JPS63141054A - Method for processing silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a color developer having excellent security (safety) by exposing the titled material contg. a specific pyrazolazole type magenta coupler, followed by processing it with the color developer which contains an aromatic primary amine color developing agent and a monoamine and does not contain a sulfurous acid ion. CONSTITUTION:The silver halide color photographic sensitive material contg. the pyrazoloazole type magenta coupler shown by the formula is exposed, followed by processing the exposed material with the color developer which contains the aromatic primary amine color developing agent and one kind of the compd. selected from the group comprising monoamine, diamine, amide and sulfonamide, etc., and does not contain substantially the sulfurous acid ion. In the formula, R1 is hydrogen atom, etc., X is a group capable of releasing by effecting a coupling reaction with hydrogen atom, etc., Za-Zc are each methine group. Thus, the color developer is remarkably improved in the safety and the coloring property, and the color image which is remarkably reduced the increase of fogging and the change of gradient and has the excellent photographic characteristics is obtd.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a processing method for silver halide color photographic light-sensitive materials, and in particular to a processing method with excellent processing properties, color development properties, and color fading properties, and furthermore, The objective is to provide a color developer with excellent stability.

(Prior Art) Conventionally, magenta couplers represented by the general formula (1) have been disclosed in Japanese Patent Application Laid-Open Nos. 59-162548, 60-43659, 59-171956, 60-172982,
No. 60-33552 and U.S. Patent No. 3,061,432
Due to its excellent hue, various studies have been conducted on it.

(Problems to be Solved by the Invention) However, when the magenta coupler of general formula (1) is processed with a conventional color developer, the photographic properties fluctuate significantly, and magenta staining occurs over time after processing. It has been found that it has a serious drawback of being easy to use.

First of all, it has become clear that fluctuations in photographic properties are significantly affected by fluctuations in the concentration of sulfite ions conventionally added to color developers.

Therefore, various preservatives and chelating agents were added to keep the above sulfite ion concentration stable, but no effective means could be found. The concentration fluctuations of the main drug became large, which also had a negative effect on photographic properties. Therefore, a preservative in place of sulfite ions is required, but triethanolamines described in U.S. Pat. No. 4,170,478 and poly(ethyleneimines) described in U.S. Pat. I couldn't get a sufficient effect.

On the other hand, regarding the occurrence of magenta stain after processing, conventional fading prevention techniques and stain prevention techniques (fading prevention techniques include, for example, U.S. Pat. No. 2,360,290, U.S. Pat.
No. 418,613, No. 2,675,314, No. 2,7
01゜197, 2,704,713, 2,72
No. 8,659, No. 2,732゜300, No. 2,735
, No. 765, No. 2,710,801, No. 2,816゜028, British Patent No. 1,363,921, JP-A-58
-24141, etc., gallic acid derivatives described in U.S. Pat.
No. 765, No. 3,698,909, Special Publication No. 1976-20
No. 977, p-alkoxyphenols described in US Pat. No. 52-6623, US Pat. '300 issue,
No. 3,573,050, No. 3,574,627, No. 3,764,337.

JP-A-52-35633, JP-A No. 52-147434,
The p-oxyphenol derivatives described in U.S. Pat. No. 52-152225, the bisphenols described in U.S. Pat.
Even if techniques such as those disclosed in JP-A-49-11330, JP-A-50-57223, JP-A-56-85747, and JP-B-Sho 56-8346 are used, sufficient effects cannot be obtained.

As described above, it has been desired to develop a technique that overcomes the drawbacks of the magenta coupler represented by the general formula (1).

(Means for Solving the Problems) As a result of various studies, the present inventors have found that the object of the present invention can be effectively achieved by using the following means. Namely.

(1) After exposing a silver halide color photographic material containing at least one type of pyrazoloazole magenta coupler represented by the following general formula (1), containing an aromatic primary amine color developing agent, Contains at least one selected from monoamines, diamines, polyamines, quaternary ammonium salts, nitroxy radicals, alcohols, ethers, oximes, amides, and sulfonamides, and contains substantially no sulfite ions. 1. A method for processing a silver halide color photographic material, the method comprising processing a silver halide color photographic material using a color developer containing no.

General formula (1) (wherein R1 represents a hydrogen atom or a substituent, or represents a hydrogen atom or a group that can be separated by a coupling reaction with an oxidized aromatic primary amine developer* Za-Zb
and Zc is methine, substituted methine, =N- or -NH
- represents one of the Za-Zb bond and Zb-Zc bond is a double bond, and the other is a single bond.

The case where Zb-Zc is a carbon-carbon double bond includes the case where it is part of an aromatic ring. Furthermore, 2j in R1 or X
It also includes the case where a multimer of i or more forms is formed. Also, Za,
When Zb or Zc is a substituted methine, it also includes the case where the substituted methine forms a dimer or more multimer,
(2) The method for processing a silver halide color photographic material according to item (1) of the invention, wherein the color developer does not substantially contain benzyl alcohol.

resolved based on.

In particular, the compounds described in (1) (i.e., monoamines, diamines, polyamines, quaternary ammonium salts, nitroxy radicals, alcohols, ethers, oximes, amides, and sulfonamides) can be used as substitutes for sulfites. It was completely unexpected that the drawbacks of the coupler of general formula (1) could be solved by using at least one type selected from the following and processing with a color developer that does not substantially contain benzyl alcohol. It was impossible.

The magenta coupler represented by the general formula (1) will be explained in detail below.

In the general formula (1), R1 represents a hydrogen atom or a substituent, or a hydrogen atom or a group that can be separated by a coupling reaction with an oxidized aromatic primary amine developer; Za, Zb and Zc are methine; , substituted methine, =N
- or -NH-, a Za-Zb bond and a Zb-Z
One of the c bonds is a double bond and the other is a single bond.* When Zb-Zc is a carbon-carbon double bond, it includes the case where it is part of an aromatic ring.

Furthermore, it includes the case where R1 or X forms a multimer of dimers or more, and also includes the case where the substituted methine forms a multimer of dimers or more when Za, Zb or Zc is a substituted methine.

In general formula (1), a multimer means one having two or more groups represented by general formula (1) in one molecule, and includes bis forms and polymer couplers. Here, the polymer coupler is a monomer having a moiety represented by general formula (1) (preferably one having a vinyl group,
A homopolymer consisting only of vinyl monomer (hereinafter referred to as vinyl monomer) may be used, or a copolymer may be prepared together with a non-color-forming ethylene-like monomer that does not couple with the oxidation product of the aromatic-grade amine developer.

The compound represented by the general formula (1) is a 5-membered ring-5-membered ring mixed nitrogen heterocyclic coupler, and its color-forming nucleus exhibits isoelectronic aromaticity with naphthalene, and is usually collectively referred to as azapentalene. It has a chemical structure. Among couplers represented by general formula (1), preferred compounds are IH-imidazo(1,2-b) pyrazoles, IH-pyrazolo(1,2-b)
5-b) Pyrazole, IH-virazo0 (5,1-e
l(1,2,4) triazoles, IH-pyrazolo(
1,5-b)(1,2,4) Triazoles, IH
-pyrazolo(1,5-d)tetrazoles and IH-pyrazolo(1,5-a)benzimidazoles, each having the general formula (Ia) (Ib) (Ic) (Id)
It is represented by (Is) and (If). Of these,
Particularly preferred compounds are (Ia), (Ic) and (Id
). A more preferred compound is (Id).

(Ia) (To) (Ic)
(Id) (Ie)
(If) Substituents R2, R3 and R4 in general formulas (Ia) to (If) are each independently a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a cyano group, an alkoxy group, an aryloxy group , heterocyclic oxy group, acyloxy group, carbamoyloxy group, silyloxy group, sulfonyloxy group, acylamino group.

Anilino group, ureido group, imide group, sulfamoylamino group, carbamoylamino group, alkylthio group, arylthio group, heterocyclic thio group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfonamide group, carbamoyl group, acyl group , sulfamoyl group, sulfonyl group, sulfinyl group, alkoxycarbonyl group.

represents an aryloxycarbonyl group, X is a hydrogen atom,
Represents a halogen atom, a carboxy group, or a group that bonds to carbon at the coupling position via an oxygen atom, nitrogen atom, or sulfur atom, and is a group that couples off.

The case where R2, R3, R, or X becomes a divalent group and forms a bis body is also included. Furthermore, general formulas (Ia) to (I
When the moiety represented by f) is present in the vinyl monomer, R2, R, or R4 represents a simple bond or linking group, and the moiety represented by general formulas (Ia) to (If) is connected through this. and the vinyl group are bonded.

More specifically, R2, R3 and R4 are hydrogen atoms, halogen atoms (e.g. chlorine atom, bromine atom, etc.), alkyl groups (e.g. methyl group, propyl group, i-propyl group, t-butyl group, trifluoromethyl group). group, tridecyl group, 3-(2,4-di-t-amylphenoxy)propyl group, 2-dodecyloxyethyl group, 3-phenoxypropyl group, 2-hexylsulfonyl-ethyl group, cyclopentyl group, benzyl group, etc.), aryl groups (e.g.
Phenyl group, 4-t-butylphenyl group, 2.4-di-
t-amylphenyl group, 4-tetradecanamidophenyl group, etc.), heterocyclic group (e.g., 2-furyl group, 2-
chenyl group, 2-pyrimidinyl group, 2-benzothiazolyl group 1, etc.), cyano group, alkoxy group (e.g., methoxy group, ethoxy group, 2-methoxyethoxy group, 2-dodecyloxyethoxy group, 2-phenoxyethoxy group,
2-methanesulfonylethoxy group, etc.), aryloxy group (e.g., phenoxy group, 2-methylphenoxy group, 4-t-butylphenoxy group, etc.), heterocyclic oxy group (e.g., 2-benzimidazolyloxy group, etc.) etc),
Acyloxy group (e.g., acetoxy group, hexadecanoyloxy group, etc.), carbamoyloxy group (e.g.,
N-phenylcarbamoyloxy group, N-ethylcarbamoyloxy group, etc.), silyloxy group (for example.

trimethylsilyloxy group, etc.), sulfonyloxy group (e.g., dodecylsulfonyloxy group, etc.), acylamino group (e.g., acetamide group, benzamide group, etc.)
Tetradecanamide group, α-(2,4-di-t-amylphenoxy)butyramide group, γ-(3-t-butyl-
4-hydroxyphenoxy)butyramide group, α-(4
-(4-hydroxyphenylsulfonyl)phenoxy)
decanamide group, etc.), anilino group (e.g., phenylamino group, 2-chloroanilino group, 2-chloro-5-tetradecanamideanilino group, 2-chloro-5-dodecyloxycarbonylanilino group, N-acetylanilino group) group, 2-chloro-5-(α-(3-t-butyl-4-hydroxyphenoxy)dodecanamido)anilino group 1, etc.), ureido group (e.g., phenylureido group, N-butyl-N'-methylureido group, group, methylureido group,
N, N-dibutylureido group, etc.), imide group (e.g., N-succinimide group, 3-penzylhydantoynyl group, 4-(2-ethylhexanoylamino)phthalimide group, etc.), sulfamoylamino groups (e.g. %N
, N-dipropylsulfamoylamino group, N-methyl-N-decylsulfamoylamino group, etc.), carbamoylamino group (e.g., carbamoylamino group, N,N
-dimethylcarbamoylamino group, etc.), alkylthio groups (e.g., methylthio group, octylthio group, tetradecylthio group, 2-phenoxyethylthio group, 3-phenoxypropylthio group, 3-(4-t-butylphenoxy)propylthio group) Base.

etc.), arylthio groups (e.g., phenylthio groups).

2-butoxy-5-t-octylphenylthio group, 3-
pentadecyl phenylthio group, 2-carboxyphenylthio group, 4-tetradecanamidophenylthio group, etc.)
, peterocyclic thio group (e.g., 2-benzothiazolylthio group 1, etc.), alkoxycarbonylamino group (e.g., methoxycarbonylamino group, tetradecyloxycarbonylamino group, etc.), aryloxycarbonylamino group (e.g., phenoxycarbonylamino group, etc.) carbonylamino group, 2,4-
Di-tart-butylphenoxyluponylamino group 1
etc.), sulfonamide groups (e.g. methanesulfonamide group, hexadecanesulfonamide group, benzenesulfonamide group, p-toluenesulfonamide group, octadecanesulfonamide group, 2-methyloxy-5-t-butylbenzenesulfonamide group) , etc.), carbamoyl group (e.g., N-ethylcarbamoyl group, N,N-dibutylcarbamoyl group, N-(2-dodecyloxyethyl)
Carbamoyl group, N-methyl-N-dodecylcarbamoyl group, N-(3-(2,4-di-tert-amylphenoxy)propyl)carbamoyl group, etc.), acyl group (
For example, acetyl group, (2,4-di-tert-amylphenoxy)acetyl group, benzoyl group, etc.), sulfamoyl group (for example, N-ethylsulfamoyl group,
N, N-dipropylsulfamoyl group, N-(2-
dodecyloxyethyl) sulfamoyl group, N-ethyl-N-dodecylsulfamoyl group, N,N-diethylsulfamoyl group 1), sulfonyl group (e.g., methanesulfonyl group, octanesulfonyl group, benzenesulfonyl group, toluene sulfonyl group, etc.), sulfinyl group (e.g., octane sulfinyl group, dodecylsulfinyl group, phenylsulfinyl group, etc.), alkoxycarbonyl group (e.g., methoxycarbonyl group, butyloxycarbonyl group, dodecyloxycarbonyl group, octadecyloxycarbonyl group) , etc.), aryloxycarbonyl group (e.g., phenyloxycarbonyl group, 3
-pentadecylphenyloxy-carbonyl group 1, etc.).

X is a hydrogen atom, a halogen atom (e.g., chlorine atom, bromine atom, iodine atom, etc.), a carboxyl group, or a group linked with an oxygen atom (e.g., acetoxy group, propanoyloxy group, benzoyloxy group, 2,4- Dichlorobenzoyloxy group, ethoxyoxaroyloxy group, bilbinyloxy group, cinnamoyloxy group, phenoxy group, 4-cyanophenoxy group, 4-methanesulfonamidophenoxy group, 4-methanesulfonylphenoxy group, α
- Naphthoxy group, 3-pentadecylphenoxy group, benzyloxycarbonyloxy group, ethoxy group, 2-cyanoethoxy group, benzyloxy group, 2-phenethyloxy group, 2-phenoxyethoxy group, 5-phenyltetrazolyloxy group , 2-benzothiazolyloxy group, etc.)
, a group linked via a nitrogen atom (eg, benzenesulfonamide group, N-ethyltoluenesulfonamide group, heptafluorobutanamide group).

2.3, 4, 5, 6. -Pentafluorobenzamide group, octane sulfonamide group, P-cyanophenylureido group, N,N-diethylsulfamoylamino group, 1
-piperidyl group, 5,5-dimethyl-2,4-dioxo-3-oxazolidinyl group, l-benzyl-ethoxy-
3-hydantoynyl group, 2N-1, 1-dioxo-3(
2H)-oxo-1,2-benzisothiazolyl group, 2
-oxo-1,2-dihydro-1-pyridinyl group, imidazolyl group, pyrazolyl group, 3,5-diethyl-1,
2,4-triazol-1-yl group, 5- or 6-promobenzotriazol-1-yl group, 5-methyl-
1,2,3,4-triazol-1-yl group, benzimidazolyl group, 3-benzyl-1-hydantoinyl group,
1-benzyl-5-hexadecyloxy-3-hydantoynyl group, 5-methyl-1-tetrazolyl group, 4-methoxyphenylazo group, 4-pivaloylaminophenylazo group, 2-hydroxy-4-propanoylphenyl azo group, etc.), groups linked via a sulfur atom (e.g., phenylthio group, 2-carboxyphenylthio group, 2-butoxy-5-t-octylphenylthio group, 4-methanesulfonamidophenylthio group, 2,5 -dibutoxyphenylthio group, 4-methanesulfonylphenylthio group, 4-
Octanesulfonamidophenylthio group, 2-butoxyphenylthio group, 4-dodecyloxyphenylthio group,
2-(2-hexanesulfonylethyl)-5-tert
-octylphenylthio group, benzylthio group, 2-cyanoethylthio group, ■-ethoxycarbonyltridecylthio group, 5-phenyl-2,3,4,5-tetrazolylthio group, 2-benzothiazolylthio group, 2-dodecylthio group group, 2-dodecylthio-5-thiophenylthio group, 2-
Phenyl-3-dodecyl-1,2,4-triazolyl-
5-thio group, etc.).

When R2, R3, R4 or X becomes a divalent group to form a bis body, this divalent group is described in more detail as follows:
Substituted or unsubstituted alkylene group (e.g., methylene group, ethylene group, 1,10-decylene group, -C)12C)
+2-O-CH2CH2-1, etc.), substituted or unsubstituted phenylene groups (e.g., 1,4-phenylene group, 1,3
-phenylene group, -NHCO-Rs-CONH- group (Rs represents a substituted or unsubstituted alkylene group or phenylene group), and the like.

When those represented by general formulas (Ia) to (If) are present in the vinyl monomer, the linking group represented by R2, R3 or R4 is an alkylene group (substituted or unsubstituted alkylene group, for example, Methylene group, ethylene group.

1.10-decylene group, -CHzCHzOCHxCH2
-, etc.), phenylene group (II! substituted or unsubstituted phenylene group).

For example, 1,4-phenylene group, 1,3-phenylene group, -NHCQ-1-CONH-1-o-, -oco-,
and aralkylene groups (e.g. -c-0-cot-, -(IJ(2CH2-0-CH,
(1 & -1ゝ., etc.).

In addition, the vinyl group in the vinyl monomer has the general formula (Ia)
It also includes cases in which substituents other than those represented by (If) are present. Preferred substituents are hydrogen atom, chlorine atom,
Or it is a lower alkyl group having 1 to 4 carbon atoms.

Acrylic acid, α
- Chloroacrylic acid, α-alacrylic acid (e.g., methacrylic acid, etc.) and esters or amides derived from these acrylic acids (e.g., acrylamide, n-butylacrylamide, t-butylacrylamide, diacetone acrylamide, methacrylamide) , methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, t-butyl acrylate, 1so-butyl acrylate, 2-
ethylhexyl acrylate, n-octyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate and β-hydroxy methacrylate), methylene dibis acrylamide, vinyl esters (e.g. vinyl acetate, vinyl propionate and vinyl laurel). rate),
Acrylonitrile, methacriconitrile. Aromatic vinyl compounds (for example styrene and its derivatives, vinyltoluene, divinylbenzene, vinylacetophenone and sulfostyrene), itaconic acid, citraconic acid.

Crotonic acid, vinylidene chloride, vinyl alkyl ether (e.g. vinyl ethyl ether), maleic acid, maleic anhydride, maleic ester, N-vinyl-
Examples include 2-pyrrolidone, N-vinylpyridine, and 2- and 4-vinylpyridine. It also includes cases where two or more of the non-color-forming ethylenically unsaturated monomers used herein are used together.

Compound examples and synthesis methods of couplers represented by the general formulas (Ia) to (If) above can be found in the documents shown below.
It is described in ゛ etc.

The compound of general formula (Ia) is disclosed in JP-A No. 59-162548.
etc., the compound of general formula (Ib) is disclosed in JP-A-60-436
59 etc., the compound of general formula (Ic) is disclosed in Japanese Patent Publication No. 47-2
7411 etc., the compound of general formula (Id) is disclosed in JP-A-59
-171956 and 60-172982, etc., and the compound of general formula (Ia) is disclosed in JP-A-60-33552, etc.
Further, the compound of general formula (If) is disclosed in U.S. Patent No. 3.061,
432 etc., respectively.

Also, JP-A No. 58-42045, No. 59-214854
, No. 59-177553, No. 59-177544 and No. 59-177557, etc., are applicable to any of the compounds of the above general formulas (Ia) to (If).

Specific examples of the pyrazoloazole coupler used in the present invention are shown below, but the invention is not limited thereto.

(G1) one (M-5) chant rt"' i1 (M-7) (M-8) (M-9) (M-10) (M-11) (M-12) (M-13) t, ;J'I3 (M-14) (M-15) (?)-16) (M-17) (M-18) rrLqllllll (M-19) (M-20) (M-21) (M-22) ■.

(M-23) ul13 (M-24) (M-25) L;t13 (M-26) (M-27) (M-28) ■.

(M-29) (M-30) (M-33) (M-34) (M-37) (M-39) (M-40) Uchi (M-42) UL4Hri (M-54) CH.

iokz (M-62) (M-63) x:y=50:50 Same below 1IuL) x:y=40:60 (M-6) x:y=50:50 (M-66) x:y= 55:45 (M-Tan) x:y=50:50 These couplers are generally present in an amount of 2 x 10''a mole to 5 x 10-L mole per mole of silver in the emulsion layer, preferably I x 10- "moles to 5 x 10-1 moles are added.

Two or more types of the above couplers etc. can be used in the same layer in order to satisfy the characteristics required of a photosensitive material, or the same compound can be added to two or more different layers.
Of course it doesn't matter.

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 (
For example, acetyl tributyl citrate), benzoic acid esters (eg octyl benzoate), alkylamides (eg diethyl laurylamide), fatty acid esters (eg dibutoxyethyl succinate).

diethyl azelate), trimesic acid esters (eg tributyl trimesate), or organic solvents having a boiling point of about 30°C to 150°C, such as lower alkyl acetates such as ethyl acetate and butyl acetate.

After being dissolved in ethyl propionate, secondary butyl alcohol, methyl isobutyl ketone, β-ethoxyethyl acetate, methyl cellosolve acetate, etc., it is dispersed in a hydrophilic colloid. The above-mentioned high boiling point organic solvent and low boiling point organic solvent may be used in combination.

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

The color developer used in the present invention contains a known aromatic primary amine color developing agent. A preferred example is a p-phenyl diamine derivative, one representative example of which is shown below. It is not limited to these.

D-I N,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
-(Methanesulfonamido)ethylcoaniline also. These p-phenyl diamine derivatives may be salts such as sulfate, hydrochloride, sulfite, p-toluenesulfonate, etc. The amount of the aromatic-grade amine developing agent used is determined by the developer solution IQ. Preferably about 0.1g to about 20g
, more preferably at a concentration of about 0.5 g to about 10 g.

In particular, it is preferable to use the color developing agent D-4 in the presence of the compound of general formula (1) because good photographic properties can be obtained with little increase in fog.

Next, pimonoamines, diamines, polyamines, quaternary ammonium salts, nitroxy radicals, alcohols, ethers, oximes, amides and sulfonamides used in the present invention will be explained.

The monoamines used in the present invention have the following general formula (II):
It is a compound represented by

General formula (II) In the formula, R11 and Ro are each independently a hydrogen atom.

represents an alkyl group, alkenyl group, aryl group, aralkyl group or heterocyclic group, Ro represents an alkyl group, alkenyl group, aryl group, aralkyl group or heterocyclic group,
Here, R21 and RZI, RZI and Ro or R1
and R23 may be linked to form a nitrogen-containing heterocycle; however, when R11 is a hydroxyalkyl group having 2 to 6 carbon atoms, H*2. R23 does not simultaneously represent an unsubstituted alkyl group having 1 to 6 carbon atoms, a hydroxyalkyl group having 2 to 6 carbon atoms, or a benzyl group.

The alkyl group represented by RRl, R■, and R23 preferably has 1 to 12 carbon atoms, even if it is a straight chain.

It may be branched or cyclic (specifically methyl group, ethyl group, n-propyl group, 1so-propyl group, n-butyl group, t-butyl group, t-amyl group, n-hexyl group,
(cyclohexyl group, etc.); The alkenyl group preferably has 2 to 6 carbon atoms, and may be linear, monobranched, or cyclic (specifically allyl group, isopropenyl group, cyclohexenyl group, etc.); aryl group The number of carbon atoms is 6
-12 is preferable (specifically phenyl group, tolyl group, naphthyl group, etc.); As the aralkyl group, one having 7 to 12 carbon atoms is preferable (specifically benzyl group, phenethyl group, etc.); heterocyclic ring The group contains a nitrogen atom, an oxygen atom and/or a sulfur atom as a hetero atom, and has a carbon number of 1.
-12 are preferable (specifically imidazolyl group,
(pyrazolyl group, triazolyl group, pyridyl group, etc.).

RZI, R1, and R1 may have a substituent other than a hydrogen atom, and specific examples of the substituent include a halogen atom (fluorine atom, chlorine atom, bromine atom, etc.),
Alkyl groups (methyl, ethyl, butyl, t-butyl, methoxyethyl, carboxymethyl, hydroxyethyl, etc.), aryl groups (phenyl, tolyl, naphthyl, etc.), alkoxy groups (methoxy, ethoxy group, methoxyethoxy group, hydroxyethoxy group, etc.), aryloxy group (phenoxy group, p-nitrophenoxy group, etc.), sulfonyl group (methanesulfonyl group, benzenesulfonyl group, etc.), sulfonamide group (methanesulfonamide group, benzenesulfonamide group, etc.), sulfamoyl group (unsubstituted sulfamoyl group, dimethylsulfamoyl group, ethylsulfamoyl group, etc.)
, carbamoyl group (unsubstituted carbamoyl group, methylcarbamoyl group, dimethylcarbamoyl group, ethylcarbamoyl group, etc.), amide group (acetamido group, benzamide group, etc.), ureido group (methylureido group, ethylureido group, phenylureido group, etc.) , alkoxycarbonylamino group (methoxycarbonylamino group, methoxyethoxycarbonylamino group, etc.), 4acyl group (acedel group, benzoyl group, etc.).

formyl group, cyano group, carboxy group, sulfo group.

Examples include hydroxy group, nitro group, alkylthio group (methylthio group, hydroxyethylthio group, carboxymethylthio group, etc.), arylthio group (phenylthio group, etc.), etc. ! When there are two or more substituents, they may be the same or different.

R* 1 RF 2, R" and R"3 or R" and R
The nitrogen-containing heterocyclic group formed by linking " is a saturated or unsaturated 3- to 8-membered ring that may contain an oxygen atom or a sulfur atom in addition to a carbon atom or a nitrogen atom, or a benzene ring or a heterocyclic group. May be fused with a ring, specifically aziridine ring, azetidine ring, pyrrolidine ring, piperidine ring, piperazine ring, pyrroline ring, imidazolidine ring, pyrazolidine ring, indoline ring, morpholine ring, pyrrole ring, imidazole ring, pyrazole ring, indole ring, indazole ring, triazole ring, tetrazole ring, phenokilidine ring, tetrahydrothiazine ring, etc., and more preferably a saturated or unsaturated 5- to 6-membered ring.

Further, these nitrogen-containing heterocycles may have a substituent, and specific examples of the substituent include the same substituents as Bml, R1, and R23.

R@1. When either HNN or H** has a carboxy group, the compound of general formula (II) preferably has 3 or more carbon atoms, and when any of Rat, Ro, and R23 is a carboxyphenyl group, the substitution position of the amino group is preferably at the meta or para position of the carboxy group.

R21 and R″'a are particularly preferably a hydrogen atom or an alkyl group, and R22 is particularly preferably an alkyl group.

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

If-20N-CM, CH, OH \-17 n-6 (HOCH, CH, soup NCH, CH, SO, CH
.

■-7HN(CH2COOH)t ll-9H, NCH2CH, So, NH,.

IJUI-1° Specific examples other than the above include compound examples A-1 to A-12 described on pages 9 to 10 of Japanese Patent Application No. 147823/1982.
Compound Examples 1-(1) to I-(22) described on pages 10 to 14 of Specification No. 61-166674; No. 61-1
Compound Example 1 described on pages 11 to 14 of Specification No. 65621
-(1) to I -(21); Compound examples I-(1) to I described on pages 10 to 16 of Specification No. 61-164515
-(42); Specification No. 61-170789, page 9~
11 Compound Examples 1-(1) to I-(11)
Compound Examples 1-(1) to I-(24) described on pages 11 to 16 of Specification No. 61-168159; No. 61-169
Compound Example 1-(1
) to I-(2G); Compound Example 1-(1
) to 1-(35): etc.

These compounds represented by the general formula (II) are
No. 1-147823, No. 61-166674, No. 61
-165621, 61-164515, 61-
No. 170789, No. 61-168159, No. 61-1
It can be obtained by the method described in 6!1789, 461-197420, etc.

The diamines used in the present invention have the following general formula (III):
It is a compound represented by

General Formula (m) In the formula, R31, Ro, R33, and R34 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an aralkyl group, or a heterocyclic group.

Specifically, R″i and Ro in the general formula (n) have the same meaning. However, when Ro is a hydroxyalkyl group having 2 to 6 carbon atoms, 132.R33 and R″4 are simultaneously a hydrogen atom,
An unsubstituted alkyl group having 1 to 6 carbon atoms and a hydroxyalkyl group having 2 to 6 carbon atoms are not included.

Here, R'a'' and Ham, Ham and R34 may be linked to form a nitrogen-containing heterocycle, and specific nitrogen-containing heterocycles include R1 and R1, Ro and Ro of the general formula (If).
Alternatively, it has the same meaning as a nitrogen-containing heterocycle formed by connecting R1 and R1.

R3' represents a divalent organic group, specifically an alkylene group, an arylene group, an aralkylene group, an alkenylene group, or a heterocyclic group, where the alkylene group and alkenylene group may be linear or monobranched, It may be cyclic, preferably having 1 to 6 carbon atoms, and specifically includes a methylene group, dimethylene group, trimethylene group, methyldimethylene group, dimethyltrimethylene group, hexamethylene group, ethylene group, butenylene group, etc. can be mentioned. The arylene group preferably has 6 to 10 carbon atoms, and specific examples include the following. The aralkylene group preferably has 7 to 12 carbon atoms, specifically -C)II-0-, -CH, -0-CH, -.

Examples include. The heterocyclic group preferably has 1 to 8 carbon atoms, and specific examples include the following. These alkylene groups, alkenylene groups, arylene groups, aralkylene groups, and heterocyclic groups may have substituents, and specific substituents include the general formula (I
It has the same meaning as the substituent for R21, Ram and R23 in I), and when there are two or more substituents, they may be the same or different.

In general formula (m), R31, R3m, 13m, R14
and Ro have a total carbon number of at least 2.

Ram, u3'', R33, and R'4 are preferably a hydrogen atom or an alkyl group, and R31 is particularly preferably an alkylene group.

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

m-8HO2CCH,NHCH,CH,NHCH,C0
OH”-90”NCR, CH, NH.

\--l Specific examples other than the above include compound examples 1-(1) to 1 described on pages 10 to 13 of Japanese Patent Application No. 173595/1982.
-(20); Specification No. 61-164515, page 10~
Compound examples 1-(1) to I-(42) described on page 16
: Compound examples 1-(1) to I-(24) described on pages 11 to 16 of Specification No. 61-168159; No. 61-169
Compound Example 1-(1
) to I-(20); Compound Example 1-(1
)~! -(13), I-(15) and I-(19)~
I-(25); etc. can be mentioned.

The compound represented by the above general formula (m) is
No. 73595, No. 61-164515, No. 61-16
No. 8159, No. 61-169789 and No. 61-18
It can be obtained by the method described in No. 6560.

The polyamines used in the present invention have the following general formula (TV
) is a compound represented by

General formula (IV) In the formula, H41, R4'', R43 and R44 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an aralkyl group or a heterocyclic group, specifically, the general formula (II ) has the same meaning as R21 and B22.

R4X and H2N, 1<43 and R44 may be linked to form a nitrogen-containing heterocycle, specifically, in the general formula (If
), Rm''nmN, R'' and R'' or R'' and R'' are connected Lt and has the same meaning as a nitrogen-containing heterocycle.

R48, 84'' and R4'l each independently represent a divalent organic group, and specifically have the same meaning as R1 in the general formula (m).

-CO-1-SO, -1-SO- or a combination of these linking groups, R4'' is R4
1, R41, R43, and R44.

m represents an integer of 0 or 1 or more.The upper limit of 0m is not particularly limited, and as long as the compound is water-soluble, it may have a high molecular weight, but usually m is preferably in the range of 1 to 3.

However, when m=o and R411 is a hydroxyalkyl group having 2 to 6 carbon atoms, R41, R41, R43, R
44 does not contain a hydrogen atom, an unsubstituted alkyl group having 1 to 6 carbon atoms, or a hydroxyalkyl group having 2 to 6 carbon atoms.

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

IV-2 (HOCH, Pseudopodium roseri) C) l, CH, N-
Take H2 force, OR).

mV-6H, N-ECH, OH, N1rH (n=500
-20,000) Specific examples other than the above include the patent application filed in 1983.
Compound Examples 1-(1) to 1-(21) described on pages 11 to 14 of Specification No. 165621: Examples of compounds 1-(1) to 1-(21) described on pages 9 to 12 of Specification No. 61-169789 1-
(2G): etc.

The compound represented by the above general formula (IV) is
It can be obtained by the method described in No. 165621 and No. 61-169789.

The quaternary ammonium salts used in the present invention are compounds represented by the following general formula (V).

General formula (V) (in the formula, R'Jtn value 17) has 11 groups &indicated, R'',
R'' and R'4 each independently represent a monovalent organic group,
R1゜R5! and R54, at least two groups may be combined to form a heterocycle containing a quaternary ammonium atom, n is an integer of 1 or more, and xe represents a counter anion. General formula (V ), H5i is a monovalent or higher, preferably monovalent to trivalent, organic group. Examples of the monovalent group of HKI include substituted or unsubstituted alkyl groups (with 1 to 1 carbon atoms).
20 alkyl groups, such as methyl, ethyl, 2-
Hydroxyethyl group, 2-ethoxyethyl group, carboxymethyl group, 3-hydroxypropyl group, 3-sulfopropyl group, benzyl group, cyclohexyl group, cyclohexylmethyl group, isobutyl group, etc.), aryl group (having 6 to 20 carbon atoms) Aryl group 1 (e.g., phenyl group, 4-methoxyphenyl group, 2,4-dichlorophenyl group, etc.)
, heterocyclic groups (heterocyclic groups having 1 to 20 carbon atoms, such as pyridin-4-yl groups), etc. Substituents that these groups may have include halogen atoms, hydroxyl groups, sulfonate groups, etc. and a carboxyl group, an optionally substituted alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, a sulfonyl group, an acyl group, and an amino group.

Examples of divalent groups in 111 include substituted or unsubstituted groups,
Alkylene group (alkylene group having 1 to 20 carbon atoms, such as ethylene group, tetramethylene group, propylene group, etc.)
, arylene group (arylene group having 6 to 20 carbon atoms, such as P-phenylene group, m-phenylene group, 0-phenylene group, etc.), heterocyclic group (heterocyclic group having 1 to 20 carbon atoms,
For example, 2,3-pyridylene groups) or
Substituents for these include halogen atoms, hydroxyl groups, sulfo groups, carboxyl groups, optionally substituted alkyl groups, aryl groups, heterocyclic groups, alkoxy groups, and aryloxy groups. A sulfonyl group, an acyl group, an amino group, and the like are preferred.

HN3. R53 and R'4 are monovalent organic groups, and preferred among them are the specific examples of monovalent groups listed for R''1. Particularly preferred monovalent groups among R1, Ro, and R84 are Substituted or unsubstituted alkyl group HN3,
Most preferably, at least one of Rs3 and R54 is a hydroxyalkyl group, an alkoxyalkyl group, or a carboxyalkyl group.

At least two of Ro, R53, and R'4 may be bonded to form a heterocycle containing a quaternary ammonium atom (eg, pyrrolidinium ring, pyridinium ring, etc.).

n is an integer of 1 or more, and the present invention also includes cases where the compound of general formula (V) is an oligomer, but n is preferably 1.
It is an integer of ˜3, more preferably 1 or 2.

xe represents any counteranion; examples of xe include halogen ions (e.g., 1jle, Bre, Fe, I
Examples include acid groups of various acids (organic or inorganic acids such as sulfuric acid, nitric acid, phosphoric acid, P-toluenesulfonic acid, and acetic acid).

Note that the compound represented by the above general formula (V) may be contained as a side chain group of a polymer added to the color developer.

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

V-1Q-CH,N'-(C,H40H)3cQ.

V-2C,H, -N'-(C,H,OH),
V2 So.

V-3NL (C2H40H), N01
eV-4(C2H,)rN"-(C2H40H)2CQ
ev-6Q-N”-(C,H,OCH,), (A
IDV-8(HOC,H,)rN'-C,H,-N'(
C, H, OH), 2NO3@ Specific examples other than the above include Compound Examples-1-(1) to 1-(25) described on pages 12 to 16 of Japanese Patent Application No. 188619/1982. be able to.

The compound represented by the above general formula (V) is
It can be obtained based on the method described in No. 88619.

The nitroxy radicals used in the present invention are compounds represented by the following general formula (VI).

General formula (VI) R''1 Bml and Ro each independently represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, R61, Ham
may be the same or different from each other, and R'1 and Ro may be linked to form a ring structure.

Hal and Ro are not hydrogen atoms at the same time, and these alkyl groups, aryl groups, or heterocyclic groups may have a substituent. Examples of such substituents include a hydroxy group, an oxo group, and a carbamoyl group. group, alkoxy group, sulfamoyl group, carboxy group, and sulfo group. Examples of the heterocyclic group include a pyridyl group and a piperidyl group.

Preferably R@L, Ha 2 is a substituted or unsubstituted aryl group or tertiary alkyl group (for example, t-butyl group).

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

Vl-I CH3CH.

VI-5CH, CH.

Specific examples other than the above include Compound Examples 1-(1) to I described on pages 10 to 13 of Japanese Patent Application No. 197760/1982.
-(36) etc. can be mentioned.

The compound represented by the above general formula (Vf) is
It can be obtained based on the method described in No. 197760.

The alcohols used in the present invention are compounds represented by the following general formula (■).

General Formula (■) In the formula, R11 is a hydroxy-substituted alkyl group (preferably 1 to 10 carbon atoms, for example, a hydroxymethyl group).

hydroxyethyl group, etc.), and R72 represents an unsubstituted alkyl group (preferably having 1 to 10 carbon atoms; for example, a methyl group, an ethyl group, etc.) or a group similar to R71. R
72 represents a hydrogen atom or a group similar to R72, x7
1 is a hydroxy group, a carboxyl group, a sulfo group, a nitro group, an unsubstituted or hydroxy-substituted alkyl group (preferably having 1 to 10 carbon atoms, for example, a methyl group, a hydroxymethyl group, an ethyl group, etc.).

Unsubstituted or substituted amide group (preferably 2 to 2 carbon atoms)
10, for example, an acetamido group, a 2-hydroxybenzamide group, etc.), or an unsubstituted or substituted sulfonamide group (preferably a carbon number of 1 to 1O1, for example, a methanesulfonamide group, a 4-methylbenzenesulfonamide group, etc.) .

In the general formula (■), x71 is preferably a hydroxy group, a carboxyl group, or a hydroxyalkyl group.

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

Vl 4 HOCH-(CHtOH)a■-5(H
OCH, Soup C-C0OH ■-6CHCHtOH)* Vll-7(HOCH, hc-CH.

Vn-8(HOCH, hc-NHCOCH.

Specific examples other than the above include compound examples 1-(1) to I- described on pages 8 to 10 of Japanese Patent Application No. 186561/1986.
(15) Compound examples 1-(1) to I-(9)5 described on pages 8 to 9 of Specification No. 61-197419 can be mentioned.

The compound represented by the above general formula (■) is
It can be obtained based on the method described in No. 86561 and No. 61-197419.

The ethers used in the present invention are compounds represented by the following general formula (■).

General formula (■) In the formula, R", R", R"tt and L are each independent dihydrogen atoms or alkyl groups (preferably 1 to 10 carbon atoms, e.g.
methyl group, ethyl group, etc.), and n represents a positive integer up to 500.

The alkyl group represented by R81, Ra2, and Ra3 preferably has 5 or less carbon atoms, more preferably 2 or less carbon atoms. R11, R82 and R''3 are very preferably hydrogen atoms or methyl groups, most preferably hydrogen atoms.

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

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

Vff[-1HO-(CH,CH,0hOHVi[-2
CH,0-(C)(,CM,0)rOH■-3CH,O
Ken CH, CM, O soup OCH.

Vl[-5HOCH, CH20CH.

VW-6C,H,0-(CH,CH2O juice OH■-7H
O-(CH, CH, O Most H average molecular weight approximately 300■-8H
Oen CH, CH□0翰H average molecular weight about 8o.

■-9HO-(CH, CH, O Most H average molecular weight approximately 3.0
00■-1o HO-(C, H2CH, O-transition H average molecular weight of about 8,000 The compound represented by the general formula (■) can be easily obtained as a commercial product.

The oximes used in the present invention are compounds represented by the following general formula (IX).

General formula (IK) In the formula, R″1 and R92 are each independently a hydrogen atom,
Represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group, and R'1 and RI
2 may be the same or different, and these groups may be connected.

Substituents for alkyl groups and aryl groups include halogen atoms, alkyl groups, aryl groups, hydroxyl groups,
Alkoxyl group 1. Aryloxy group, amino group, carboxyl group, sulfo group, phosphonic acid group, carbamoyl group, sulfamoyl group.

Examples include sulfonyl group, ureido group, acyl group, acylamino group, sulfonamide group, alkylthio group, arylthio group, nitro group, cyano group, etc., and these include two or more or two or more kinds of substituents on alkyl and aryl groups. Furthermore, the hydroxyl group, carboxyl group, and sulfo group may be a salt of an alkali metal (eg, sodium, potassium, etc.).

Preferred examples of R91 and R92 are alkyl groups substituted with halogen atoms, hydroxyl groups, alkoxyl groups, amino groups, carboxyl groups, sulfo groups, phosphonic acid groups, nitro groups, and unsubstituted alkyl groups.

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

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

1X-IN-OH Specific examples other than the above include compound examples 1-(1) to
(20) etc. can be mentioned.

The compound represented by the above general formula (IK) is
-198987 based on the method described.

The amides and sulfonamides used in the present invention are compounds represented by the following general formula (X).

General formula (X) In the formula, xlo, x1''2 are each independent co-1 or bar sQ, -, L, R101, R102, R1
03, R104, HLO5 and 1410G each independently represent a hydrogen atom or an unsubstituted or substituted alkyl group; R1O? represents an unsubstituted or substituted alkylene group, an unsubstituted or substituted arylene group, or an unsubstituted or substituted aralkylene group. α1m and n each independently represent 0 or 1.

R'. 1, R102, R103, R104, R'''2t
[R""1' The alkyl group represented by t+ in the table may be linear, branched, or cyclic, and preferably has 1 to 12 carbon atoms.

Examples of substituents include halogen atoms (fluorine atoms, chlorine atoms, bromine atoms), alkoxy groups (methoxy groups, ethoxy groups, etc.), aryloxy groups (phenoxy groups, etc.), sulfonyl groups (methylsulfonyl groups, ethylsulfonyl groups,
phenylsulfonyl group, etc.).

Sulfonamide group (methylsulfonamide group, benzenesulfonamide group, etc.), sulfamoyl group (unsubstituted sulfamoyl group, methylsulfamoyl group, dimethylsulfamoyl group, phenylsulfamoyl group, etc.), carbamoyl group (unsubstituted carbamoyl group, etc.) group, methylcarbamoyl group, phenylcarbamoyl group, etc.), amide group (acetylamide group, phenylamide group, etc.), ureido group (methylureido group, phenylureido group, etc.), alkoxycarbonylamino group (methoxycarbonylamino group, ethoxycarbonyl group, etc.) amino group, etc.), cyano group, acyl group (acetyl group, benzoyl group, etc.), nitro group,
Examples include alkylthio groups (such as methylthio groups), arylthio groups (such as phenylthio groups), hydroxyl groups, sulfo groups, and carboxy groups.

The alkylene group represented by H2O2 may be linear, branched, or cyclic, and preferably has 1 to 6 carbon atoms, and specifically includes a methylene group, a dimethylene group, a trimethylene group, a methyldimethylene group, and a dimethyl group. Examples include trimethylene group, hexamethylene group, -〇-1-[F]-, and the like. The arylene group preferably has 6 to 10 carbon atoms, and specific examples include the following. The aralkylene group preferably has 7 to 12 carbon atoms, and specific examples thereof include -C8, -0, -C, +, -CH, and -C. These alkylene groups, arylene groups,
As the substituent for the aralkylene group, the above-mentioned R1@1. R
101, H2O2, R"', R10s and rJR"" substituents can be mentioned. When the substituent is 2
If there are more than one, they may be the same or different.

As RLO7, an alkylene group is particularly preferable.

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

X-6H, NSO, NH302NH.

Specific examples other than the above include compound examples 1-(1) to 1 described on pages 11 to 16 of Japanese Patent Application No. 1986-201861.
-(27) etc.

The compound represented by the above general formula (X) is
It can be obtained based on the method described in No. 01861.

The amount of the compound represented by the general formulas (Il) to (X) to be added is preferably 0.01 g to 100 g per color developer IQ.
g, more preferably 0.1 g to 20 g.

Further, the compounds of general formulas (Il) to (X) of the present invention can be used in systems using aromatic primary amine color developing agents.
It has particularly remarkable preservation performance when used in combination with compounds that directly stabilize TfL image agents.

Water-soluble antioxidants are generally known as compounds that directly stabilize the developing agent, such as hydroxylamines and hydroxamic acids.

Examples include hydrazines, hydrazides, phenols, α-hydroxyketones, α-aminoketones, and sugars.

Details of water-soluble antioxidants that are preferably used in combination are explained below.

Hydroxylamines are represented by the following general formula (X[).

General Formula (XI) In the formula, R111 and R113 each independently represent a hydrogen atom, an unsubstituted or substituted alkyl group, an unsubstituted or substituted alkenyl group, or an unsubstituted or substituted aryl group.

It is preferable that RIXl and R11m are an alkyl group or an alkenyl group, and it is more preferable that at least one of them has a substituent. Furthermore, R''1 and R112 may be linked together with a nitrogen atom to form a heterocycle.

Alkyl groups and alkenyl groups may be linear, branched, or cyclic, and substituents include halogen atoms (F, CD,
Br, etc.), aryl groups (phenyl group, p-chlorophenyl group, etc.), alkoxy groups (methoxy group, ethoxy group, methoxyethoxy group, etc.), aryloxy groups (phenoxy group, etc.), sulfonyl groups (methanesulfonyl group, P- toluenesulfonyl group, etc.), sulfonamide group (methanesulfonamide group, benzenesulfonamide group, etc.), sulfamoyl group (diethylsulfamoyl group, unsubstituted sulfamoyl group, etc.), carbamoyl group (unsubstituted carbamoyl group, diethylcarbamoyl group, etc.) ),
Amide group (acetamide group, benzamide group, etc.).

Ureido groups (methylureido groups, phenylureido groups, etc.), alkoxycarbonylamino groups (methoxycarbonylamino groups, etc.), allyloxycarbonylamino groups (
phenoxycarbonylamino group, etc.), alkoxycarbonyl group (methoxycarbonyl group, etc.), aryloxycarbonyl group (phenoxycarbonyl group, etc.), cyano group, hydroxy group, carboxy group, sulfo group, nitro group, amino group (unsubstituted amino group) , diethylamino group),
Examples include alkylthio groups (such as methylthio groups), arylthio groups (such as phenylthio groups), and heterocyclic groups (such as morpholyl groups and pyridyl groups).

Here, R111 and R112 may be the same or different,
Furthermore, the substituents of R111 and R1L'' may be the same or different.

Further, the number of carbon atoms in R"1.R"" is preferably 1 to 10.

The nitrogen-containing heterocycle formed by linking R1'' and R11'', which is particularly preferably 1 to 5, includes a piperidyl group,
Examples include pyrrolisilyl group, N-furkylpiperazyl group, morpholyl group, indolinyl group, and benztriazolyl group.

Preferred substituents for R111 and R112 are a hydroxy group, an alkoxy group, a sulfonyl group, an amide group, a carboxy group, a cyano group, a sulfo group, a nitro group, and an amino group.

Specific examples of the compound represented by the general formula (X[) used in the present invention are shown below, but the scope of the present invention is not limited to these compounds.

do not have.

Shaku-(1) OH C,H,-N-C2H40CH.

XI-(2) OH 1soC,H,-N-C,H,OCH.

XI-(3) OH CH, -N-C, H4QC, H.

Summer-(4) OH nC4H, -N-C2H4oCH3 CH.

■-(12) OH CH, -N-C, H, CONH.

”-(19) HO-N So.

“22) HO-N9-QC,H.

XI-(34) NH,OH The synthesis of the compound represented by the general formula (X[) is described in U.S. Patent Nos. 3,661,996, 3,362,961, and 3
, 293,034, Japanese Patent Publication No. 42-2794, U.S. Patent No. 3,491,151, U.S. Patent No. 3,655,764,
It can be synthesized by the known methods described in No. 3,467.711, No. 3,455.916, No. 3,287,125, and No. 3,287,124.

These compounds may form salts with various acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, oxalic acid, and acetic acid.

Hydroxamic acids are compounds represented by the following general formula (Xn).

General formula (Xll) In the formula, A01 is a hydrogen atom, a W-substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted 7-mino group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted Unsubstituted alkoxy group, substituted or unsubstituted aryloxy group, substituted or unsubstituted carbamoyl group, substituted or unsubstituted sulfamoyl group, acyl group, carboxy group, hydroxyamino group, or hydroxy-SO, -1 or - Represents SO-* R'' is a hydrogen atom.

a that represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted 7-aryl group A'' and R121 may be linked to form a ring structure.Y121 is a hydrogen atom or a hydrogen atom formed by a hydrolysis reaction. Represents a possible group.

When A1'' and R121 are groups having substituents, these substituents include halogen atoms, aryl groups, alkyl groups, alkoxy groups, aryloxy groups, hydroxy groups, sulfonyl groups, sulfonamide groups, sulfamoyl groups, and sulfonyl groups. group, amide group.

Can open ureido groups, cyano groups, hydroxyaminocarbonyl groups, carboxy groups, nitro groups, amino groups, alkoxycarbonyl groups, aryloxycarbonyl groups, alkylthio groups, arylthio groups, heteroa groups (pyridyl groups, morpholino groups, etc.) .

Specific examples of Y'' representing a group that can become a hydrogen atom through a hydrolysis reaction include the following.

l) A method of protecting with an ester bond or a urethane bond,
That is, Y121 represents -c -RL 22, where:
■ As R10, I! Substituted or unsubstituted alkyl group.

Examples include a substituted or unsubstituted aryl group and a substituted or s-substituted amino group.

2) The method of protecting with an imidomethyl blocking group described in JP-A-57-158638, ie, Y121.

where Z represents a plurality of atoms necessary to complete a heterocycle having at least one 5- or 6-membered ring.

--In the general formula (Xll), A121 is preferably a substituted or unsubstituted alkyl group, aryl group, amino group, alkoxy group or aryloxy group. Particularly preferred are substituted or unsubstituted amino groups, alkoxy groups, or aryloxy groups.

The number of carbon atoms is preferably 1 to 10.

x''L is preferably 10-.

R121 is preferably a hydrogen atom.

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

Xfl-2CH3-C-NH-OH Fin Xn-3C4H, 0-C-N) I-OH Feedback Compound examples I-(1) to I-(37) described on pages 12 to 23 of the specification can be mentioned.

The compound of the above general formula (1) is disclosed in Japanese Patent Application No. 61-186559.
It can be obtained based on the method described in No.

Hydrazines and hydrazides are represented by the following general formula (XII
This is a compound represented by I).

General Formula (XIII) In the formula, R131, R132 and R133 each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, aryl group or heterocyclic group.

R134 is a hydroxy group, a hydroxyamino group, a substituted or unsubstituted alkyl group, an aryl group, a heterocyclic group,
@X131 representing an alkoxy group, an aryloxy group, a carbamoyl group, or an amino group represents a divalent group selected from u-co-, -so, - and -C-, and n is 0 or 1. However, when n-0,
R134 represents a substituted or unsubstituted group selected from an alkyl group, an aryl group and a heterocyclic group. R'''
1 and R134 may jointly form a heterocycle.

To describe the general formula (XIII) in more detail, R131,
R″0 and R13″ are each independently a hydrogen atom, a W-substituted or unsubstituted alkyl group (preferably a carbon number of 1 to
20, such as methyl group, ethyl group, sulfopropyl group,
(carboxybutyl group, hydroxyethyl group, etc.), aryl group (preferably having 6 to 20 carbon atoms, such as phenyl group, 2,5-dimethoxyphenyl group, 4-hydroxyphenyl group, 2-carpoxyphenyl group, etc.) or Terocyclic group (preferably 1 to 20 carbon atoms, e.g. pyridine-4
-yl group, etc.).

R134 is a hydroxy group or a hydroxyamino group.

Substituted or unsubstituted alkyl group (preferably 1 to 20 carbon atoms, such as methyl group, ethyl group, sulfopropyl group, carboxybutyl group, hydroxyethyl group, cyclohexyl group, benzyl group, etc.).

Aryl groups (preferably 6 to 20 carbon atoms, such as phenyl, 2,5-dimethoxyphenyl, 4-hydroxyphenyl, 2-carboxyphenyl, etc.), heterocyclic groups (preferably 1 to 20 carbon atoms, such as pyridine) -4
-yl group, etc.), alkoxy group (preferably 1 carbon number)
~20, such as methoxy group, ethoxy group, methoxyethoxy group, benzyloxy group, cyclohexyloxy group, etc.)
, aryloxy group (preferably has 6 to 20 carbon atoms, such as phenoxy group, p-methoxyphenoxy group, etc.), carbamoyl group (preferably has 1 to 20 carbon atoms, such as carbamoyl group, N,N-diethylcarbamoyl group, hydrazinocarbonyl group) etc.) or an amino group (preferably carbon number O to 20, e.g. amino group, N-phenylamino group,
hydrazino group, etc.).

NH ■ x”1 represents a divalent group selected from -co-, -so, - and -〇-, n is O or 1. However, n=
When 0, R134 represents a substituted or unsubstituted group selected from an alkyl group, an aryl group, and a heterocyclic group. R10 and R1''4 may jointly form a petero ring.

In general formula (XIII), R''1, R11 and R13
3 is preferably a hydrogen atom or an alkyl group, and most preferably R131 and R10 are hydrogen atoms.

In general formula (XIII), R134 is preferably a haalkyl group, aryl group, alkoxy group, carbamoyl group or amino group. X L31 is -CO- or -SO
, - is preferable, and -CO- is most preferable.

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

C,H.

Xllll-2NH,NH(CH,hso,HXIII-
3NH,NH-(CH2 juice 0HXIII-4NH,-N
N-CH.

C, H40H Xllll-6NH, NHCOCH.

Xllll-7NH, NHCOOC2H.

Xllll-9NH, NH3O2-0-CH.

Xllll-10NH, NHCONH.

Xllll-11NH, NHCONH-QXIII-12
NH, NH30, H XIII-14NH, NHCOCONHNH.

Specific examples other than the above include compound examples (1-1) to (
1-32), etc.

The compound of general formula (XIII) (7) above is patent application No. 61-1
It can be obtained based on the method described in No. 70756.

Phenols are compounds represented by the following general formula (XIV).

General formula (XIV) In the formula, R141 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 sulfonamido group, a ureido group, Represents an alkylthio group, arylthio group, nitro group, cyano group, amino group, formyl group, acyl group, sulfonyl group, alkoxycarbonyl group, aryloxycarbonyl group, alkoxysulfonyl group, or aryloxysulfonyl group, which further includes a substituent. It may have.

When there are two or more R141s, their types may be the same or different, and when they are adjacent, they may combine with each other to form a ring @ R14'' is a hydrogen atom or can be hydrolyzed 0m and n representing groups each represent an integer from 1 to 5.

To describe general formula (XIV) in more detail, R141 is:
Hydrogen atoms, halogen atoms (F, Cfi, Or, etc.)
, alkyl groups (methyl group, ethyl group, t-butyl group, etc.), aryl group (phenyl group, etc.), alkoxy group (methoxy group, ethoxy group, etc.), aryloxy group (phenoxy group, etc.), carboxyl group, sulfo group, Carbamoyl group, sulfamoyl group, amide group (acetamide group, benzamide group, etc.), sulfonamide group (methanesulfonamide group, benzenesulfonamide group, etc.),
ureido group, alkylthio group (methylthio group, etc.),
Arylthio group (phenylthio group, etc.), nitro group,
Cyano group.

Amino group, formyl group, acyl group (acetyl group, etc.),
Sulfonyl group (methanesulfonyl group, benzenesulfonyl group, etc.), alkoxycarbonyl group (methoxycarbonyl group, etc.), aryloxycarbonyl group (phenoxycarbonyl group, etc.), alkoxysulfonyl group (methoxysulfonyl group, etc.) or aryloxysulfonyl group (phenoxycarbonyl group, etc.) sulfonyl group, etc.).

When R141 is further substituted, examples of the substituent include a halogen atom, an alkyl group, an aryl group, a hydroxyl group, an alkoxy group, an aryloxy group, a carboxyl group, a sulfo group, a carbamoyl group, a sulfamoyl group, an amide group, a sulfonamido group, Ureido group, alkylthio group, arylthio group, nitro group, cyano group, amino group, formyl group, acyl group, sulfonyl group, alkoxycarbonyl group, aryloxycarbonyl group, alkoxysulfonyl group, aryloxysulfonyl group, and heterocyclic group ( morpholyl group, pyridyl group, etc.). Furthermore, these substituents.

R141 may be substituted with two or more or two or more types, and when there are two or more R141, the types may be the same or different, and when they are adjacent, they may be bonded to each other to form a ring. R In L and its substituents, the carboxyl group and sulfo group may form salts with alkali metals (Na, K, etc.), and the amino group may form salts with various acids such as hydrochloric acid.

R"" is based on a hydrogen atom or a hydrolyzable group. A hydrolyzable group is a group that can become a hydrogen atom by hydrolysis, and a specific example thereof is R14-=
-c-R-43 (here, R143 represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted amino group). That is, it is a method of protecting with an ester bond or a urethane bond.

Another example is protection with an imidomethyl blocking group as described in JP-A-57-TSGSAG. In other words, it represents the multiple atoms necessary to complete a heterocycle having two-membered rings. ). Moreover, m and n are each integers from 1 to 5.

In general formula (XIV), R141 is preferably an alkyl group, a halogen atom, 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,
These are nitro group and cyano group.

Among these, an alkoxy group, an alkylthio group, an amino group, and a nitro group are particularly preferable, and it is more preferable that these are in the ortho or para position of the (oR142) group, and
The number of carbon atoms in R141 is preferably 1 to 10, particularly preferably 1 to 6.

Preferred R142 is a hydrogen atom or a hydrolyzable group having 1 to 5 carbon atoms. Also (oR1
When there are two or more quaternary groups, it is more preferable that they are located at the ortho or para positions of each other V).

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

Specific examples other than the above include Compound Examples 1-(1) to I described on pages 14 to 27 of Japanese Patent Application No. 188742/1982.
-(42); Specification No. 61-203254, page 13~
Compound examples (1) to (41) described on page 25 can be mentioned.

The compound of the above general formula (xIv) is disclosed in Japanese Patent Application No. 61-1887.
It can be obtained based on the method described in No. 42 and No. 61-203254.

α-Hydroxyketones and α-aminoketones are compounds represented by the following general formula (XV).

General formula (XV) In the formula, RL S 1 represents a hydrogen atom, a substituted or unsubstituted alkyl group, an aryl group, an alkoxy group, an aryloxy group, or an amino group, and R152 represents a hydrogen atom or a substituted or unsubstituted alkyl group. ax'' represents a hydroxyl group or a substituted or unsubstituted amino group.

To describe the general formula (XV) in more detail, RL S 1 is a hydrogen atom, a substituted or unsubstituted alkyl group (preferably 1 to 20 carbon atoms, such as a methyl group, an ethyl group, a hydroxymethyl group, a methoxyethyl group, cyclohexyl group, etc.), aryl group (preferably 6 to 20 carbon atoms, e.g. phenyl group, 2-hydroxyphenyl group, etc.), alkoxy group (preferably 1 to 20 carbon atoms, e.g. methoxy group, ethoxy group, methoxyethoxy group, etc.) ), aryloxy group (preferably 6 to 201 carbon atoms, e.g. phenoxy group, 4-methoxyphenoxy group, etc.), or amino group (preferably 0 to 201 carbon atoms, e.g. amino group, N, N
-diethylamino group, N-phenylamino group, etc.).

R'' is a hydrogen atom, a substituted or unsubstituted alkyl group (preferably 1 to 20 carbon atoms, e.g. methyl group, ethyl group, hydroxymethyl group, etc.) or an aryl group (preferably 6 to 20 carbon atoms, e.g. phenyl group) group, 2-hydroxyphenyl group, etc.) *R"" and R"" may jointly form a carbocycle or a heterocycle.

xll is a hydroxyl group or a substituted or device amino group (preferably carbon number O to 20; for example, an amino group, N
, N-diethylamino group, morpholino group, etc.).

In the general formula (XV), RL f l is preferably a hydrogen atom, a substituted or unsubstituted alkyl group, an aryl group, or an alkoxy group, and R I S 2 is a hydrogen atom or a substituted or unsubstituted alkyl group. It is preferable that

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

XV-10 ■ CH3CCH,OH Shil"13 (-+ - Shil"i Shil'i3V-40 Tumor CH, CCH, NHC, H.

XV-50 HC-CH,OH Specific examples other than the above include compound examples (1) to (18
) etc.

°゛The compound of general formula (XV) above is patent application No. 61-184.
It can be obtained based on the method described in No. 328.

Below, the saccharides used in the present invention will be explained in detail.

Sugars (also called carbohydrates) consist of monosaccharides and polysaccharides.
Monosaccharides, many of which have the general formula C, H,, O, generally include aldehydes or ketones of polyhydric alcohols (called aldoses and ketoses, respectively) and their reduced, oxidized, dehydrated derivatives, and amino acids. A general term for a wider range of derivatives such as sugars and thiosaccharides. Moreover, polysaccharide refers to a product obtained by dehydration condensation of two or more of the above-mentioned monosaccharides.

More preferred among these saccharides are aldoses having a reducing aldehyde group and derivatives thereof, and particularly preferred among these are those corresponding to monosaccharides.

Specific examples of saccharides that can be used in the present invention are listed below, but the present invention is not limited thereto. (These optical isomers can also be used in the same way.) XVI-1: D- Ochylose XVI-2: L-arabinose XVI-3: D-ribose XVI-4: D-deoxyribose XVI-5:
D-glucose XVI-6: D-galactose XVI-7: D-mannose XVI-8: Glucosamine XVI-9: L-sorbose XVI-10: D-sorbitol 0-C
-H ■ -C-OH -C-OH ■ CH,OH The above saccharides are available as commercial products.

The amounts of these compounds of general formulas (XI) to (XV) and saccharides added to the color developer are determined by the color developer IQ.
Preferably 0.01g to 50g, more preferably 0
．． It is 5g to 20g.

Other sulfite ions, known as preservatives, are not substantially contained in the color developer of the present invention, and "substantially" means that they may be added to the extent that they do not affect the photographic properties. ~o, oosmol #l is preferably O~0.002 mol/Q.

The color developer of the present invention also includes preservatives such as U.S. Patent No. 3,615,503 and British Patent No. 1,306,
Hydroxyacetones described in No. 176, JP-A-52-1
α-aminocarbonyl compounds described in JP-A-43020 and JP-A-53-89425, various metals described in JP-A-57-44148 and JP-A-57-53749, etc., JP-A-57-52
- Various saccharides described in No. 102727, No. 59-16014
α,α′-dicarbonyl compound described in No. 1, No. 59-1
Salicylic acids described in No. 80588, No. 56-75647
The gluconic acid derivatives described in the above may be contained as necessary, and two or more of these preservatives may be used in combination as necessary, and addition of an aromatic polyhydroxy compound is particularly preferred.

The color developer of the present invention preferably does not substantially contain benzyl alcohol from the viewpoint of fogging and increase in stain after processing.
5.00 per ρ of color developer. OwrQ or less, preferably 2
m11 or less, more preferably not at all.

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 the buffering agent 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-propanediol salt, valine salt, proline salt, trishydroxyaminomethane salt, lysine salt, etc. can be used. Especially carbonates, phosphates, and tetraborates.

Hydroxybenzoate has excellent solubility and buffering capacity in the high pH range of pl (9.0 or higher), has no adverse effects on photographic performance (fogging, etc.) even when added to color developers, and is inexpensive. It is particularly preferable to use these buffers because of these advantages.

Specific examples of these buffers include sodium trirum carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate, sodium borate, boric acid. Potassium, sodium tetraborate (borax), potassium tetraborate, sodium 0-hydroxybenzoate (sodium salicylate).

Examples include potassium O-hydroxybenzoate, sodium 5-sulfo-2-hydroxybenzoate (sodium 5-sulfosalicylate), 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 In
It is preferable that it is more than O01 mol/Q~0.
Particularly preferred is 4 mol In.

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, such as the aminopolycarboxylic acids described in Japanese Patent Publication No. 48-30496 and Japanese Patent Publication No. 44-30232, Japanese Patent Publication No. 56-97347, Japanese Patent Publication No. 56-39359, and West German Patent No. 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
Phosphonocarboxylic acids described in No. 06 and the like.

Others JP-A-58-195845, JP-A No. 58-2034
Examples thereof include compounds described in No. 40 and Japanese Patent Publication No. 53-40900. Specific examples are shown below, but the invention is not limited to these.

Nitrilotriacetic acid, diethylenetriaminepentaacetic acid.

Ethylenediaminetetraacetic acid, N,N,N-trimethylenephosphonic acid, ethylenediamine-N,N,N',N'-
Tetramethylenephosphonic acid, transcyclohexanediaminetetraacetic acid, 1,2-diaminopropanetetraacetic acid, glycol ether diaminetetraacetic acid, ethylenediamine orthohydroxyphenylacetic acid, 2-phosphonobutane-1,
2,4-tricarboxylic acid, 1-hydroxyethylidene-
1,1-diphosphonic acid, N,N'-bis(2-hydroxybenzyl)ethylenediamine-N,N'-diacetic acid, etc.

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

The amount of these chelating agents added may be sufficient as long as it is sufficient to sequester metal ions in the color developer.For example, IQ
It is about 0.1g to 10g per serving.

Any development accelerator can be added to the color developer if necessary. However, the color developer of the present invention preferably does not substantially contain benzyl alcohol from the viewpoints of pollution, formulation properties, and fog prevention.

The compounds of the above-mentioned general formulas (n) to (X) 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 Publication No. 37-16088.

No. 37-5987, No. 38-7826, No. 44-1
No. 2380, No. 45-9019 and U.S. Patent No. 3,8
Thioether compounds represented in No. 13,247 etc.
p-phenylenediamine compounds disclosed in JP-A-52-49829 and JP-A-50-15554;
Quaternary ammonium salts shown in Japanese Patent Publication No. 0-137726, Japanese Patent Publication No. 44-30074, Japanese Patent Publication No. 56-156826 and Japanese Patent Publication No. 52-43429 1, etc., U.S. Patent No. 2.4
No. 94,903, No. 3,128,182, No. 4,23
No. 0,796, No. 3,253,919, Special Publication No. 1979-
No. 11431, U.S. Patent No. 2.482.546, U.S. Pat.
, 596,926 and 3,582,346, etc., Japanese Patent Publication No. 37-16088, 4
No. 2-25201, U.S. Patent No. 3,128,183,
Polyalkylene oxides shown in Japanese Patent Publications No. 41-11431, No. 42-23883, U.S. Patent No. 3,532,501, etc., l-phenyl-3-pyrazolidones, imidazoles, etc. are added as necessary. be able to.

In the present invention, any antifoggant can be added if necessary. As antifoggants, alkali metal halides such as sodium chloride, potassium bromide, potassium iodide, and organic antifoggants can be used. Examples of organic antifoggants include benzotriazole, 6-nidrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chlorobenzotriazole, 2-thiazolyl-benzimidazole. Representative examples include nitrogen-containing heterocyclic compounds such as , 2-thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolizine, and adenine.

The color developer used in the present invention preferably contains a fluorescent brightener.
Diamino-2,2'-disulfostilbene compounds are preferred, the amount added is Og ~ 5g/Q, preferably 0.1g ~
4gIQ.

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. Although it is preferable that the amount of replenishment is small, it is 20 to 600 mfi, preferably 50 to 300 mfi, per rrl of photosensitive material. More preferably 1001
The base is ~200+sjl.

Next, the bleaching solution, bleach-fixing wave, 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 (m) (e.g., aminopolymers such as ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid) can be used. complex salts with carboxylic acids, aminopolyphosphonic acids, phosphonocarboxylic acids, and organic phosphonic acids) or organic acids such as citric acid, tartaric acid, and malic acid; persulfates;
Hydrogen peroxide and the like are preferred.

Among these, organic complex salts of iron (m) are particularly preferable from the viewpoint of rapid processing and prevention of environmental pollution, and aminopolycarboxylic acids, aminopolyphosphonic acids, or organic Examples of phosphonic acids or their salts include ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, 1,3-diaminopropanetetraacetic acid,
Examples include propylene diaminetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, iminodiacetic acid, glycol ether diaminetetraacetic acid, and the like.

These compounds may be sodium, potassium, lithium or ammonium salts; among these compounds are iron ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, 1,3-diaminopropanetetraacetic acid, methyliminodiacetic acid; (III)
Complex salts 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. A ferric ion complex salt may be formed in a solution using a chelating agent such as aminopolycarboxylic acid, aminopolyphosphonic acid, or phosphonocarboxylic acid.
Aminopolycarboxylic acid iron complexes are preferred among iron complexes, which may be used in excess to form an iron ion complex salt, and the amount added is 0. O1 to 1.0 mol/Ω preferably 0
．． 05-0.50 molar IQ.

Various compounds can be used as bleach accelerators in the bleach solution, bleach-fix solution and/or their pre-bath. For example, U.S. Pat. No. 3,893,858; German Pat. No. 1,290; Specification No. 812, JP-A-53-
Publication No. 95630, Research Disclosure No. 17
129 (July 1978 issue), compounds having a mercapto group or disulfide bond, and
No. 8506, JP-A No. 52-20832, Mukai 53-32
Thiourea compounds described in No. 735, 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 rehalogenating agent such as ammonium iodide) may be included. 1 with pH 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.
More than one type of inorganic acid, organic acid, alkali metal or ammonium salt thereof, or a corrosion inhibitor such as ammonium nitrate or 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; Bisthioglycolic acid, 3,6-cythia 1
, 8-octanediol, etc., and water-soluble silver halide solubilizers such as thioureas, and these can be used alone or in combination of two or more. In addition, a special bleach-fixing solution consisting of a combination of a fixing agent and a large amount of a halide such as potassium iodide as described in JP-A-55-155354 can also be used.8 In the present invention, thiosulfate Particularly preferred is ammonium thiosulfate.

The amount of fixing agent per IQ is preferably 0.3 to 2 moles, more preferably 0.5 to 1.0 moles.

The pH range of the bleach-fixing solution or fixing solution is preferably 3 to 10, more preferably 5 to 9.

Further, the bleach-fix solution may contain various other optical brighteners, 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., sodium sulfite, potassium sulfite, ammonium sulfite, etc.) and bisulfites (e.g., ammonium bisulfite, sodium bisulfite, bisulfite, etc.) as preservatives. (e.g., potassium metabisulfite, etc.), metabisulfites (e.g., potassium metabisulfite, sodium methybisulfite, ammonium metabisulfite, etc.). These compounds are approximately 0.0 in terms of sulfite ion.
It is preferable to contain 2 to 0.50 mol IQ, more preferably 0.04 to 0.40 mol IQ.

Sulfites are commonly added as preservatives, but other preservatives include ascorbic acid, carbonyl bisulfite adducts,
Alternatively, a carbonyl compound or the like may be added.

Furthermore, buffering agents, optical brighteners, chelating agents, antifoaming agents, antifungal agents, etc. 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 photosensitive material (for example, depending on the materials used such as couplers), the purpose, the temperature of the washing water, the number of washing tanks (number of stages), the replenishment method such as countercurrent or forward flow, and various other conditions. Can be set. Among these, the relationship between the number of flushing tanks and the amount of water in the multistage countercurrent method is described in the Journal of the Society of Motion Picture and Television Engineers.
theSociety of Motion Pict
ure and Television Engineering
rs) Vol. 64, P, 248-253 (May 1955 issue). Normally, the number of stages in the multi-stage countercurrent system is preferably 2 to 6, particularly 2.
-4 is preferred.

According to the multi-stage countercurrent method, the amount of washing water can be greatly reduced, for example, 0.5 Ω to 1 n or less per photosensitive material, but bacteria can multiply due to the increased residence time of water in the tank. In the processing of the color photosensitive material of the present invention, problems such as the floating substances generated adhering to the photosensitive material occur, and as a solution to such problems, Japanese Patent Application No.
The method for reducing calcium and magnesium described in No. 32 can be used very effectively. In addition, chlorine-based disinfectants such as isothiazolone compounds and thiabendazoles described in JP-A No. 57-8542, chlorinated sodium isocyanurate described in JP-A No. 61-120145,
Benzotriazole, copper ion, etc. described in Patent Application No. 105487/1987, "Chemistry of Antibacterial and Antifungal Agents" by Hiroshi Horiguchi, Hygiene Technology Synthesis "Sterilization, Disinfection, and Antifungal Technology of Microorganisms", Japan Antibacterial and Antifungal It is also possible to use fungicides listed in the interacademic "Encyclopedia of antibacterial and fungicidal agents."

Further, in the washing water, a surfactant as a draining agent and a chelating agent typified by EDTA as a water softener can be used.

The pH of the washing water in the processing of the photosensitive material of the present invention is 4 to 4.
9, preferably 5-8. The washing water temperature and washing time can be set in various ways depending on the characteristics of the photosensitive material, its use, etc.
Generally, a range of 20 seconds to 10 minutes at 15 to 45°C, preferably 30 seconds to 5 minutes at 25 to 40°C is selected.

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 solution, such as an aldehyde compound represented by formalin, or a film suitable for dye stabilization.
Examples include buffering agents and ammonium compounds for adjusting to H. or.

In order to prevent the proliferation of bacteria in the solution and to impart antifungal properties to the photographic material after processing, the various disinfectants and antifungal agents described above can be used.

Furthermore, surfactants, optical brighteners, and hardeners may be added. In the processing of the photosensitive material of the present invention, when stabilization is performed directly without going through a water washing step, JP-A-57-
No. 8543, No. 58-14834, No. 59-184343
No. 60-220345, No. 60-238832,
No. 60-239784.

60-239749, 61-4054, 61-11
All known methods described in No. 8749 and the like 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 has been reduced by a multi-stage countercurrent system, into a bleach-fixing bath, which is a pre-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,
Can be applied to any processing process, such as color paper, color reversal paper, color direct positive photosensitive material, color positive film, color negative film, color reversal film, etc., but especially to color paper and color reversal paper. It is preferable to apply

The silver halide emulsion of the light-sensitive material used in the present invention may have a halogen composition such as silver iodobromide, silver bromide, silver chlorobromide, or silver chloride. When performing low replenishment treatment, a silver chlorobromide emulsion or a silver chloride emulsion containing 60 mol% or more of silver chloride is preferred, and a silver chloride content of 80 to 100 mol% is particularly preferred. In addition, when high sensitivity is required and it is necessary to suppress fog during production, storage, and/or processing, silver chlorobromide emulsions containing 50 mol% or more of silver bromide or Silver iodide emulsions (which may contain 3 mol% or less of silver iodide) are preferred, and more preferably 70 mol% or more of silver iodide.
Silver chloroiodobromide is preferred, where the silver iodide content is between 3 and 15
Mol% is preferred.

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, or may have different phases. 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, the value (expressed in yen) is preferably 2 μm or less and 0.1 μm or more, and particularly preferably 1.5 μm.
It is less than μ■ and more than 0.15μ. 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 (monodispersity is defined as the above-mentioned type). (preferably one with a variable rate) can be mixed in the same layer or coated in separate layers. 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.
~8 or more than 8 tabular grains account for 5 of the total projected area of one grain
An emulsion containing 0% or more may also be used.

These various emulsions may be a mixture of these various crystal forms, and may be either a surface latent image type in which a latent image is formed primarily on the surface or an internal latent image type in which a latent image is formed inside the grains.

The photographic emulsion used in the present invention is described in Research Disclosure (HD) vol, 170 Item No. 1.
7643(x, n, m) (December 1978).

The emulsion used in the present invention is usually physically ripened.

Use those that have been chemically ripened and spectrally sensitized.

Additives used in such processes are listed in Research Disclosure Vol. 176, No. 17643 (1978).
(December 2016) and Vol. 187, No. 18716 (
(November 1979), and the relevant sections 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 RD18
7161 Chemical sensitizer page 23 64
Page 8 right column 2 Sensitivity increasing agent Same as above 3 Spectral sensitizer Page 23-24 Page 648 Right column ~ 4 Supersensitizer 649
Page right column 5 Brighteners Page 24 6 Antifoggants and stabilizers Pages 24-25 Page 649 Right column 7 Coupler Page 25 8 Organic solvents Page 25 9 Light absorbers, 649 Right column ~ Filter dyes Pages 25-26 650 Left Column 10 Ultraviolet absorber 11 Anti-stain agent Page 25 right column 650
Page left to right column Additive type RD17643
RD1871612 Dye image stabilizer page 25 13 Hardener page 26 651
Page left column 14 Binder page 26
Same as above 15 Plasticizer, lubricant page 27 6
50 Right column 16 Coating aids, surfactants pages 26-27
Same as above 17 Static inhibitor page 27
Various color couplers can be used in the present invention. Here, the term "color coupler" refers to a compound that can generate 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 found in Research Disclosure (RD) 17.
643 (December 1978) ■-D Section and 187
No. 17 (November 1979).

The color coupler incorporated in the light-sensitive material is preferably diffusion-resistant by having a pallast group or being polymerized, and the coupling active position is substituted with a leaving group rather than a hydrogen atom equivalent color coupler. Two-equivalent color couplers are preferable, such as couplers in which the amount of silver coated can be reduced.0 Couplers in which color-forming dyes have appropriate diffusivity, non-color-forming couplers, or DIR couplers that release a development inhibitor upon coupling reaction, or DIR couplers that promote development. Couplers that release agents 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
The use of two-equivalent yellow couplers is preferred in the present invention, as described in U.S. Pat. Nos. 3,408,194 and 3,447,928;
3.933,501 and 4,022,62
0, etc., or Japanese Patent Publication No. 55-10739, U.S. Patent No. 4,
No. 401,75.2, No. 4.326,024, RD
18053 (April 1979), British Patent No. 1,42
No. 5,020, West German Application Publication No. 2,219,917,
Typical examples include the nitrogen atom separation type yellow couplers described in Japanese Patent No. 2,261,361, Japanese Patent No. 2,329,587, and Japanese Patent No. 2,433.812. α-pivaloylacetanilide couplers have excellent color fastness, especially light fastness;
- Penzoylacetanilide 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, are exemplified. 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.
Representative examples include U.S. Patent Nos. 2,311,082, 2,343,703, 2,600,788, 2,908,573, and 3,062,653. ,
No. 3,152,896 and No. 3,936,01
It is stated in issue 5 etc. As a leaving group for a two-equivalent 5-pyrazolone coupler, U.S. Pat.
No. 9 or the nitrogen atom leaving group described in U.S. Pat.
The arylthio group described in No. 351, 897 is preferred.

Further, the 5-pyrazolone coupler having a ballast group described in European Patent No. 73,636 provides high color density.

As a pyrazoloazole coupler, U.S. Patent No. 3,
369,879, preferably pyrazolo(5,1-c)(1,2,4) triazoles as described in U.S. Pat. No. 3,725,067, Research Disclosure 24220 (
Pyrazolotetrazoles and Research Disclosure 24230 (June 1984) and Research Disclosure 24230 (June 1984)
Imidazo (1) described in European Patent No. 119,741 in terms of low yellow sub-absorption and light fastness of color-forming dyes.
, 2-bl pyrazoles are preferred, as described in European Patent No. 119
, pyrazolo (1,5-b) (1,2,
4) Triazoles are particularly preferred.

Cyan couplers that can be used in the present invention include oil-protected naphthol 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. Further, specific examples of phenolic couplers are given in U.S. Patent Nos. 2,369,929 and 2.8.
No. 01,171, No. 2,772,162, No. 2,
No. 895,826, etc. Cyan couplers that are robust to humidity and temperature are preferred in the present invention and are typically described in U.S. Pat. No. 3,772.
Phenolic cyan coupler having an alkyl group greater than or equal to ethyl group at the meta-position of the phenol nucleus described in U.S. Pat. No. 2,772.162 and U.S. Pat.
8゜308, same No. 4,126,396, same No. 4,3
No. 34,011, No. 4,327,173, West German Patent Publication No. 3,329,729, and Japanese Unexamined Patent Publication No. 1983-16
2,5-diacylamino substituted phenolic couplers such as those described in US Pat. No. 6,956 and US Pat.
No. 622, No. 4,333,999, No. 4,451
This is a phenolic coupler having a phenylureido group at the 2-position and an acylamino group at the 5-position, which is described in , No. 559 and No. 4,427,767 of the same.

Granularity can be improved by using a coupler in which the coloring dye has an appropriate diffusibility. Examples of such dye-diffusive couplers are magenta couplers in U.S. Pat. No. 4,366,237 and British Pat. , 234,533 describes specific examples of yellow, magenta or cyan couplers.

Dye-forming couplers and special couplers listed above.

A typical example of a polymerized dye-forming coupler that may form a dimer or more polymer is U.S. Pat. No. 3,451
, No. 820 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. 4,36.
7.282.

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 couplers used in the present invention can be incorporated into the light-sensitive material by one of a variety of 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 of latex dispersion method, effects, and specific examples of latex for impregnation are described in U.S. Pat. It is described in ゜230, etc.

The typical usage amount of color couplers is in the range of 0.001 to 1 mole per mole of photosensitive silver halide, preferably 0.001 to 1 mole for yellow couplers. Ol or 0
．． 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 Vol. 176 Itea+ 17643
X V term (P, 27) X1 term (p.

2g) (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, Examples 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.

(Example) Hereinafter, one specific example of the present invention will be shown and the present invention will be explained in further detail. However, the present invention is not limited to the following examples.

Example 1 Table A was placed on a paper support laminated on both sides with polyethylene.
A multilayer color photographic paper with the layer structure shown in Figure 1 was prepared. The coating solution was prepared as follows.

Preparation of first layer coating solution To 19.1 g of yellow coupler (a) and 4.4 g of color image stabilizer (b), 27.2 g of ethyl acetate and 7.7 ann of solvent (c) were added and dissolved. % Sodium Dodecylbenzenesulfonate 1 containing 8 mfl
It was emulsified and dispersed in 0% gelatin aqueous solution 185@Q. On the other hand, silver chlorobromide emulsion (silver bromide 90.0 mol%, Ag 70 g/
kg) and the blue-sensitive sensitizing dye shown below at a concentration of 5.0 kg per mole of silver. A sample containing 10-' moles of OX was prepared. The above emulsified dispersion and this emulsion were mixed and dissolved to prepare a first layer coating solution having the composition shown in Table A. The coating solutions for the second to seventh layers were also prepared in the same manner as the first layer coating solution.

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

The following spectral sensitizing dyes were used in each layer.

Blue-sensitive emulsion layer (5.OX 10'-4 mol per mol of silver halide) Green-sensitive emulsion layer (4.OX 10-' mol per mol of silver halide)
and (7.OX 10-s moles per mole of silver halide)
Red-sensitive emulsion layer (0.9 x 10-mol per mole of silver halide)
For the red-sensitive emulsion layer, the following compounds were added at 2.6 x 10-' moles per mole of silver halide.

In addition, 1-(5-methylureidophenyl)-5-mercaptotetrazole was added to the blue-sensitive emulsion layer, green-sensitive emulsion layer, and red-sensitive emulsion layer at a concentration of 8% per mole of silver halide, respectively.
．． 5 X 10-' mol, 7.7 X 10-' mol,
2.5X 10-' moles were added.

Further, for the blue-sensitive emulsion layer and the green-sensitive emulsion layer, 4-hydroxy-6-methyl-1,3,3a, 7-titrazaindene was added at 1.2X10-" mole and 1.1X10-" mole per mole of silver halide, respectively. Mol added.

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

and Table A The structural formulas of the compounds used in this example, such as couplers, are as follows.

(,) Yellow coupler (b) Color image stabilizer (c) Solvent Shirisushi 4 hours.

(d) Color mixing inhibitor (e) Magenta coupler See Table 1 (f) Color image stabilizer (g) Color image stabilizer (h) Solvent (i) Ultraviolet absorber 2:9:8 mixture (filtl(j) ) Color mixing inhibitor (k) Solvent 0=P-(〇-C,H,, (iso)).

(ρ) Cyan coupler (@) Color image stabilizer Shi4FisLjノ.

A 5:8:9 mixture eυ (n) polymer (0) solvent Color photographic papers were prepared in which the magenta couplers were changed as shown in Table 1. The resulting color photographic paper was exposed through an optical wedge and then processed in the following steps.

Outdoor process 5 - Partial Time - Partial color development
38℃ 1 minute 40 seconds bleach fixing 30-34
℃ 1 minute 00 seconds■ 30-34℃ 2
0 second rinse■ 30-34℃ 20 second rinse■
Dry for 20 seconds at 30-34℃ 70
~80°C for 50 seconds (3-tank countercurrent flow from rinsing ■ to ■) The composition of each treatment liquid is as follows.

Ai Uni Current Taka Shusui 8
001 Compound A of the present invention 1st
See table diethylenetriaminepentaacetic acid
1.0g nitrilotriacetic acid
2.0g Benzyl alcohol See Table 1 Diethylene glycol
10+on sodium sulfite
See Table 1 Potassium bromide
0.5g potassium carbonate
30g whitening agent (IIHITEX 4B
(manufactured by Jumin Chemical) Add 1.5g of water
1000aQρl
10.25 Bleach-fix solution water 4
00uQ ammonium thiosulfate (70%)
200n+fl sodium sulfite
20 g iron ethylenediaminetetraacetate (m
) Ammonium 60 g Disodium ethylenediaminetetraacetate 10 g Add water
1o00+aRPH (25℃)
7.00 Rinse liquid benzotriazole 1.0
g Add water 100
0mQp)100O℃)
7.50 On the other hand, a part of the above color developer was taken as IQ beer and allowed to stand at 30° C. for 30 days in an open system, and then processed using this aging solution in the above processing step.

The treatment using the color developer solution (aged solution) left for 30 days was called the aged solution test, and the treatment using the color developer solution (fresh solution) before being left was called the fresh solution test.

The photographic properties obtained through the fresh liquid test and the aged liquid test were evaluated as
Shown in the table.

Photographic properties were expressed in two points: Dmlゎ at magenta density and gradation.

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

Rate: Comparative magenta coupler M-1 Comparative magenta coupler opening Comparative magenta coupler M-1 From Table 1, in the comparative example, D m in the aged solution
The increase in in and the change in gradation are large (Nα1 to 6,
&8-11, &29). In addition, when a coupler other than the present invention is used, even if the color developer of the present invention is used, D wr
The change in L n is large (Nl17).

According to the present invention, the fluctuations in the above photographic properties are reduced, and the effect is more pronounced in the absence of benzyl alcohol (comparison of Nα32 and Nα39-41, and comparison of &36 and Na42-44) .

Example 2 Under the condition of Nα20 in Example 1, Magenta Cobrado 37 was used as M-91M-44, M-45, M-4.
7, M-52, and M-58, and similar experiments were conducted, and the same favorable results as in Example 1 were obtained.

Example 3 Table B was placed on a paper support laminated on both sides with polyethylene.
A multilayer color photographic paper with the layer structure shown in Figure 1 was prepared. The coating solution was prepared as follows.

First layer coating solution preparation Yellow coupler (aH9, 1g and color image stabilizer (b)
) to 4.4 g of ethyl acetate 27.2+*I2 and solvent (
c) 7.7+Q was added and dissolved, and this solution was emulsified and dispersed in 185IIfl of a 10% aqueous gelatin solution containing 8d of 10% sodium dodecylbenzenesulfonate. on the other hand,
Silver chlorobromide emulsion (silver bromide 1.0 mol%, Ag 10g/k
5 g of the blue-sensitive sensitizing dye shown below per mole of silver.
．． A sample containing 10-' moles of OX was prepared. The above emulsified dispersion and this emulsion were mixed and dissolved to prepare a first layer coating solution having the composition shown in Table B. The coating solutions for the second to seventh layers were also prepared in the same manner as the first layer coating solution. ■-Oxy-3,5-dichloros-triazine sodium salt was used as the gelatin hardening agent for each layer.

The following spectral sensitizing dyes were used in each layer.

Blue-sensitive emulsion layer (5.OX 10-' mol per mol of silver halide)
Green-sensitive emulsion layer (4.OX to 'mol per mole of silver halide)
and (7.OX 10-' moles per mole of silver halide)
Red-sensitive emulsion layer (0.9 x 10-' mol per mol of silver halide) The following compound was added to the red-sensitive emulsion layer in an amount of 2.6 x 10-' mol per mol of silver halide.

In addition, 1-(5-methylureidophenyl)-5-mercaptotetrazole was added to the blue-sensitive emulsion layer, green-sensitive emulsion layer, and red-sensitive emulsion layer at a concentration of 8% per mole of silver halide, respectively.
．． 5 X 10-' mol, 7.7 X 10-' mol,
7.5X 10-' moles were added.

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

and Table B Table B (Sold as O) Yellow coupler (a) 1-color image stabilizer (b)
), color mixture inhibitor (d), one-color image stabilizer (f), ultraviolet absorber (i), color mixture inhibitor (j), solvent (k), cyan coupler (Ω), color image stabilizer (-), Polymer (n) and solvent (0) are the same as in Example 1.

The structural formulas of the compounds used in this example, such as couplers other than those mentioned above, are as follows.

(a) magenta coupler see Table 2 (g) also color image stabilizer U (k) a 1:1 mixture (by volume) of solvent It was processed in the following processing steps with different values.

Color development at 35°C for 45 seconds Bleach fixing at 35°C
Stable for 45 seconds at 135°C Stable for 20 seconds at 235°C Stable for 20 seconds at 335°C Dry for 20 seconds Stable at 70-80°C for 60 seconds The solution was a 3-tank countercurrent water wash from Stable 3 to Stable 1. The processing solutions used are as follows.

Tateuniri Dogai Additive C (compound of the present invention) See Table 2 Additive D (compound of the present invention) See Table 2 Sodium sulfite See Table 2 Potassium carbonate 30 g Nitrilotriacetic acid 1 g Sodium chloride 1.5 [c Color developing agent (see Table 2) 0.01 mol brightener (4,4'-diaminostilbene type)
Add 3.0g water 1
000+onpH10,05 EDTA Fe(m)Nl(,2H,060gEDT
A ・2Na Fist 2H 204g Ammonium thiosulfate (70%) 12
0mfl sodium sulfite 1
6 g glacial acetic acid
Add 7g water to 100
0 Emperor Ω pH 5.5 Gen' L Kai Formalin (37%) 0
．． 1m11 bismuth chloride
0.35g ammonia water (26%)
2, 5mfl nitrilotriacetic acid/3Na
1. OgEDTA・4HO, 5゜Sodium sulfite 1.0g
5-chloro-2-methyl-4-isothiazoline-50m
g3-ion water was added and 1000 d was carried out in the same manner as in Example 1 to determine the changes in photographic properties between the fresh solution and the aged solution, and the results are shown in Table 2.

According to the present invention, changes in photographic properties due to aging of the processing solution are small, and this effect is particularly large when a color developing agent (d) is used.

Skewer: See Example 1 for comparative magenta couplers M-i and M-port.

Skewer: Color developing agents (a) to (b) represent the following compounds.

*3: (CH, CH, NH)Hn=500-200
0 Example 4 In the Nα10 experiment in Example 3, magenta coupler M-37 was used as M-6, 8-16, M-27, M
A similar experiment was conducted except for changing to -42, -43, M-44, M-45, G57, and G58.
Similar to Example 3, favorable results were obtained.

Example 5 The first layer (bottom layer) to the seventh layer (
A photographic paper sample was prepared by sequentially applying and forming the uppermost layer). The coating solution for each layer was 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 as follows. In other words, 200g of yellow coupler, anti-fading agent (r)!
13.3 g, high boiling point solvent (p) log and solvent < q)
After heating and dissolving a mixture of 5g and 600ml of ethyl acetate as an auxiliary solvent at 60°C, Alkanol B (trade name, alkylnaphthalene sulfonate, manufactured by DuPont) was added.
5% aqueous gelatin solution 3 containing 330+sn of 5% aqueous solution of
Then, this liquid was emulsified using a colloid mill to prepare a coupler dispersion.

Ethyl acetate was distilled under reduced pressure from this dispersion, and a sensitizing dye for a blue-sensitive emulsion layer and 1-methyl-2-mercapto-5-acetylamino-1,3,4-triazole were added to emulsion 1.
,400g (96.7g as Ag, 170g of gelatin)
g), and then add 10% gelatin aqueous solution 2,6
00g was added to prepare a coating solution. The coating liquids for the second to seventh layers are as follows.

It was prepared according to the composition of Table C according to the first layer.

However, photographic paper was prepared using each of the magenta couplers shown in Table 3 below as the third layer magenta coupler.

Table C Table c (4 sell) The compounds used in this example are as follows.

UV absorber (n): 2-(2-hydroxy-3,5-di-tert-amylphenyl)benzotriazole UV absorber (0): 2-(2-hydroxy-3,5-di-tert-butylphenyl) Benzotriazole solvent (p) Nidi(2-ethylhexyl) phthalate solvent (9) Nidibutyl phthalate anti-fading agent (r): 2,5-di-tert-amylphenyl-3,5-di-tert-butylhydroxybenzoate color mixing inhibitor (S): 2,5-di-tert-octylhydroquinone anti-fade agent (t): 1,4-di-tert-amyl-2,5-dioctyloxybenzene anti-fade agent (U): 2,2'-methylenebis-( 4-methyl-6-tart
-Butylphenol Also, the following were used as sensitizing dyes in each emulsion layer.

Blue-sensitive emulsion layer; anhydro-5-methoxy-5'-methyl-3,3'-disulfopropylselenacyanine hydroxide; green-sensitive emulsion layer; anhydro-9-ethyl-5,5'-diphenyl-3,3 '-Disulfoethyl oxacarpocyanine hydroxide red-sensitive emulsion layer: 3,3'-diethyl-5-methoxy-
9,9'-(2,2-dimethyl-1,3-propano)thiadicarpocyanine iodide The following substances were also used as stabilizers for each emulsion layer.

1-Methyl-2-mercapto-5-acetylamino-1
, 3°4-triazole and the following were used as anti-irradiation dyes.

4-(3-carboxy-5-hydroxy-4-(3-(
3-Carboxy-5-oxo-1-(4-sulfonatophenyl)-2-pyrazolin-4-ylidene)-1-propenyl)-1-pyrazolyl)benzenesulfonate-dipotassium salt N,N'-(4, 8-dihydroxy-9,1
0-dioxo-3,7-cissulfonatoanthracene-1
,5-diyl)bis(aminomethanesulfonate)-tetrasodium salt and 1,2-bis(vinylsulfonyl)ethane were used as a hardening agent.

The couplers used are as follows.

After imagewise exposure, the yellow coupler, magenta coupler, cyan coupler (see Table 3) and the multilayer color photographic paper obtained as above were subjected to continuous processing in the following processing steps.

J1 Co. 11 Works ['''' Color development 38℃ 3 minutes 30 seconds 160 ■Ω/
ls" bleach fixing 30℃ 1 minute 30 seconds 10 strokes Q/ls" rinse ■ 30℃ 40 seconds rinse ■ 30℃ 40 seconds rinse ■ 30℃ 40 seconds 20 shafts Q/1m
``Drying: 60 to 70°C for 50 seconds The composition of each treatment solution used in the 3-tank countercurrent system from rinse (① to ②) is as follows.

Tomo J Knee 1" 1 cup Kyu 2 Dasori j Katana [Additive E'
(See Table 3) 0.03 mol 0.04 mol Additive F (#) 0.03 mol 0
．． 04 mol potassium carbonate 30.0
g 30.0g potassium bromide
1.4g - Sodium sulfite
See Table 3 Add water 10100
OlooomQ pH10,1010,50 Bleach tank and replenisher are the same EDTA Fe(m)Nl14.2H2060gEDT
A ・2Na ・:QItO 4g ammonium thiosulfate (70%) 120mQ sodium sulfite 16g glacial acetic acid
Add 7g water
100 axis QPH5,5 Rinse liquid (tank liquid and refill liquid are the same) 2-methyl-4-inthiazolin-3-one 1
0n+g2-octyl-4-isothiazolin-3-one 10+sg bismuth chloride (40%)
0.5g nitrilo-N,N,N-trimethylenephosphone 1.0g acid (40%) 1-hydroxyethylidene-1,1-diphosphone
2. # (60%) Fluorescent brightener (4,4'-diaminostilbene type)
1.0g ammonia water (26%)
Add 2.0mA water
At 1000mf100O
p) + 7.5 Continuous processing (running test) was performed under each condition until three times the tank capacity (2012) of color developer was replenished. Changes in G (green) density in the stain and gradation areas at the start of the running process and the end of the running process were measured using a Fuji self-recording densitometer. Furthermore, after the sample at the end of the running process was left at 80° C. (5 to 10 RH) for one month, the change in G concentration in the stain portion was measured again.

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

According to the present invention, there is little change in photographic properties due to running, and there is also little increase in magentastin over time after processing.

$1: See Example 1 for comparative magenta couplers M-i and M-c.

Umbrella 2: Increase in D sin at the end of running relative to D ■ in at the start of running.

Fist 3: Increase in G density in the gradation area at the end of running compared to G density in the gradation area during running.

-4: Increase in D win after 1 month at 80°C with respect to D win of the sample at the end of running.

Example 6 Tests were conducted simultaneously with &6 and 14 of Example 5, except that equimolar moles of the following compounds were used in place of ll-8 and ll-2 used as additives E in &6 and 14 of Example 5.

The compounds used were ll-1, ■-11, m-6, TV-1
, ■-6, V-1, V-4, V-8, VI-1, ■-4
．． ■-7, ■-3゜■-7, IK-2, IK-3, X-
1,X-6.

As a result, ΔDmin, Δgradation, and ΔDmin after time
As in Example 5, favorable results were obtained.

Example 7 In place of the rinse solution used in Example 5, a running test was conducted in the same manner as with Na6, using ion-exchanged water (calcium and magnesium ions each below the applica level), and similarly excellent results were obtained. Obtained.

(Effects of the Invention) According to the present invention, when processing a photosensitive material containing a specific magenta coupler, the stability and color development of the color developer are significantly improved, and as a result, the color developer can be used after a certain period of time. Even with the processing method, increases in fog and changes in gradation were significantly suppressed, and color images with excellent photographic properties were obtained.

Such effects of the present invention were particularly remarkable in color developing solutions that do not substantially contain benzyl alcohol, which has a high pollution load.

Furthermore, even in continuous processing, the increase in fog is significantly reduced, and the stability of the obtained color images over time is excellent. Processing method name: [
520) Fuji Photo Film Co., Ltd. 6. The number of inventions will increase due to the amendment.
``Detailed Description of the Invention'' Column Procedural Amendment Written April 3, 1986

Claims (2)

[Claims] (1) After exposing a silver halide color photographic material containing at least one type of pyrazoloazole magenta coupler represented by the following general formula (I), containing an aromatic primary amine color developing agent, Monoamines, diamines, polyamines, quaternary ammonium salts, nitroxy radicals, alcohols, ethers, oximes,
A method for processing a silver halide color photographic light-sensitive material, which comprises processing with a color developer containing at least one selected from amides and sulfonamides and substantially free of sulfite ions. General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R_1 represents a hydrogen atom or a substituent, and X represents a hydrogen atom or a coupling reaction with an oxidized aromatic primary amine developer. Represents a group that can leave.Za, Zb
and Zc is methine, substituted methine, =N- or -NH
-, one of the Za-Zb bond and the Zb-Zc bond is a double bond, and the other is a single bond. The case where Zb-Zc is a carbon-carbon double bond includes the case where it is part of an aromatic ring. Furthermore, 2 with R_1 or X
It also includes the case where a multimer of more than one mer is formed. Also, Za,
When Zb or Zc is a substituted methine, it also includes the case where the substituted methine forms a dimer or more multimer. ) (2) Claim (1) characterized in that the color developer does not substantially contain benzyl alcohol.
A method for processing a silver halide color photographic light-sensitive material as described in .