The emulsion used in the present invention is usually one that has been subjected to physical ripening, chemical ripening, and spectral sensitization.

Additives used in such processes are described in Research Disclosure Vol. 176, No. 17643 (January 1978).
February) and Volume 187, 18716 (1979
(November 2013), and the relevant parts are summarized in the table below.

Known photographic additives that can be used in the present invention are also listed in the two Research Disclosures mentioned above, and their locations are shown in the table below.

Additive type RD17643 RD18716
1 Chemical aggravating agents Page 23 Page 648 Right column 2 Sensitivity enhancers Same as above 4 Brighteners Page 24 5 Anti-fog agents Pages 24-25 Page 649 Right column - 6
Cover - page 25 7 Organic solvent page 25 9 Ultraviolet absorber 11 Dye image stabilizer page 25 12 Hardener page 26 page 651 left column 1
3 Binder page 26 Same as above 14 Plasticizer,
Lubricant Page 27 Page 650 Right column Various color couplers can be used in the present invention. Here, the color coupler refers to a compound that generates a dye through a coupling reaction with an oxidized product of an aromatic primary amine developer. Typical examples of useful color couplers include naphthol or phenolic compounds, pyrazolone, etc. or pyrazoloazole compounds and open-chain or heterocyclic ketomethylene compounds.Specific examples of these cyan, magenta, and yellow couplers that can be used in the present invention are given in Research Disclosure (RD) 17643 (December 1978).
18717 (November 1979).

The color coupler incorporated in the light-sensitive material is preferably diffusion-resistant by having a ballast group or being polymerized. A two-equivalent color coupler substituted with a leaving group is better than a four-equivalent color coupler whose coupling active position is a hydrogen atom in coating fff! The amount can be reduced 0
Couplers in which the color-forming dye has adequate diffusivity, non-color-forming couplers, or DIR couplers that release a development inhibitor or couplers that release a development accelerator upon the campling reaction can also be used.

A representative example of the yellow coupler that can be used in the present invention is an oil-protected acylacetamide coupler. A specific example is the U.S. Special Kitsuki 2.40
No. 7,210, No. 2,875.057 and No. 3
, 265,506, etc. In the present invention, it is preferable to use a two-equivalent yellow coupler;
3.933,501 and 4. ．． 022゜6
Oxygen atom separation type yellow couplers described in No. 20, etc., or Japanese Patent Publication No. 10739/1983, and US Special Publication No. 4, Kitsuki 4.
, No. 401,752, No. 4,326.024, RD
-18053 (April 1979), UK Special Kitsuki 1.42
No. 5,020, West German Application No. 2.219,917,
No. 2,261°361, No. 2,329,587 and No. 2. 4. A typical example thereof is a nitrogen atom dissociative yellow coupler described in Japanese Patent No. 3,812. α-pivaloylacetanilide couplers have excellent color fastness, particularly light fastness, while α-penduylacetanilide couplers provide high color density.

Specific examples of these yellow couplers are described below, but preferred yellow couplers in the present invention are not limited to these.

(Y-1) (Y-2) (Y-3) N C■.

(Y-4) (Y-5) ε Book i 7''' □ G-off Magenta couplers that can be used in the present invention include needle protection type indashilon-based or anaamotyl-based couplers, preferably 5-pyrazolone-based 5 Preferred examples include viradulazole couplers.5-pyrazolone couplers are substituted at the 3-position with an arylamine group or an acylamino group. , U.S. Patent No. 2.3
1:, No. 082, No. 2,343,703, No. 7.
600.788, 2,908.573), 3
, 062,653, 3,152°196, and 3,936,015. As the leaving group for the two-equivalent 5-pyrazolone coupler, the nitrogen atom leaving group described in U.S. Pat. No. 4,310.61I or the aryl group 7J described in U.S. Pat. European Special Kitsuki 73, 63
No. 6: 5-pyrazolone system having the ballast group described above
°Color provides high color density.

Pyrazoloazole couplers are 5N-01 fused nitrogen hetero couplers (hereinafter referred to as 5-N-petero ring couplers and O
=p), and its color-producing nucleus has isoelectronic aromaticity with nasotalene, and is usually a4. It has a chemical structure collectively known as dobentalene. Among pyrazoloazole couplers, preferred compounds include I H-imidazo (1,2
-b) Pyrazole, IH-pyrazoOC5,-1-c]
(1,2,4) triazoles, IH-pyrazolo(1,5-b)[1,2,4)) riazoles and I
H-pyrazolo(], 5-d) tetrazoles.

Specific examples of these magenta couplers are listed below, but the more preferred magenta couplers in the present invention are not limited to these.

(M~3) c8u+(t) (M-5) Cyan couplers that can be used in the present invention include oil-protected naphthol-based and phenol-based couplers, which are described in U.S. Special Kitsuki No. 2,474゜293. The naphthol-based coupler described, preferably US Toku Kitsuki 4.052
, No. 212, No. 4゜146.396, No. 4,22
Typical examples thereof include the oxygen atom elimination type two-equivalent naphthol couplers described in No. 8.233 and No. 4,296.200. Further, specific examples of phenolic couplers include U.S. Special Kitsuki No. 2,369.929 and No. 2,8
No. 01,171, No. 2.772.162, No. 2,
895.826, etc.

Among these, in the present invention, it is more preferable to use the cyan coupler of general formula (C) in the red-sensitive emulsion layer from the viewpoint of stability of photographic properties during continuous processing.

(In the formula, R1 represents an alkyl group, a cycloalkyl group, an aryl group, an amino group, or a heterocyclic group. R2 represents an acylamino group or an alkyl group having 2 or more carbon atoms. R3 represents a hydrogen atom, a halogen atom, or an alkyl group. or represents an alkoxy group.Also, R3 may be combined with R2 to form a ring.ZI is a hydrogen atom, a halogen atom, or an alkoxy group that can be separated in reaction with an oxidized product of an aromatic primary amine color developing agent. Indicate the bracket.

Preferred cyan couplers are not limited to these.

Cy.

(C-6) Granularity can be improved by using a coupler in which the coloring dye has an appropriate diffusibility. Examples of such dye-diffusive couplers are given in U.S. Pat. No. 4,366.237 and British Patent No. 2,125,570 for magenta couplers; , 234.533 describes specific examples of yellow, magenta or cyan couplers.

The dye-forming couplers and the special couplers described above may form dimers or more polymers. A typical example of a polymerized dye-forming coupler is U.S. Pat. No. 3,451,82.
No. 0 and No. 4,080°211. Specific examples of polymerized magenta couplers are described in British Patent No. 2,102,173 and U.S. Patent No. 4,367.2.
It is described in No. 82.

The various couplers used in the present invention can be used in combination of two or more types in the same layer of the photosensitive layer in order to satisfy the characteristics required for the photosensitive material, or the same compound can be used in two or more different layers. It is also possible to introduce more than one.

To introduce the coupler into the silver halide emulsion layer, known methods such as those described in US Pat. No. 2,322,027 can be used. For example, phthalic acid alkyl esters (dibutyl phthalate, dioctyl phthalate, etc.),
Phosphate esters (diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, dioctyl butyl phosphate), citric acid esters (
(e.g. acetyl tributyl citrate), benzoic acid esters (e.g. octyl benzoate), alkylamides (e.g. diethyl laurylamide), fatty acid esters (e.g. dibutoxyethyl succinate, diethyl acelate), trimesic acid esters (e.g. trimesic acid or organic solvents with a boiling point of about 30°C to 150°C, such as lower alkyl acetates such as ethyl acetate, butyl acetate, ethyl propionate, secondary butyl alcohol, methyl isobutyl ketone, β-ethoxyethyl acetate, methyl After dissolving in cellosolve acetate etc., it is dispersed in hydrophilic colloid. What are the above-mentioned high boiling point organic solvents and low boiling point organic solvents? May be used accordingly.

The coupler used in the present invention can be introduced into the light-sensitive material by various known dispersion methods. An example of a high boiling point organic solvent used in the oil-in-water dispersion method is U.S. Pat. No. 2,322,027.
It is written in the number etc.

Further, the process, effects, and specific examples of latex for impregnation of the Latin lath dispersion method as one of the polymer dispersion methods are disclosed in U.S. Patent No. 4.199.363 and West German Patent Application (OLS) No. 2,541.274. 2,541,230, etc., and a dispersion method using an organic solvent soluble polymer is described in PCTJP 87100492.

It is used in the above-mentioned oil droplet dispersion method. As the 8 agent, for example, phthalic acid alkyl ester (dibutyl phthalate!/-
phosphate, dioctyl phthalate, etc.), phosphoric acid esters (diphenyl phosphate, triphenyl phosphate, etc.)
・, tricresyl phosphate, dioctyl phosphate), citric acid esters (e.g. acetyl tributyl citrate), benzoic acid esters (e.g. octyl benzoate), alkylamides (e.g. diethyl laurylamide), fatty acid esters (e.g. dibutoxyethyl succinate, diethyl azelate), trimesic acid esters (e.g. tributyl trimesate), etc., or batter solvents with a boiling point of about 30°C to 150°C, such as lower alkyl acetate, butyl acetate, etc. Acetate, ethyl propionate, secondary butyl alcohol, methyl isobutyl ketone, β-ethoxyethyl acetate, methyl cellosolve acetate, etc. may be used in combination.

Typical usage amounts for color couplers range from o, aox to 1 mole per mole of light-sensitive silver halide, preferably from 0.01 to 0.2 mole for yellow couplers.
5 moles, 0.003 to 0.00 for magenta couplers.
3 mol, and for cyan couplers 0.002 to 0.
It is 3 moles.

The photographic material used in the present invention is coated on a commonly used plastic film (cellulose nitrate, cellulose acetate, polyethylene terephthalate, etc.), a flexible support such as paper, or a rigid support such as glass. be done. For details on the support and coating method, see Research Disclosure, Volume 176, ILeml 7643.
It is described in Section XV (P, 27) Section X1 (P, 28) (December 1978 issue).

In the present invention, a reflective support is preferably used.

A "reflective support" is a material that increases the reflectivity and makes the dye image formed in the silver halide emulsion layer clearer. Such a reflective support includes titanium oxide, zinc oxide, These include those coated with a hydrophobic resin containing dispersed light-reflecting substances such as calcium carbonate and calcium sulfate, and those using a hydrophobic resin containing dispersed light-reflecting substances as a support.

Next, preferred embodiments of the present invention will be described below.

(1) The processing method according to claim 1, wherein the color developer substantially does not contain hydroxylamine.

(2) The processing method according to claim 1, wherein the color developer contains an organic preservative.

(3) The amount of silver coated in the silver halide color photographic light-sensitive material is 0.
．． The treatment method according to claim 1, characterized in that the amount is 80 g/m or less.

(Example-1) The silver halide emulsion (1) of the pre-malignant silver halide emulsion layer was prepared as follows: 11! did.

(1 liquid) L5. Care, 2□=5O treatment 5. Care) 25g (2 liquids) Sulfuric acid (IN) 20cc (3
Liquid) The following compound (1%) 3ccc
I (3 □ H3 (4M) (5 liquids) AgNOt 25g
Add H2C to 130cc (6 liquids) "KBr O・70'A g N O
z 100 g [HzO added 285 cc (1 liquid) to 6
It was heated to 0°C, and (liquid 2) and (liquid 3) were added. Thereafter, (liquid 4) and (liquid 5) were added simultaneously over a period of 60 minutes. 10 minutes after the addition of (4 liquids) and (5 liquids), (6't
& ) and (liquid 7) were added simultaneously over a period of 25 minutes. After 5 minutes of addition, the temperature was lowered and desalted. Water and dispersed gelatin (
pl=5 lime-treated gelatin), adjusted the pH to 6.0, average particle size 1.0 mμ coefficient of variation (standard deviation divided by average particle size; s/d) 0° 11, bromide A monodisperse cubic silver chlorobromide emulsion containing 1 mol % of silver was obtained. Triethylthiourea was added to this emulsion to perform optimal chemical sensitization. Furthermore, after that, the following spectral sensitizing dye (Sen-
1) to I\7 per 1 l of silver halide emulsion
'Mole added.

Silver halide emulsion (2) in the green-sensitive silver halide emulsion layer and silver halide emulsion (3) in the red-sensitive silver halide emulsion layer.
) were also prepared in the same manner as above by changing the amount of chemicals, temperature, and addition time.

A spectral sensitizing dye (Sen) was added to silver halide emulsion (2).
-2) was added at 5X10-' mol per mol of the emulsion, and for silver halide emulsion (3), a spectral sensitizing dye (Sen
3) per mole of emulsion. 9XIO-' moles were added.

The shapes, average grain sizes, halogen compositions, and coefficients of variation of silver halide emulsions (1) to (3) are as shown below.

(1) Cube 0.11 1.0 0,11 (2) Cube 0.45 1.0 0.09 (3) Cube 0
．． 34 1.8 0.10 (Sen -1) I (CHz)n (CHz)4sO3ToN(Cz
lls) 2 (Sen -2) Using the prepared silver halide emulsions (1) to (3), a multilayer color photographic material having the layer structure shown below was prepared.

The coating solution was prepared as follows.

19.1 g of yellow coupler (ExY) was added to 2 ml of ethyl acetate to prepare the coating solution for the first layer.
7.2cc and solvent (Solv 1) 3°8CC
This solution was mixed with 10% gelatin containing 8 cc of 10% sodium dodecylbenzenesulfonate (pl=
5) Water was emulsified and dispersed in 185 cc of liquid. On the other hand, a silver halide emulsion (1) was prepared in which a blue-sensitive sensitizing dye (Sen-1) was added at 5.0×10 −' moles per mole of silver.

The above emulsified dispersion and this emulsion layer 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-
For the 9 red-sensitive emulsion layer using dichloro-5-4 riazine sodium salt, the following compound was added in an amount of 1.9XIO-' mol per mol of silver halide.

In addition, for the blue-sensitive emulsion layer, 4-hydroxy-6-methyl-1,3,3a,7-chitrazaindene was added to the halogenated i
1.0 x 10-'' mole was added per mole of barb.

In addition, 1-(5
-medylureidophenyl)-5-mercaptotetrazole at 1.0% per mole of silver halide, respectively. OX],
0-'mol,! ,,5XlO-'' moles were added.

Further, 2.5XIO-' mol of 2-amino-5-mercapto-1,3,4-thiadiazole was added per mol of silver halide to the red-sensitive emulsion layer.

The composition of each layer is shown below.

(Constituent layer) Paper support laminated on both sides with polyethylene support [white pigment: Ti (h (2.7 g/r
rf) and bluish dyes (including ultramarine) No.-N (blue-sensitive layer) Silver halide emulsion (1) 0.26 Gelatin (p+=5 lime treatment > 1.13 Yellow color (ExY) 0.66 solvent(
Solv-1) 0. 28 Second N (mixing prevention layer) Gelatin (Lime treatment of PL Mi 5) 0.89 Mixing prevention agent (Cpd ~ 1) 0.08) Vehicle (Solv -1)
0. 20 solvent (Solv-2)
0. 20 dye (T-1)
0.005 Third layer (green sensitive layer) Silver halide emulsion (2) 0. 29 Gelatin (Lime treated with p+=5) 0.99 Magenta Coupler (ExM-1) 0. 25 color image stabilizer (Cpd-2) 0. 10 color image stabilizer <Cpd-3) 0. 05 Color image stabilizer (Cpd-4) 0. 07 color image stabilizer (Cpd~5) 0.017 volume (
Solv-2)
0. 19 Solvent (Solv-3)'
0. 15 Fourth layer (ultraviolet absorption layer) Gelatin (lime treatment with pl=5) 1.42 Ultraviolet absorber (UV-1) 0.52'tR combination inhibitor (Cpd -1) 0. '06?
Container (Solv-4)
0. 2 6 dye (T-210,01
5 Fifth layer (red-sensitive layer) Silver halide emulsion (3) 0. 22 Gelatin (Lime treated with pT=5) 1.06 Cyankabra (ExC-1) 0. 08(ExC
2) 0. 03 (ExC-3)
0. 19 color image stabilizer (Cpd-6)
0. 32 color image stabilizer (Cpd-7)
0. 18-ton capacity (Solv-4)
0. 10 solvent (Sol
v-5) 0. 10 solvent (Sol
v-6) 0. 11 Sixth layer (ultraviolet absorption layer) Gelatin (lime treatment with pl = 5) 0.4837 External radiation absorber (LJ■-1) 0.18 Solvent (Solv
-4) 0. 08 dye (T-2)
01005 Seventh layer (protective layer) Gelatin (p, I = 5 lime treatment) 1.33 Acrylic modified copolymer of polyvinyl alcohol (degree of modification 17%) 0.05 Liquid paraffin 0.03 (ExY) Yellow coupler ( (Equivalent to Y-2) (ExM-1) Magenta coupler (Equivalent to M-1) (ExC-1) Cyan coupler (Equivalent to C-2) (Ex
C-2) Cyan coupler (equivalent to C-1) (ExC-3
) Cyan coupler (corresponding to C-3) The structure of the compound used is as follows.

(Cpd-1) Color mixing prevention agent H (Cpd-2) Color image stabilizer C1h [;111 (Cpd-3) Color image stabilizer (Cpd-4) Color image stabilizer (Cpd-5) Color image stabilizer (Cpd-6) Color image stabilizer 1-+CHz CHYf- ＾0NHC, Hq (t) Average bone 7-mass; 60. oo.

(Cpd-7) Color image stabilizer n++ cnHl(t) 4:2:5:mixture (weight ratio) (Ul-1) Ultraviolet absorber H CsH++ (t) 0■12:1. O: 3 mixture (ffi amount ratio) (S
1) Solvent (Solv-2) Solvent (5olv4) Solvent 0=P(0-Cq H,,-5io)+(Solv-5
) Solvent (T-1) (T-2) ++0 0H
Ill l1
1pH Cl1z.

Next, samples 102 to 111 were prepared by changing the types of gelatin used in the first to seventh layers as shown in Table 1.

The following experiment was conducted to investigate the photographic properties of these coated samples.

First, the coated sample was subjected to gradation exposure for sensitometry using a sensitometer (Model FWH manufactured by Fuji Photo Film Co., Ltd., color temperature of light source: 3200°K). The exposure at this time was carried out at an exposure time of I/l 0 seconds and an exposure amount of 250 CMS.

Next, continuous processing (running test) was carried out using the following processing steps and the following processing solution composition until twice the tank capacity of the color developer was replenished.

``■ Excessive processing'' Degree: Poetry 1L (Amount: Illusion heavy color development 38°C 45 seconds 65ml 6N Bleach fixing 30-36°C 45 seconds +61d 8ffi rinse■ 30-37°C 20 seconds -41 rinse■ 30
~37°C 20 seconds -41 rinse■ 30~37'C
20 seconds -42 rinse ■ 30~37°C 30 seconds 2
00% 4p Sensitivity Drying 70-80" C60 seconds Photosensitive material In (per [Rinse: tank countercurrent method from ■ to ■") The composition of each processing solution is as follows.

Left i two current plate remains” Oioka filtration x sprinkling
800m1 800
methylenediamine-N.

N,N',N'-tetramethylenephosphonic acid 3.5g 6.5
g Organic preservative A (χ-19) 0.04 mol
O,08mol Sodium chloride 4.6g
- Potassium carbonate 25 g
25 g N-ethyl-N-(β methanesulfonamidoethyl)-3-methyl-4-aminoaniline sulfate 5.0 g 12.0
g Organic preservative B (X [V-1) 0.05 mol
0.05 mo + optical brightener (4,4'-diaminostilbane J-" and -1" yl Add water 100Cld 100
0dpH (25°C'I 1.0.05
10.85I-White''-Chikuichioka (tank liquid top replenishment liquid is the same) water
400ml ammonium thiosulfate (70%)
l OOd Sodium sulfite
17g Iron (III) ammonium ethylenediaminetetraacetate 55g Disodium ethylenediaminetetraacetate 5g Ammonium bromide 40g Ice vinegar
-f- Add water to 1000 mILp
H (25°C) 5.40 Rinse liquid (
Tank fluid and refill fluid are the same) Ion exchange water (3 pp each of calcium and magnesium)
below m), process the sensitometry at the start and end of the running test, and measure blue (B), green (G) and red (
R) minimum density (Dmin) and maximum density (Dmax)
and gradation (0.5 in log E from a point that does not represent a density of 0.5).
3. The amount of change in the density difference up to the density point on the high exposure side) due to continuous processing was measured using a Macbeth densitometer, and the results are shown in Table 2.

At the same time, unexposed color 4 was processed at the end of the run for evaluation of yellow, magenta, and cyan stain after processing.
After treatment, each sample was incubated at 80°C and 70% relative humidity for 10 minutes.
The samples were stored for several days and changes after storage were examined, and the results are shown in Table 2.

From Table 2, sample 1 containing more than 10 wt% of acid-treated gelatin compared to sample 101.102, which contains only a drop of 10 wt%.
It can be seen that samples Nos. 03 to 111 show little variation in photographic properties due to continuous processing, and the increase in staining after processing is also significantly reduced.

Further, the layer containing acid-treated gelatin may be any layer,
It can be seen that it is more preferable to contain l 5 wt % or more than l 0 wt % or more.

Further, from the comparison between Samples 103 and 111, it can be seen that acid-treated gelatin having a higher isoelectric point is more preferable.

(Example 2) Sample 301 was prepared in the same manner as Sample 104, except that the yellow, magenta, and cyan couplers used in the first, third, and fifth layers of Sample 104 of Example 1 were changed as shown in Table 3. ~3
10 was created. (The couplers were replaced in equimolar amounts.

Regarding Samples 301 to 310 in Table 3, the photographic characteristics of continuous processing and the stain after processing were investigated in the same manner as in Example 1.
All samples were good.

(Example 3) Organic preservative A (X-1) of the color developer used in Example 1
Color developers (]) to (2) were prepared using the compounds shown in Table 4 in place of 9) and B(XIV i).

/ / Table 4 Sample 104 was continuously processed in the processing steps of Example 1 using color developers (1) to (22), and the photographic properties and stain after processing were investigated. Development containing hydroxylamine!
(1), (2) and developer containing sulfite (2), (3)
), the effect was diminished and the photographic properties (especially maximum density and gradation) changed slightly; however, in the case of developer solution (4 ) to (22), the photographic properties hardly changed and the storage stability after processing was good.

(Example 4) The first layer, third layer, and fifth layer of sample 104 used in Example 1
Sample 10 except that the amount of coated silver in the layer was changed as shown in Table 5.
Samples 501 to 5 (]4 were prepared in the same manner as in 4. (Unit: g/ITf) Table 5 After imagewise exposure of the above photosensitive material, using a paper processing machine,
Continuous processing (running test) was performed using the following processing steps and processing solution until twice the tank capacity for color development was replenished.

JIAIL process Temperature: Low light intensity * Capacitive color development 39°C 60 seconds 30dt 4ff
i Bleach fixing 30-36°C 45 seconds 215ml! 4
N Stable ■ 30~37'C 20 seconds -2i Stable ■ 30~37'C 20 seconds -21 Stable ■ 30~37''C 20 seconds -22 Stable ■ 30~37'C 30 seconds 250d 21 Dry
Drying: 70 to 85° C., 60 seconds *per 1rd photosensitive material (4 tank countercurrent system from stable ■ to ■) The composition of each processing solution is as follows.

Sadan 2 retreats 14 ”Basuke Sukeshin J Ryosui
800m1800m
j! Ethylenediaminetetraacetic acid 5.0g 5.0
g5.6-cyhydroxyhensen-1.2.4-trisulfonic acid 0.3g 0.3g
Organic preservative A (X-19) 0.04mol 0
．． 09mof sodium chloride 8.4g
- Potassium carbonate 25g
25gN=ethyl-N-(βmethanesulfonamidoethyl)-3-methyl-4-aminoaniline sulfate 5.0g 15.0
gOrganic preservative B (X IV 1) 0.05m
ol 0.06mol Fluorescent Whitening M (4,4' Monodiaminostyl Bakelite 2.LE 5.
0 and add water 1. OOOml
1. OOOm1pH (25°C) 10.
25 11.00! "I constant - standing liquid (tank liquid and replenisher liquid are the same) water
400rd ammonium thiosulfate (70%)
100d sodium sulfite
17g Iron(III) ammonium ethylenediaminetetraacetate 55g Disodium ethylenediaminetetraacetate 5g Wood vinegar
9 Add water
1000mlp100O'C) Also, constant coating (tank liquid and replenisher liquid are the same) Formalin (37%) 0.1g Photographic properties during continuous processing and staining after processing were investigated in the same manner as in Example 1, and the amount of coated silver was Is it 0°80g/IT? Compared to the larger samples 501 and 502, samples 503 and 504 with a weight of 0.8 g/I or less were superior in terms of photographic properties during continuous processing and thermal sine after processing.

Patent Applicant Fuji Photo Film Co., Ltd. Procedural Amendment 1, Case Indication Patent Application No. 13 of 1988! Tata 6
No. 2, Name of the invention Processing method for silver halide color photographic light-sensitive materials Relationship with the person making amendments in 38 Patent applicant Address 210 Nakanuma, Minamiashigara City, Kanagawa Prefecture Name (520) Fuji Photo Film Co., Ltd. Contact address 106 Nishiazabu 2, Minato-ku, Tokyo
Chome 26-3oυ4, Subject of amendment The description in column 5 of "Detailed Description of the Invention" of the description and the section of "Detailed Description of the Invention" of the description of the contents of the amendment will be amended as follows.

1) Change the structural formula of page to (M-, -j) to “ and correct it.

2) Structural formula of tth/page (M-≠) and correct it.

3) First, general formula (C) on page 1 is [General formula (c) and correct it.

4) The structural formula of page t≠ (C-7) is [ /ρ2− 5) Structural formula of page #4 (cpct-Hiroshi) and correct it.

6) Page 102 Correct the structural formula of (Cpd-j).

1999? Display of Monthly Day 16 Case 1985 Patent Application No. 73! Puri No. 2, Name of the invention Processing method for silver halide color photographic light-sensitive materials 3, Relationship with the case of the person making the amendment Patent applicant Location 210 Nakanuma, Minamiashigara City, Kanagawa Prefecture Name (520) Fuji Photo Film Co., Ltd. Contact information 106 Tokyo Port! Nishiazabu 2
Chogetsu 26-30 No. 4, Subject of amendment The description in the "Detailed Description of the Invention" column 5 of the description and the "Detailed Description of the Invention" section of the description are amended as follows.

■) Page 14, line 4 "Hydroquinamines" "Hydroxylamines" and correct it.

2) Page 58, line 13 "Trauss cyclo" "Transcyclo" (to be under pressure)

3) Page 63, line 17 "Usually 5.5-8" "Usually 4.5-8" and correct it.

4) In Table 4 on page 116, '(1) J ["Hydroxyamine" in the organic preservative AJI is corrected to "Hydroxylamine."

5) In Table 4 on page 116, '(18)J, r)W-10J in the column ``Organic preservative B'' is corrected to ``Megumi-10''.

6) On page 116, line 4, after "It was good." [In particular, color developers (4), (5), (5), which are combinations of hydroxylamines or hydrazines and amines.
7), (11) to (14), (21), and (22), the effect was remarkable as in Example 1. ” is inserted.

Claims (1)

[Claims] A method in which a silver halide color photographic light-sensitive material is continuously processed with a color developer containing at least one aromatic primary amine color developing agent, in which at least one layer of a high silver chloride emulsion containing 80 mol% or more of silver chloride is added. and in which 10 wt% or more of the total coated gelatin is acid-treated gelatin, the color developer is replenished in an amount of 20 to 120 ml per 1 m^2 of the silver halide photographic light-sensitive material. 1. A method for processing a silver halide color photographic material, which comprises processing with a certain color developer.