JPH01186939A - Processing method for silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a silver halide color photographic sensitive material having excellent color formability by processing the silver halide color photographic sensitive material with a specific color developing soln. after exposing. CONSTITUTION:The silver halide color photographic sensitive material is processed, after exposing, by the color developing soln. contg. at least one kind of arom. primary amine color developing agents. at least one kind of the hydrazines and hydrazides expressed by formula I and at least one kind selected from the monoamines expressed by formula II and the condensed ring type amines expressed by formula III. In formulas, R<1>-R<3> denote a hydrogen atom, alkyl group, etc.; R<4> denotes a hydrogen atom, hydroxy group, etc. X<1> denotes a divalent group; (n) denotes 0 or 1. R<5>-R<7> denote a hydrogen atom, alkyl group, etc.; X denotes a trivalent atomic group necessary for perfecting the condensed ring; R<8>, R<9> denote an alkylene group, etc. The stability and color formability of the color developing soln. are thereby improved and an increase in fogging at the time of continuous processing is decreased.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a method for processing a silver halide color photographic light-sensitive material, and in particular, it relates to a method for processing a silver halide color photographic material, and in particular, a method that improves the stability and color development of a color developer, and , relates to a processing method in which the rise in capri during continuous processing is significantly reduced.

(Prior Art) Color developers containing aromatic primary amine color developing agents have long been used to form color images, and currently play a central role in color photographic image forming methods. Fulfilling.

However, the color developer mentioned above has the problem that it is very easily oxidized by air and metals, and when an oxidized developer is used to form a color image, the color image has an increased capri, sensitivity, and color image. It is well known that the desired photographic characteristics cannot be obtained due to the rounding of the tones.

Accordingly, various means for improving the preservation properties of color developers have been studied, and among them, the most common method is to use hydroxylamine and sulfite ions in combination. However, when hydroxylamine is decomposed, ammonia is generated, which does not cause capri, and sulfite ion acts as a competitive compound for the developing agent and inhibits color development. It is hard to say that it is preferable as a compound (preservative) that improves the preservability of the developer.

% Sulfite ion has been used for a long time as a compound that improves the retention of various developing agents or completely prevents the decomposition of hydroxylamine. When used in a system that does not contain benzyl alcohol, the color density is significantly reduced.

JP-A-54-353 as a compound to replace sulfites
Alkanolamines described in No. 2 and JP-A-56-943
As stated in issue 49? Diethyleneimines have been proposed, but even with these compounds, sufficient effects cannot be obtained.

In addition, in order to improve the stability of color developers, various preservatives and intermediate rate agents have been investigated. For example, as a preservative, JP-A-52-49828,
No. 9-160142, No. 56-47038, and aromatic polyhydrocarbon compounds described in U.S. Pat. No. 3,746,544, etc.; Compounds with a neutral radical, JP-A-52-143020 and JP-A-53-8942
α-aminocarginyl compound described in No. 5, JP-A-57-
Metal salts described in No. 44148 and No. 57-53749,
and samic acid described in JP-A No. 52-27638. Also ml? As a rate agent.

Amino 4 radicals/acids described in Japanese Patent Publication Nos. 48-30496 and 44-30232, JP-A-56-97347
No., Special Publication No. 56-39359 and West German Patent No. 2,227
, organic phosphonic acids described in No. 639, JP-A-52-10
No. 2726, No. 53-4273Q, No. 54-1211
No. 27, No. 55-126241 and No. 55-6595
Phosphonocarboxylic acids described in No. 6, etc., and other JP-A No. 5
Examples thereof include compounds described in Japanese Patent Publication No. 8-195845, No. 58-203440, and Japanese Patent Publication No. 53-4090Q.

(Problems to be Solved by the Invention) However, even when these techniques are used, satisfactory results have not been obtained because the preservation performance is insufficient and photographic properties are adversely affected. In particular, the emergence of an excellent preservative to replace sulfites is desired.

Furthermore, benzyl alcohol, which is very effective as a color development accelerator for color developing agents, is widely used in developing solutions for silvery oxide color photographic light-sensitive materials. Because of the problems such as the difficulty of

Furthermore, it is described in JP-A-58-95345 and JP-A-59-232342 that color photographic materials containing silver chlorobromide emulsions with a high chlorine content are susceptible to fogging during color development. When using such an emulsion,
A preservative that has low emulsion solubility and excellent preservative performance is essential, but no preservative that is fully satisfactory in this sense has yet been found.

An object of the present invention is to provide a method for processing a silver halide color photographic material in which the amount of damage is significantly reduced.

Another object of the present invention is to provide a complete method for processing a silver halide color photographic light-sensitive material that exhibits excellent color development even though it is processed with a color developer that does not substantially contain benzyl alcohol.

(Means for solving the problem) It has been found that the above purpose can be effectively achieved by the second son method described below.

After exposure, the silver halide color photographic material is mixed with at least one aromatic primary amine color developing agent, at least one of hydrazines and hydrazino groups, and at least one selected from monoamines and fused cyclic amines. 1. A method for processing a silver halide color photographic light-sensitive material, the method comprising processing a silver halide color photographic material with a color developer containing the following.

The compounds used in the present invention will be explained in detail below.

The compound of general formula (1), the hydrazine analogs consisting of the dihydrazines and the k-dracites used in the present invention will be explained in detail below.

R', R2 and R are each independently a hydrogen atom, a substituted or unsubstituted alkyl group (preferably a carbon number of 1 to 20
, for example, a methyl group, an ethyl group, a sulfopropyl group, a carboxydiptyl group, a hydrodiethyl group, a cyclohexyl group, a benzyl group, a phenethyl group, etc.), a substituted or unsubstituted aryl group (preferably having 6 to 20 carbon atoms, e.g. phenyl group, 2.5-dimethoxyphenyl group, 4-hydroxyphenyl group, 2-cal is xyphenyl group) or substituted or unsubstituted heterocyclic group (preferably 1 to 20 carbon atoms, preferably 5 to 6 carbon atoms) It is a membered ring containing at least one of oxygen, nitrogen, sulfur, etc. as a heteroatom, such as pyridin-4-yl group, N-acetylbizelidin-4-yl group, etc.).

R4 is a hydrogen atom, a hydroxy group, a substituted or unsubstituted hydrazino group (for example, a hydrazino group, a methylhydrazino group, a phenylhydrazino group, etc.), a substituted or unsubstituted alkyl group (preferably a carbon number of 1 to 20, for example, methyl 4-substituted or unsubstituted aryl group (preferably 6 to 6 carbon atoms) 20.Example,
phenyl i, 2,5-dime)-? diphenyl group, 4
-hydroxyphenyl group, 2-cal is xyphenyl group,
2-carxyphenyl group, 4-sulfophenyl group, etc.), substituted or unsubstituted heterocyclic group (preferably carbon number 1-20, preferably 5-6 membered, and heteroatoms include oxygen, nitrogen, sulfur) (e.g., pyridin-4-yl group, imidazolyl group, etc.), a substituted or unsubstituted alkoxy group (preferably a carbon number of 1 to 201, e.g., methoxy group, methoxy group).

methoxy group, benzyloxy group, cyclohexyl group, octyl group, etc.), substituted or unsubstituted oroxy group (preferably 6 to 20 carbon atoms, e.g. phenoxy group, p-methoxyphenol group) , p-cal M
df diphenyl group, p-sulfophenoxy group, etc.), a substituted or unsubstituted carbamoyl group (preferably a carbon number of 1 to 20°, e.g. an unsubstituted carbamoyl group, N, N-
Diethylcarbamoyl group, phenylcarzanyl group!
l'> 9 is a substituted or unsubstituted amino group (preferably carbon number θ to 20; for example, an amino group, a hydroxyamino group, a methylamine group, a hexylamino group, a methoxydiethylamino group, a diethylamino group, a sulfonate group); Ethylamino group, N-phenylamino group, p-sulfophenylamino group >Vt.

R' e R' e R' and R40 as further substituents.

Halodan atoms (chlorine, bromine, etc.), droxy groups, alkali groups, sulfo groups, amino groups, alco groups, amido groups, sulfonamido groups, carbamoyl groups, sulfamoyl groups, alkyl groups, aryl groups, arylthio groups , ruthio group in alkali, arylthio group, nitro group, cyano group, sulfonyl group, sulfinyl group, etc., which may be further substituted.

xl is preferably a divalent organic residue, specifically, for example, -co-1-so□-1 and -C-
represents. n is 0 or 1. It's nine, and when n ■ 0,
R4 represents a group selected from substituted or unsubstituted alkyl groups, aryl groups, and heterocyclic groups. R and R and R3 and R4 may jointly form a heterocyclic group.

When n is 0, at least one of R-H is preferably a substituted or unsubstituted alkyl group. In particular, R'
e R2e R' and R4 are preferably a hydrogen atom or a substituted or unsubstituted alkyl group. (However, R
, R, R, and R are never hydrogen atoms at the same time. ) In particular, when R, R and R3 are hydrogen atoms, and R4 is a substituted or unsubstituted alkyl group, R1 and R3 are hydrogen atoms, and R2 and R4 are substituted or unsubstituted alkyl groups. or when R and R are hydrogen atoms, and BS and R4 are substituted or unsubstituted alkyl groups (in this case, ns and R4 may jointly form a heterocycle).

In the case of n5sl, -CO- is preferable as Xl, and R
4 is preferably a substituted or unsubstituted amino group,
R1-R3 are preferably substituted or unsubstituted alkyl groups.

“N is preferably 0.

The alkyl group represented by R1-R4 preferably has 1 to 10 carbon atoms, more preferably 1 to 10 carbon atoms.
~7. Preferred substituents for the alkyl group include hydroxyl group, carboxylic acid group,
Mention may be made of sulfonic groups and phosphonic acid groups. When there are two or more substituents, they may be the same or different.

The compound of general formula (1) is "t R2e R'#
It may form a bis body, a tris body, or a polymer linked by R'.

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

CH, NHNHCH.

HOOCCH2NHNHCH2COOHNH2NH-Yu CH2+r-NHNH2NH2NHCH2CH20H NH2NH-(CH2) 4-5o3HNH2NH-(
CH2) 3- C00H (Summer -17) NH2NHCH2CH2COONm NH2NHCH2COONm H2NNHCH2CH2So, Na C41 (Jn) H2NNHCHCOOH C4H7 (Company) )I2NN -+CHCOOH) 2 H2NN-eCM2C H, 8038m)2H2NN-+
CH2C) (2CH,, So, Na) 2 gates H2NNHCHCOOH (I-31) H2 Average molecular weight approx. 4,000 Average molecular weight approx. 20,000 NH2NICONH2 NH NU2NHCNH2 NH2NHCONHNH2 NH2NISO3H NH2NH8O□N HNH2 CH3NHNH8O2NHNHCH.

NH2NHCONH-(CH2), -NHCONH
NH2NH2NHCOCONHNH2 NH2COCONHNH2 (I-49) (l-56) NHcONHNH2 l Na0,5CH2CH2NHCNHNH2 (I-61) (I HOOCCH2CH2NHCNHNH2NH2NHCO
OC2H5 (I-64) NH2NHCOCH3 NH2NHCH2PO3H2 H2 (CH,), CCONHNH2 (CH,), C0CNHNH2 N C0NHNH.

HOCH2CH2go2NHNH2 (I-81) NaO,5CH2CH2CONHNH2H2NCONH
CH2CH2So2NHNH2(1-84) H2NN) 61-173468 specification page 9~
Examples of the compounds described on page 19 and the like are given.

Many of the compounds represented by the general formula (1) are available as commercial products, and are also available from "Organic Syntheses J
C (111°Vol, 2*pp 208-21
3: Joar, Am*r, Chem.

Soc, 36, 1747 (1914): Oil Chemistry, 24, 31 (1975); Jour,
Org, Chem-+ 25 e 44 (1960)
: Pharmaceutical Journal, 91.1127 (1971): “Organic Synthesis xJ (Organic 5y
ntheses ) # Ce1l eVol, 1=p
450: New Experimental Chemistry Course, Volume 14.

I[1, p 1621-1628 (Maruzen): B@
i1. t2.

559: B@l 1- * 3 + 117:
E, B6Mohr et al-) rnarg, S
yn, e 4 s 32 (1953): F* J*
Wilson *E, C, P1ekering, J
, Chem, 5ee-e 123 e 394 (1
923) SN, J, L@onard+ J, H,
Boysre J, Org.

Chem, 15.42 (1950): Organl c 5ynth
eses) e Col 1, Mol, Lp
1055: P-A-8, Sm1th+ r D
*rvsitives ofhydrazln* a
nd other hydrogen
avingn-n-bondsJ #p 120
~124s p 130~131;〒HE BENJ
AMTN/CUMMING8 COMPANY.

(1983): 5tanlsy Re 5andi
Er Waif Karo.

``Organie Functional Group
PraparatlonsJ +Vol1. L5e
It can be synthesized according to general synthesis methods such as cond Editions p 457.

The amount of the hydrazines and hydrazides represented by the general formula (1) used in the present invention is as follows:
0.0111-501 preferably 0.11-30I
, more preferably 0.51 to log.

Monoamines in the present invention are compounds represented by the following general formula (II).

General formula (It) R-N-R' In the formula, R, R, and R represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an aral group, or a heterocyclic group. Here, R5 and R6, R5 and R2, or R and R may be connected to form a nitrogen-containing complex*1-.

Here, R, R, and R may have a substituent. R,
R and R are particularly preferably a hydrogen atom or an alkyl group.

Examples of the substituent include a hydroxyl group, a sulfone group, a cargexyl group, a halodane atom, a nitro group, and an amine group.

Specific examples of the compound represented by general formula (1) are listed below, but the present invention is not limited thereto.
゛1 N-G-CH2CH20H) 3 H2NCH2CH20H H2NCH2CH20H)2 OH C,H,5N+C) (2CHCH20H) 2 to 5 ■-10 (HOCH2CH2+2NCH2CH2So 2CM3
■Bow I HN(-CH2COOH) 2 ■-12! (00CCH2CH2CHCOOH OH2 H2NCH2CH2S02NH2 ■ -14 H2N - C (- CH20H) 3 ■ - 16 HOCH2CHCOOH OH2 ■ -17 00H.

H-18 II-19 As the above-mentioned compound, commercially available products can mainly be used.

The fused cyclic amines in the present invention are represented by the following general formula (10):
It is a compound represented by

General formula (to) ＼R9 In the formula,
Represents an alkenylene group or an aralkylene group.

Therefore, R'#R' may be the same or different from each other.

Among general formulas (2), particularly preferred are general formulas (1-
These are compounds represented by a) and (1-b).

(R12) In the formula, X2 is one! -Represents N or ΣCH. R10゜/ / R11 is defined in the same way as in general formula (XW), and R
represents R, a group similar to R, or -CH, C-.

is preferred. The number of carbon atoms in R, R, and R is preferably 6 or less, more preferably 3 or less, and most preferably 2.

Preferably, R, R, and R are an alkyl group or an arylene group, and most preferably an alkyl group.

In the formula, R and R are defined as in general formula (2).

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

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

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

1l-1 [1-5 CH20H ■-8 CH3 ll-10 III -11 H ll-13 ll-14 ■-16 ■-18 General formula according to the present invention (many compounds in the song are easily available commercially) is possible.

In addition, it can be synthesized according to the following literature.

*Khim, Get@rotslk1.8o@dim
,, (2) e272-5 (1976).

・υ, 8. U3329fu701-10J
an 1967.6pp.

-U, S, US 3375252. 26 Mar
1968.2pp-・Khim, G@t@ratsl
lcl, 8o@din-s (a) @1123~
6 (1976).

-U, S, US 4092316.30 May 19
78.7pp.

The amount of the compound of general formula (II) and (B) to be added is 0.1 g to 50 g per color developer 11, preferably o, s11.
~20I.

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

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

D-IN, N-diethyl-p-7 22-diamine D-22-amino-5-diethylaminotoluene D-3
2-amino-5-(N-ethyl-N-laurylamino)
Toluene D-44-(N-ethyl-N-(β-hydroxyethyl)amino)aniline/D-52-methyl-4-[N-ethyl-N-(β-hydroxyethyl)aminecoaniline D-64- Amino-3
-Methyl-N-ethyl-N-[β-(methanesulfonamido)ethyl]-aniline D-7,N-=(2-amino-5-diethylaminophenylethyl)methanesulfonamide D-8N, N--/ Methyl-p-phenylenediamine D-94-amino-3-methyl-N-ethyl-N-
Methoxyethylaniline D-104-amino-3-methyl-N-ethyl-N-β
-Ethoxyethylaniline D-114-amino-3-methyl-N-ethyl-N-β
-Phthoxyethylaniline Among the above p-phenylenediamine derivatives, 4-amino-3-methyl-N-ethyl-N-(β-(
methanesulfonamido)ethyl]-aniline (exemplified compound D-6).

Further, these p-phenylenediamine derivatives may be salts such as sulfate, hydrochloride, sulfite, and p-)luenesulfonate. The amount of the aromatic-grade amine developing agent used is preferably about 0.1 g to about 2
1, and preferably from about 0.51 to about 10.9.

The color developer preferably does not substantially contain benzyl alcohol in view of any necessary development enhancement. Here, "substantially no benzyl alcohol is contained" means that the amount of dibenzyl alcohol used in color development 111) is 2d or less. Preferably, it does not contain any benzyl alcohol.

In addition, color developers require other preservatives such as sulfites such as sodium sulfite, potassium sulfite, sodium bisulfite, potassium bisulfite, sodium metasulfite, potassium metasulfite, and CalS-nyl sulfite adducts. It can be added accordingly. The amount added to these color developers is 011 to 2011/l or less, preferably OI
i~511/1 Other preservatives US Pat. No. 3,61
5,503 and British Patent No. 1,306,176, α-aminocardenyl compounds described in JP-A-52-143020 and JP-A-53-89425, JP-A-57-44148 and 57-537
Various harvested metals described in No. 49 etc., JP-A-52-10272
Various saccharides described in No. 7, α described in No. 59-160141
, α'-radical may contain nylation, etc., as necessary, and two or more of these preservatives may be used in combination as necessary, even if necessary. Particularly preferred is the addition of an aromatic polyhydroxy compound.

The color developer used in the present invention preferably has a pH of 9
-12, preferably 9-1.1.0, and the color developer may contain other known developer component compounds.

In order to maintain the above-mentioned -, it is preferable to use various buffering agents. Buffers include carbonate, phosphate, borate, tetraborate, hydroxybenzoate, glycine salt, N
, N-dimethylglycine salt, leucine salt, norleucine salt, guanine salt, 3,4-dihydroxyphenylalanine salt, alanine salt, aminobutyrate, 2-amino-2-methyl-1,3-pro/4-diol salt, valine Salts such as florin salt, trishydroxyamine methane salt, lysine salt, etc. can be used. In particular, carbonates, phosphates, tetraborates, and hydroxybenzoates are soluble at pH 9.0.
These buffering agents have excellent buffering capacity in the above-mentioned high range, have no adverse effects on photographic performance (fogging, etc.) even when added to color developing solutions, and are inexpensive. Particularly preferred.

Specific examples of these buffers include sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, dipotassium phosphate, disodium phosphate, dipotassium phosphate, sodium borate, and boric acid. Potassium, sodium tetraborate (borax), potassium tetraborate, sodium O-hydroxybenzoate (sodium salicylate), potassium 0-hydroxybenzoate, sodium 5-sulfo-2-hydroxybenzoate (5-sulfosalicylic acid) sodium), potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate), and the like. However, the present invention is not limited to these compounds.

The amount of the buffer added to the color developer is 0.1 mol/!
It is preferably 0.1 mol/l to 0.1 mol/l or more.
Preferably it is 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.

The chelating agent is preferably an organic acid compound, for example %
Aminopolycarzanic acids described in Bunsho 48-30496 and Bunsho 44-30232, JP-A-56-97347, Japanese Patent Publication No. 56-39359, and West German Patent No. 2,227
, organic phosphonic acids described in No. 639, JP-A-52-10
No. 2726, No. 53-42730, No. 54-1211
No. 27, No. 55-126241 and No. 55-6595
Phosphonobutanoic acids described in No. 06, etc., and other JP-A No. 1973
Compounds described in Japanese Patent Publication No. 8-195845, No. 5B-203440, and Japanese Patent Publication No. 53-40900 can be obtained. Specific examples are shown below, but the invention is not limited to these.

Nitrilotriacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, N,N,N-)rimethylenephosphonic acid, ethylenediamine-N,NON',N'-tetramethylenephosphonic acid, transcyclohexanecyaminetetraacetic acid, 1.2- Diaminopropane tetraacetic acid, glycol ether diamine tetraacetic acid, ethylenediamine orthohydroxyphenylacetic acid, 2-phosphonobutane-1,2,4-
Tricardic acid, 1-hydroxyethylidene-1,1-
diphosphonic acid, N,N'-bis(2-hydroxybenzyl)ethylenediamine-NIN'-diacetic acid, etc.

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
This F) is about 0.11i to 1011.

Any development accelerator can be added to the color developer if necessary. However, the color developer of the present invention does not substantially contain benzyl alcohol in terms of pollution, liquid formulation properties, and capri prevention.

The compounds of general formula (1) and the compounds of general formulas (u) and (II) used in the present invention have a remarkable effect on the stability of color developing solutions that do not substantially contain benzyl alcohol.

Other development accelerators include Japanese Patent Publications No. 37-16088, No. 37-5987, No. 38-7826, No. 44-
No. 12380, No. 45-9019 and U.S. Patent No. 3,
813,247, etc., p-7 22 diapone compounds shown in JP-A-52-49829 and JP-A-50-15554, JP-A-50-137726, JP-B-Sho. 44 -30074, JP-A-56-156826 and JP-A-52-43429,
Quaternary ammonium salts represented by U.S. Patent No. 2.
No. 494,903, No. 3,128,182, No. 4.2
No. 30.796, No. 3,253.919, Special Publication No. 1977
-11431, U.S. Pat.
-25201, U.S. Pat. No. 3,128,183, Japanese Patent Publication No. 41-11431, No. 42-23883, and U.S. Pat. Diru-3-pyrazolidones, imidazoles, etc. can be added as necessary.

In the present invention, any anti-capri agent can be added as required. 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 anti-capri agents include benzotriazole, 6-nitroindazole, 5-nitroindazole,
Nitrogen-containing heterocycles such as 5-methylbenzotriazole, 5-nitropenztriazole, 5-chloro-penztriazole, 2-thiacylylinoximidazole, 2-thiazolylmethyl-benzimidazole, indazole, hydroxyazoinsyridine, adenine Compounds can be cited as representative examples.

The color developer used in the present invention preferably contains a fluorescent brightener. As a fluorescent whitening agent, 4.4'-
Cyamino-2,2'-disulfostilbene compounds are preferred, the amount added is OIi~511/1, preferably 0.1
．． 9' to 411/l.

Further, various surfactants such as alkaline sulfonic acid, arylphosphonic acid, aliphatic carnic acid, and aromatic carunic acid may be added as required.

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. It is preferable that the replenishment amount is small, but it is 20 to 600 - preferably 5 per 1 m of photosensitive material.
0~3001Li! ! It is. More preferably 100-
~200d.

Next, the bleaching solution, bleach-fixing solution, and fixing solution used in the present invention will be explained.

As the bleaching agent used in the bleaching solution or bleach-fixing solution used in the present invention, any bleaching agent can be used, but in particular, organic complex salts of iron (II) (for example, aminopolycals such as ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid) are used. Preferred are complex salts of phosphonic acids, aminopolyphosphonic acids, phosphonocarboxylic acids, and organic phosphonic acids) or organic acids such as citric acid, tartaric acid, and malic acid; persulfate salts; hydrogen peroxide, and the like.

Among these, organic complex salts of iron ([1) are particularly preferred from the viewpoint of rapid processing and prevention of environmental pollution. Examples of aminopolycarbonic acids, aminopolyphosphonic acids, organic phosphonic acids, or salts thereof useful for forming organic complex salts of iron(III) include ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, 1.3-/ /amino prono 9
cyclotetraacetic acid, propylenediaminetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, iminodiacetic acid, glycol ether diaminetetraacetic acid,
etc. can be mentioned.

These compounds may be sodium, potassium, lithium or ammonium salts. Among these compounds, iron(1) complex salts of ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaxianetetraacetic acid, 1,3-diaminopropanehydroacetic acid, and methyliminodiacetic acid are preferred because they have a high bleaching edge.

These ferric ion complex salts may be used in the form of complex salts, or ferric salts such as ferric sulfate, ferric chloride, ferric nitrate, ferric ammonium sulfate, and ferric phosphate. etc. and aminopolycarganic acid, aminopolyphosphonic acid, phosphonocal? A ferric ion complex salt may be formed in solution using a chelating agent such as phosphoric acid or the like. In addition, a chelating agent can be used as a second
It may be used in excess to form an iron ion complex salt. Among iron complexes, aminopolyphosphonic acid iron complexes are preferred, and the addition t is preferably 0.01 to 1.0 mol/l, preferably O
, OS~0.50 mol/l.

Bleach solution, bleach-fix solution and /''
A variety of compounds can be used as bleach accelerators.

For example, U.S. Pat.
Publication No. 5630, Research Disclosure No. 171
No. 29 (July 1978 issue), compounds having a mercapto group or disulfide bond, and
No. 506, JP-A-52-20832, JP-A No. 53-327
Thiourea compounds described in No. 35, US Pat. No. 3,706,561, and halides such as iodine and bromide ions are preferred because they have excellent bleaching properties.

In addition, the bleach or bleach-fix solution used in the present invention may contain bromides (e.g., potassium bromide, sodium bromide, ammonium bromide), chlorides (e.g., potassium chloride, sodium chloride, ammonium chloride), or iodides. (
For example, a rehalonating agent such as ammonium iodide) can be included. If necessary, one or more inorganic substances having a buffering capacity 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, alkali metal or ammonium salts thereof, or corrosion inhibitors such as ammonium nitrate and guanidine 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, a thiosulfate such as sodium thiosulfate or ammonium thiosulfate; a thiocyanate such as sodium thiocyanate or ammonium thiocyanate; Ethylene bisthiodalicholic acid, 3,6-dithia-1
, 8-octanediol, and water-soluble silver halide solubilizers such as thioureas. These 'fr:L types or a mixture of two or more of these can be used. 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, the use of thiosulfates, particularly ammonium thiosulfates, is preferred. The amount of fixing agent per 11 is preferably in the range of 0.3 to 2 moles, more preferably in the range of 0.5 to 1.0 moles. One area of the bleach-fix solution or fixer is preferably 3 to 10, more preferably 5 to 10.
9 is particularly preferred.

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

The bleach-fixing solution and fixing solution in the present invention contain sulfites (e.g., sulfite, potassium sulfite, ammonium sulfite, etc.), bisulfites (e.g.,
ammonium bisulfite, sodium bisulfite, potassium bisulfite, etc.);

These compounds are approximately 0.02 to 0.02 in terms of sulfite ion.
The content is preferably 0.50 mol/l, more preferably 0.04 to 0.40 mol/l.

As a preservative, sulfites are commonly added, but other preservatives include ascorbic acid, Calga-ni bisulfite adducts,
Alternatively, a calyl compound or the like may be added.

Furthermore, buffering agents, fluorescent brighteners, chelating agents, antifoaming agents, antifungal agents, and the like may be added as necessary.

The silver halide color photographic light-sensitive material used in the present invention is generally subjected to desilvering treatment such as fixing or bleach-fixing, followed by washing with water and/or stabilizing treatment.

The amount of water used in the washing process varies widely depending on the characteristics of the optical material (for example, depending on the materials used such as couplers), the purpose, the temperature of the washing water, the number of washing tanks (the number of stages), the replenishment method such as countercurrent or forward flow, and various other conditions. Can be set to . Among these, the relationship between the number of flushing tanks and the amount of water in the multi-stage countercurrent method is described in the Journal
1of the 5ociety of Motion
Pictur@ind T@levisionEng
ineers) Volume 64, P, 248-253 (19
You can request it using the method described in the May 1955 issue. Normally, the number of stages in the multistage countercurrent system is preferably 2 to 6.
Particularly preferably 2 to 4.

According to the multistage countercurrent method, the amount of washing water can be greatly reduced, for example, to 0.5~11 or less per 1 m of photosensitive material, but it increases the residence time of water in the tank, causing bacteria to grow. As a solution to such problems in the processing of the color photosensitive material of the present invention, problems such as the floating matter that propagates and adheres to the photosensitive material occur.
The method of reducing calcium and magnesium described in No. 1632 can be used very effectively. Also,
Inthiazolone compounds and thiabendazoles described in JP-A No. 57-8542, No. 6l-1201454t4
Chlorinated disinfectants such as chlorinated sodium incyanurate described in C, benzotriazole described in Japanese Patent Application No. 105487/1987, copper ions, etc. "Chemistry of antibacterial and fungicidal agents" by Hiroshi Horiguchi, "Microorganisms" edited by Sanitation Technology Association Sterilization, sterilization, and anti-mold technology
It is also possible to use the fungicides described in "Encyclopedia of Antibacterial and Antifungal Agents," edited by the Japan Antibacterial and Antifungal Society.

Furthermore, a surfactant can be used as a draining agent, and a chelating agent such as EDTA K can be used as a water softener.

- of the washing water in the processing of the photosensitive material of the present invention is 4 to 9
The number is preferably 5 to 8. The washing water temperature and washing time can also be set depending on the characteristics of the photosensitive material, its use, etc., but generally it is 20 seconds to 10 minutes at 15 to 45°C, preferably 2
A range of 30 seconds to 5 minutes is selected at 5 to 40°C.

The above-mentioned water washing step can be followed or the stabilizing solution can be directly treated without going through the water washing step. A compound having an image stabilizing function is added to the stabilizing liquid, such as an aldehyde compound represented by formalin, or a membrane suitable for dye stabilization.
Examples include buffering agents and ammonium compounds to adjust the temperature. Further, in order to prevent the proliferation of bacteria in the liquid and to impart anti-mold properties to the photographic material after processing, the various disinfectants and anti-mold agents described above can be used.

Furthermore, a surfactant, a fluorescent brightener, and a hardening agent can also be added. In the processing of the photosensitive material of the present invention, when stabilization is performed directly without passing through a water washing step,
No. 8543, No. 58-14834, No. 59-184343
No. 60-220345, No. 60-238832, 6
No. 0-239784, No. 60-239749, 61-4
All known methods described in No. 054, No. 61-118749, etc. can be used.

In addition, it is also a preferable embodiment to use chelating agents such as 1-hydroxyethylidene-1,1-diphosphonic acid and ethylenediaminetemethylenephosphonic acid, and magnesium and bismuth compounds.

The liquid used in the water washing and/or stabilization step can also be used in the previous step. An example of this is to flow the overflow of washing water, which is reduced by a multi-stage countercurrent system, into the bleach-fixing bath that is the previous bath, and replenishing the bleach-fixing bath with concentrated liquid to reduce the amount of waste liquid. .

If the method of the present invention uses a color developer,
It can be applied to any processing step. For example, it can be applied to the processing of color developers, color reversal paper, color direct positive photosensitive materials, color positive films, color negative films, color reversal films, etc., but especially color e/coo, color reversal film, etc. Application to /g is preferred.

The silver halide emulsion of the light-sensitive material used in the present invention may be of any halogen composition, such as silver iodobromide, silver bromide, silver chlorobromide, or silver chloride. For example, when performing quick processing or low replenishment processing such as color e-li-1, add 60% silver chloride.
Silver chlorobromide emulsions or silver chloride emulsions containing at least one mole of silver chloride are preferred, and a silver chloride content of 80 to 100 moles is particularly preferred. In addition, when high sensitivity is required and capri during production, storage, and/or processing must be kept particularly low, silver bromide emulsions containing 50 mol of silver bromide or silver bromide emulsions containing 50 mol of silver bromide Silver emulsions (which may contain up to 3 moles of silver iodide in total) are preferred, where the silver iodide content is preferably from 3 to 15 moles.

The silver halide grains used in the present invention may have different phases inside and on the surface, may have a multiphase structure such as a bonded structure, or may consist of a uniform phase throughout the grain. Moreover, they may be mixed.

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

In the case of tabular grains, it is expressed in yen. ) 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 (variation rate) obtained by dividing the standard deviation value in the grain size distribution curve of the silver halide emulsion by the average grain size (variation rate) is within a factor of 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 emulsion layers having substantially the same color sensitivity (monodispersity is defined as ) can be mixed in the same layer or coated in separate layers. Furthermore, a polydisperse silver halide emulsion of 2 or more grains 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) may have a crystalline form or coexistence of these, and may also have an irregular shape such as a spherical shape.
It may have all of these crystal forms, or it may have a composite form of these crystal forms, or it may have a composite form of these crystal forms. Further, tabular grains may be used, and in particular, tabular grains having a length/thickness ratio of 5 to 8 or 8 or more may surround an emulsion that accounts for 50% or more of the total projected area of the grains. An emulsion consisting of a mixture of these various crystal forms may also be used. These various emulsions may be of the surface latent image type, in which the latent image is mainly formed on the surface, or of the internal latent image type, in which the latent image is formed inside the grains.

The photographic emulsion used in the present invention is described in Research Disclosure (RD) vol, 170 It@mA1.
7643 (1, Il, I) (December 1978).

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, A17643 (January 1978).
(February) and Vol. 187, No. 18716 (November 1979), 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 harvest RD17643 RD18716
1 Chemical sensitizer page 23 page 648 right column 2
Sensitivity enhancer Same as above 3 Spectral sensitizer
Pages 23-24 Page 648 Right column ~ 4 Supersensitizer
Page 649 Right column 5 Brightener Page 24 7 Coupler Page 25 8 Organic solvent Page 25 10 Ultraviolet absorber 11 Anti-stain agent Page 25 Right column Page 650 Left to right column 12 Dye image stabilizer Page 25 13 Hardener Page 26 Page 651 left column 14
Binder page 26 Same as above 15 Plasticizer, lubricant Page 27 650 right column 17 Static inhibitor page 27 Same as above Various color couplers can be used in civil engineering inventions. The term "color coupler" as used herein refers to a compound capable of producing a dye through a coupling reaction with an oxidized product of an aromatic primary amine compound. Typical examples of useful color couplers include naphthol or phenolic compounds, pyrazolones 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) ■-○ and RD 18717 (November 1979).
described in patents cited in May).

The color coupler incorporated in the light-sensitive material is preferably diffusion-resistant by having a pallast group or being polymerized. Compared to the equivalent color coupler whose coupling active position is a hydrogen atom, the amount of coated silver can be reduced by using a two-equivalent color coupler substituted with a leaving group. 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 coupling 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 U.S. Patent No. 2,40
No. 7,210, No. 2,875,057 and No. 3
, No. 265, 506, etc. The use of divalent yellow couplers is preferred for the present invention; U.S. Pat. No. 3,408,194;
Same No. 3,933,501 and Same No. 4,022,6
20, etc., or Japanese Patent Publication No. 55-10739, U.S. Patent No. 4
．． No. 401,752, No. 4,326,024, RD
18053 (April 1979), British Patent No. 1,425
, 020, West German Application No. 2,219,917, West German Application No. 2,261,361, West German Application No. 2,329,587 and West German Application No. 2,433,812, etc. A typical example of this is yellow coupler. α-piparoylacetanilide couplers have excellent color fastness, especially light fastness;
Benzoylacetanilide couplers provide high color density.

Magenta couplers that can be used in the present invention include oil-protected indacylon or cyanoacetyl couplers, preferably pyrazoloazole couplers such as 5-pyrazolone and pyrazolotriazoles. The 5-pyrazolone coupler is preferably a coupler in which the 3-position is substituted with an arylamino group or an acylamino group from the viewpoint of the hue and color density of the coloring dye. , the same λ3
No. 43,703, No. 2,600.788, No. 2.
No. 908,573, No. 3,062,653, No. 3
．． No. 152,896 and No. 3,936,015, etc. As a leaving group for a two-equivalent 5-pyrazolone coupler, the nitrogen atom leaving group described in U.S. Pat. No. 4,310.619 or U.S. Pat.
, 897 is preferred. Further, the 5-pyrazolone coupler having a palust group described in European Patent No. 73,636 provides high color density.

As a pyrazoloazole coupler, U.S. Patent No. 3,
369,879, preferably the pyrazolo[5,1-e)(:1,2°4]triazoles described in U.S. Pat. No. 3,725,067, Research Disclosure 24220 ( 1
(June 984)? Lazolotetrazoles and Research Disclosure 24230 (1984
Examples include pyrazolopyrazoles described in June 2013).

Imidazo [l,
2-b) Pyrazoles are preferred, as described in European Patent No. 119.
Pyrazolo[1,5-b](1,2,4
]) Riazole is particularly preferred.

Cyan couplers that can be used in the present invention include oil-protected 7-thol couplers and phenolic couplers, such as the naphthol couplers described in U.S. Pat. No. 2,474,293 and preferably U.S. Pat. No. 4,052.
, No. 212, No. 4.146,396, No. 4,22
Typical examples include two-equivalent naphthol couplers of the oxygen atom elimination type described in No. 8,233 and No. 4,296,200. Specific examples of phenolic couplers include U.S. Pat.
No. 01,171, No. 2.772,162, No. 2,
No. 895,826, etc. Humidity and temperature robust cyan couplers are preferably used in the present invention and are typically described in U.S. Pat. No. 3,772.
, 002, a phenolic cyan coupler having an alkyl group greater than or equal to an ethyl group at the meta-position of the phenol nucleus, U.S. Pat. No. 2,772,162, U.S. Pat. No. 3.75
No. 8,308, No. 4,126,396, No. 4.3
No. 34,011, No. 4,327,173, West German Patent Publication No. 3,329,729 and Japanese Unexamined Patent Publication No. 1983-166
2,5-diacylamino substituted phenolic couplers such as those described in US Pat. No. 956 and US Pat.
No. 22, No. 4,333,999, No. 4.451,
These include phenolic couplers containing a phenylureido group at the 2-position and an acylamino group at the 5-position, which are described in Japanese Patent No. 559 and No. 4,427,767.

In particular, in the treatment method of the present invention, the following general formula (C-1
) By using at least one cyan coupler represented by K, it is possible to obtain good photographic properties with less fog. Such an effect is noteworthy.

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

General formula (C-1) (wherein, R represents an alkyl group, a cycloalkyl group, an aryl group, an amino group, or a heterocyclic group. R represents a hydrogen atom, a halogen atom, an alkyl group, and R represents an alkoxy group. R3 may be combined with R2 to form a ring.
This refers to a group that can be separated in reaction with an oxidized product of a class amine color developing agent. ) In the general formula (C-1), the alkyl group for R1 is preferably an alkyl group having 1 to 32 carbon atoms, such as a methyl group, a butyl group, a tridecyl group, a cyclohexyl group,
Examples of the aryl group include:
Examples of the heterocyclic group include a phenyl group and a naphthyl group, and examples of the heterocyclic group include a 2-pyridyl group and a 2-furyl group.

In the case of the amine group for R1, a phenyl-substituted amino group which may contain a substituent is particularly preferred.

R1 further represents an alkyl group, an aryl group, an alkyl or aryloxy group (for example, a methoxy group, a dodecyloxy group, a methoxyethoxy group, a phenyloxy group, 2,
4-tar is an amylphenoxy group, 3-tar is a butyl-4-hydroxy722yloxy group, naphthyloxy group, etc.), car is an xy group, and alkyl or aryl car is a nyl group (for example, an acetyl group, tetradecanoyl group). benzoyl group, etc.), alkyl or aryloxycar-nyl group (e.g., methoxycar is nyl group, phenoxyl group is nyl group), acyloxy group (e.g.
acetyl group, benzoyloxy group), sulfamoyl group (e.g., N-ethylsulfamoyl group, N-octadecylsulfamoyl group, etc.), carbamoyl group (e.g., N-ethylcarbamoyl group, N-methyl-dodecylcarbamoyl group) groups), sulfonamide groups (e.g.
Methanesulfonamide group, benzenesulfonamide group, acylamino group (e.g., acetylamide group, benzamide group, ethoxyl is nylamino group, phenylamino group is nylamino group, etc.), imide group (e.g., succinimide group, hydantoinyl group, etc.) , a sulfonyl group (eg, methanesulfonyl group), a human tetraxy group, a cyano group, a nitro group, and a halogen atom.

In general formula (C-1), 2 represents a hydrogen atom or a coupling-off group. group, methoxycarbamoylmethoxy group, carboxypropyloxy group, methylsulfonyl ethoxy group, etc.), aryloxy group (
For example, 4-chlorophenoxy group, 4-methoxyphenoxy group, etc.), acyloxy group (e.g., acetoxy group, tetrazocalyloxy group, benzoyloxy group, etc.), sulfonyloxy group (e.g., methanesulfonyloxy group, toluene group, etc.) sulfonyloxy group, etc.), amide group (e.g., dichloroacetylamino group, methanesulfonylamino group, toluenesulfonylamino group, etc.), alkoxy group is a nyloxy group (e.g., ethoxycardenyloxy group, benzyloxy group is a nyloxy group), nato)
, aryloxycar is a nyloxy group (for example, phenoxycar is a nyloxy group, etc.), aliphatic or aromatic thio group (for example, phenylthio group, tetrazolylthio group, etc.), i is do group (for example, succinimide group, hymentynyl group, etc.) , N-heterocycle (eg, 1-pyrazolyl group, 1-penztriazolyl group, etc.), aromatic azo group (eg, phenylazo group, etc.), and the like. These leaving groups may include photographically useful groups.

81 of general formula (C-1) or R2 is a dimer or,
A larger number of multimers may be formed.

Specific examples of the cyan coupler represented by the general formula (C-1) are listed below, but the present invention is not limited thereto.

(C-5) (t)C5H,.

(t)c6g,.

(C-14) (C-16) 2H5 (″)’5flll (C-18) (C-19) (C-21) (t)c, horse.

(t) c5H11 (t) c5I11゜υ (Y3 EC-26) The cyan coupler represented by the above general formula (C-1) is
%FflF! No. 859-166956, Special Publication No. 1977-1
It can be synthesized based on the description in No. 1572 and the like.

Granularity can be improved by using a coupler in which the coloring dye has an appropriate diffusibility. Examples of such dye-diffusive power graphs include magenta couplers in U.S. Pat. No. 4,366,237 and British Pat. No. 3,234,533 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 in two or more layers in the same photosensitive layer, or in two or more different layers using the same compound, in order to satisfy the characteristics required for the photosensitive material. It can also be introduced into

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 and effects of the latex dispersion method, as well as specific examples of latex for impregnation, are described in U.S. Pat. No. 4,199,363 and West German Patent Application (OLS).
Nos. 2,541,274 and 2,541,230
It is written in the number etc.

The standard amount of color coupler used is in the range of 0.001 to 1 mole per mole of photosensitive iron halide, S
and preferably 0.01 to 0 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. For details on the support and coating method, see Research Disclosure Volume 176 Itsm 17643XV
It is described in Section (P, 27)X■ Section (P, 28) (December 1978 issue).

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

A "reflective support" is something that enhances the reflectivity and makes the dye image formed in the silver halide emulsion layer clearer. Such a reflective support includes titanium oxide, zinc oxide, Examples include those coated with a hydrophobic resin containing a dispersed light-reflecting substance such as calcium carbonate and calcium sulfate, and those using a hydrophobic resin containing a dispersed light-reflecting substance as a support (Example) The present invention will be described below. The present invention will be explained in more detail by showing specific examples. However, the present invention is not limited to the following examples.

Example 1 As a color developer, prepare a processing solution with the following formulation.9.

Color developer compound ω) (compound of general formula (1), etc.) Listed in Table 1 Sodium sulfite 0.2. ii
l Potassium carbonate 30 JE
DTA-2Nm 1.
9 Sodium chloride 1.5g Add water to 1000+ dr
10.05 Place the sample (&1 to 30) of the color developer thus prepared in a test tube with an aperture ratio (opening area/sample area) of 0.02 crx-'
The cells were placed in each cell at a controlled temperature of 35°C and circulated for 4 weeks. After 4 weeks, the loss due to evaporation was corrected with distilled water, and the residual rate of the aromatic primary Amifka 2-developing agent was measured and calculated by liquid chromatography.

The results are shown in Table 1.

Table 1 ・1 Indicates the number of the exemplified compound described in the text.

Fist 2 Indicates the number of the exemplary compound described in the text.

*4 -(-CH2CH2Nlf9 n=500~2
000 As is clear from Table 1, the use of the compound of general formula (1) alone (sample 41.2) is not sufficient, and the use of compounds such as triethanolamine, polyethyleneimine, or m-7 with N, N- Even when used in combination with diethylhydroxylamine, the residual rate cannot be said to be sufficient (Sample A3.4.5).

However, as is clear from Samples A6 to 17, by using the compound represented by General 2〇, G[D in combination with the compound of general formula (1), the residual rate of the developing agent is significantly improved. It can be seen that the stability of the color developer is improved.

Example 2 In samples A6 and 7 of Example 1, compound l-28, -44, l-58 or l- was substituted for compound 1-7.
Example 1 was carried out in the same manner as in Example 1 using
Similar favorable results were obtained.

Example 3 In samples A7 and 8 of Example 1, compounds 11-4, -5, and -5 were substituted for compounds 1-3 and 1fi-1.
-10, ■-15, l-2, m-5, ■-8, ■-11
Example 1 using in combination with compound 1-12 or I-7
As a result of carrying out the same procedure as in Example 1, favorable results were obtained as in Example 1.

Example 4 A multilayer 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.

(2nd layer blood liquid preparation So-coupler (ExY-1) 19.11 and color image stabilizer (Cpd-1) 4.4g and ethyl acetate 27g
．． 2W and high boiling point solvent (Solv-1) 7.70C (
8.0 g) was added and dissolved, and this solution was emulsified and dispersed in 1 sscc of IOS gelatin water bath solution containing 10% sodium dodecylbenzenesulfonate gCC. This emulsified dispersion and emulsions EM7 and EM8 were mixed and dissolved, and the gelatin concentration was adjusted to have the following composition.
Manufactured. The coating solutions for the second to seventh layers were also subjected to lil# in the same manner as the coating solution for the first layer. l-oxy-3,5-dichloro-l-triazine sodium salt was used as the gelatin hardening agent for each layer.

(Cpd-1) was used as the thickener.

(Layer structure) The composition of each layer is shown below. The number is the coating amount (g/m”)
′. Silver halide emulsions represent coating amounts in terms of silver.

Support polyethylene laminate paper [contains polyethylene nine-white content (T102) and bluish dye on the first layer side. ] Layer-1 (actual sensitivity) Monodispersed silver chlorobromide emulsion (EM7) spectrally sensitized with a sensitizing dye (Exa-1) 0.1
Monodisperse silver chlorobromide emulsion (EMS) spectrally sensitized with 5 sensitizing dye (ExS-1) 0.1
5 Gelatin 1.86 Yeo-coupler (ExY-1) 0.8
Two-color image stabilizer (CPd-2) 0.
19 solvent (Solmer 1)
0.35 Second layer (color mixing prevention layer) Gelatin 0.99 Color mixing prevention agent (Cpd-3) 0.08 Third J'l (green sensitive layer) Spectral sensitization with sensitizing dye (Exa-2, 3) Monodisperse silver chlorobromide emulsion (1M9) 0.12 Monodisperse silver chlorobromide emulsion spectrally sensitized with sensitizing dye (Exa-2,3) (EMI O) 0.2
4 Gelatin 1.24 Magenta coupler (ExM-1) 0.39
Color image stabilizer (Cpd-4) 0.2
Five-color image stabilizer (Cpd-5) 0.
12 Solvent (Solv-2) 0
．． 25 Fourth layer (ultraviolet absorption layer) Gelatin 1.60 UV absorber (cpa-6/cpd-77Cpd-8=3/
2/6: Weight ratio) 0.70 Color mixing prevention agent (
Cpd-9) 0.05 bath medium (So
lv-3) 0.42 Fifth skin (red sensitive layer) Monodispersed silver chlorobromide emulsion (EMII) spectrally sensitized with sensitizing packets (ExS-4, 5) 0.07 Sensitizing dye (E
Monodisperse silver chlorobromide emulsion spectrally sensitized with xS-4,5) (
EM12) 0.16 gelatin
0.92 cyan coupler (ExC-1)
1.46 Cyan Kagura (ExC-
2) 1.84 color image stabilizer (Cpd-
7/Cpd-8/Cpd-10=3/4/2: Weight ratio>0.17 Dispersion polymer (Cpd-11
) 0.14 Solvent (Solv-1)
0.20 Sixth layer (ultraviolet absorption layer) Gelatin 0.54 Ultraviolet absorber (Cpd-6/Cpd-8/Cpd-10=
115/3: Jii, quantity ratio) 0.21
Solvent (Solv-4) 0.
08 Seventh layer (retention layer) Gelatin L33 Acrylic modified copolymer of polyvinyl alcohol (degree of modification 17%) 0.17 Liquid paraffin 0.03 In addition, at this time, as an irradiation prevention dye, (Cpd
-12, cpa-x3) was used.

Furthermore, each layer contains Alkanol
exF-120 (manufactured by Dainippon Ink Co., Ltd.)' was used. (Cpd-14,15) was used as a stabilizer for silver halide.

Details of the emulsion used are as follows.

EM7 Cube 1.1 1.0 0.
1OEM 8 Cube 0.8 1.0
0.1 OEM 9 Cube 0.45 1.5
0.09EMIO cube 0.34 1.5
0.09EMII Cube 0.45
1.5 0.09EM12 Cube 0.3
4 1.6 0.10 The structural formula of the compound used is as follows.

xY-2 xM-1 Cl.

ExC-1 ExC-2 ExS-1 So, IN(C2H5)3 ExS-2 803HN (C2H5).

ExS-3 ExS-4 ExS-5 pd-1 80, K pd-2 pa-3 H pd-4 pa-s pd-6 pd-7 C4H, (tJ Cpd-8 Cpd-9 H H Cpd-10 Cpd -11 1%CH2-CH÷n (!1=100~
1000) coNHc4n91t) Cpd-12 So, K 80. Kpd-13 Cpd-14 H Cpd-15 Solmer 1 Dibutyl phthalate Solmer 2 Trioctyl phosphate Solmer 3
Trinonyl Phosphate Solmer 4 Tricresyl Phosphate The resulting color photographic paper, after wedge exposure, was processed in the following processing steps in which the composition of the color developer was varied.

Color development 35℃ 45 seconds white fixation
Stable at 35°C for 45 seconds 135°C Stable for 20 seconds Stable at 235°C for 20 seconds 3 Dry at 35°C for 20 seconds Stable at 70-80°C for 60 seconds The solution was 3-tank countercurrent water washing from Stable 3 to 1. The processing solutions used are as follows.

Color developer additive C (compounds of general formula CI), etc.) See Table 2 Additives D (General 2〇), compounds of (g), etc.) See Table 2 Benzyl alcohol See Table 2 Diethylene glycol See Table 2 Sodium anthite 0.29 Potassium carbonate 30. 9 Nitrilotriacetic acid 1y Sodium chloride 1.5g Brightener (UVIT)
li! CK Ciba Geigy) a, add og water 1000 + d voice
i o, o s Whitening fixer EDTAF@(llDNH4・2H2060&1m)T
A-2Nm-2H2049 Ammonium thiosulfate (7096) 120+
+d Sodium sulfite 16. 9
Add glacial acetic acid 7II water lQQQsg voice
5.5 Stable liquid bismuth chloride 0.3!1 Aqueous ammonia (26 u) 2.5d nitrilotriacetic acid, 3Nm 1.0#EDTA
・4H0.5N Sodium sulfite 1.0II Add water to 10100Os,
A portion of the above color developer was brought to a bee force of 11 and left in an open system at 35° C. for 40 days, and then this aged solution was used to perform the above-mentioned geography process.

Processing using the color developer solution (aged solution) left for 40 days was defined as an aged solution test, and processing using the color developer solution (fresh solution) before being left was defined as a fresh solution test.

Table 2 shows the changes in photographic properties obtained through the fresh solution test and the aged solution test.

Photographic properties were expressed in two points: a change in Dmin in magenta density and a change in gradation.

Dmin represents the minimum density, and the gradation is expressed as a change in density from a point representing a density of 0.5 to a density point on the high exposure side of 0.3 in LogE.

However, by using the compound of the present invention, the change in photographic properties of the escape liquid over time is reduced (% [As
-18), when % does not contain benzyl alcohol,
It can be seen that the effect is large and very desirable.

Example 5 Color photographic paper prepared in the same manner as in Example 4 was exposed to light in a wedge pattern, and then subjected to various color developing solutions in the following processing steps.
Running process until replenishing 3 times the tank capacity (
Continuous processing) tests were conducted.

Color development 35℃ 45 seconds 160st/m”
Heading fixation 35℃ 45 seconds 10 (hwj/m
"Rinse 0 30℃ 20 seconds - Rinse■
30℃ 20 seconds - rinse■ 30
℃ 20 seconds 200m roux 3 drying 60~
70° C. for 30 seconds - Rinse: 3-tank countercurrent method from rinse (■) to (2) The composition of each saturated solution used is as follows.

Additives C and D Optical brighteners (see Table 3)
4,4-minostilbene series) 3. og
4. og ethylenediaminetetraacetic acid 1.0g
1.59 potassium carbonate 30.0! 1
30.0 #Sodium chloride 14,9
0.11i benzyl alcohol See Table 3 Diethylene glycol See Table 3 Add water
1000mg 1000dpH10.1
010,50 El)'rA F-(t)NH4・2H@
60pEDTA ・2Nm ・2H20417
Ammonium thiosulfate (70 t) izow
tSodium sulfite 16! i Add 7g of glacial acetic acid to 1000++d voice
5.5 benzotriazole
1. In addition to O1 water and gold
At 1000100O
Voice 7.50 Using the above processing solution, perform the processing in the above processing step, and adjust the B (blue), G (green), and R (red) of the unexposed areas at 11 degrees ( Stin) was measured using a Fuji self-recording densitometer. Furthermore, after the sample at the end of the running process was left at 80°C (5~10RH) for 2 months,
B, G, and R111 degrees of the unexposed area were measured again.

The results of the changes in photographic properties obtained are shown in Table 3.

From the results in Table 3, it can be seen that in Experiments A1 to A4, the sting increases significantly as a result of the running process, whereas in Experiments A1 to A4, the sting increases significantly.
3, it can be seen that the increase in sting is extremely small. Also, when looking at the change over time after the completion of the treatment, the increase in staining in Experiments A5 to 13 was very small compared to Experiment A1-4Ic.

Example 6 A double-sided polyethylene laminate paper treated with corona discharge processing was coated with MIIs 1 (bottom layer) to 7 as described in Table B.
A photographic paper sample was prepared by sequentially coating and forming the layers (top layer). The coating solution for each layer is prepared as follows. The details of the structural formulas of the couplers, color image stabilizers, etc. used in the coating solution will be described later.

The coating liquid for the first layer was prepared by pressing as follows. Namely, 200 g of yellow coupler, 93 g of anti-fading agent (r)
．． 3#, high boiling point source m(p) 10 fl and solvent (ψ5
g and 600 d'i of ethyl acetate as an auxiliary solvent was dissolved by heating at 60°C, and alkanol B (8 product names,
Alkylnaphthalene sulfonate (manufactured by DuPont) 5
5 Tigelatin aqueous solution containing 330m% aqueous solution 3300-
mixed with. This liquid was then emulsified using a colloid mill to prepare a coupler dispersion. Ethyl acetate was distilled off under reduced pressure from this dispersion, and the sensitizing dye for the blue-sensitive emulsion layer and 1-
Methyl-2-mercaguto-5-acetylamino-1゜3
．． 4-) 96.7 as 1,4001Ag of emulsion with lyazole added! 1, containing 170.9 g of gelatin), and further added 2.600 g of a 10 gelatin aqueous solution to prepare a coating solution. The coating liquids for the second to seventh layers are shown in Table B.
It was prepared according to the composition of the first layer.

However, photographic paper was prepared using each of the cyan couplers shown in Table 4 below as the fifth layer cyan coupler.

The compounds used in this example are as follows.

UV absorber (II): 2-(2-hydroxy-3,5-di-ter-7-milphenyl) IJ azole UV absorber (0): 2-(2-hydroxy-3,5-di-ter tar butylphenyl)pensito+77 so/L/solvent C)
Ni(2-ethylhexyl) phthalate solvent (q) Nidibutyl phthalate antifading agent (r): 2,5-di-ter to amyl phenyl-3,5-di-ter
@r Butyl hydroxybenzoate color mixing inhibitor (S): 2.5-? -ter is octylhydroquinone anti-fade agent (T): 1.4-ter is amyl-2,5-dioctyloxybenzene anti-fade agent (U): 2.2'-methylenepi,%-(4-methyl-6- tar
Butylphenol and the following were used as sensitizing dyes in each emulsion layer.

Blue-sensitive emulsion layer: anhydro-5-methoxy-5'-methyl-3,3'-disulfoprobil hetanocyanine hydroxide Green-sensitive emulsion layer: AnhyPμm9-ethyl-5,5'-diphenyl-3, 3'-disulfoethyl oxacal? Cyanine hydroxide red-sensitive emulsion layer; 3,3'-diethyl-5-methoxy-9
, 9'-(2,2-/methyl-1,3-proΔ])thiadical cyanine iozide The following substances were also used as stabilizers for each emulsion layer.

1-Methyl/l/-2-mercapto-5-acetylamino-1,3,4-) riazole and the following were used as anti-irradiation dyes.

4-(3-carxy-5-hydroxy-4-(3-(
3-caloxy-5-oxo 1-(4-sulfonatophenyl)-2-bilazolin-4-ylidene)-1-benyl)-1-birasolyl)benzenesulfonate-dipotassium salt N,N'- (4,8-&?)PoAcy9.10-dioquine-3,7-cissulfonatoanthracene-1,5-diyl)bis(aminomethanesulfoner) -? ) la sodium salt (1,2-bis(vinylsulfonyl)ethane was used as agent Ia).

The couplers used are as follows.

Yellow Coupler Magenta Turnip 2-〇t Cyan Coupler See Table 4 The multilayer color photographic paper obtained as described above was subjected to wedge-shaped exposure and then processed in the following processing steps.

Color development 45 seconds 35℃ bleach fixing 45 seconds 35℃ rinse (3 tank cascade) 2 minutes 30℃ drying
The Kyuri solution used at 80°C for 1 minute is as follows.

Color developer water 80M sodium sulfite See Table 4 Sodium chloride LM additives C, D
See Table 4 Potassium carbonate
30. 9KOH tap) 110.10 Bleach-fixing solution Ammonium thiosulfate (7056) 150w
j Sodium sulfite is g Ethylenediamine iron (2) ammonium 60 l
Ethylenediaminetetraacetic acid 10 11
Add water and add 1000 tIt of ammonia water to 2-methyl-4-isothiazolin-3-one
10 1! rg2-octyl-4-isothiazoline-
3-one 10 ■Bismuth chloride (40ch)
0.5.9 Ammonia water (26%
) at 2.0gmgKOH
-7,5 In the above region, in the same manner as in Example 4, part of the fresh solution and color developer was
The Dmin and gradation of cyan were determined using the aged solution after being left for a day.

Dmi m and vjkvI4 of aged solution versus fresh solution
The increase in 1 is shown in Table 4.

From the results in Table 4, compared to Experiments A1-3, Experiments 4-1
8, even if a developer left for 40 days was used, Dm i
It can be seen that the changes in n and gradation are small, and the photographic properties are extremely stabilized. In particular, as a cyan coupler
c-9” or EC-1” (Experiment A6,
7, 10, 11, 13, 15, 17, and 18) and when the sulfite concentration in the developer is small (experimentally shown in 8 to 18), the photographic properties are more stabilized.

Cyan coupler A) t B) t Example 7 Experiment A6 of Example 6 Instead of cyan coupler C-9 using VC, cyan coupler C-3, C-10, or C-
When the same procedure as in Example 6 was carried out using No. 14, similarly favorable results were obtained.

(Effect of the invention) The present invention significantly improves the stability and color development of color developers, and as a result, increases in fog and gradation changes are significantly suppressed even in processing methods using color developers after aging. A color image with excellent photographic properties was obtained.

In particular, general formula (C-1)-t? When the cyan coupler shown above was used, a color image with little variation in gradation compared to Capri was obtained.

Claims (1)

[Claims] (1) After exposing the silver halide color photographic light-sensitive material, at least one aromatic primary amine color developing agent, at least one hydrazine or hydrazide represented by the following general formula (I), and the general formula A silver halide color photographic light-sensitive material processed with a color developer containing at least one selected from monoamines represented by (II) and fused ring amines represented by general formula (III). Processing method. General formula (I) ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ In the formula, R^1, R^2, and R^3 each independently represent a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. R^4 represents a hydrogen atom, a hydroxy group, a hydrazino group, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, a carbamoyl group, or an amino group. X^1 represents a divalent group. n is 0 or 1. However, when n=0, R^4 represents an alkyl group, an aryl group, or a heterocyclic group. R^3 and R^4 may jointly form a heterocycle. General formula (II) ▲There are numerical formulas, chemical formulas, tables, etc.▼ In the formula, R^5, R^6, and R^7 represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an aralkyl group, or a heterocyclic group. . Here, R^5 and R^6, R^5 and R
^7 or R^6 and R^7 may be connected to form a nitrogen-containing heterocycle. General formula (III) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, X represents a trivalent atomic group necessary to complete the condensed ring, and R^8 and R^9 are alkylene groups and arylene groups. , represents an alkenylene group or an aralkylene group. Here, R^8 and R^9 may be the same or different.