JPH07111566B2 - Processing method of silver halide color photographic light-sensitive material in which variation of magenta density is improved - Google Patents

Description

Detailed Description of the Invention

 [Industrial field of application] The present invention relates to a method for processing a silver halide color photographic light-sensitive material.
For more details, please refer to Antioxidant that has no harmful effect on the human body.
Related to the processing method that can obtain stable photographic performance even when using an agent
In addition, there is little oxidative decomposition of the treatment liquid and tar is generated.
Related to a processing method with less. [Prior Art] In recent years, in the industry, silver halide color photographic light-sensitive
The material can be processed quickly and the processing stability is excellent.
Therefore, a technique for obtaining stable photographic characteristics is desired. That is, silver halide color photographic light-sensitive materials are
-Running process with automatic processor
Is being carried out, but one of the
As a ring, the development process is completed within the
To be returned to the user
It ’s becoming even more demanding to return in time
There is. Furthermore, in recent years, it has been used in storefronts such as photo shops and supermarkets.
A photosensitive material that has been installed by an automatic processor and has been enjoyed by users.
Is required to be processed on the spot and returned.
It In addition, a copying apparatus that irradiates a document with light to copy it on a photosensitive material
Became available on the market.
However, it takes less time to develop the photosensitive material on which the original is copied.
User is required, and rather, such a copying machine requires a user.
Wants to get the copied photosensitive material immediately
is the current situation. With the demand for speeding up, as described above,
Concentrated in large quantities with automatic processors provided in the laboratory
Because of the tendency to process color photosensitive materials,
ー In a store such as a market
Installed and processed on the spot, or even silver halide color
-Equipped with the development method of photographic light-sensitive material as it is in a copying machine,
Recently, the tendency to make color copies indoors has become particularly noticeable.
Came. However, there are significant problems with this trend.
I found out that I was there. In other words, color feeling
When color developing the optical material, the color developer may
Sulphite to prevent performance deterioration due to air oxidation
And hydroxylamine has been used. However, Hide
Roxylamine is harmful to the human body (P.G.Stecher.
e Merck Index-An Encyclopedia of Chemical and Dru
gs ”8th Ed (1953)), Poisonous and Deleterious Substances Control Law
Hydroxylamine and its water-soluble salts are designated as deleterious substances.
Has been. Therefore process in a large laboratory
Even in that case, be careful when handling it.
Special problems for home-based amateur self-processing
There are many. Therefore, in-house self-processing and color development methods
When carrying out color copying equipped with
Development of Antioxidant to Replace Hydroxylamine
Is strongly desired. 2-animone as an antioxidant replacing hydroxylamine
U.S. Pat.
823,017 and 3,615,503, respectively. Shi
However, in all of these, the compound itself is unstable,
And there is no effect of preventing color fog. On the other hand, hydroquinone or N-alkyl-p-amido
Developer containing phenol as a developing agent (black and white photo
For), Satsukarose (sucrose) as an antioxidant
It is known that Satsukarose is an aromatic primary amine
As an antioxidant in the color developer containing
It has almost no effect. Ascorbic acid and its derivatives are black and white photographic developers.
It is also known as an antioxidant for color developing solutions.
They have the drawback that they inhibit color development and lead to a decrease in color density.
It is inferior to hydroxylamine in color developers. Further, α-hydroxy aromatic amides described in JP-A-52-7729.
Hydroxam Oxidation Compound described in JP-A-52-27638
And α-aminocarbonyl compounds described in No. 52-143020
And monosaccharides described in No. 52-102727, described in No. 52-140324
Amino acid derivatives of are disclosed. When monosaccharides and amino acid derivatives are used in large quantities
Although it shows considerable homeostasis, it is easily decomposed by heat
In addition, it has characteristics that are not favorable for pollution. As a typical compound of the α-aminocarbonyl compound, D
-Glucosamine hydrochloride is known, but this compound
Possibly less stable than hydroxylamine. The hydroxamic acid compound has a homeostatic property of hydroxyamine
Although it has the same degree of homeostasis, it is costly and produces color.
There is a drawback that the development density is likely to decrease. As mentioned above, the previously used hydroxy
Considered as an antioxidant (preservative) to replace silamine
The above-mentioned materials have been poorly preserved or are exposed to heat.
There is a problem that it may be decomposed or the coloring efficiency may be reduced.
However, the current situation is that it has not been put to practical use until the present stage. The present inventors have proposed a color developing solution which replaces hydroxylamine.
As a result of diligent study on antioxidants,
The ruamine derivative does not have the above-mentioned problems,
It was found that the homeostatic ability was also high, but the
As the discussion proceeded, the following became clear. That is, an alkyl-substituted hydroxylamine derivative was used.
The maximum dye density when running with a color developer
That the magenta dye density is variable,
It was found that the main cause of the phenomenon was due to the sulfite concentration. This
This fact was completely unexpected to the present inventor. Conventionally, color development occurs when sulfite is added to the color developer.
Although the fact that the concentration decreases is known, hydroxy
Alkyl-substituted hyaluronan is more
Droxylamine is a unique substance that tends to significantly reduce the color density.
There are many phenomena. These problems are caused by changes in photographic characteristics on a daily or weekly basis.
It takes a lot of work to connect and obtain stable photographic characteristics.
This is a major obstacle to the actual processing work. The present inventors have made diligent studies in view of such a situation.
As a result, represented by the general formula (a), (b) or (c)
Silver halide color photographic light-sensitive material containing coupler
Alkyl-substituted hydroxyl group represented by the above general formula [I]
By processing with a color developer containing an amine derivative,
Found that the above problems can be solved
Then, the present invention has been completed. OBJECTS OF THE INVENTION Accordingly, the object of the present invention is to provide hygiene and antioxidants as antioxidants.
Do not use hydroxylamine, which has pollution problems,
The above-mentioned deterioration of photographic quality does not occur with alternative antioxidants.
It is to provide a method for forming a color image. [Constitution of Invention] The above object of the present invention is to provide at least one layer of halo on a support.
Silver halide color photographic light-sensitive material having silver genide emulsion layer
After imagewise exposure of the dye, at least p-phenylenediamine
Processing with a color developer containing a color developing agent
In the method of processing a silver halide color photographic light-sensitive material,
The silver halide color photographic light-sensitive material has the following general formula
Fewer couplers represented by (a), (b) or (c)
It is contained in at least one layer, and the color developing solution has the following general formula.
Containing hydroxylamines represented by [I]
Of silver halide color photographic light-sensitive material characterized by
Achieved by law. General formula (a)General formula (b)General formula (c)(In the general formulas (a), (b) and (c), Za, Zb and
Zc is a nonmetallic source necessary for forming nitrogen-containing heterocycles.
Represents a group of children. Xa, Xb and Xc are hydrogen atoms or
Is a group capable of leaving during the reaction with the oxidant of the color developing agent.
Represents Ra, Rb, Rc, Rd, Re, Rf and Rg are each a hydrogen atom or
Represents a substituent. However, Rg is a value represented by the general formula (c).
Release during the reaction between the puller and the oxidant of the color developing agent
It is a substituent that never happens. Y₁Is a carbon atom or nitrogen
Represents an atom. Y₂Represents a carbon atom or a hetero atom
YouIs Y₁And Y₂Even if the bond between them is a single bond, it is a double bond.
Indicates that you may do it. However, Y₁Is a carbon atom and Y₁And Y₂of
N if the bond between them is a double bond₃Is 1 and n_FourIs 0
And Rc is the coupler and color developed by the general formula (a).
Does not separate upon reaction with the oxidant of the developing agent
A substituent, Y₁Is a carbon atom and Y₁And Y₂The bond between
In case of₃And n_FourAre both 1. Again Y₁Is a nitrogen atom
And Y₁And Y₂N is a double bond₃And n_FourAre both 0
Yes, and Y₂Is a heteroatom and Y₁Is a nitrogen atom and Y₁
And Y₂N if the bond between is a single bond₃Is 1 and n_FourIs 0
Is. The caps represented by the general formulas (a), (b) and (c)
Ra is the position where Xa is bound and Xb is bound
The color-developing agent only at the position
Reacts with the oxidant of. ) General formula [1]Where R₁And R₂Each has a hydrogen atom or a substituent
It represents an optional alkyl group. However, R₁And R₂Is the same as
Is never a hydrogen atom. Next, the present invention will be specifically described. The above general formulas (a), (b), (c) according to the present invention (a)General formula (b)General formula (c)In the magenta coupler represented by, Za, Zb and Zc
Represents a group of non-metal atoms necessary to form a nitrogen-containing heterocycle.
However, Xa, Xb and Xc are each a hydrogen atom or a color developing agent.
It represents a substituent capable of splitting off upon reaction with an oxidant. Ra, Rb, Rc, Rd, Re, Rf and Rg are hydrogen atoms or
Or represents a substituent. However, Rg is a coupler and a color developing agent represented by the general formula (c).
Does not leave upon reaction with the oxidant of the image drug
It is a substituent. Y₁Represents a carbon atom or a nitrogen atom. Y₂Is a carbon atom or
Represents a heteroatom.Is Y₁And Y₂Even if the bond between is a single bond,
Indicates that you may be present. Y₃， Y_FourAnd Y_FiveRepresents a carbon atom or a nitrogen atom, respectively.
You n₁， N₂， N₃， N_Four， N_Five， N₆And n₇Are 0 or 1 respectively
is there. However, Y₁Is a carbon atom and Y₁And Y₂When the bond between is a double bond
If n₃Is 1 and n_FourIs 0, and Rc is a general formula
A coupler represented by (a) and an oxidant of a color developing agent
Y is a substituent that does not leave during the reaction of₁But
Y at carbon atom₁And Y₂N is a single bond between₃as well as
n_FourAre both 1. Also, Y₁Is a nitrogen atom and Y₁And Y₂Is bound
N for a double bond₃And n_FourAre both 0 and Y₂Is
Is a heteroatom, Y₁Is a nitrogen atom and Y₁And Y₂The bond between
N for a single bond₃Is 1 and n_FourIs 0. The formulas (a), (b) and (c)
The puller has a position where Xa is bonded and a position where Xb is bonded.
Color development only at the positions where Xc and Xc are bonded.
It undergoes a coupling reaction with the oxidant of the main drug. Examples of the substituent represented by Ra, Rb, Rc, Rd, Re or Rf include
For example, halogen atom, alkyl group, cycloalkyl group,
Lucenyl group, cycloalkenyl group, alkynyl group, ant
Group, heterocyclic group, acyl group, sulfonyl group, sulfone group
Innyl group, phosphonyl group, carbamoyl group, sulfamo
Ile group, cyano group, spiro compound residue, bridged hydrocarbon
Compound residue, alkoxy group, aryloxy group, heterocycle
Oxy group, siloxy group, acyloxy group, carbamoyl
Oxy group, amino group, acylamino group, sulfonamide
Group, imido group, ureido group, sulfamoylamino group,
Alkoxycarbonylamino group, aryloxycarbo
Nylamino group, alkoxycarbonyl group, aryloxy
Cycarbonyl group, alkylthio group, arylthio group,
And a telocyclic thio group. Examples of the halogen atom include chlorine atom and bromine atom.
The chlorine atom is particularly preferable. As an alkyl group represented by Ra, Rb, Rc, Rd, Re or Rf
Are those having 1 to 32 carbon atoms, alkenyl groups, alkynyl groups
Are those having 2 to 32 carbon atoms, cycloalkyl groups, cyclo
The lower alkenyl group has 3 to 12 carbon atoms, especially 5 to 7 carbon atoms.
Are preferred, alkyl group, alkenyl group, alkynyl
The group may be linear or branched. In addition, these alkyl groups, alkenyl groups, alkynyl
Group, cycloalkyl group, cycloalkenyl group are substituents
[Eg aryl, cyano, halogen atom, heterocycle,
Cycloalkyl, cycloalkenyl, spiro compound residue
Group, bridged hydrocarbon compound residue, acyl, carboxy
Ci, carbamoyl, alkoxycarbonyl, aryl
Substitution through a carbonyl group such as xyloxycarbonyl
, Further substituting through a hetero atom {specifically
Is hydroxy, alkoxy, aryloxy, heterocycle
Oxy, siloxy, acyloxy, carbamoyloxy
Substituted through an oxygen atom such as nitro, amino
(Including dialkylamino etc.), sulfamoylami
No, alkoxycarbonylamino, aryloxycal
Bonylamino, acylamino, sulfonamide, imimi
Compounds that substitute via a nitrogen atom, such as
Kirthio, arylthio, heterocyclic thio, sulfonyl,
Positioning via sulfur atom such as sulfinyl and sulfamoyl
Substituents, or substituted via a phosphorus atom such as phosphonyl
And the like}]. Specifically, for example, methyl group, ethyl group, isopropyl
Group, t-butyl group, pentadecyl group, heptadecyl group,
1-hexylnonyl group, 1,1′-dipentylnonyl group,
2-chloro-t-butyl group, trifluoromethyl group, 1
-Ethoxytridecyl group, 1-methoxyisopropyl
Group, methanesulfonylethyl group, 2,4-di-t-amyl
Phenoxymethyl group, anilino group, 1-phenylisop
Ropyl group, 3-m-butane sulfone aminophenoxyp
Ropyr group, 3-4 '-{α- [4 "(p-hydroxy ester
Benzenesulfonyl) phenoxy] dodecanoylamino}
Phenylpropyl group, 3- {4 '-[α- (2 ", 4"-
Di-t-amylphenoxy) butanamide] phenyl}
-Propyl group, 4- [α- (o-chlorophenoxy) thene
Tradecanamidophenoxy] propyl group, allyl group,
Examples thereof include a cyclopentyl group and a cyclohexyl group. The aryl group represented by Ra, Rb, Rc, Rd, Re or Rf is
A phenyl group is preferable, and a substituent (for example, an alkyl group,
Alkoxy group, acylamino group, etc.)
Yes. Specifically, a phenyl group, a 4-t-butylphenyl group,
2,4-di-t-amylphenyl group, 4-tetradecane
Midphenyl group, hexadecyloxyphenyl group, 4'-
[Α- (4 ″ -t-butylphenoxy) tetradecane
[Mido] phenyl group and the like. The heterocyclic group represented by Ra, Rb, Rc, Rd, Re or Rf is
5- to 7-membered ones are preferred, which may be substituted,
It may be condensed. Specifically, a 2-furyl group, a 2-chi
Enyl group, 2-pyrimidinyl group, 2-benzothiazolyl
Groups and the like. As the acyl group represented by Ra, Rb, Rc, Rd, Re or Rf,
For example, acetyl group, phenylacetyl group, dodecanoyl
Group, α-2,4-di-t-amylphenoxybutanoyl group
Alkylcarbonyl group such as benzoyl group, 3-penta
Decyloxybenzoyl group, p-chlorobenzoyl group, etc.
And the arylcarbonyl group. As a sulfonyl group represented by Ra, Rb, Rc, Rd, Re or Rf
Is an alkyl group such as a methylsulfonyl group or a dodecylsulfonyl group.
Alkylsulfonyl group, benzenesulfonyl group, p-tolu
Examples include arylsulfonyl groups such as enesulfonyl group
To be As a sulfinyl group represented by Ra, Rb, Rc, Rd, Re or Rf
Is an ethylsulfinyl group, octylsulfinyl
Group, an alkyl group such as a 3-phenoxybutylsulfinyl group
Rusulfinyl group, phenylsulfinyl group, m-pen
Arylsulfides such as tadecylphenylsulfinyl group
Examples thereof include an inynyl group. As a phosphonyl group represented by Ra, Rb, Rc, Rd, Re or Rf
Is an alkylphosphonyl group such as a butyloctylphosphonyl group.
Alkoxy group such as phenyl group and octyloxyphosphonyl group
Aryl groups such as sulfonyl and phenoxyphosphonyl groups
Aryl such as xyphosphonyl group and phenylphosphonyl group
And a ruphosphonyl group. The carbamoyl group represented by Ra, Rb, Rc, Rd, Re or Rf is an
A rualkyl group, an aryl group (preferably a phenyl group), etc.
It may be substituted, for example, N-methylcarbamoyl group,
N, N-dibutylcarbamoyl group, N- (2-pentadecyl
Ruoctylethyl) carbamoyl group, N-ethyl-N-
Dodecylcarbamoyl group, N- {3- (2,4-di-t-
Amylphenoxy) propyl} carbamoyl group and the like.
To be The sulfamoyl group represented by Ra, Rb, Rc, Rd, Re or Rf is
Alkyl group, aryl group (preferably phenyl group), etc.
It may be substituted, for example N-propylsulfamoy.
Group, N, N-diethylsulfamoyl group, N- (2-pepylene group
Ntadecyloxyethyl) sulfamoyl group, N-ethyl
L-N-dodecylsulfamoyl group, N-phenylsulfate
Examples thereof include famoyl group. Spiro compound residue represented by Ra, Rb, Rc, Rd, Re or Rf
For example, spiro [3.3] heptan-1-yl etc.
Can be mentioned. Bridged carbonized compound residue represented by Ra, Rb, Rc, Rd, Re or Rf
Is, for example, bicyclo [2.2.1] heptane-1-i
Le, tricyclo [3.3.1.1^3'7] Decan-1-yl,
7,7-Dimethyl-bicyclo [2.2.1] heptan-1-yl
Etc. The alkoxy group represented by Ra, Rb, Rc, Rd, Re or Rf is
By substituting the above-mentioned substituents for the alkyl group
, For example, methoxy group, propoxy group, 2-
Ethoxy ethoxy group, pentadecyloxy group, 2-dode
Syloxyethoxy group, phenethyloxyethoxy group, etc.
Is mentioned. An aryloxy group represented by Ra, Rb, Rc, Rd, Re or Rf
And phenyloxy is preferable, and the aryl nucleus is further
As the substituent or atom for the aryl group,
It may be substituted, for example, a phenoxy group, p-t-
Butylphenoxy group, m-pentadecylphenoxy group, etc.
Is mentioned. Heterocyclic oxy group represented by Ra, Rb, Rc, Rd, Re or Rf
Are preferably those having a 5- to 7-membered heterocycle,
The heterocycle may further have a substituent, for example,
3,4,5,6-tetrahydropyranyl-2-oxy group, 1-
A phenyltetrazole-5-oxy group may be mentioned. Ra, Rb, Rc, Rd, Re or Rf represents a siloxy group,
It may be substituted with an alkyl group or the like, for example, trimethyl
Lucyloxy group, triethylsiloxy group, dimethylbutyl
Examples thereof include a siloxy group. As an acyloxy group represented by Ra, Rb, Rc, Rd, Re or Rf
Are, for example, alkylcarbonyloxy groups,
Such as a rubonyloxy group, which further has a substituent
May be, specifically, acetyloxy group, α-chlora
Examples thereof include a cetyloxy group and a benzoyloxy group. Carbamoyloxy represented by Ra, Rb, Rc, Rd, Re or Rf
The group may be substituted with an alkyl group, an aryl group or the like.
For example, N-ethylcarbamoyloxy group, N, N-di
Ethylcarbamoyloxy group, N-phenylcarbamoy
And a ruoxy group. The amino group represented by Ra, Rb, Rc, Rd, Re or Rf is an alkyl group.
Groups, aryl groups (preferably phenyl groups) etc. are substituted
, For example, ethylamino group, anilino group, m
-Chloranilino group, 3-pentadecyloxycarboni
Luanilino group, 2-chloro-5-hexadecanamide
Examples thereof include a nilino group. As an acylamino group represented by Ra, Rb, Rc, Rd, Re or Rf
Is an alkylcarbonylamino group, an arylcarbonyl group
Ruamino group (preferably phenylcarbonylamino group)
And the like, which may further have a substituent.
Cetamide group, α-ethylpropanamide group, N-phene
Nylacetamide group, dodecane amide group, 2,4-di-t
-Amylphenoxyacetamide group, α-3-t-butyl
Examples include 4-hydroxyphenoxybutanamide group and the like.
To be A sulfonamide group represented by Ra, Rb, Rc, Rd, Re or Rf
Is an alkylsulfonylamino group, arylsulfon
Examples thereof include a nylamino group, which may further have a substituent.
Yes. Specifically, methylsulfonylamino group, pentadecyl
Lesulfonylamino group, benzenesulfonamide group, p
-Toluenesulfonamide group, 2-methoxy-5-t-
Amylbenzenesulfonamide group and the like can be mentioned. The imide group represented by Ra, Rb, Rc, Rd, Re or Rf has an open chain structure.
Or a cyclic one, which has a substituent
Also, for example, succinimide group, 3-heptadecylco
Succinimide group, phthalimide group, glutarimide group, etc.
Is mentioned. The ureido group represented by Ra, Rb, Rc, Rd, Re or Rf is
A kill group, an aryl group (preferably a phenyl group), etc.
It may be substituted, for example, N-ethylureido group,
N-methyl-N-decylureido group, N-phenyluree
Examples thereof include an id group and an Np-tolylureido group. Sulfamoylamine represented by Ra, Rb, Rc, Rd, Re or Rf
Group is an alkyl group or an aryl group (preferably phenyl).
Group) etc., for example N, N-dibutyl
Sulfamoylamino group, N-methylsulfamoylua
Examples include mino group and N-phenylsulfamoylamino group.
To be Alkoxycarbonyl represented by Ra, Rb, Rc, Rd, Re or Rf
The luamino group may further have a substituent,
For example, methoxycarbonylamino group, methoxyethoxy
Carbonylamino group, octadecyloxycarbonyl group
Examples include mino group. Aryl oxycal represented by Ra, Rb, Rc, Rd, Re or Rf
The bonylamino group may have a substituent, for example,
Phenoxycarbonylamino group, 4-methylphenoxy
A carbonylamino group may be mentioned. Alkoxycarbonyl represented by Ra, Rb, Rc, Rd, Re or Rf
Group may further have a substituent, for example, methoxy group.
Sicarbonyl group, butyloxycarbonyl group, dodecyl
Oxycarbonyl group, octadecyloxycarbonyl
Group, ethoxymethoxycarbonyloxy group, benzyl group
A xycarbonyl group etc. are mentioned. Aryloxycarl represented by Ra, Rb, Rc, Rd, Re or Rf
The bonyl group may further have a substituent, for example, a phenyl group
Enoxycarbonyl group, p-chlorophenoxycarboni
Group, m-pentadecyloxyphenoxycarbonyl group
Etc. Ra, Rb, Rc, Rd, Re or Rf represents an alkylthio group,
It may have a substituent, for example, an ethylthio group,
Dodecylthio group, octadecylthio group, phenethylthio group
Group and a 3-phenoxypropylthio group. The arylthio group represented by Ra, Rb, Rc, Rd, Re or Rf is
The phenylthio group is preferable, and it may have a substituent.
For example, phenylthio group, p-methoxyphenylthio
Group, 2-t-octadecylphenylthio group, 3-octa
Decylphenylthio group, 2-carboxyphenylthio
Group, a p-acetaminophenylthio group, and the like. Heterocyclic thio group represented by Ra, Rb, Rc, Rd, Re and Rf
, A 5- to 7-membered heterocyclic thio group is preferable, and further condensed
It may have a ring or may have a substituent. example
For example, 2-pyridylthio group, 2-benzothiazolylthio group,
2,4-diphenoxy-1,3,5-triazole-6-thio group
Is mentioned. Rg and Y₁Is a carbon atom and Y₁And Y₂The bond between is a double bond
The coupler represented by Rc and the acid of the color developing agent
As a substituent that does not leave during the reaction with the compound
Is, for example, an alkyl group, an aryl group, a cycloalkyl
Group, alkenyl group, cycloalkenyl group, alkynyl
Group, heterocyclic group, acyl group, sulfonyl group, sulfini
Group, phosphonyl group, carbamoyl group, sulfamoyl
Group, cyano group, spiro compound residue, bridged hydrocarbon compound
Residue, siloxy group, carbamoyloxy group, alkoxy
Carbonyl group, aryloxycarbonyl group
It Above, specific examples of each group include, for example, the specific examples of Ra described above.
What is shown as. By reaction with oxidant of color developing agent represented by Xa, Xb, Xc
Examples of the substituent capable of leaving include a halogen atom (chlorine
Atom, bromine atom, fluorine atom, etc.), carbon atom, oxygen
A group substituting through an atom, a sulfur atom, or a nitrogen atom
Can be mentioned. The group substituting through the carbon atom includes carboxyl
Group, hydroxymethyl group, triphenylmethyl group,
Corresponding to Xa, Xb, and Xc respectively, the formula (a ′)Formula (b ')Formula (c ')(Ra 'is Ra, Rb' is Rb, Rc 'is Rc, Rd' is Rd,
Re ′ is Re, Rf ′ is Rf, Rg ′ is Rg, n₁′ Is n₁When,
n₂′ Is n₂And n₃′ Is n₃And n_Four′ Is n_FourAnd n_Five′ Is n_FiveWhen,
n₆′ Is n₆And n₇′ Is n₇And Y₁′ Is Y₁And Y₂′ Is Y₂And Y₃′
Is Y₃And Y_Four′ Is Y_FourAnd Y_Five′ Is Y_FiveAnd Za ′ is Za and Zb ′ is
Zb and Zc ′ are synonymous with Zc, and R₁~ R₆Is hydrogen, aryl
Represents a group, an alkyl group or a heterocyclic group. )
Groups are exemplified. The group substituting through an oxygen atom is, for example, an alkoxy group.
Si group, aryloxy group, heterocyclic oxy group, acyl group
Xy group, sulfonyloxy group, alkoxycarbonyl group
Xy, aryloxycarbonyloxy, alkyl
Oxalyloxy group, alkoxy oxalyloxy group
Can be mentioned. The alkoxy group may further have a substituent, for example,
Toxy group, 2-phenoxyethoxy group, 2-cyanoeth
Xy group, phenethyloxy group, p-chlorobenzyloxy
And the like. The aryloxy group is preferably a phenoxy group,
The aryl group may further have a substituent. concrete
Include phenoxy group, 3-methylphenoxy group, 3-dodecane
Sylphenoxy group, 4-methanesulfonamide phenoxy
Si group, 4- [α- (3′-pentadecylphenoxy) bu
Tanamido] phenoxy group, hexadecylcarbamoyl
Methoxy group 4-cyanophenoxy group, 4-methanesulfon
Nylphenoxy group, 1-naphthyloxy group, p-methoxy group
Examples thereof include a ciphenoxy group. The heterocyclic oxy group is a 5- to 7-membered heterocyclic oxy group.
Si group is preferable, may be a condensed ring, and may have a substituent.
You may have. Specifically, 1-phenyltetrazoli
And a 2-benzothiazolyloxy group.
Be done. Examples of the acyloxy group include acetoxy group and butyryl group.
Alkylcarbonyloxy group such as ryloxy group, cinna
An alkenylcarbonyloxy group such as a moyloxy group,
Arylcarbonyloxy groups such as benzoyloxy groups
Is mentioned. The sulfonyloxy group is, for example, butane sulfonyl group.
Examples thereof include a ruoxy group and a methanesulfonyloxy group. The alkoxycarbonyloxy group is, for example, eth
Xycarbonyloxy group, benzyloxycarbonyl group
A xy group is mentioned. The aryloxycarbonyloxy group is phenoxy.
Examples thereof include a carbonyl group. Examples of the alkyloxalyloxy group include methyl
An oxalyloxy group may be mentioned. Examples of the alkoxyoxalyloxy group include ethoxy group
Examples thereof include oxalyloxy group. Examples of the group substituting via a sulfur atom include alkyl
Thio group, arylthio group, heterocyclic thio group, alkyl group
A xythiocarbonylthio group is mentioned. Examples of the alkylthio group include butylthio group and 2-cyano.
Ethylthio group, phenethylthio group, benzylthio group, etc.
Can be mentioned. The arylthio group is phenylthio group, 4-methane
Sulfonamide phenylthio group, 4-dodecylpheneti
Ruthio group, 4-nonafluoropentanamide phenethyl
Thio group, 4-carboxyphenylthio group, 2-ethoxy
Examples include -5-t-butylphenylthio group. Examples of the heterocyclic thio group include 1-phenyl-1,2,
3,4-tetrazolyl-5-thio group, 2-benzothiazoli
Examples thereof include a ruthio group. Examples of the alkyloxythiocarbonylthio group include dode
Examples thereof include a siloxythiocarbonylthio group. Examples of the group substituting through the nitrogen atom include general
ExpressionSome of them are listed below. R here₇And R₈Is hydrogen
Atom, alkyl group, aryl group, heterocyclic group, sulfa
Moyl group, carbamoyl group, acyl group, sulfonyl group,
Aryloxycarbonyl group, alkoxycarbonyl group
Represents R₇And R₈May combine to form a heterocycle
Yes. However, R₇And R₈Are not both hydrogen atoms. The alkyl group may be linear or branched and is preferably carbon.
Numbers 1 to 22. Also, the alkyl group has a substituent
The substituent may be, for example, an aryl group or an aryl group.
Lucoxy group, aryloxy group, alkylthio group, ant
Group, alkylamino group, arylamino group,
Sylamino group, sulfonamide group, imino group, acyl
Group, alkylsulfonyl group, arylsulfonyl group,
Lubamoyl group, sulfamoyl group, alkoxycarbonyl
Group, aryloxycarbonyl group, alkyloxy group
Rubonylamino group, aryloxycarbonylamino
Group, hydroxyl group, carboxyl group, cyano group, halo
An example is a gen atom. Specific examples of the alkyl group
Are, for example, ethyl group, octyl group, 2-ethylhexyl group.
Examples thereof include a sil group and a 2-chloroethyl group. R₇Or R₈The aryl group represented by has 6 to 6 carbon atoms.
32, particularly preferably a phenyl group or a naphthyl group,
The group may have a substituent, and the substituent may be the above R.₇or
Is R₈As a substituent to the alkyl group represented by
And alkyl groups. As the aryl group
Physical examples include phenyl group and 1-naphthyl
Group and a 4-methylsulfonylphenyl group. R₇Or R₈The heterocyclic group represented by is a 5- or 6-membered heterocyclic group.
Preferred is a fused ring, which may have a substituent.
May be. Specific examples include 2-furyl group and 2-quinoli
Group, 2-pyrimidyl group, 2-benzothiazolyl group, 2
-Pyridyl group and the like. R₇Or R₈The sulfamoyl group represented by
Alkylsulfamoyl group, N, N-dialkylsulfa
Moyl group, N-arylsulfamoyl group, N, N-dia
Reel sulfamoyl group and the like.
Group and aryl group are the same as the above-mentioned alkyl group and aryl group.
It may have the substituents mentioned above. Sulfamoy
Specific examples of the radical group include, for example, N, N-diethyl sulfa.
Moyl group, N-methylsulfamoyl group, N-dodecyl
Sulfamoyl group, Np-tolylsulfamoyl group
Can be mentioned. R₇Or R₈The carbamoyl group represented by
Rucylcarbamoyl group, N, N-dialkylcarbamoyl
Group, N-arylcarbamoyl group, N, N-diarylcar
Rubamoyl group and the like.
Examples of the reel group are the alkyl group and the aryl group.
It may have a substituent. Specific examples of carbamoyl group
Are, for example, N, N-diethylcarbamoyl group, N-
Methylcarbamoyl group, N-dodecylcarbamoyl group,
Np-cyanophenylcarbamoyl group, Np-tri
And a rucarbamoyl group. R₇Or R₈Examples of the acyl group represented by
Rucarbonyl group, arylcarbonyl group, heterocyclic
A carbonyl group, the alkyl group, the aryl group, the
The heterocyclic group may have a substituent. As an acyl group
Specific examples include hexafluorobutano
Group, 2,3,4,5,6-pentafluorobenzoyl group,
Cetyl group, benzoyl group, naphthoyl group, 2-furylca
Examples thereof include a rubonyl group. R₇Or R₈The sulfonyl group represented by is alkyl
Sulfonyl group, arylsulfonyl group, heterocyclic sulfo
Examples thereof include a nyl group, which may have a substituent.
Examples of ethanesulfonyl group, benzenesulfo
Nyl group, octane sulfonyl group, naphthalene sulfonyl group
Group, a p-chlorobenzenesulfonyl group, and the like. R₇Or R₈The aryloxycarbonyl group represented by
Having the above-mentioned aryl groups as substituents
And specifically include a phenoxycarbonyl group and the like.
To be R₇Or R₈The alkoxycarbonyl group represented by
It may have a substituent described for the alkyl group.
Methoxycarbonyl group and dodecyloxy group
Examples include carbonyl group and benzyloxycarbonyl group.
To be R₇And R₈5 to 6-membered as the hetero ring formed by combining
Preferred, which may be saturated or unsaturated, or aromatic
It may or may not have a group property and may be a condensed ring.
Yes. Examples of the heterocycle include N-phthalimido group, N
-Succinimide group, 4-N-urazolyl group, 1-N-
Hydantoinyl group, 3-N-2,4-dioxooxazoli
Dinyl group, 2-N-1,1-dioxo-3- (2H) -oxy
So-1,2-benzthiazolyl group, 1-pyrrolyl group, 1-
Pyrrolidinyl group, 1-pyrazolyl group, 1-pyrazolidini
Group, 1-piperidinyl group, 1-pyrrolinyl group, 1-i
Midazolyl group, 1-imidazolinyl group, 1-indolyl
Group, 1-isoindolinyl group, 2-isoindolyl group,
2-isoindolinyl group, 1-benzotriazolyl group,
1-benzimidazolyl group, 1- (1,2,4-triazolyl
Group), 1- (1,2,3-triazolyl) group, 1- (1,2,
3,4-tetrazolyl) group, N-morpholinyl group, 1,2,3,4
-Tetrahydroquinolyl group, 2-oxo-1-pyrrolidi
Nyl group, 2-1H-pyridone group, phthalazione group, 2-o
And oxo-1-piperidinyl group and the like.
The cyclic group is an alkyl group, an aryl group, an alkyloxy group,
Reeloxy group, acyl group, sulfonyl group, alkyl group
Mino group, arylamino group, acylamino group, sulfone
Amino group, carbamoyl group, sulfamoyl group, alk
Ruthio group, arylthio group, ureido group, alkoxy group
Rubonyl group, aryloxycarbonyl group, imide group,
Nitro group, cyano group, carboxyl group, halogen atom, etc.
May be substituted by. Further, it is formed of Za, Zb, Zc, Za ′, Zb ′ or Zc ′.
Examples of the nitrogen-containing heterocycle include a pyrrole ring, a pyrazole ring,
Midazole ring, triazole ring, thiazoline ring, oxa
Examples thereof include a zoline ring or a tetrazole ring. Y₂The hetero atom represented by is exemplified by nitrogen. Nitrogen-containing compounds formed by Za, Zb, Zc, Za ', Zb' or Zc '
Examples of the substituent that the heterocycle may have include Ra.
Specific examples of such substituents are given below.
Formulas (a-1) to (a-11), (b-1) to (b-8),
R in (c-1) to (c-14)₅₂， R₅₄， R₅₈， R₆₀，
R₆₃~ R₇₅， R₇₇， R₇₉， R₈₃， R₈₅， R₈₈~ R₉₀Is bound
When the substituent is absent, as in the
Oxidation of the coupler and the color developing agent at the position having
Substitutes for groups that do not leave due to reaction with the body. Further, in the general formulas (a) to (c), an oxidant of the color developing agent is used.
Substituents that do not leave during the reaction of
Ri, R₁₁~ R₄₂， R₅₁~ R₈₈(The carbon or nitrogen to which is bound) is (Ra ″ is Ra, Rb ″ is Rb, Rc ″ is Rc, Rd ″ is Rd,
Re ″ is Re, Rf ″ is Rf, Rg ″ is Rg, and n₁″ Is n₁When,
n₂″ Is n₂And n₃″ Is n₃And n_Four″ Is n_FourAnd n_Five″ Is n_FiveAnd n₆″
Is n₆And n₇″ Is n₇And Y₁″ Is Y₁And Y₂″ Is Y₂And Y₃″ Is Y
₃And Y_Four″ Is Y_FourAnd Y_Five″ Is Y_FiveAnd Za ″ is Za and Zb ″ is Zb
, And Zc ″ have the same meaning as Zc.)
Of course, so-called bis type couplers are also included in the present invention. Coupler represented by formula (a), (b) or (c)
Examples of the polymer coupler derived from
The coupler moiety represented by (a), (b) or (c)
Having a monomer, preferably an ethylenically unsaturated double bond
Homopolymerized or copolymerized with other monomers
One of them is. Ingredients represented by the general formula (a), (b) or (c)
The following are examples of body examples. In the formulas (a-1) to (c-14), Xa₁~ Xa₁₁Xa and Xb₁~
Xb₈Xb and Xc₁~ Xc₁₄Xc and R₁₁~ R₂₀Is Ra and R₅₁~ R
₆₃Is Rg and R_{twenty one}~ R₂₉Is Re and R₆₄~ R₇₅Is Rg and R₃₀~ R₄₂
Is Rf and R₇₆~ R₉₀Is synonymous with Rg, the same kind is exemplified
To be done. Further, the compound represented by each formula and the exemplified compounds described below are
Each includes tautomers. Tables with formulas (a) to (c)
Among those given, preferred is the formula (a-2),
(A-3), (a-4), (b-1), (b-3),
(B-4), (c-2), (c-3), (c-4),
Represented by (c-9), (c-10), (c-12)
And especially (a-3), (b-1), (c-3),
These are represented by (c-9) and (c-10). The substituent on the heterocycle in the compound represented by each formula (for example,
Ra ~ Rg, R₁₁~ R₄₂， R₅₁~ R₉₀) About preferable things
It will be described below. When the coupler according to the present invention is used for positive image formation, Xa
~ Xc, Xa₁~ Xa₁₁ Xb₁~ Xb₈， Xc₁~ Xc₁₄The carbon to which
As the substituent of the carbon atom adjacent to the atom, the following condition 1
The following conditions are more preferable.
When 1 and 2 are satisfied, the following are particularly preferable.
This is the case where the conditions 1, 2 and 3 are satisfied. Condition 1 The root atom directly connected to the heterocycle is a carbon atom. Condition 2 Only one hydrogen atom is bonded to the carbon atom
Or no binding at all. Condition 3 All bonds between the carbon atom and adjacent atoms are single bonds.
It is the case. The most preferable substituent on the heterocycle is
It is represented by a general formula. General formulaR in the formula₁₀₁， R₁₀₂And R₁₀₃Are hydrogen atom and halogen respectively
Atom, alkyl group, cycloalkyl group, alkenyl group,
Cycloalkenyl group, alkynyl group, aryl group, het
B ring group, acyl group, sulfonyl group, sulfinyl group,
Suphonyl group, carbamoyl group, sulfamoyl group, sia
Group, spiro compound residue, bridged hydrocarbon compound residue,
Lucoxy group, aryloxy group, heterocyclic oxy group,
Roxy group, acyloxy group, carbamoyloxy group,
Mino group, acylamino group, sulfonamide group, imide
Group, ureido group, sulfamoylamino group, alkoxy
Carbonylamino group, aryloxycarbonylamino
Group, alkoxycarbonyl group, aryloxycarboni
Group, alkylthio group, arylthio group, heterocyclic thio
Represents a group, R₁₀₁， R₁₀₂And R₁₀₃At least two of them are water
Not a prime atom. Also, the R₁₀₁， R₁₀₂And R₁₀₃Two of, for example R₁₀₁When
R₁₀₂Is a saturated or unsaturated ring (eg cycloal)
Can, cycloalkene, heterocycle),
R in the ring₁₀₃Bond to form a bridged hydrocarbon compound residue.
May be done. R₁₀₁~ R₁₀₃The group represented by may have a substituent.
R₁₀₁~ R₁₀₃Specific examples of the group represented by
The substituent which may be present is represented by the above general formula (a).
Specific examples of the group represented by Ra and substituents can be given. Also, for example, R₁₀₁And R₁₀₂A ring formed by combining and R₁₀₁~
R₁₀₃Examples of bridged hydrocarbon compound residues formed by
And as the substituent which it may have, the above-mentioned general formula
Cycloalkyl and cycloalkyl represented by Ra in (a)
Specific examples of kenyl, heterocyclic group, and bridged hydrocarbon compound residue
And its substituents. Among the above general formulas, (i) R is preferable.₁₀₁~ R₁₀₃When two of are alkyl groups, (ii) R₁₀₁~ R₁₀₃One of, eg R₁₀₃Is a hydrogen atom
Yes, the other two R₁₀₁And R₁₀₂Are combined with the root carbon atom
When they together form a cycloalkyl, Further preferred among (i) is R₁₀₁~ R₁₀₃2 in
One is an alkyl group and the other one is a hydrogen atom or
This is the case of a rukyll group. Here, the alkyl and the cycloalkyl further have a substituent.
Optionally the alkyl, the cycloalkyl and their substitutions
As a specific example of the group, Ra in the general formula (a) is represented by
Specific examples of alkyl, cycloalkyl and their substituents
Is mentioned. In addition, the substituents on the heterocycle (eg Ra to Rg, R₁₁~ R₄₂， R₅₁~
R₉₀) At least one of which is represented by the following general formula
Is preferred. General formula −R¹-SO₂-R² Where R¹Is alkylene, R²Is alkyl, cycloalk
Represents le or aryl. R¹The alkylene represented by is preferably a carbon in the straight chain portion.
A number of 2 or more, more preferably 3 to 6, straight chain,
It doesn't matter whether it branches. In addition, this alkylene has a substituent
May be. Examples of the substituent include Ra in the general formula (a).
When is an alkyl group, the substituent that the alkyl group may have
What was shown as a group is mentioned. Preferred substituents include phenyl.
It R¹Preferred specific examples of the alkylene represented by
You R²The alkyl group represented by may be linear or branched. Specifically, methyl, ethyl, propyl, iso-propy
Ru, butyl, 2-ethylhexyl, octyl, dodeci
Le, tetradecyl, hexadecyl, octadacil, 2-
Hexyldecyl and the like can be mentioned. R²5- to 6-membered cycloalkyl groups represented by
Is preferred, and examples thereof include cyclohexyl. R²The alkyl and cycloalkyl represented by have a substituent
It may be, for example, the above-mentioned R¹As a substituent to
What was illustrated is mentioned. R²Specific examples of the aryl represented by are phenyl,
Examples include naphthyl. The aryl group has a substituent
Good. Examples of the substituent include a straight chain or branched chain group.
In addition to Rukiru, the aforementioned R¹Examples of the substituents to
Can be mentioned. When there are two or more substituents, those substituents are
It may be one or different. Further, when the coupler according to the present invention is used for negative image formation,
, Xa to Xc, Xa₁~ Xa₁₁， Xb₁~ Xb₈， Xc₁~ Xc₁₄Joins
As the substituent of the carbon atom adjacent to the carbon atom,
It is preferable that Condition 1 be satisfied, and more preferable that
This is the case where the conditions 1 and 2 are satisfied. Condition 1 The root atom directly connected to the heterocycle is a carbon atom. Condition 2 At least two hydrogen atoms are bonded to the carbon atom
ing. The most preferable substituent on the heterocycle is
It is represented by a general formula. General formula R₁₀₄-CH₂-Where R₁₀₄Is a hydrogen atom, halogen atom, alkyl group,
Chloroalkyl group, alkenyl group, cycloalkenyl group,
Alkynyl group, aryl group, heterocyclic group, acyl group, sulfur group
Rufonyl group, sulfinyl group, phosphonyl group, carbamo
Yl group, sulfamoyl group, cyano group, spiro compound residue
Group, bridged hydrocarbon compound residue, alkoxy group, aryl
Oxy group, heterocyclic oxy group, siloxy group, acyloxy
Si group, carbamoyloxy group, amino group, acylamino
Group, sulfonamide group, imide group, ureido group, sulf
Amamoylamino group, alkoxycarbonylamino group,
Reel oxycarbonyl amino group, alkoxy carbonyl
Group, aryloxycarbonyl group, alkylthio group,
It represents an arylthio group or a heterocyclic thio group. R₁₀₄The group represented by R may have a substituent, R₁₀₄
Specific examples of the group represented by and the position which the group may have
As the substituent, Ra in the general formula (a) is represented.
Specific examples of the group and substituents can be mentioned. R₁₀₄Preferred as is a hydrogen atom or an alkyl group.
It Specific examples of the compound used in the present invention are shown below. The numbers in the table represent the following groups. 1-CH₃ 2-C₂H_Five 3- (i) C₃H₇ 4-C_FourH₉ 5- (t) C_FourH₉ 6- (i) C_FourH₉ 7-C_FiveH₁₁ 8- (t) C₈H₁₇ 9-C₁₁H_{twenty three} 10 −C₁₂H_{twenty five} 11 −C₁₅H₃₁ 12-C₁₇H₃₅  20-CH₂N (C₂H_Five)₂ 21-CH₂CH₂NHSO₂C₁₆H₃₃  31 − (CH₂)₃SO₂C₁₂H_{twenty five}(t) 32 − (CH₂)₃SO₂C₁₂H_{twenty five}  81-CN 91-COCH₃ 92-COC₃H₇  95-CONH₂  99-COOCH₃ 100-COOC₂H_Five 101-COOC₈H₁₇ 102-COOC₁₂H_{twenty five} 103-COOC₁₅H₃₁ 111 F 112 Cl 113 Br 126-NHCOC₁₃H₂₇ 127-NHCOC₁₆H₃₃  132-NHSO₂CH₃  141 -OCH₃ 142-OC₂H_Five 143-OC₁₂H_{twenty five} 145 -OCH₂CH₂OCH₃ 146 −OCH₂CONHCH₂CH₂OCH₃ 147 -OCH₂CH₂SO₂CH₃  161-OCOC₂H_Five 162 −OCOC (CH₃)₃ 172-SCH₂CH₂OH 173 -SC₁₆H₃₃ 174-SCH₂COOH The color tone of the coloring dye produced by the coupler of the present invention is
Arrangement of ring-constituting atoms, types of substituents, and further color developing agents
Although it may change depending on conditions such as the type of
Can be used for multicolor photography, but red
However, even if the color tone is
It can be used for color photographs and the like. The coupler of the present invention usually contains 1 × per mol of silver halide.
Ten^-3Mol to 1 mol, preferably 1 x 10^-2Mole-8 × 10^-1
It can be used in the molar range. In addition, the coupler of the present invention is compatible with other types of magenta couplers.
It can also be used together. The present invention is directed to a silver halide color image containing a water-soluble dye.
Accelerates decolorization of the dye for true light-sensitive materials
Has the effect of preventing. Therefore, also the effect of the dye
Can be enhanced. Such dyes include filter dyes and
Dyes used for various purposes such as prevention of diation
Yes, oxanol dye, hemioxanol dye, melody
Cyanine dye, cyanine dye, styryl dye, azo dye
Is wrapped. Among them, oxanol dyes; hemioxano
And merocyanine dyes are useful. Can be used
Specific examples of dyes are West German Patent No. 616,007 and British Patent 584,609.
No. 1,177,429, Japanese Patent Publication No. 26-7777, 39-22069
No. 54-38129, JP-A No. 48-85130, and No. 49-99620.
No. 49-114420, No. 49-129537, No. 50-28827
No. 52-108115, No. 57-185038, British Patent 1,878,
961, 1,884,035, 1,912,797, 2,098,891
No., No. 2,150,695, No. 2,274,782, No. 2,298,731,
2,409,612, 2,461,484, 2,527,583, 2,5
33,472, 2,865,752, 2,956,879, 3,094,41
No. 8, No. 3,125,448, No. 3,148,187, No. 3,177,078,
3,247,127, 3,260,601, 3,282,699, 3,4
09,433, 3,540,887, 3,575,704, 3,653,90
No. 5, No. 3,718,472, No. 3,865,817, No. 4,070,352,
No. 4,071,312, PB Report 74175, PHOTO.ABS.12
8 ('21), etc. In the present invention, a conventional hydroxyl group is added to the color developer.
Compound represented by the above general formula [1] in place of the min sulfate
Is used. In the general formula [1], R₁And R₂Having a substituent represented by
The alkyl group which may be present preferably has 1 to 5 carbon atoms,
Particularly, those having 1 to 3 carbon atoms are preferable. Represented by the formula
R in the compound₁And R₂A compound in which both are alkyl groups
preferable. In the general formula [1], R₁And R₂Is represented by
The substituent that the group may have includes a sulfo group and a hydrido group.
Roxyl group, alkoxy group (methoxy group, ethoxy group,
Propyloxy group, etc.), carboxyl group, amino group, etc.
And these include, for example, U.S. Pat.
No. 125, No. 3,293,034, No. 3,287,124, etc.
Some hydroxyamines are mentioned. Hereinafter, preferable specific examples represented by the general formula [1] will be described.
Indicates compound. (I-1) CH₉-NH-OH (I-2) C₂H_Five-NH-OH (I-3) iso-C₉H₇-NH-OH (I-4) C₈H₇-NH-OH (I-5) HO-CH₂-NH-OH (I-6) CH₉-OC₂H_Four-NH-OH (I-7) HO-C₂H_Four-NH-OH (I-8) HOOC-C₂H_Four-NH-OH (I-9) HO₉S-C₂H_Four-NH-OH (I-10) N₂H-C₉H₆-NH-OH (I-11) C₂H_Five-OC₂H_Four-NH-OH (I-12) HO-C₂H_Four-OC₂H_Four-NH-OH The compound represented by the general formula [I] is usually hydrochloride or sulfuric acid.
Salt, p-toluenesulfonate, oxalate, phosphoric acid
Used in the form of salt such as salt and acetate. The concentration of the compound of the present invention in the color developing solution is usually the same as that of the preservative.
Concentration similar to that used for hydroxylamine, eg
For example, 0.2 g / l to 50 g / l is preferably used, and more preferably
Is 0.5 g / l to 30 g / l, more preferably 1.0 g / l
~ 20g / l. Further, the compounds of the present invention are two or more kinds.
It may be used together to maintain the preservative property of the color developing agent and the image preservation.
It is preferable to arbitrarily select from the viewpoint of improving the survival. A color developing agent used in the color developing solution used in the present invention;
As a p-phenylenediamine system having a water-soluble group
Compounds are preferable from the viewpoint of achieving the object of the present invention. The p-phenylenediamine compound having a water-soluble group is
Water-soluble groups such as N, N-diethyl-p-phenylenediamine
Compared to para-phenylenediamine compounds that do not have
There is no contamination of the light material, and the skin is rash.
Not only does it have the advantage of being difficult,
In combination with the compound represented by the general formula [1]
With the above, the object of the present invention can be efficiently achieved.
It The water-soluble group is a group of p-phenylenediamine compounds.
Having at least one on a mino group or benzene nucleus
And specific water-soluble groups include-(CH₂)_n-CH₂OH, − (CH₂)_m-NISO₂− (CH₂)_n-CH₉, − (CH₂)_mO- (CH₂)_n-CH₂, − (CH₂CH₂O)_nC₉H_{2m + 1} (M and n each represent an integer of 0 or more.) -COOH, -SO₃Preferred examples include H and the like. Specific examples of color developing agents preferably used in the present invention
The compounds are shown below. Illustrative color developing agent Of the above-illustrated color developing agents, preferred are those used in the present invention.
Shinano is an example No. (A-1), (A-2), (A-
3), (A-4), (A-6), (A-7) and (A
-15), particularly preferably (A-
1). The above color developing agents are usually hydrochlorides, sulfates, p-toluene.
It is used in the form of salts such as sulfonic acid salts. The color developing agent having a water-soluble group used in the present invention is
Normal color developer 1 x 10 per 1^-3~ 2 x 10^-1Molar range
It is preferable to use in, but color is developed from the viewpoint of rapid processing.
2.0 × 10 per developer^-3~ 2 x 10^-1More molar range
preferable. The color developer used in the present invention contains
Developer components can be included. As an alkaline agent, for example, sodium carbonate, potassium carbonate
System, sodium hydroxide, potassium hydroxide, silicate,
Sodium taborate, potassium metaborate, phosphoric acid 3 Na
Thorium, potassium triphosphate, borax, etc. alone or
Combined to maintain pH stabilization effect without precipitation
It can be used in combination within a range. Is it necessary for further preparation?
Or for the purpose of increasing the ionic strength.
Disodium hydrogen phosphate, dipotassium hydrogen phosphate, bicarbonate
Sodium, potassium bicarbonate, various salts such as borate
Can be used. If necessary, use inorganic and organic antifoggants.
It can be added. Further, a development accelerator can be used if necessary.
Development accelerators include U.S. Pat. Nos. 2,648,604 and 3,6.
71, 247 and various Japanese patent publications No. Sho 44-9503.
Lydinium compounds and other cationic compounds,
Of thallium nitrate, a cationic dye such as nosafranine
Such neutral salts, U.S. Pat.Nos. 2,533,990 and 2,531,832
No. 2,950,970, No. 2,577,127, and Shokoku Sho
Polyethylene glycol described in 44-9504 and its inducement
Nonionic compounds such as conductors and polythioethers
Organic solvents, organic amines, and ethanol described in JP-A-44-9509
Alcohol, ethylenediamine, diethanolamine,
Triethanolamine and the like are included. Also US Patent No. 2,
No. 304,925, benzyl alcohol,
Netyl alcohol, and acetylene glyco
, Methyl ethyl ketone, cyclohexanone, thioe
Ethers, pyridine, ammonia, hydrazine, amines
And the like. Further, if necessary, the color developer used in the present invention may
Ethylene glycol, methyl cellosolve, methanol
, Acetone, dimethylformamide, β-cyclodextyl
Strings, other Japanese Patent Publication Nos. 47-33378 and 44-9509
The compounds described in the publication are used for increasing the solubility of the developing agent.
It can be used as a machine solvent. Furthermore, it is also possible to use an auxiliary developer together with the developing agent.
Wear. Examples of these auxiliary developers include N-methyl
-P-aminophenol hexalfate (meth
, Phenidone, N, N′-diethyl-p-aminophen
Nol hydrochloride, N, N, N ', N'-tetramethyl-p-phen
Nilenenediamine hydrochloride, etc.
The amount added is usually preferably 0.01 g to 1.0 g / l. Besides this
Also, if necessary, mixed coupler, rash agent, colored
Coupler, development inhibitor release type coupler (so-called DIR
Coupler), or development inhibitor releasing compound, etc. are added.
You can also Furthermore, other anti-stain agents, anti-sludge agents,
Various additives such as a multi-layer effect accelerator can be used. The color developer used in the present invention has the following general formula [I],
Contains a chelating agent represented by [II] or [III]
be able to. General formula [I] A-COOM General formula [II] B-PO₃M₂ General formula (III)In the formula, A and B each represent a monovalent group or atom,
It may be an inorganic substance or an organic substance. D is
Represents an aromatic ring or a heterocyclic ring which may have a substituent,
Represents a hydrogen atom or an alkali metal atom. The crack represented by the general formula [I], [II] or [III]
Among the chelating agents, the chelating agent preferable in the present invention is as follows.
A compound represented by any of the general formulas [IV] to [XV]
It General formula [IV] Mm₁Pm₁O₃m₁ General formula [V] Mn₁+₂Pn₁O₃n₁+1 General formula [VI] A₁-Ri-Z-R₂-COOH general formula (VII)In the formula, E is a substituted or unsubstituted alkylene group, cycloalkyl
Ruylene group, phenylene group, -R₇OR₇−, −R₇OR₇OR₇−
Or −R₇ZR₇Represents-, Z is> N-R₇−A₆Or> NA
₆Represents R₁~ R₇Is a substituted or unsubstituted alkylate
A group, A₁~ A₆Is a hydrogen atom, --OH, --COOM or
Is -PO₃M₂Represents the hydrogen atom or the alkali metal source
Represents a child, m₁Is an integer from 3 to 6, n₁Represents an integer from 2 to 20
Forget General formula [VIII] R₈N (CH₂PO₃M₂)₂ Where R₈Is a lower alkyl group, an aryl group, an aralkyl group
Or a nitrogen-containing 6-membered ring group [as a substituent, -OH, -OR or -CO
May have OM], and M is a hydrogen atom or
Lucari represents a metal atom. General formula [IX]Where R₉~ R₁₁Are hydrogen atom, -OH, lower alkyl (
-OH, -COOM or -PO as a substituent or substituent₃(M)₂Have
B)₁~ B₃Is a hydrogen atom, --OH, --C
OOM, −PO₃(M)₂Or −N (J)₂Where J is a hydrogen atom, low
Primary alkyl group, C₂H_FourOH or −PO₃M₂And M is hydrogen
Represents an atom or an alkali metal, and n and m are 0 or
Represents 1. General formula [X]Where R₁₂And R₁₃Are hydrogen atom and alkali metal atom C, respectively₁
~ C₁₂Alkyl group of C₁~ C₁₂Alkenyl group or cyclic group
Represents a rukyll group. General formula (XI)Where R₁₄Is C₁~₁₂Alkyl group of C₁~₁₂Arco
Xy group, C₁~₁₂Monoalkylamino group, C_Two~₁₂of
Dialkylamino group, amino group, C₁~ C_{twenty four}Aryloxy
Base, C₆~_{twenty four}The arylamino group and amyloxy group of
Represent, Q₁~ Q₃Is -OH, C₁~_{twenty four}Alkoxy group of
Rukyroxy group, allyloxy group, -OM₁(M₁Is a cation
Represents a), an amino group, a morpholino group, a cyclic amino group,
Rukylamino group, dialkylamino group, arylamino group
Represents a group or an alkyloxy group. General formula (XII)General formula (XIII)Where R₁₅， R₁₆， R₁₇And R₁₈Are hydrogen atom and halogen
Atom, sulfo group, substituted or unsubstituted alkyl group having 1 to 7 carbon atoms, -OR₁₉, -COOR₂₀，Alternatively, it represents a substituted or unsubstituted phenyl group. R₁₉，
R₂₀， R_{twenty one}And R_{twenty two}Are each hydrogen atom or carbon atom number 1-18
Represents an alkyl group, and n represents 1 or 2. General formula (XIV)Where R_{twenty three}And R_{twenty four}Is a hydrogen atom, a halogen atom or sulfo
Represents a group. General formula (XV)Where R₂₉And R₃₀Are hydrogen atom, phosphate group, and
Bonic acid group, -CH₂COOH, −CH₂PO₃H₂Or the salt thereof
I, X₃Represents a hydroxyl group or a salt thereof, W₁， Z₁And Y₁Is
Hydrogen atom, halogen atom, hydroxyl group, cyano group,
Carboxyl group, phosphate group, sulfo group or their
Represents a salt, an alkoxy group or an alkyl group. Also m₃Is 0
Or 1, n₃Is an integer from 1 to 4, I₁Is 1 or 2, p₂Is 0 to 3
An integer, q₁Represents an integer of 0 to 2. Specific examples of chelating agents represented by the above general formulas [IV] to [XV]
Examples include: [Exemplary chelating agent] (1) Na_FourP_FourO₁₂ (2) Na₃P₃O₉ (3) N_FourP₂O₇ (4) H_FiveP₃O_Ten (5) Na₆P_FourO₁₃  (15) (HOC₂H_Four)₂NCH₂COOH In the present invention, the general formulas [IV], [V], [VII], [V
III], [IX], [XII] and [XV] chelates
It is more effective to use an agent, and more preferably
Chelate represented by the general formula [VII], [VIII] or [IX]
Is to use the agent. In the present invention, particularly preferred chelating agent
(6), (7), (14), (19), (31), (44),
Chelate represented by (81), (82), (93) or (98)
Is to use the agent. Two or more of these chelating agents
It can also be used in combination. Any of the above general formulas [I] to [III] used in the present invention
The chelating agent shown there is 1 x 10 per color developer.
^-FourIt can be added in the range of 1 mol to 1 mol, preferably
Is 2 × 10^-Four~ 1 x 10^-1It can be added in the molar range.
More preferably 5 × 10^-Four~ 5 x 10^-2Add in molar range
Can be added. Each component of the above color developing solution is sequentially added to water as a solvent.
It can be prepared by adding and stirring. In this case water
Water with low solubility is
It can be added by mixing with a machine solvent or the like. One more time
Generally, multiple components that can coexist stably are
Thick aqueous solution or solid state prepared in advance in a small container
Was added to water and stirred to prepare the color developer of the present invention.
can do. In the present invention, the color developer is used in any pH range.
Yes, but pH 9.5 to 13.0 from the viewpoint of rapid processing
Is more preferably used at pH 9.8 to 13.0
It In the present invention, the processing temperature for color development is 30 ° C. or higher,
50 ° C or less, the higher the processing temperature, the faster and faster
This is preferable because it enables decolorization, but on the contrary, the homeostasis may deteriorate.
There is also a problem of rinsing, more preferably 30 ℃ or more, 45 ℃
The range is as follows. Color development time is about 3 minutes and 30 seconds, which is generally done in the past.
However, the effect of the present invention is more remarkable as the treatment time is shorter.
Therefore, the present invention is suitable for rapid processing. In the present invention, it has a fixing ability after color development processing.
The processing liquid having the fixing ability is a fixing liquid.
If so, a bleaching process is performed before that. The bleacher
Used in bleaching or bleach-fixing solutions
As a bleaching agent, a metal complex salt of an organic acid is used.
Complex salts oxidize the metallic silver produced by development to generate halogens.
At the same time as changing to silver halide, the uncolored part of the color former is colored.
It has an action and its structure is aminopolycarboxylic acid.
Or organic acids such as acid and citric acid such as iron, cobalt, copper, etc.
It is a metal ion coordinated with. Such an organic acid
Most preferred compounds used to form metal complexes of
The organic acid may be polycarboxylic acid or aminopolycarbohydrate.
Acids may be mentioned. These polycarboxylic acids or
Nopolycarboxylic acid is also an alkali metal salt, ammonium salt
Alternatively, it may be a water-soluble amine salt. The following are typical representative examples of these.
be able to. [1] Ethylenediaminetetraacetic acid [2] Diethylenetriaminepentaacetic acid [3] Ethylenediamine-N- (β-oxyethyl)-
N, N ', N'-triacetic acid [4] Propylenediaminetetraacetic acid [5] Nitrilotriacetic acid [6] Cyclohexanediaminetetraacetic acid [7] Iminodiacetic acid [8] Dihydroxyethylglycine citric acid (or sake
Stony acid)

[9] Ethyletherdiaminetetraacetic acid [10] Glycoletheraminetetraacetic acid [11] Ethylenediaminetetrapropionic acid [12] Phenylenediaminetetraacetic acid [13] Ethylenediaminetetraacetic acid disodium salt [14] Ethylenediaminetetraacetic acid tetra (trimethylammonium) Salt [15] Ethylenediaminetetraacetic acid tetrasodium salt [16] Diethylenetriaminepentaacetic acid pentasodium salt [17] Ethylenediamine-N- (β-oxyethyl)-
N, N ', N'-triacetic acid sodium salt [18] Propylenediaminetetraacetic acid sodium salt [19] Nitrilotriacetic acid sodium salt [20] Cyclohexanediaminetetraacetic acid sodium salt The bleaching solution used is an organic acid as described above. In addition to containing a metal complex salt as a bleaching agent, various additives can be included. As the additive, it is particularly preferable to contain an alkali halide or an ammonium halide, for example, a rehalogenating agent such as potassium bromide, sodium bromide, sodium chloride, ammonium bromide, a metal salt or a chelating agent. In addition, it is possible to appropriately add pH buffers such as borate, acid salt, acetate, carbonate, and phosphate, and known bleaching solutions such as alkylamines and polyethylene oxides. . Further, the fixer and the bleach-fixer are ammonium sulfite,
Sulfites such as potassium sulfite, sodium bisulfite, ammonium metabisulfite, potassium metabisulfite, sodium metabisulfite, boric acid, borax, sodium hydroxide,
A pH buffering agent comprising various salts such as potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, ammonium hydroxide can be used alone or in combination of two or more kinds. When processing is performed while replenishing the bleach-fixing solution (bath) with a bleach-fixing replenisher, the bleach-fixing solution (bath) may contain thiosulfate, thiocyanate, sulfite or the like. The replenisher may contain these salts and may be replenished to the treatment bath. In the present invention, the bleaching solution may be optionally blown with air or blown with oxygen in the bleach-fixing bath and in the storage tank for the bleach-fixing replenisher in order to increase the activity of the bleach-fixing solution, or a suitable one. An oxidizing agent such as hydrogen peroxide, bromate, persulfate or the like may be added as appropriate. In the processing method of the present invention, silver may be recovered by a known method from a processing solution containing a soluble silver complex salt such as a fixing solution and a bleach-fixing solution as well as a stabilizing solution for washing with water. For example, electrolysis method (French Patent No. 2,299,667), precipitation method (JP-A-52-7)
3037, German Patent No. 2,331,220), an ion exchange method (Japanese Patent Laid-Open No. 51-17114, German Patent No. 2,548,237), a metal substitution method (British Patent No. 1,353,805) and the like can be effectively used. In the processing method of the present invention, after color development processing, after bleaching and fixing (or bleach-fixing) processing, it is possible to carry out stable processing without washing with water, or to carry out stabilizing processing after washing with water. In addition to the above steps, known auxiliary steps such as hardening, neutralization, black-and-white development, reversal, and washing with a small amount of water may be added as necessary. The silver halide grains used in the silver halide color photographic light-sensitive material to which the processing method of the present invention is applied can contain silver bromide and / or silver iodide in addition to silver chloride. Examples thereof include silver halide grains composed of silver halide, silver bromide, silver iodobromide and the like. In the present invention, when a silver chlorobromide emulsion, particularly a high silver chloride emulsion, is used, there is little influence on sensitometry,
It is also suitable for rapid processing, and the effect of using the antioxidant of the present invention is remarkable. Specifically, the silver chloride content is 70 mol%
Above, particularly preferably 90 mol% or more of silver chlorobromide emulsion is preferable as an emulsion to which the present invention is applied. The crystal of the silver halide grain used in the present invention may be a normal crystal, a twin crystal or any other crystal, and any ratio of {100} plane to {111} plane can be used. Further, the crystal structure of these silver halide grains may be uniform from the inside to the outside or may have a layered structure (core / shell type) in which the inside and the outside are different. Further, these silver halides may be of a type that forms a latent image mainly on the surface or may be of a type that is formed inside the grain. Further, tabular silver halide grains (Japanese Patent Application Laid-Open No. 58-113934, Japanese Patent Application No. 59-
No. 170070) can also be used. The silver halide grains used in the present invention may be those obtained by any of the acid method, the neutral method and the ammonia method. Further, for example, a method may be used in which seed particles are formed by an acidic method and further grown by an ammonia method having a high growth rate to grow to a predetermined size. When the silver halide grains are grown, the pH, pAg, etc. in the reaction vessel are controlled, and the amount of silver ions corresponding to the growth rate of the silver halide grains as described in JP-A-54-48521 is used. It is preferable to sequentially and simultaneously inject and mix halide ions with halide ions. The silver halide grains according to the present invention are preferably prepared as described above. The composition containing the silver halide grains is referred to herein as a silver halide emulsion. These silver halide emulsions include active gelatin; sulfur sensitizers such as allylthiocarbamide, thiourea, and cystine; sulfur sensitizers; selenium sensitizers; reduction sensitizers such as stannous salt and thiourea dioxide. Noble metal sensitizers such as gold sensitizers, specifically potassium aurithiocyanate, potassium chloroaurate, and 2-orothio-3-.
Sensitizers of methylbenzothiazolium chloride and the like or water-soluble salts such as ruthenium, palladium, platinum, rhodium and iridium, specifically ammonium chloroparadate, potassium chlorobratinate and sodium chloroparadate (these or Some of them act as sensitizers or antifoggants depending on the amount.) Etc. alone or in combination (for example, gold sensitizer and sulfur sensitizer, gold sensitizer and selenium sensitizer). It may be chemically sensitized by the combined use with a sensitizer). The silver halide emulsion according to the present invention is chemically ripened by adding a sulfur-containing compound, and before, during, or after the chemical ripening, at least one kind of nitrogen-containing heteroaryl having a hydroxytetrazaindene and a mercapto group. You may make it contain at least 1 sort (s) of a ring compound. The silver halide used in the present invention contains a suitable sensitizing dye in an amount of 5 × 10 ^{−3 to} 3 × 10 ^{−3 with} respect to 1 mol of silver halide in order to impart photosensitivity to a desired light-sensitive wavelength region. It may be optically sensitized by adding a mole. Various kinds of sensitizing dyes can be used, and one kind or a combination of two or more kinds of sensitizing dyes can be used. Examples of the sensitizing dye that can be advantageously used in the present invention include the following. That is, as a sensitizing dye used in a blue-sensitive silver halide emulsion, for example, West German Patent 929,080 and U.S. Pat.
No. 2,493,748, 2,503,776, 2,519,001,
2,912,329, 3,656,959, 3,672,897, 3,6
94,217, 4,025,349, 4,046,572, British patent 1,
242,588, Japanese Examined Patent Publication Nos. 44-14030, 52-24844 and the like can be mentioned. Examples of sensitizing dyes used in green-sensitive silver halide emulsions include, for example, U.S. Patents 1,939,201, 2,072,908, 2,733,149, and
Typical examples thereof include cyanine dyes, merocyanine dyes and complex cyanine dyes such as those described in 2,945,763 and British Patent 505,979. Further, as the sensitizing dye used in the red-sensitive silver halide emulsion, for example, U.S. Pat.Nos. 2,269,234 and 2,270,378,
Representative examples thereof include cyanine dyes, merocyanine dyes, or complex cyanine dyes such as those described in Nos. 2,442,710, 2,454,629, and 2,776,280. Furthermore, U.S. Patents 2,213,995 and 2,493,7
Cyanine dyes, merocyanine dyes or complex cyanine dyes such as those described in No. 48, No. 2,519,001, West German Patent 929,080, etc. can be advantageously used for a green-sensitive silver halide emulsion or a red-sensitive silver halide emulsion. These sensitizing dyes may be used alone or in combination. The photographic light-sensitive material of the present invention may be optionally optically sensitized to a desired wavelength range by a spectral sensitization method using a cyanine or merocyanine dye alone or in combination. A particularly preferable example of the spectral sensitization method is, for example, Japanese Patent Publication No. 43936/43936, which relates to a combination of benzimidazolocarbocyanine and benzoxazolocarbocyanine.
No. 43, No. 22884, No. 45-18433, No. 47-37443,
48-28293, 49-6209, 53-12375, JP
52-23931, 52-51932, 54-80118, 58-1
53926, 59-116646, 59-116647 and the like. Further, as a combination of a carbocyanine having a benzimidazole nucleus and another cyanine or merocyanine, for example, Japanese Patent Publication Nos. 45-25831, 47-11114 and 47
-25379, 48-38406, 48-38407, 54-345
No. 35, No. 55-1569, JP-A No. 50-33220, No. 50-38526
No. 51, No. 51-107127, No. 51-115820, No. 51-135528
No. 52-104916 and No. 52-104917. Furthermore, examples of combinations of benzoxazolocarbocyanine (oxacarbocyanine) with other carbocyanines include, for example, JP-B-44-32753 and 46-11627.
JP-A-57-1483, and those relating to merocyanine include, for example, JP-B-48-38408, 48-41204, and 50-
40662, JP-A-56-25728, 58-10753, 58-9
1445, 59-116645, 50-33828 and the like. Further, examples of combinations of thiacarbocyanine with other carbocyanines include, for example, Japanese Patent Publication Nos. 43-4932 and 43
-4933, 45-26470, 46-18107, 47-8741
JP-A-59-114533 and the like, and the method described in JP-B-49-6207 using zeromethine or dimethine merocyanine, monomethine or trimethine cyanine and styryl dyes can be advantageously used. In order to add these sensitizing dyes to the silver halide emulsion according to the present invention, a dye solution such as methyl alcohol, ethyl alcohol, acetone, dimethylformamide, or a fluorinated alcohol described in JP-B-50-40659 can be used. It is used by dissolving it in the hydrophilic organic solvent. The silver halide emulsion may be added at any time from the start of chemical ripening, during ripening, and at the end of ripening, and in some cases, it may be added immediately before the emulsion coating. The photographic coupler used in the present invention is preferably a cyan compound, a phenol compound or a naphthol compound. These cyan couplers may be not only 4-equivalent type couplers but also 2-equivalent type couplers like the yellow couplers. Specific examples of cyan couplers include U.S. Pat.
929, 2,434,272, 2,474,293, 2,521,908
No., No. 2,772,162, No. 2,895,826, No. 3,034,892,
3,311,476, 3,458,315, 3,476,563, 3,5
83,971, 3,591,383, 3,758,308, 3,767,41
No. 1, 3,772,002, 3,933,494, 4,004,929,
4,126,396, 4,334,011, 4,327,173, West German patent application (OLS) 2,414,830, 2,454,329, 3,329,7
29, JP-A-48-59838, 51-26034, 48-5055
No. 51, No. 51-146827, No. 52-69624, No. 52-90932,
Examples thereof include those described in JP-A-58-95346 and JP-B-49-1572. As the photographic yellow coupler, an open chain ketomethylene compound which has been conventionally used can be used, and a benzoylacetanilide type yellow coupler and a piparoylacetanilide type yellow coupler which are generally widely used can be used. Further, a 2-equivalent type yellow coupler in which the carbon atom at the coupling position is substituted with a substituent capable of leaving during the coupling reaction is also advantageously used. Examples of these are US Patent 2,875,057
No., No. 3,265,506, No. 3,664,841, No. 3,408,194,
No. 3,277,155, No. 3,447,928, No. 3,415,652, Japanese Patent Publication No. 49-13576, JP-A No. 48-29432, No. 48-68834,
49-10736, 49-122335, 50-28834, 50
-132926 and the like together with the synthetic method. The amount of the above diffusion-resistant coupler used in the present invention is generally from 0.05 to 1 mol per mol of silver in the photosensitive silver halide emulsion layer.
2.0 mol. In the present invention, it is preferably used as a DIR compound in addition to the above diffusion resistant coupler. Further, in addition to the DIR compound, a compound that releases a development inhibitor upon development is also included in the present invention.
297,445, 3,379,529, West German patent application (OLS) 2,41
7,914, JP-A Nos. 52-15271, 53-9116, and 59-12
Examples thereof include those described in 3838 and 59-127038. The DIR compound used in the present invention is a compound capable of reacting with an oxidized product of a color developing agent to release a development inhibitor. A typical example of such a DIR compound is a DIR coupler in which a group capable of forming a compound having a development inhibitory action when released from the active site is introduced into the active site of the coupler, for example, British Patent 935,454. , U.S. Patent 3,227,5
54, 4,095,984, 4,149,886, etc. The above-mentioned DIR coupler has a property that, when it undergoes a coupling reaction with an oxidized product of a color developing agent, the coupler nucleus forms a dye, while releasing a development inhibitor. Further, in the present invention, U.S. Patent Nos. 3,652,345, 3,928,041, and 3,958,993.
No. 3,961,959, No. 4,052,213, JP-A-53-110529.
No. 54-13333, No. 55-161237, etc., a compound that releases a development inhibitor but does not form a dye when subjected to a coupling reaction with an oxidant of a color developing agent is described. . Furthermore, the mother nucleus forms a dye or a colorless compound when reacted with an oxidant of a color developing agent as described in JP-A-54-145135, JP-A-56-114946 and JP-A-57-154234. On the other hand, the present invention also includes a so-called timing DIR compound in which the released timing group is a compound that releases the development inhibitor by an intramolecular nucleophilic substitution reaction or an elimination reaction. Further, the timing group as described above is present in the coupler mother nucleus which forms a completely diffusible dye when it reacts with the oxidized product of the color developing agent described in JP-A-58-160954 and JP-A-58-162949. It also includes a bound timing DIR compound. The amount of the DIR compound contained in the light-sensitive material is preferably in the range of 1 × 10 ^-4 mol to 10 × 10 ^-1 mol per mol of silver. The silver halide color photographic light-sensitive material used in the present invention may further contain various photographic additives. For example, antifoggant, stabilizer, ultraviolet absorber, described in Research Disclosure Magazine 17643,
A color stain preventing agent, a fluorescent whitening agent, a color image fading preventing agent, an antistatic agent, a hardening agent, a surfactant, a plasticizer, a wetting agent and the like can be used. In the silver halide color photographic light-sensitive material used in the present invention, hydrophilic colloids used for preparing an emulsion include gelatin, derivative gelatin, a graft polymer of gelatin and another polymer, a protein such as alpmine and casein. , Hydroxyethyl cellulose derivatives, cellulose derivatives such as carboxymethyl cellulose, starch derivatives, polyvinyl alcohol, polyvinyl imidazole,
Any one such as a single or copolymer synthetic hydrophilic polymer such as polyacrylamide is included. As a support for the silver halide color photographic light-sensitive material used in the present invention, for example, baryta paper, polyethylene-coated paper, polypropylene synthetic paper, and a reflective layer are provided. Or a transparent support used in combination with a reflector, for example, a glass plate, cellulose acetate, a polyester film such as cellulose nitrate or polyethylene terephthalate, a polyamide film, a polycarbonate film, a polystyrene film, and the like, and other ordinary transparent supports Good. These supports are appropriately selected according to the purpose of use of the light-sensitive material. Various coating methods such as taping coating, air doctor coating, curtain coating, and hopper coating can be used for coating the silver halide emulsion layer and other photographic constituent layers used in the present invention. U.S. Patent 2,761,791
No. 2,941,398, the simultaneous coating method of two or more layers can also be used. In the present invention, the coating position of each emulsion layer can be arbitrarily determined. For example, in the case of a full-color photographic light-sensitive material for photographic paper, it is preferable to sequentially arrange a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer from the support side. . Each of these light sensitive silver halide emulsion layers may consist of two or more layers. In the light-sensitive material of the present invention, it is optional to provide an intermediate layer having an appropriate thickness depending on the purpose, and further, a filter layer,
Various layers such as an anti-curl layer, a protective layer and an antihalation layer can be appropriately combined and used as constituent layers.
A hydrophilic colloid which can be used in the emulsion layer as described above can be similarly used as a binder in these constituent layers, and various hydrophilic colloids can be contained in the emulsion layer as described above. The above photographic additives can be incorporated. In the method for processing a silver halide color photographic light-sensitive material of the present invention, a color paper is used as the silver halide color photographic light-sensitive material as long as it is a light-sensitive material processed by a so-called internal development method containing a coupler in the light-sensitive material. It can be applied to any silver halide color photographic light-sensitive material such as a color negative film, a color positive film, a color positive paper, a slide color reversal film, a movie color reversal film, a TV color reversal film and a reversal color paper. [Specific effects of the invention] As described above, according to the processing method of the present invention, in place of hydroxylamine, which is toxic to the human body and is a poisonous substance, the storage stability is excellent and the change with time of the developer, especially the sulfurous acid concentration. It is possible to provide a processing method of a silver halide color photographic light-sensitive material which is capable of obtaining stable photographic performance with respect to changes in the image and which is suitable for rapid processing. [Examples] Hereinafter, the present invention will be specifically described with reference to Examples, but the embodiments of the present invention are not limited thereto. Example 1 The following color developing solution was prepared. (Color developer) Potassium sulfite 4.0 × 10 ^-3 mol Sodium chloride 0.3g Potassium carbonate 25.0g Antioxidant (shown in Table 1) 5.0g Polyphosphoric acid (TPPS) 2.0g Color developing agent (Exemplary compound A-1) 5.0g Fluorescent brightener (4,4'-diaminostilbene type) 2.0 g Potassium hydroxide and water were added to make it 1. Note that ph is 10.1
It was set to 5. 5 ppm of ferric ion, 3 ppm of copper ion and 100 ppm of calcium ion (FeCl ₃ , CuSO ₄・ 6H _{2 respectively)}
O and CaCl ₂ are dissolved and added), and the opening ratio at 50 ° C
30cm / l (air contact area is 30cm for 1 developer)
^{It was} stored in a ² l) glass container for 1 week, and the appearance (blueness and tar) of the color developing solution was observed after 1 week. However, the appearance of the liquid was evaluated according to the following four grades. Multiple tar generation Blackening + browning (very discolored) -Almost no discoloration is shown in Table 1. As is clear from Table 1, when the antioxidant of the present invention is used, the storability of the color developing solution is good even if it contains iron ions and copper ions, and is as high as or more than that of the hydroxylamine sulfate. Has been improved. On the other hand, it is clear that the acid inhibitors other than the present invention have poor storage stability of liquids and cannot be very substitutes for hydroxylamine. Further, when the exemplified compound (105), which is a polyhydroxy compound, is used instead of polyphosphoric acid, the appearance of the solution after one week is improved by one rank or more. Example 2 The following layers were sequentially coated on a polyethylene-coated paper support from the support side to prepare a light-sensitive material. The polyethylene coated paper has an average molecular weight of 100,
000, density 0.95 polyethylene 200 parts by weight and average molecular weight 2,
000, 6.8 wt% of anatase type titanium oxide was added to a mixture of 20 parts by weight of polyethylene having a density of 0.80, and a coating layer having a thickness of 0.035 mm was formed on the surface of the fine paper having a weight of 170 g / m ² by the extrusion coating method, The back side was provided with a coating layer of 0.040 mm thickness made of polyethylene only. After pretreatment by corona discharge on the polyethylene-coated surface of this support, each layer was sequentially coated. First layer: a blue-sensitive silver halide emulsion layer consisting of a silver halide emulsion of AgBr: AgCl = 10: 90, which contains 350 g of gelatin per mol of silver halide and has the following structure per mol of silver halide. Dye Sensitized with 2.5 × 10 ^-4 mol (using isopropyl alcohol as a solvent), dissolved in dibutyl phthalate and dispersed in 2,5-di-t-butylhydroquinone 200 mg
/ m ² and the following Y-1 as a yellow coupler in an amount of 2 × 10 ^-1 mol per mol of silver halide, and the amount of silver is 300 mg / m ² . Second layer: di-t-octylhydroquinone 300 mg / m ² dissolved and dispersed in dibutyl phthalate, and as a UV absorber 2-
(2'-hydroxy-3 ', 5'-di-t-butylphenyl) benzotriazole, 2- (2'-hydroxy-
5'-t-butylphenyl) benzotriazole, 2-
(2'-hydroxy-3'-t-butyl-5'-methylphenyl) -5-chlorobenzotriazole and 2-
200 mg / (2'-hydroxy-3 ', 5'-di-t-butylphenyl) -5-chloro-benzotriazole mixture
A gelatin layer containing m ² is coated so as to have a gelatin content of 1900 mg / m ² . Third layer: a green-sensitive silver halide emulsion layer comprising a silver halide emulsion of AgBr: AgCl = 10: 90, the emulsion containing 450 g of gelatin per mol of silver halide and having the following structure per mol of silver halide. Sensitizing dye As a magenta coupler sensitized with 2.5 × 10 ⁻⁴ mol and dissolved and dispersed in a solvent in which dibutyl phthalate and triclenylene phosphate were mixed at a ratio of 2: 1, the couplers shown in the following Table 3 were added to 1.5 mol per mol of silver halide. It contains X10 ^-1 mol and is coated so that the amount of silver will be 230 mg / m ² . In addition, 0.3 mol of 2,2,4-trimethyl-6-lauryloxy-7-t-octylchroman was contained as an antioxidant per mol of the coupler. Fourth layer: di-t-octylhydroquinone 30 mg / m ² dissolved and dispersed in dioctyl phthalate and 2 as an ultraviolet absorber
-(2'-hydroxy-3 ', 5'-di-t-butylphenyl) benzotriazole, 2- (2'-hydroxy-
5'-t-butylphenyl) benzotriazole, 2-
(2'-hydroxy-3'-t-butyl-5'-methylphenyl) -5'-chlorobenzotriazole and 2
A mixture of-(2'-hydroxy-3 ', 5'-t-butylphenyl) -5-chloro-benzotriazole (2: 1.
5: 1.5: 2) the gelatin amount in the gelatin layer containing 500 mg / m ² is applied so that the 1900 mg / m ^2. Fifth layer: a red-sensitive silver halide emulsion layer comprising a silver halide emulsion of AgBr: AgCl = 10: 90, the emulsion containing 500 g of gelatin per mol of silver halide and having the following structure per mol of silver halide. Sensitizing dye Sensitized with 2.5 × 10 ^-5 mol, dissolved in dibutyl phthalate and dispersed in 2,5-di-t-butylhydroquinone 150 mg / m ² and the following cyan coupler and C'-1 as silver halide 1 Contains 3.5 × 10 ^-1 mol per mol, silver amount 280 mg
It is coated to be / m ² . Sixth layer: The gelatin layer is coated so that the amount of gelatin is 900 mg / m ² . The silver halide emulsions used in the above-mentioned photosensitive emulsion layers (first, third and fifth layers) were prepared by the method described in JP-B-46-7772, and sodium thiosulfate pentahydrate was used for each. Chemically sensitized with 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene as a stabilizer, bis (vinylsulfonylmethyl) ether as a hardener and saponin as a coating aid. . (Compounds used in Examples) The color paper sample thus prepared was subjected to stepwise exposure and processed in the following processing steps. Processing Step (1) Color development 35 ° C. 45 seconds (2) Bleach fixing 35 ° C. 45 seconds (3) Washing with water 25 ° C. to 35 ° C. 1 minute 30 seconds The composition of the processing solution used is as follows. (Color developer) A developer according to the color developer formulation of Example 1. (Color developer
No.1,2,3,4,6,8,11,12,13,14 and 15 equivalent,
However, ferric ion, copper ion and calcium ion were not added. ) (Bleaching and fixing tank liquid) Ethylenediaminetetraacetic acid ferric ammonium dihydrate 60.0g Ethylenediaminetetraacetic acid 3.0g Ammonium thiosulfate (70% solution) 100.0ml Ammonium sulfite (40% solution) 27.5ml Ammonium water or glacial acetic acid pH5. Adjust to 50. Processing was carried out according to the processing steps (however, the antioxidant and the sulfite ion concentration in the color developing solution are as shown in Table 3), and the maximum color reflection density of the magenta dye after the processing was measured. Table 3 shows the results of determining the maximum color reflection density of the magenta dye by changing the sulfite ion concentration by setting the maximum color reflection density when the sulfite ion concentration is 0 as 100. As is clear from Table 3, when hydroxylamine sulfate is used as a preservative (antioxidant) for the color developing solution, it tends to fluctuate due to fluctuations in sulfite concentration, but it is more remarkable when the preservative of the present invention is used. It tends to fluctuate. However, by using the coupler of the present invention, the variation in the magenta dye density is improved with a smaller variation as compared with the comparative coupler. The exemplified compounds I-1, I-3, I-6, I-13, I-17,
The same experiment as above was carried out for I-18 and I-18, and the same results as I-2 and I-20 were obtained. Example 3 A multilayer color light-sensitive material sample consisting of each layer having the following composition was prepared on a cellulose triacetate film support. First layer: Antihalation layer Gelatin layer containing black colloidal silver Second layer: Intermediate layer (gelatin layer) Third layer: First red-sensitive emulsion layer Silver iodobromide (Silver iodide: 3.5 mol%, average grain size) 0.5 μm monodisperse spherical particles) Silver coating amount 0.8 g / m ² Silver iodobromide (silver iodide: 3 mol%, monodisperse spherical particles having an average particle size of 0.5 μm) Silver coating amount 0.8 g / m m ² Sensitizing dye I (below): 6 × 10 ^-5 mol per mol of silver Sensitizing dye II (below): 1.5 × 10 ^-5 mol per mol of silver Cyan coupler (below) ... 0.044 mol per mol of silver Fourth layer: second red-sensitive emulsion layer Silver iodobromide (silver iodide: 5 mol%, monodisperse spherical particles having an average particle size of 1.0 µm) ... Silver coating amount: 2.0 g / m ² Sensitizing dye I …… 3.5 × 10 ^-5 mol per 1 mol silver Sensitizing dye II …… 1.0 × 10 ^-5 mol per 1 mol silver Cyan coupler (below) …… to 1 mol silver On the other hand, 0.020 mol 5th layer: Intermediate layer 2nd layer Same sixth layer: first green-sensitive emulsion layer Silver halide emulsion (silver iodide: 4.0 mol%, average grain size 0.5 μ)
m monodisperse spherical particles) Silver coating amount 1.8 g / m ² Sensitizing dye III: 3.3 × 10 ⁻⁵ mol per 1 mol of silver Sensitizing dye IV: 1.1 × 10 per 1 mol of silver ^-5 mol Magenta coupler (Table 4) ... 12 g per 1 mol of silver 7th layer: second green-sensitive emulsion layer Silver halide emulsion (silver iodide: 5.0 mol%, average grain size 1.0 μ)
m monodisperse spherical particles) Silver coating amount 1.8 g / m ² Sensitizing dye III: 2.65 × 10 ^-5 mol sensitizing dye VI: 0.89 × 10 1 mol of silver ^-5 mol Magenta coupler (Table 4) ... 0.02 mol per mol of silver Eighth layer: yellow filter layer Gelatin layer containing yellow colloidal silver in aqueous gelatin solution. Ninth layer: First blue-sensitive low-sensitivity emulsion layer Silver iodobromide (silver iodide: 5.6 mol%, monodisperse spherical particles with an average particle size of 0.4 μm) Silver coating amount 1.5 g / m ² yellow coupler (see below) ) …… 0.25 mol per mol of silver 10th layer: second blue-sensitive emulsion layer Silver iodobromide (silver iodide: 6 mol% monodisperse spherical particles having an average particle size of 0.90 μm) …… Silver coating amount 1.21 g / m ² Yellow coupler (below) …… 0.06 mol per 1 mol of silver 11th layer: 1st protective layer Silver iodobromide (silver iodide: 1 mol% monodisperse spherical particles having an average particle size of 0.70 μm) ... Silver coating amount 0.5 g Gelatin layer containing emulsion dispersion of UV absorber 12th layer: 2nd protective layer Gelatin layer containing trimethylmethacrylate particles (diameter 1.5 μm). In addition to the above composition, a gelatin hardening agent and a surfactant were added to each layer. Sensitizing dye I: anhydro-5,5'-dichloro-3,3 '-(γ
-Sulfopropyl) -9-ethyl-thiacarbocyanine hydroxide / pyridinium salt Sensitizing dye II: anhydro-9-ethyl-3,3'-di- (γ
-Sulfopropyl) -4,5,4 ', 5'-dibenzothiacarbocyanine hydroxide triethylamine salt Sensitizing dye III: anhydro-9-ethyl-5,5'-dichloro-3,3'-di- ( (γ-sulfopropyl) oxacarbocyanine sodium salt Sensitizing dye IV: anhydro-5,6,5 ′, 6′-tetradichloro-1,1′-diethyl-3,3′-di {β- [β- (Γ-sulfopropoxy) ethoxy]} ethyl imidazolocarbocyanine hydroxide sodium salt After the light-sensitive material was exposed stepwise, it was processed by an automatic processor according to the following steps. CL-NP34 (Konishi Rokusha Kogyo Co., Ltd.) was modified and used as the automatic processor. Processing process (38 ℃) Number of tanks Processing time (1) Color development 1 tank 3 minutes 15 seconds (2) Bleach 1 tank 3 minutes 15 seconds (3) Stationary 1 tank 3 minutes 15 seconds (4) Water washing 2 minutes The composition of the color developing solution used is as follows. Potassium carbonate 30g Sodium hydrogen carbonate 2.5g Potassium sulfite 5g Sodium bromide 0.1g Potassium iodide 2mg Antioxidant (Table 4) 5.0g Sodium chloride 0.6g 4-Amino-3-methyl-N-ethyl-N- (β- Hydroxylethyl) aniline sulfate 4.8g potassium hydroxide 1.2g Add water to make 1 and adjust to pH 10.06 with potassium hydroxide or 20% sulfuric acid. The composition of the color developing replenisher used is as follows. Potassium carbonate 40 g Sodium hydrogen carbonate 3 g Potassium sulfite 7 g Sodium bromide 0.2 g Antioxidants (Table 4) 7.0 g 4-Amino-3-methyl-N-ethyl-N- (β-hydroxylethyl) aniline sulfate 6.0 g Water Potassium oxide 2g Add water to make 1 and adjust to pH 10.12 with potassium hydroxide or 20% sulfuric acid. The composition of the bleaching solution used is as follows. Ethylenediaminetetraacetic acid ammonium iron 100 g Ethylenediaminetetraacetic acid disodium 10 g Ammonium bromide 150 g Glacial acetic acid 10 mg Add water to make 1 and adjust to pH 5.8 with aqueous ammonia or glacial acetic acid. The composition of the bleaching replenisher used is as follows. Ethylenediaminetetraacetic acid ammonium iron 120g Ethylenediaminetetraacetic acid disodium 12g Ammonium bromide 178g Glacial acetic acid 21ml Add water to make 1 and adjust to pH 5.8 with ammonium water or glacial acetic acid. The composition of the fixing solution used is as follows. Ammonium thiosulfate 150g Anhydrous sodium bisulfite 12g Sodium metabisulfite 2.5g Ethylenediaminetetraacetic acid 2 sodium 0.5g Sodium carbonate 10g Add water to make 1. The composition of the stationary replenisher used is as follows. Ammonium thiosulfate 200 g Anhydrous sodium bisulfite 15 g Sodium metabisulfite 5 g Ethylenediaminetetraacetic acid disodium 0.8 g Sodium carbonate 14 g Add water to make 1. Replenishment of each replenisher is as follows: 1 m ^{2 of} light-sensitive material, 1450 ml of color developing replenisher and 925 m of bleaching replenisher.
l The bleaching bath was replenished and the fixing replenisher was replenished to the 925 ml fixing bath. A running experiment was carried out for about 20 days until a replenisher solution twice the volume of the color developing solution was replenished, and staircase exposure was performed at the start of the running process, after 10 days of running, and after 20 days of running. The sample was processed, and the maximum color transmission density of the magenta dye was measured by a densitometer PDA-65 (manufactured by Konishi Roku Photo Industry Co., Ltd.). The concentration of the photosensitive material using hydroxylamine sulfate as the antioxidant of the color developing solution and Comparative 1 as the coupler was set to 100 at the beginning of the running process, and after 10 days and 2
The concentration at each time point after 0 days is shown. In addition, the sulfite ion concentration at that time was determined by the iodine method (experiment and calculation of quantitative analysis (I
I), Kyoritsu Shuppan, Seiji Takagi, pages 420-445). The results are shown in Table 4. As is clear from Table 4, in the case where the antioxidant of the present invention was combined with the light-sensitive material using the comparative coupler as compared with the running variation when the hydroxylamine sulfate was used as the antioxidant of the color developing solution. Running fluctuation is very large. However, when a light-sensitive material using the coupler of the present invention is developed with a color developer containing the antioxidant of the present invention, running fluctuations are significantly reduced.

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Claims (1)

[Claims] Claims: 1. A silver halide color photographic light-sensitive material having at least one silver halide emulsion layer on a support is imagewise exposed, and then, with a color developer containing at least a p-phenylenediamine color developing agent. In the method for processing a silver halide color photographic light-sensitive material to be developed, the silver halide color photographic light-sensitive material is represented by the following general formula (a),
(B) or (c), except that the coupler of the chemical formula (d) is contained in at least one layer, and the color developing solution contains hydroxyamines represented by the following general formula [1]. A method of processing a silver halide color photographic light-sensitive material, comprising: General formula (a) General formula (b) General formula (c) General formula (d) (In the general formulas (a), (b) and (c), Za, Zb and
Zc represents a group of non-metal atoms necessary for forming a nitrogen-containing heterocycle. Xa, Xb and Xc each represent a hydrogen atom or a group capable of splitting off upon reaction with an oxidized product of a color developing agent. Ra, Rb, Rc, Rd, Re, Rf and Rg each represent a hydrogen atom or a substituent. However, Rg is a substituent that does not separate during the reaction between the coupler represented by formula (c) and the oxidant of the color developing agent. Y ₁ represents a carbon atom or a nitrogen atom. Y ₂ represents a carbon atom or a hetero atom. Represents that the bond between Y ₁ and Y ₂ may be a single bond or a double bond. However, when Y ₁ is a carbon atom and the bond between Y ₁ and Y ₂ is a double bond, n ₃ is 1, n ₄ is 0, and Rc is a coupler represented by the general formula (a). When Y ₁ is a carbon atom and the bond between Y ₁ and Y ₂ is a single bond, n ₃ and n ₄ are both 1 Is. When Y ₁ is a nitrogen atom and the bond between Y ₁ and Y ₂ is a double bond, n ₃ and n ₄ are both 0, Y ₂ is a hetero atom, Y ₁ is a nitrogen atom, and Y ₁
When the bond between X and Y ₂ is a single bond, n ₃ is 1 and n ₄ is 0. Incidentally, the couplers represented by the general formulas (a), (b) and (c) can be used as a color developing agent only at the position where Xa is bonded, the position where Xb is bonded and the position where Xc is bonded. Coupling reaction with oxidant. ) General formula [1] [In the formula, R ₁ and R ₂ each represent a hydrogen atom or an alkyl group which may have a substituent. However, R ₁ and R ₂ are not hydrogen atoms at the same time. ]