JPH07120026B2 - Processing method of silver halide color photographic light-sensitive material - Google Patents

Description

Detailed Description of the Invention [Industrial applications]

The present invention relates to a method of processing a silver halide color photographic light-sensitive material (hereinafter referred to as a light-sensitive material), and more specifically, a dye having excellent storage stability when stored for a long period of time after the process of washing with water is omitted. The present invention relates to a method for processing a silver halide color photographic light-sensitive material capable of forming an image.

[Prior art]

Generally, a light-sensitive material is subjected to processing steps such as color development, bleaching, fixing, stabilizing, bleach-fixing and washing after image exposure.
In such a treatment process, the depletion of water resources and the increase in cost for washing water due to an increase in crude oil prices have become more and more serious problems in recent years. Therefore, as a method of omitting the washing treatment step or reducing the amount of washing water extremely, a multi-stage countercurrent stabilization treatment technique as described in JP-A-57-8543 and JP-A-58-1
A treatment technique using a water-washing alternative treatment liquid containing a bismuth complex salt as described in Japanese Patent No. 34636 has been proposed. These technologies are technologies for reducing pollution by reducing the amount of replenishment of the stabilizing solution for washing and reducing pollution, but the photographic images obtained by applying these technologies are extremely insufficient in storage stability over time. Techniques for improving such problems have been proposed, and techniques for preventing leuco formation of cyan dyes by performing a final treatment in the presence of a soluble iron complex salt as a technique for improving fading of cyan dye images under high temperature and high humidity. JP 58-148
Known by No. 34. However, most of the actual fading of photographic images is due to light and aging, and the development of technology to prevent fading due to the effects of both light and aging is naturally desired. There is a demand for technology to prevent this.

[Object of the Invention]

Therefore, it is an object of the present invention to provide a method for processing a light-sensitive material which does not substantially use washing water and has a low energy cost and a low pollution load. Another object of the present invention is to provide a method of processing a light-sensitive material capable of forming a stable color photographic image during long-term storage without using washing water.

[Constitution of the invention]

 As a result of intensive studies, the present inventor found that the following general formula
Cyan couplers represented by [I], [II] and [III]
At least one selected from the general formulas [IV] and [V]
At least one selected from the compounds represented by
Represented by [VI], [VII], [VIII], [IX] and [X]
Containing at least one selected from the compounds
A silver halide color photographic light-sensitive material is developed after image exposure.
To do this, we use thiosulfate as a fixing agent,
After stabilization treatment by washing, the processed photosensitive material is
Thiosulfate 0.1 μg / cm²Characterized by containing more than
Depending on the processing method of the silver halide color photographic light-sensitive material
It has been found that the above object can be achieved. General formula [I]Where R and R₁One is a hydrogen atom and the other is less
Both are linear or branched alkyl groups having 2 to 12 carbon atoms,
X is a hydrogen atom or an acid of an aromatic primary amine color developing agent
Represents a group capable of leaving by a coupling reaction with a compound, R₂
Represents a ballast group. General formula (II)General formula (III)In the formula, Y is -COR_Four,‐CONHCOR_FourOr-CONHSO₂R_Four(R_FourIs an alkyl group, alk
Nyl group, cycloalkyl group, aryl group or heterocyclic group
Represents R_FiveIs a hydrogen atom, alkyl group, alkenyl group,
Represents a chloroalkyl group, an aryl group or a heterocyclic group, R_Four
And R_FiveAnd may combine with each other to form a 5- or 6-membered ring.
Yes. ), R₃Represents a ballast group, Z is a hydrogen atom or
Is a capry with oxidants of aromatic primary amine color developing agents
Represents a group capable of splitting off by ringing. General formula (IV)Where X₁Is a hydrogen atom or -OZ₁Represents Z₁Is a hydrogen atom, a sulfonyl group, an acyl group, an alkoxy group
Rubonyl group, carbamoyl group, alkyl group or alkenyl group
Represents a radical. R₆, R₇And R₈Are hydrogen atom and halogen atom
Child, cyano group, sulfo group, alkyl group, alkenyl group,
Alkoxy group, alkylthio group, aryl group, -SO₂R₉
Or −COR₉Represents R₉Is a hydroxy group, an alkyl group,
It represents a lucoxy group, an aryloxy group or an amino group. General formula [V][In the formula, R_Ten, R₁₁, R₁₂And R₁₃Are hydrogen atom and alkyl
Group, aralkyl group, aryl group, halogen atom, alcohol
Xy group, alkylthio group, alkylsulfonyl group, sulfur
E group, arylsulfonyl group, alkylsulfinyl group
Group, arylsulfinyl group, acylamino group, acylo
Xy group, carbamoyl group, alkoxycarbonyl group,
Syl group, sulfonamide group, sulfamoyl group or cal group
Represents a boxy group. ] General formula [VI]General formula (VII)General formula [VIII][In the formula, R₁₄Is a hydrogen atom, a halogen atom, an alkyl group,
It represents an aryl group or an alkoxy group. R₁₅Or R_{twenty two}Can be the same or different, each
Represents an elementary atom or an alkyl group. Y₁Is a hydrogen atom, an acyl group, an alkoxycarbonyl group,
Represents a luvamoyl group or a sulfonyl group, each of which is the same.
May also be different. l represents an integer of 1, 2 or 3 and m represents an integer of 0 to 2.
You However, l + m is 4 or less. ] General formula [IX][In the formula, R_{twenty three}Is a hydrogen atom, an alkyl group, an aryl group or
Represents a heterocyclic group, R_{twenty four}, R_{twenty five}, R₂₇And R₂₈Are hydrogen atoms,
Alkyl group, aryl group, alkoxy group or acylamido
R represents the₂₆Is an alkyl group, aryl group, phenoxy
Represents a Si group or an alkoxy group. Furthermore, R_{twenty three}And R_{twenty four}When
May be closed to form a ring. ] General formula [X][In the formula, G is a hydroxy group or its alkali-labile pre
Represents a cursor; each R₂₉Individually represents an alkyl group, an aryl group, or a nitrogen group.
Heteroatoms selected from elemental, oxygen, sulfur and selenium
Represents a heterocycle having R;₃₀, R₃₁And R₃₂Are hydrogen atom, halogen atom, and
Group, alkoxy group, aryl group or aryloxy group
Represents The present invention will be described in detail below. Stabilization treatment that substantially omits the water washing treatment step is fixed or
Direct stabilization from bleach-fix solution
In the case of continuous processing, the fixer or bleach-fixer components as described above
And a large amount of soluble silver complex salt and its decomposition products are retained in the stabilizing solution.
The long-term stability of the photographic image, mainly due to it
Deteriorates. Therefore, in order to maintain the long-term stability of color images, fixing
Solution or bleach-fix solution component or soluble silver complex salt or its decomposition product
Processing that does not remain in the photosensitive material at all, generally sufficient water
Number of tanks when washing or stabilizing treatment without washing with water
The method of increasing the amount of liquid or adding a large amount of stabilizing solution
There is. However, these methods are costly as mentioned above.
It is contrary to the purpose of reducing and reducing pollution, and
Not a good method. Therefore, stabilization of the color image
Low cost and low pollution stabilization treatment is a trade-off.
Thinking like a person in charge, a lot of research has been done.
We haven't got enough results yet. The inventors of the present invention have diligently studied to solve these two tradeoff characteristics.
As a result of our research, we found that the residual image in the processed photosensitive material
Thiosulfate, which is known to deteriorate image preservation,
Represented by the general formula [I], [II] or [III] of the present invention
Cyan coupler and a compound represented by the general formula [IV] or [V]
Selected from compounds represented by general formulas [VI] to [X]
When left in a light-sensitive material containing
Worth noting is that cyan is affected by both light and storage over time.
It was found that the fading property of the dye image is improved. Also, for the purposes of the present invention, thiosulfate is ammonium.
It is desirable that the salt is
The present invention is particularly effective when the pH of the emulsion film surface is in the range of 2.5 to 9.0.
It is effective, and the thiosulfate remaining in the processed light-sensitive material is 0.
5 μgf / cm²~ 50 μg / cm²In the range of, the effect of the present invention
The present inventors have found that
It 50 μg / cm²If it exceeds, the surface condition of the photosensitive material will be
Precipitation of crystals is observed and uneven, which is not preferable. The cyan dye-forming coupler according to the present invention has the general formula
It can be represented by [I] to [III].
[I] will be further described. In the present invention, R in the general formula [I] is₁, Charcoal represented by R
A linear or branched alkyl group having a prime number of 2 to 12 is, for example, an ethyl group.
Group, propyl group, and butyl group. In the general formula [I], R₂The ballast group represented by
The coupler is substantially expanded from the layer to which the puller is applied to other layers.
Bulky enough to keep the coupler from
It is an organic group having the size and shape given to the child.
It A typical ballast group has a total carbon number of 8 to 32
Examples thereof include an alkyl group and an aryl group, and preferably
The total carbon number is 13-28. These alkyl groups and aryls
As the substituent of the group, for example, an alkyl group, an aryl group,
Alkoxy group, allyloxy group, carboxy group, acyl
Group, ester group, hydroxy group, cyano group, nitro group,
Carbamoyl group, carbonamido group, alkylthio group,
Arylthio group, sulfonyl group, sulfonamide group, sulfur
Rufamoyl group, halogen, alkyl group
As the substituent of, the aryl group excluding the alkyl group is
The substituents mentioned above can be mentioned. Preferred as the ballast group is represented by the following general formula.
It is something.R₃₃Represents an alkyl group having 1 to 12 carbon atoms, Ar is phenyl
Represents an aryl group such as a group, and this aryl group has a substituent.
You may have. As the substituent, an alkyl group, a hydro group
Xy group, halogen atom, alkylsulfonamide group, etc.
Among them, the most preferable one is a branch such as t-butyl group.
Alkyl groups of Of the color developing agent defined by X in the general formula [I]
A group that can be split off upon coupling with an oxidant is well known to those skilled in the art.
As is known, it is common to determine the number of equivalents of a coupler.
In addition, it affects the coupling reactivity. As a typical example,
Chlorine, halogen represented by fluorine, aryloxy
Group, substituted or unsubstituted alkoxy group, acyloxy group,
Sulfonamide group, arylthio group, heteroylthio group
Group, heteroyloxy group, sulfonyloxy group, carba
A moyloxy group etc. are mentioned. As a more specific example
JP-A-50-10135, 50-120334, 50-130414
No. 54, No. 54-48237, No. 51-146828, No. 54-14736, No. 4
7-37425, 50-123341, 58-95346, Sho 48-3
6894, U.S. Pat.Nos. 3,476,563, 3,737,316 and 3,
The groups described in each publication of 227,551 are mentioned. Next, exemplified compounds of the cyan coupler represented by the general formula [I]
Examples include, but are not limited to: General Formula [I] Exemplary Compound The method for synthesizing the exemplified compound of the present invention is shown below, but other
The exemplified compounds can also be synthesized by the same method. Synthesis Example of Exemplified Compound C-5 [(1) -a] 2-Nitro-4,6-dichloro-5-e
Synthesis of tylphenol 33 g of 2-nitro-5-ethylphenol, 0.6 g of iodine and
Dissolve 1.5 g of ferric chloride in 150 ml of glacial acetic acid. 40 ℃ to this
Then, 75 ml of sulfuryl chloride is added dropwise over 3 hours. Dripping
Precipitate formed on the way was completed with the addition of sulfuryl chloride.
After that, by heating under reflux, the reaction is dissolved. Heating reflux
Takes about 2 hours. Crystals formed by pouring the reaction solution into water
Is purified by recrystallization with methanol. (1) -a confirmation
Was performed by nuclear magnetic resonance spectrum and elemental analysis. [(1) -b] 2-Nitro-4,6-dichloro-5-d
Synthesis of tylphenol 21.2 g of the compound [(1) -a] was dissolved in 300 ml of alcohol.
Dissolve it, add a catalytic amount of Raney nickel to it, and
Hydrogen was passed through until there was no more hydrogen absorption. After the reaction
The ice ax was removed and the alcohol was distilled off under reduced pressure. Residue
[(1) -b] of the above is subjected to the next acylation without purification.
It was. [(1) -c] 2 [(2,4-di-tert-acylpheno
Xy) acetamide] -4,6-dichloro-5-ethylphenyl
Synthesis of the enol [1 (1) -b] The crude amino compound 18.5 g obtained in [500 ml]
Dissolved in a mixed solution of glacial acetic acid and 16.7 g of sodium acetate,
To this was added 2,4-di-tert-aminophenoxyacetic acid chloride 2
Add acetic acid solution prepared by dissolving 8.0 g in 50 ml of acetic acid at room temperature.
It Add dropwise over 30 minutes, stir for another 30 minutes, and then place the reaction mixture in ice water.
inject. The precipitate formed is collected by filtration, dried, and washed with acetonitrile.
The desired product can be obtained by recrystallizing twice. Definite target
It was confirmed by elemental analysis and nuclear magnetic resonance spectrum.Next, the general formula [II] or [III] used in the present invention
The cyan coupler represented by will be described. The general
In formulas [II] and [III], Y is -COR_Four,‐CONHCOR_FourOr-CONHSO₂R_FourIs a group represented by. This
Here, R_FourIs an alkyl group, preferably an alkyl group having 1 to 20 carbon atoms.
Kill group (eg methyl, ethyl, t-butyl, dodecyl
Etc.), an alkenyl group, preferably an alkenyl having 2 to 20 carbon atoms.
Group (eg allyl group, heptecenyl group, etc.), cyclo
Alkyl groups, preferably of 5 to 7 membered rings (eg cyclo
Hexyl), aryl groups (eg phenyl group, tolyl)
Group, naphthyl group, etc.), heterocyclic group, preferably nitrogen atom
5 members containing 1 to 4 children, oxygen atoms or sulfur atoms
6-membered heterocyclic group (eg, furyl group, thienyl group,
And an azothiazolyl group). R_FiveIs a hydrogen atom or R_Four
Represents a group represented by. R_FourAnd R_FiveIs bound to each other and nitrogen source
A 5- to 6-membered heterocycle containing a child may be formed. Na
Oh, R_FourAnd R_FiveAny substituent can be introduced into
For example, an alkyl group having 1 to 10 carbon atoms (eg ethyl, i-propyl
Ropyr, i-butyl, t-butyl, t-octyl, etc.), Ally
Group (eg phenyl, naphthyl, etc.), halogen atom
(Fluorine, chlorine, bromine, etc.), cyano, nitro, sulfone
Amide groups (eg methanesulfonamide, butanesulfone)
Amide, p-toluenesulfonamide, etc.), sulfa
Moyl group (eg methylsulfamoyl, phenylsulfate
Famoyl, etc.), sulfonyl groups (eg methanesulphonyl)
, P-toluenesulfonyl, etc.), fluorosulfoni
Group, a carbamoyl group (eg dimethylcarbamoyl, fluorine
Phenylcarbamoyl etc.), oxycarbonyl group (eg
Ethoxycarbonyl, phenoxycarbonyl, etc.), reed
Group (eg acetyl, benzoyl etc.), heterocyclic group
(Eg pyridyl group, pyrazolyl group etc.), alkoxy
Groups, aryloxy groups, acyloxy groups, etc.
You can In the general formulas [II] and [III], R₃Is the general formula [I
Cyan couplers represented by I] and [III] and the cyan couplers
Diffusion resistance to cyan dye formed from uncoupler
Represents a ballast group required to give. Preferably carbon number
4-30 alkyl, aryl or heterocyclic groups
It For example, a linear or branched alkyl group (eg t-butyl
Le, n-octyl, t-octyl, n-dodecyl, etc.), alk
Nyl group, cycloalkyl group, 5-membered or 6-membered ring hetero
A ring group etc. are mentioned. In the general formulas [II] and [III], Z is a hydrogen atom or
During the coupling reaction with the oxidation product of the color developing agent
Represents a releasable group. For example, a halogen atom (eg salt
Elemental, bromine, fluorine, etc.), substituted or unsubstituted alkoxy
Group, aryloxy group, heterocyclic oxy group, acyloxy group
Si group, carbamoyloxy group, sulfonyloxy group, a
Rukylthio group, arylthio group, heterocyclic thio group, sulphyl group
Examples include honamide group, and more concrete examples
U.S. Pat.No. 3,741,563, JP-A-47-37425, JP-B-48-36
894, JP-A-50-10135, 50-117422, 50-13044
1, No. 51-108841, No. 50-120343, No. 52-18315,
53-105226, 54-14736, 54-48237, 55-32
071, 55-65957, 56-1938, 56-12643,
56-27147, 59-146050, 59-166956, 60-245
No. 47, No. 60-35731, No. 60-37557
Some of them are listed. In the present invention, the following general formula [XI], [XII] or [X
Cyan couplers represented by III] are more preferable. General formula (XI)General formula (XII)General formula (XIII)In the general formula [XI], R₃₄Is a substituted or unsubstituted aryl
A group (particularly preferably a phenyl group). The aryl group
When has a substituent, the substituent is -SO₂R₃₇, Ha
Rogen atom (eg fluorine, bromine, chlorine etc.), -CH₃,
‐NO₂, -CN, -COR₃₇, -COOR₃₇, -SO₂OR₃₇, At least one substituent selected from is included. Where R₃₇Is an alkyl group, preferably having 1 to 20 carbon atoms
Alkyl groups (eg methyl, ethyl, tert-butyl,
Each group such as decyl), an alkenyl group, preferably having 2 carbon atoms
~ 20 alkenyl groups (eg allyl group, heptadecenyl
Groups), cycloalkyl groups, preferably 5- to 7-membered ring groups
(Eg cyclohexyl group), aryl group (eg
Phenyl group, tolyl group, naphthyl group, etc.), R₃₈Is water
Elementary atom or R₃₇Is a group represented by. Of the phenolic cyan coupler represented by the general formula [XI]
Suitable compounds are R₃₇Is a substituted or unsubstituted phenyl group
And cyano, nitro as a substituent to the phenyl group,
‐SO₂R₃₉(R₃₉Is an alkyl group), halogen atom, trif
A compound such as luoromethyl. In the general formulas [XII] and [XIII], R₃₅, R₃₆Is al
A kill group, preferably an alkyl group having 1 to 20 carbon atoms (for example,
Methyl, ethyl, tert-butyl, dodecyl etc.), alke
Nyl group, preferably alkenyl group having 2 to 20 carbon atoms (eg,
Allyl, oleyl, etc.), cycloalkyl groups, preferably
Is a 5- to 7-membered ring group (eg cyclohexyl), aryl
Groups (eg phenyl, tolyl, naphthyl, etc.),
Telocyclic group (nitrogen atom, oxygen atom, or sulfur atom
5- to 6-membered heterocycles containing 1 to 4 are preferred, for example
Examples include furyl group, thienyl group, and benzothiazolyl group.
Is represented). The R₃₇, R₃₈And R in the general formulas [XII] and [XIII]₃₅,
R₃₆Can be further introduced any substituent,
Specifically, in the general formulas [II] and [III], R_FourWell
Or R_FiveCan be introduced into So
As a substituent, a halogen atom (chlorine atom, fluorine
Fluorine atoms, etc.) are preferred. Z and R in the general formulas [XI], [XII] and [XIII]
₃Have the same meanings as in general formulas [II] and [III], respectively.
ing. R₃Preferred examples of the ballast group represented by
It is a group represented by the general formula [XIV]. General formula (XIV)In the formula, J represents an oxygen atom, a sulfur atom or a sulfonyl group.
, K represents an integer of 0 to 4, l represents 0 or 1, and
If K is 2 or more, there are 2 or more R₄₁Are the same but different
R may₄₀Is a straight or branched chain having 1 to 20 carbon atoms
And a substituted alkylene group such as aryl group,
R₄₁Represents a monovalent group, preferably a hydrogen atom or halogen
Atoms (eg chromium, bromine), alkyl groups, preferably
Is a linear or branched alkyl group having 1 to 20 carbon atoms (for example,
Methyl, t-butyl, t-pentyl, t-octyl, dodeci
Radicals, pentadecyl, benzyl, phenethyl, etc.),
Aryl group (eg phenyl group), heterocyclic group (preferably
Is a nitrogen-containing heterocyclic group), an alkoxy group, preferably a straight chain
Or a branched alkoxy group having 1 to 20 carbon atoms (for example, meth
Xy, ethoxy, t-butyloxy, octyloxy, de
Each group such as siloxy, dodecyloxy, etc.), mariruoki
Si group (eg phenoxy group), hydroxy, acyloxy
Si group, preferably alkylcarbonyloxy group, aryl
Lecarbonyloxy group (eg acetoxy group, benzoyl group
Luoxy group), carboxy, alkyloxycarbonyl
A group, preferably a straight-chain or branched alkyl group having 1 to 20 carbon atoms.
Luoxycarbonyl group, aryloxycarbonyl group,
Phenoxycarbonyl, an alkylthio group, preferably
Preferably, it has 1 to 20 carbon atoms, an acyl group, preferably 1 carbon atom.
~ 20 linear or branched alkylcarbonyl groups, acyl
An amino group, preferably a straight or branched chain having 1 to 20 carbon atoms
Alkyl carboxamide, benzene carboxamide, sulfo
Amide group, preferably linear or branched having 1 to 20 carbon atoms
Alkylsulfonamide group or benzenesulfonamido
Group, carbamoyl group, preferably straight chain having 1 to 20 carbon atoms
Or branched alkylaminocarbonyl group or phenyl
Aminocarbonyl group, sulfamoyl group, preferably charcoal
Linear or branched alkylamino sulphonyl having a prime number of 1 to 20
Group or phenylaminosulfonyl group. Next, a cyan coupler represented by the general formula [II] or [III]
Examples of specific compounds are shown below, but are not limited to these.
Yes. [Compound example] These cyan couplers are synthesized by a known method.
For example, U.S. Patents 2,772,162 and 3,758,308
No. 3, No. 3,880,661, No. 4,124,396, No. 3,222,176,
British Patents 975,773, 8,011,693, 8,011,694,
JP-A-47-21139, 50-112038, 55-163537,
56-29235, 55-99341, 56-116030, 52-6932
No. 9, 56-55945, 56-80045, 50-134644, average
And British patent 1,011,940, U.S. patent 3,446,622, and 3,
996,253, JP-A-56-65134, 57-204543, 57-2
04544, 57-204545, Japanese Patent Application No. 56-131312, 56-13
1313, 56-131314, 56-131309, 56-131311
Nos. 57-149791, 56-130459, and JP-A-59-146050.
Issue 166956, Issue 60-24547, Issue 60-35731, Issue 60-3
It can be synthesized by the synthesis method described in 7557, etc.
It In the present invention, a compound represented by the general formula [I], [II] or [III]
The cyan coupler used is within the range not deviating from the object of the present invention.
In combination with a conventionally known cyan coupler,
Can be In addition, general formulas [I], [II] and
The cyan coupler [III] can also be used in combination. The cyan represented by the general formulas [I] to [III] according to the present invention
When the coupler is contained in the silver halide emulsion layer,
Usually about 0.005 to 2 mol per mol of silver halide, preferably
It is preferably used in the range of 0.01 to 1 mol. Next, general formulas [IV] and [V] will be described in detail. In the general formula [IV], X₁Is a hydrogen atom or -OZ₁Base
Represent Z₁Is a hydrogen atom, an acyl group (eg acetyl, propionyl
, Stearoyl, benzoyl, etc.), alkoxycar
Bonyl group (eg methoxycarbonyl, ethoxycarbo
(Nyl, phenoxycarbonyl, etc.), carbamoyl group
(For example, N, N-dimethylcarbamoyl, N, N-diethylcarb
Luvamoyl etc.), sulfonyl groups (eg methanesulfo)
Nyl, benzenesulfonyl, etc.), alkyl groups (carbon number
1-20, such as methyl, ethyl, dodecyl, beta
Or alkenyl group (with 2 to 20 carbon atoms)
So, for example, allyl, butenyl, methallyl, etc.)
Which may be the same or different. R₆, R₇And R₈Are a hydrogen atom and a halogen atom (for example,
(Fluorine, chlorine, bromine, iodine, etc.), cyano group, -SO₂R
₄₂, -COR₄₂Or the substituted or unsubstituted
Kill group (having 1 to 20 carbon atoms such as methyl, ethyl,
Hexyl, dodecyl, pentadecyl, octadecyl, t
-Butyl, t-octyl, benzyl, etc.), alkenyl
A group (having 2 to 30 carbon atoms, such as allyl or butenyl
), Alkoxy groups (eg methoxy, butkin, hex
(Sadecyloxy, benzyloxy, etc.), alkylthio
Groups (eg methylthio, octylthio, hexadecylti
O, benzylthio, etc.) or an aryl group (eg,
Phenyl). Where R₄₂Is a hydroxy group or
Is an unsubstituted alkyl group (having 1 to 30 carbon atoms, such as
Methyl, octyl, dodecyl, hexadecyl, octade
Silyl), an alkoxy group (eg methoxy, butyro)
Xy, octyloxy, dodecyloxy, hexadecyl
Oxy, octadecyloxy, etc.), aryloxy groups
(Eg phenoxy, naphthyloxy etc.), vinyl
Groups or amino groups (eg ethylamino, propyl
Amino, dodecylamino, hexadecylamino, octa
Decylamino, benzylamino, anilino, etc.)
You Each of the groups described above may have an appropriate substituent,
Examples of the substituent of are, for example, an alkoxy group and an aryl group.
Si group, hydroxy group, alkoxycarbonyl group, aryl
Ruloxycarbonyl group, halogen atom, carboxy group,
Sulfo group, cyano group, alkyl group, alkenyl group, ant
Group, alkylamino group, arylamino group, carba
Moyl group, alkylcarbamoyl group, arylcarbamo
Yl, acyl, sulfonyl, acyloxy and other groups
Is an acylamino group. Specific examples of the compound of the general formula [IV] are shown below.
It is not limited to these. R in the general formula [V]_Ten, R₁₁, R₁₂And R₁₃Is the same
May be different and have hydrogen atoms, straight or branched chains
An alkyl group having 1 to 30 carbon atoms (eg, methyl group, ethyl group)
Group, isopropyl group, octyl group, dodecyl group, benta
Decyl group, octadecyl group), aralkyl having 7 to 30 carbon atoms
Group (eg benzyl group), aryl having 6 to 20 carbon atoms
Groups, (eg phenyl groups), halogen atoms (eg salts
Element, bromine, fluorine, iodine), alkoxy group (eg metho
Xy, ethoxy, methoxyethoxy, octyloxy
Si group, dodecyloxy group), alkylthio group (eg methyl
Ruthio group, butylthio group, dodecylthio group, hexadecyl
Ruthio group, octanodecylthio group), alkylsulfoni
Group (eg methylsulfonyl group, dodecylsulfonyl group
Groups), sulfo groups, arylsulfonyl groups (eg phenyl groups)
Rusulfonyl group, 4-dodecylphenylsulfonyl
Groups), alkylsulfenyl groups (eg methylsulfi
Nyl group, octadecylsulfinyl group), arylsul
Finyl group (eg phenylsulfinyl group), acyl
Amino group (eg, acetylamino group, hexanamide
Group dodecane amide group, octadecane amide group, benzua
Amide group), acyloxy group (eg acetoxy, dodecyl
Xy, octadecyloxy), carbamoyl groups (eg N
-Methylcarbamoyl, N- (2-ethylhexyl),
Carbamoyl, N-hexadecylcarbamoyl, N-fu
(Alkenylcarbamoyl), alkoxycarbonyl group (eg
For example, ethoxycarbonyl, isostearyloxykaneboni
, Hexadecylcarbonyl), an acyl group (eg
Chill, Octanoyl, Dodecanoyl, Octadecanoy
, Benzoyl), sulfonamide groups (eg methans
Lefonamide, dodecanesulfonamide, benzenesul
Phonamide, 4-dodecylbenzenesulfonamide),
Sulfamoyl group (eg sulfamoyl, methylsulfate
Famoyl, 2-ethylhexyl sulfamoyl, dode
Silsulfamoyl, Hexadecylsulfamoyl, F
Phenylsulfamoyl), which represents a carboxy group. Specific examples of the compound represented by the general formula [V] are shown below.
Are not limited to these. The compound represented by the general formula [IV] or [V] is water-soluble
Those that are not soluble in water are non-emulsifiable.
It is added to the milk layer and / or the emulsion layer. Addition amount is 1 × 10^-Five~
5 x u 10^-3mol / m²And preferably 1.0 × 10^-Four~ 1.3 ×
Ten^-3mol / m²Is. The light-sensitive material of the present invention has the following general formula [VI] to
It is preferable to contain the compound represented by [X]. In the general formulas [VI] to [VIII], R₁₄Is a hydrogen atom,
Rogen atoms (such as fluorine, chlorine, bromine, and iodine groups)
Etc.) or a substituted or unsubstituted alkyl group, respectively
(C1-C20, such as methyl, ethyl, benzene
Dil), aryl groups (eg phenyl), or ar
Coxy group (eg methoxy, ethoxy, benzyloxy
Etc.). R₁₅Or R_{twenty two}Can be the same or different and
Child, substituted or unsubstituted alkyl group (having 1 to 20 carbon atoms)
Such as methyl, ethyl, dothesyl, octa
Decyl) etc. Y₁Is a hydrogen atom, an acyl group (eg, acetyl, stearloy)
, Benzoyl, chloroacetyl, etc.), alkoxyca
Rubonyl group (eg methoxycarbonyl, ethoxycarl
Carbonyl, phenoxycarbonyl, etc.), carbamoyl group
(For example, N, N-dimethylcarbamoyl, N, N-dimethylcarb
Such as vamoyl) or a sulfonyl group (eg methans)
And the same for each.
But it can be different. l is an integer of 1, 2 or 3 and m is an integer of 0 to 2
Represent However, l + m is 4 or less. Each of the above groups may have an appropriate substituent,
The substituent is the same as the substituent described in the general formula [IV].
The same thing can be mentioned. The compounds of the general formulas [VI] to [VIII] are exemplified below. General formula [IX]However, R_{twenty three}Is a hydrogen atom, an alkyl group, an aryl group or
Represents a heterocyclic group, R_{twenty four}, R_{twenty five}, R₂₇And R₂₈Is a hydrogen atom, al
Kill group, aryl group, alkoxy group or acylamino
Represents a group, R₂₆Is an alkyl group, aryl group, phenoxy
Represents a group or an alkoxy group. Furthermore, R_{twenty three}And R_{twenty four}When
May be closed to form a methylenedioxy ring. These compounds are described in U.S. Patent Nos. 3,935,016 and 3,983.
No. 2,944, No. 4,254,216, JP-A-55-21004.
Japanese Patent Laid-Open No. 54-145530, British Patent Publication No. 2,077,455,
2,062,888 specification, U.S. Pat.Nos. 3,764,337 and 3,432,
No. 300, No. 3,574,627, No. 3,573,050
52-152225, 53-20327, 53-17729, 55-
6321 gazette, British patent 1,347,556, British patent publication
No. 2,066,975, Japanese Patent Publication No. 54-12337, No. 45-31625
Compounds described in the official gazette and U.S. Pat.No. 3,700,455
Including things. Specific examples of the compound of the general formula [IX] are as follows. General formula [X]In the above formula, G is a hydroxy group or its alkali
Unstable precursor; each R₂₉Individually, Archi
Group (preferably having 1 to 30 carbon atoms), aryl group (preferably
C6-30) or nitrogen, oxygen, sulfur and selenium
Heterocyclic group having one or more heteroatoms selected from
(Preferably having 5 to 30 carbon atoms); R₃₀, R₃₁And R₃₂
Are each preferably a hydrogen atom, a halogen atom or an alkyl group.
Is a C1-30), alkoxy group (preferably a C1
~ 30), aryl groups (preferably 6-30) or aryl
It is a ruoxy group (preferably having 6 to 30 carbon atoms). The compound represented by the general formula [X] does not spread in the layer of the light-sensitive material.
Those with sufficient bulk to be dispersible are preferred.
Yes. Preferably R₃₁Is alkyl having 1 to 4 carbons or carbon
R is an alkoxy of the numbers 1 to 4.₃₀And R₃₂Is a hydrogen atom
Is. As described above, G is a hydroxy group or a hydroxy group
This is an alkaline unstable precursor. Alkaline instability
In the precursor, the hydrogen atom of the hydroxy group is chlorine
It is replaced by a blocking group which is removed on contact with.
Typical nablocking groups are hydrolytic or intermolecular nucleophiles
It can be removed by sex replacement. Removed by hydrolysis
Typical groups that can be removed are acyl groups such as aliphatic and
And aromatic carbonyl and sulfonyl groups. Intermolecular
Typical groups that can be removed by nucleophilic substitution are US Pat.
No. 310,612. The aforementioned alkyl, alkoxy, aryl and aryl
The ruoxy substituent can be further substituted. That's it
Representative of such substituents are halogen, nitro, and alkyl.
Ru, aryl, alkenyl, alkoxy, aryloxy
Si, alkenyloxy, heterocyclyl, alkylcarb
Rubonyl, arylcarbonyl, alkenylcarboni
Ru, alkylsulfonyl, arylsulfonyl, alk
Lesulfonyl, amino, aminocarbonyl, aminosul
Fonyl, carboxy, alkoxycarbonyl, aryl
Oxycarbonyl and alkenyloxycarbonyl
Can be mentioned. Thus, alkyl is, for example, aryl
Including alkyl and aryloxyalkyl,
Are, for example, alkaryl and alkoxyaryl.
And alkenyl is, for example, aralkenyl.
Includes. As the amine moiety of these additional substituents,
Includes primary, secondary and tertiary amines and acylated amines.
You can Specific examples of the compound of the general formula [X] are shown below. The formulas [VI] to [X] used in the present invention are represented by
The water-soluble compounds are difficult to dissolve in water.
Soluble substances are added as emulsions to the non-milk layer and / or emulsion layer
To do. Addition amount is 1 × 10^-Five~ 5 x 10^-3mol / m²And is preferred
1.0 × 10^-Four~ 1.3 × 10mol / m²Is. The pH of the emulsion film surface of the processed light-sensitive material in the present invention is 2.5.
It is preferably in the range of to 9.0, particularly preferably 3.2
It should be in the range of ~ 6.2. PH adjustment of this emulsion film surface
For this reason, the stabilizer should not contain various alkaline agents or acid agents.
One can also be used. What is the pH of the emulsion film surface above in the dye-containing layer of the light-sensitive material?
Of hydrogen ion molar concentration in the swollen state with pure water
The common logarithm of the reciprocal, which is the usual pH measurement method for measuring the pH.
The reference electrode is a calomel electrode with a glass electrode
To measure. Measure the lowest surface coating pH with pure water
Therefore, a flat type composite single electrode is generally used. For incorporating the thiosulfate of the present invention into a processed light-sensitive material
Was added to the solution containing thiosulfate at the end of processing.
It is contained by dipping the material, or as a fixing agent
Thiosulfate is used in the fixing solution and the
In the fixer, the stabilization treatment is performed without washing.
There is a method of leaving the above thiosulfate in the light-sensitive material. Book
In the present invention, thiosulfate is used as the fixing agent to stabilize the washing alternative.
It is preferable to leave it in the light-sensitive material by processing.
Good Thiosulfates include sodium, potassium and quaternary ammonium salts.
In the present invention, cation species are included.
The type is not particularly limited, but ammonium salts are preferable.
It In the present invention, thiosulfate contained in the processed light-sensitive material
The amount of salt is 0.1 μg / cm²And preferably 0.2 μg / cm²~Ten
0 μg / cm²Is most preferably 0.5.
μg / cm²~ 50 μg / cm²It is in the range of. The amount of thiosulfate contained in the processed light-sensitive material
For measurement, ANSI pH4.8 (1978) or P.S.E.10 (2) 86
Using the methylene blue method described in (1966)
it can. In the present invention, after color development, a processing solution having fixing ability is used.
Processing means photosensitive material after processing with a normal color developer.
Of fixing bath or bleach-fixing bath for the purpose of fixing the dye
It refers to the process of using. Details of the color developer, fixer and bleach-fixer
Will be described later. In the present invention, treatment with a treatment liquid having fixing ability
Subsequent treatment with a stabilizing solution instead of washing with water
When fixing, wash directly with the fixing bath or bleach-fixing bath.
This indicates that processing is performed with an alternative stable number.
The process is based on the conventionally known fixing bath or bleach-fixing bath.
After that, it is completely different from the process of washing with water and treating with a stabilizing solution
ing. As described above, in the present invention, treatment with a stabilizing solution as a substitute for washing with water
Is a stabilization treatment immediately after treatment with a treatment solution having fixing ability.
Of stabilization treatment that does not actually wash with water.
The treatment liquid used for the stabilization treatment is washed with water.
The alternative stabilizing solution is called the stabilizing bath or stabilizing bath. An antifungal agent may be contained in the stabilizing solution for washing with water of the present invention.
preferable. Preferably used antifungal agent is hydroxy
Benzoic acid compounds, alkylphenol compounds, thia
Zol compounds, pyridine compounds, guanidine compounds
Compounds, carbamate compounds, morpholine compounds, quaternary
Phosphonium compounds, ammonium compounds, urea compounds
Compounds, isoxazole compounds, propanolamine
Compounds, sulfamide derivatives and amino acid compounds
is there. The hydroxybenzoic acid compound is hydroxybenzoic acid.
Methyl as an ester compound of acid and hydroxybenzoic acid
Luster. Ethyl ester, propyl ester, buty
And the like, but preferably hydroxybenzoic acid
N-butyl ester, isobutyl ester, propyl ether
Steal, more preferably the hydroxybenzoic acid
It is a mixture of three esters. Alkylphenol compounds have an alkyl group of C1-6
A compound that has an alkyl group as a substituent.
The preferred phenolic compound is orthophenylpheno
And orthocyclohexylphenol. A thiazole-based compound has a nitrogen atom and sulfur atom in the five-membered ring.
A compound having a child, preferably 1,2-benzisothiazole
Azolin-3-one, 2-methyl-4-isothiazoline 3
-One, 2-octyl-4-isothiazolin-3-one,
5-chloro-2-methyl-4isothiazolin-3-one,
2- (4-thiazolyl) benzimidazole. Pi
Specific examples of lysine compounds include 2,6-dimethylpyridyl
1,2,4,6-trimethylpyridine, sodium-2-pyriline
Zinthiol-1-oxide, etc., but preferably
Sodium-2-pyridinethiol-1-oxad
It The guanidine compounds are specifically cyclohexidine and
Lihexamethylene biguanidine hydrochloride, dothesyl guani
Gin hydrochloride, etc., preferably dodecylguanidine
And its salts. Carbamate compounds are specifically methyl-1- (petit
Lucabamoyl) -2-benzimidazole carbamay
And methyl imidazole carbamate. The morpholine compound is specifically 4- (2-nitroptyi)
Le) morpholine, 4- (3-nitroptyl) morpholine
Etc. Quaternary phosphonium compounds are tetraalkylphosphonium
There are various salts, such as tetra-alkoxyphosphonium salt, but
More preferably, it is a tetraalkylphosphonium salt.
Physically preferred compound is tri-n-butyl-tetradecyl
Phosphonium chloride and tri-phenyl nitrof
It is a phenylphosphonium chloride. The quaternary ammonium compound is specifically benzalkonium
Salt, benzethonium salt, tetraalkylammonium
There are salts and alkylpyridinium salts.
Decyldimethylbenzyl ammonium chloride, dide
Syldimethylammonium chloride, lauryl pyridi
There are, for example, nickel chloride. The urea compound is specifically N- (3,4-dichloroenene
) -N '-(4-chlorophenyl) urea. The isoxazole compound is specifically 3-hydroxy-5-
Examples include methyl-isoxazole. Propanolamine-based compounds are the same as n-propanols.
There are so-propanols, specifically DL-2-benzyl alcohol.
Mino-1-propanol, 3-diethylamino-1-propano
2-dimethylamino-2-methyl-1-propanol,
3-amino-1-propanol, idbropropanolamine,
Diisobropanolamine, NN-dimethyl-isobropa
There are nolamine and the like. The sulfamide derivative is specifically fluorinated sulfamide.
De, 4-chloro-3,5-dinitrobenzenesulfamide, su
Rufanilamide, acetosulfamine, sulfapili
Gin, sulfaguanidine, sulfathiazole, sul
Fadiazine, sulfamelazine, sulfamethazine,
Sulfoisoxazole, homosulfamine, sulf
Isomidine, sulfaguanidine, sulfamethizole
Le, sulfapyrazine, phthalisosulfathiazo
And succinyl sulfathiazole. Amino compounds are specifically N-lauryl-β-alanine
There is. Among the above antifungal agents, the antifungal agent is preferably used in the present invention.
Compounds are pyridine compounds and guanidine compounds.
Substance, a quaternary ammonium compound. The addition amount of the antifungal agent to the washing alternative treatment liquid is 1
It is used in the range of 0.002 g to 50 g, preferably 0.0
Used in the range of 05g-10g. Desired to be added to the stabilizing solution as a substitute for washing used in the present invention
An example of the compound is an ammonium compound. These are the ammonium salts of various inorganic and organic compounds.
Supplied, but specifically ammonium hydroxide, bromide
Ammonium, ammonium carbonate, ammonium chloride,
Ammonium hypophosphite, ammonium phosphate, phosphorus
Ammonium acid, ammonium fluoride, acid fluoride
Monium, ammonium fluoroborate, ammonium arsenate
Um, ammonium hydrogen carbonate, ammonium hydrogen fluoride
System, ammonium hydrogen sulfate, ammonium sulfate, iodide
Ammonium, Ammonium nitrate, Ammonium pentaborate
System, ammonium acetate, ammonium adipate, lau
Ammonium phosphotricarboxylate, Ammonium benzoate
, Ammonium carbamate, ammonium citrate
System, ammonium diethyldithiocarbamate, formic acid
Ammonia, ammonium hydrogen malate, hydrogen oxalate
Ammonium, ammonium hydrogen phthalate, hydrogen tartrate
Ammonium, ammonium thiosulfate, ammonium sulfite
Um, Ammonium ethylenediaminetetraacetate, 1-Hydride
Roxyethylidene-1.1-ammonium diphosphonate,
Ammonium lactate, ammonium malate, maleic acid
Ammonium, ammonium oxalate, ammonium phthalate
Ni, ammonium picrate, pyrrolidine dithioca
Ammonium lumbamate, ammonium salicylate, co
Ammonium succinate, ammonium sulfanilate, liquor
Ammonium tartrate, ammonium thioglycolate, 2,
4,6, -trinitrophenol ammonium and the like.
These may be used alone or in combination of two or more. The amount of ammonium compound added is 0.00 per stabilizer.
It is in the range of 1 mol to 1.0 mol, preferably 0.002 to 0.2.
It is in the molar range. The pH of the stabilizing solution for washing with water in the present invention is more effective in the present invention.
In order to achieve the goal, preferably in the range of 2.5-12.0
Yes, more preferably in the range of pH 4.0 to 10.0, especially
The pH is preferably in the range of 4.0 to 9.0. An organic acid salt (quencher
Acid, acetic acid, succinic acid, oxalic acid, benzoic acid, etc.), pH adjustment
Agent (phosphate, borate, hydrochloric acid, sulfate, etc.), optical brightening
Agent, polyvinylpyrrolidone, polyethylene glycol,
Activator, hardener, or metal chelating agent, surface active
Agents, preservatives, metal salts such as Bi, Mg, Zn, Ni, Al, Sn, Ti, Zr
Can be added. The amount of these compounds added is
An alternative to washing with light, which is necessary and maintained to maintain the pH of the stabilizing bath.
Stability during storage of color photographic images and adverse effects on precipitation
How to use a combination of amounts that do not affect the sound
But it doesn't matter. Time, amount of replenishment, and temperature in treatment with stabilizing solution as a substitute for washing with water
Does not prevent thiosulfate residue from remaining on the light-sensitive material
Is important, and the time is generally in the range of 10 seconds to 5 minutes.
The replenishment rate is 10 ml / m²~ 2l / m²And the temperature is 5 ℃
It is in the range of 50 ° C. In the present invention, when the number of stabilizing tanks is 1 to 5, the effect of the present invention
Fruits are large, especially 1 to 3 tanks, at most
It is preferably 9 tanks or less. That is, the amount of replenisher is the same
If so, the more tanks there are, the more thiosulfuric acid in the final stabilizing bath will be.
Since the acid concentration becomes low, the effect of the present invention becomes weak. The light-sensitive material to which the method of the present invention is applied has a halogen on a support.
Coated with a silver halide emulsion layer and a non-photosensitive layer (non-emulsion layer)
The silver halide emulsions are silver chloride and bromide.
Silver, silver iodide, silver chlorobromide, silver chloroiodide, silver iodobromide, silver chloroiodobromide
Whichever silver halide is used
Yes. . These emulsion layers and non-photosensitive layers are used in the photographic industry.
Do not include any known couplers and additives.
And, for example, yellow dye forming couplers, magen
Dye forming coupler, cyan dye forming coupler, stable
Agents, sensitizing dyes, gold compounds, high boiling organic solvents, fog prevention
Agent, dye image fading prevention agent, color stain prevention agent, optical brightener,
Antistatic agents, hardeners, surfactants, plasticizers, wetting agents and
And an ultraviolet absorber and the like can be appropriately contained. The light-sensitive material to which the method of the present invention is applied may be
An emulsion layer containing various photographic additives as described above and
And each non-photosensitive layer, etc., corona discharge treatment, flame
On a support that has been treated or treated with UV irradiation, or
By coating on a support through an undercoat layer and an intermediate layer,
Manufactured. As the support used advantageously, for example,
Bavaria paper, polyethylene coated paper, polypropylene compound
Transparent paper, glass plate, cellulos used together with synthetic paper and reflector
Acetate, cellulose nitrate or poly
Polyethylene film such as ethylene terephthalate, poly
Amide film, Polycarbonate film, Polystyrene
Ren film etc. Most of the silver halide emulsion layer and the non-light-sensitive layer are transparent.
Normally, it is a hydrophilic colloid layer containing a hydrophilic binder.
ing. As the hydrophilic binder, gelatin,
Or acylated gelatin, guanidylated gelatin, flux
Phenylcarbamylated gelatin, phthalated gelatin, shea
Zera such as noethanol gelatin and esterified gelatin
A tin derivative is preferably used. As a hardening agent for hardening this hydrophilic colloid layer
Is, for example, chromium salt (chromium alum, chromium acetate,
Th), aldehydes (formaldehyde, glyoxer)
Compound, glutaraldehyde, etc.), N-methylol compound
Thing (dimethylol urea, methylol dimethyl hydantoy
Dioxane derivative (2,3-dihydroxydio
Active vinyl compounds (1,3,5-triacryl)
Royl-hexahydro-s-triazine, 1,3-vinyl
Sulfonyl-2-propanol, etc.), active halogenation
Compound (2,4-dichloro-6-hydroxy-s-triazi
), Mucohalogenates (mucochloric acid, mucofe
(Noxic acid, etc.), etc., alone or in combination
Used. In the present invention, the light-sensitive material uses a coupler as a high-boiling organic solvent.
So-called oil pro that contains the dispersed ones
This is especially effective in the case of tect type. This high boiling organic
As a solvent, organic acid amides, carbamates, ester
, Ketones, urea derivatives, especially dimethylphthale
, Ethyl phthalate, di-propyl phthalate,
Di-butyl phthalate, di-n-octyl phthalate,
Diisooctyl phthalate, diamyl phthalate, dino
Phthales such as nyl phthalate and diisodecyl phthalate
Acid ester, triclenzel phosphate, trife
Nilfesfate, tri- (2-ethylhexyl) f
Phosphorus such as phosphate and trisononyl phosphate
Acid ester, dioctyl separate, di- (2-ethyl
Hexyl) sebacate, diisodecyl sebacate, etc.
Sebacate ester, glycerol tripropione
Glycerin such as glycerol and glycerol tributyrate
Stell, other, adipic acid ester, glutaric acid
Steal, succinate, maleate, huma
Acid ester, citric acid ester, di-tert-amyl
Phenol, phenol such as n-octylphenol
The effect of the present invention is great when a derivative is used. In the color development in the present invention, aromatic primary amine color development is used.
An image base is used, and various color photographic prints are used as the developing base.
Known items that are widely used in
Included. These developers are aminophenol-based and
A p-phenylenediamine derivative is included. these
Compounds are more stable than free and are generally in salt form, eg
Used in the form of hydrochloride or sulphate. Also these changes
In general, the amount of the compound is about 0.1 g to about 30 g for the color developer 1.
, About 1 g to about 15 for Color Developer 1
Use at a concentration of g. Examples of the aminophenol-based developer include o-amino.
Phenol, p-aminophenol, 5-amino-2-
Oxytoluene, 2-amino-3-oxytoluene, 2
-Oxy-3-amino-1,4-dimethylbenzene, etc.
included. Particularly useful aromatic primary amine color developing agents are N, N'-
A dialkyl-p-phenylenediamine compound,
Alkyl and phenyl groups can be replaced by any
May be. Among them, a particularly useful compound example is N-
N'-diethyl-p-phenylenediamine hydrochloride, N-
Methyl-p-phenylenediamine hydrochloride, N, N-dimethyl
Ru-p-phenylenediamine hydrochloride, 2-amino-5-
(N-ethyl-N-dodecylamino) -toluene, N-
Ethyl-N-β-methanesulfonamide ethyl-3-me
Cyl-4-aminoaniline sulfate, N-ethyl-N-β
-Hydroxyethylaminoaniline, 4-amino-3-
Methyl-N, N'-diethylaniline, 4-amino-N-
(2-Methoxyethyl) -N-ethyl-3-methylani
Examples include phosphorus-p-toluene sulfonate.
Wear. The color developer contains the above-mentioned aromatic primary amine color developer.
In addition to the various components normally added to color developers,
Minutes, for example sodium hydroxide, sodium carbonate, carbonate
Alkaline agents such as helium, alkali metal thiocyanates
Salt, alkali metal halide, benzyl alcohol,
Optional inclusion of water softeners and thickeners
You can also Aromatic primary amine color development as color developing agent
The pH value of a color developer using a developing agent is usually 7 or more.
Most commonly about 10 to about 13. The processing liquid having fixing ability in the present invention is used as a fixing agent.
For example, thiosulfate (described in JP-A-57-185435),
Thiocyanate (described in British Patent 565135, JP Sho
54-137143), halide (JP-A-52-1306)
39 publication), thioether (Belgian patent 626970)
No.), thiourea (British Patent No. 1189416)
Description) etc. can be used. Of these fixatives
However, it is thiosulfate that the effect of the present invention works effectively.
is there. When the processing solution having fixing ability is a bleach-fixing solution,
In this case, the effect of the present invention is particularly remarkable, and as the bleaching agent,
Ferric complex of organic acid (described in Japanese Examined Patent Publication No. 54-38895)
55-500704, JP-A-56-52748, 5
9-149358). Further, the processing liquid having the fixing ability used in the present invention is fixed.
If it is a processing solution intended for processing, float it in the preceding process.
What kind of bleach is used for bleaching when whitening?
Can also be used, red blood salt, iron chloride (UK patent 736881
No. specification, Japanese Patent Publication No. 56-44424) Persulfate (Germany
Japanese Patent No. 2141199), hydrogen peroxide (Japanese Patent Publication Sho 58-
No. 11617, No. 58-11618), organic acids
2 Iron complex salt (described in JP-A-57-70533, JP-A-58-43454)
Report description, Japanese Patent Application No. 58-40633, etc.)
You can The water-stabilizing substitute solution for washing used in the treatment method of the present invention is
Processing solutions containing soluble silver complex salts such as bleach-fixing solution and bleach-fixing solution
Silver may be recovered from the physical solution by a known method. For example, electricity
Solution method (described in French Patent 2,299,667), precipitation method (JP
JP-A-52-73037, German Patent 2,331,220
), Ion exchange method (described in JP-A-51-17114, Germany
Japanese Patent No. 2,548,237) and metal replacement method (UK patent)
Permission 1,353,805) can be effectively used.

【Example】

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto. Example 1 Cyan couplers of the present invention shown in Table 1 and the following comparative couplers (1) to (3) 5.0 g each, high boiling point organic solvent tricresyl phosphate (hereinafter TCP) 3.0 g and ethyl acetate 20 g, A mixed solution containing dimethylformamide in the required amount was heated to 60 ° C. to dissolve it, and then this was added to 100 ml of a 5% aqueous gelatin solution containing 10 ml of a 5% aqueous solution of alkanol B (alkylnaphthalene sulfonate, manufactured by DuPont). The mixture was mixed and dispersed with an ultrasonic disperser to obtain a dispersion. Next, the cyan coupler shown in Table 1 is 10 mol% based on silver.
The resulting dispersion was added to a silver chlorobromide emulsion (containing 30 mol% of silver chloride), and 1.5 × 10 5 of the exemplified compounds of the present invention (general formulas [IV] to [X]) shown in Table 1 were added. ^-4 mol / m ² and comprising as added (respectively 1.5 × for combination 10 ^-4 mol /
m ² ), and as a hardening agent, 1,2- (vinylsulfonyl) ethane was added at a ratio of 12 mg per 1 g of gelatin, and the coated silver amount was 10 mg / 100 cm ² on a polyethylene coated paper support.
Was applied. In this way, the No.
Samples No. 1 to No. 15 were prepared. Each of these samples was exposed and processed according to the following steps. Standard processing step [1] Color development 38 ° C 3 minutes 30 seconds [2] Bleach fixing 33 ° C 1 minute 30 seconds [3] Stabilization treatment 25 ° C to 35 ° C 3 minutes [4] Drying 75 ° C to 100 ° C About 2 Composition of processing solution <Color development tank solution> Benzyl alcohol 15ml Ethylene diglycol 〃 Potassium sulfite 2.0g Potassium bromide 1.3g Sodium chloride 0.2g Potassium carbonate 30.0g 3-Methyl-4-amino-N-ethyl-N- (β -Methanesulfonamidoethyl) -aniline sulfate 5.5g Optical brightener (triazinyl stilbene type) 1.0g Hydroxyamine sulfate 3.0g 1-Hydroxyethylidene-1,1-diphosphonic acid 0.4g Hydroxyethyliminodiacetic acid 5.0g Magnesium chloride hexahydrate 0.7g 1,2-dihydroxybenzene-3,5-disulfonic acid disodium salt 0.2g Add water to make 1 and adjust pH to 10.20 with KOH and H ₂ SO ₄ . <Bleaching fixing tank liquid> Ethylenediaminotetraacetic acid ferric ammonium dihydrate
60g Ethylenediaminetetraacetic acid 3g Ammonium thiosulfate (70% dissolved) 100ml Ammonium sulfite (40% dissolved) 27.5ml Adjust the pH to 7.1 with potassium carbonate or glacial acetic acid and add water to bring the total volume to 1. <Stabilizing tank solution for washing alternatives> 5-chloro-2-methyl-4-isothiazolin-3-one 0.02g 2-methyl-4-isothiazolin-3-one 0.02g ethylene glycol 1.0g 2-octyl-4-isothiazoline-3 -On 0.01g 1-Hydroxyethylidene-1,1-diphosphonic acid (60% aqueous solution) 3.0g BiCl ₃ (45% aqueous solution) 0.65g Ammonium thiosulfate 10.0g Add water to bring the total to 1, KOH and H ₂ SO Adjust to pH 7.2 at pH ₄ . For comparison, a washing process was also performed in which the stabilizing process was changed to washing with water at 30 ° C. Next, the developed sample was replaced with a constant temperature and humidity incubator at 70 ° C. and 70% RH (relative humidity) and a light resistance tester using a xenon arc lamp every day and stored for one month. Sakura Densitometer PD
It was measured with A-65 (manufactured by Konishi Rokusha Kogyo Co., Ltd.), and the reduction rate (fading rate) of the cyan dye concentration after storage was determined as a percentage. The results are shown in Table-1. In addition, when the residual thiosulfate concentration in the processed light-sensitive material was measured by the methylene blue method, all the samples washed with water for comparison were zero, and all the samples treated with the stabilizing solution alternative to water washing were
The amount was 4.1-5.2 μg / cm ² . The pH of the emulsion film surface is
It was between 6.3 and 6.8 for all the samples washed with water, and between 4.4 and 5.2 for the samples that had been subjected to the water washing alternative treatment. From the results shown in Table 1, samples (NO. 4, No. 5 and No. 6) using a coupler other than the present invention as a cyan coupler, the general formula [IV] or [V] even when the cyan coupler of the present invention was used. ] A sample which does not contain the compound of [] and a sample which does not contain the amount of thiosulfate of the present invention in the processed light-sensitive material even when the cyan coupler of the present invention is used in combination with the compound of the general formula [IV] or [V]. It can be seen that the cyan dye fading rates are uniformly high, and in comparison with these, the cyan dye fading of the sample according to the present invention is extremely small. Furthermore, it can be seen that when the compounds of the general formulas [VI] to [X] are used in combination, the color fading of the cyan dye is further reduced. Example-2 C-1 and C-instead of C-8 as cyan couplers, respectively.
2, Sample No. 1, No. 7 and No. 11 of Example 1 except that C-10, C-12, C-29, C-31, C-51, C-77 and C-88 were used. As a result of carrying out the same experiment as above, the same effects of the present invention as those obtained when C-8 was used as the cyan coupler were obtained. Example-3 For the sample No. 14 of Example-1, p
H was changed with KOH and H ₂ SO ₄ as shown in Table 2, and the same treatment as in Example-1 was performed. The treatment was carried out in a process without washing with water, in which stabilization treatment was directly performed after bleach-fixing. The storage condition of the sample after the treatment was the same as in Example 1. The results are shown in Table-2. As can be seen from Table-2, the pH of the emulsion film surface of the present invention is 2.5 to 9.0.
Is preferable, and a range of 3.2 to 6.2 is particularly preferable. Example-4 Sakura color paper (manufactured by Konishi Rokusha Kogyo Co., Ltd.) was subjected to picture-wise exposure, and then continuously treated with the following treatment steps and treatment solutions. Standard processing step [1] Color development 38 ° C 3 minutes 30 seconds [2] Bleach fixing 33 ° C 1 minute 30 seconds [3] Stabilization treatment 25 ° C to 35 ° C 3 minutes [4] Drying 75 ° C to 100 ° C About 2 Min. <Color development tank liquid> Benzyl alcohol 15 ml Ethylene glycolyl 〃 Potassium sulfite 2.0 g Potassium bromide 1.3 g Sodium chloride 0.2 g Potassium carbonate 30.0 g 3-Methyl-4-amino-N-ethyl-N- (β-methanesulfone Amidoethyl) -aniline sulfate 5.5g Optical brightener (triazinyl tylbene derivative) 1.0g Hydroxylamine sulfate 3.0g 1-Hydroxyethylidene-1,1-diphosphonic acid 0.4g Hydroxyethyliminodiacetic acid 5.0g Chloride Magnesium, hexahydrate 0.7 g 1,2-dihydroxybenzene-3,5-disulfonic acid disodium salt 0.2 g Water is added to adjust the pH to 1 and the pH is adjusted to 10.20 with KOH and H ₂ SO ₄ . <Color development replenisher> Benzyl alcohol 20.0 ml Ethylene glycol 20.0 ml Potassium sulfite 3.0 g Potassium carbonate 30.0 g Hydroxylamine sulfate 4.0 g 3-Methyl-4-amino-N-ethyl-N- (β-methansulphonamide ethyl ) -Aniline sulfate 7.5g Optical brightener (triazinyl stilbene derivative) 2.5g 1-Hydroxyethylidene-1,1-diphosphonic acid 0.5g Hydroxyethyliminodiacetic acid 5.0g Magnesium chloride hexahydrate 0.8g 1 0.3 g of 2,2-dihydroxybenzene-3,5-disulfonic acid disodium salt was added to adjust the pH to 1.70 with KOH. <Bleaching and fixing tank liquid> Ethylenediaminetetraacetic acid diiron ammonium dihydrate 60
g Ethylenediaminetetraacetic acid 3g Ammonium thiosulfate (70% soluble) 100ml Ammonium sulfite (40% dissolved) 27.5g Adjust the pH to 7.1 with potassium carbonate or glacial acetic acid and add water to bring the total volume to 1. <Bleach-fixing replenisher A> Ethylenediaminetetraacetic acid ferric ammonium salt 260 g Potassium carbonate 420 g Water is added to bring the total amount to 1. The pH of this solution is 6.7 ± 0.1. <Bleach-fixing replenisher B> Ammonium thiosulfate (70% dissolution) 500 ml Ammonium sulfite (40% dissolution) 250 ml Ethylenediaminetetraacetic acid 17 g Glacial acetic acid 85 ml Add water to bring the total volume to 1. The pH of this solution is 5.3 ± 0.1. <Stabilizing tank replacement solution and replenisher> 5-chloro-2-methyl-4-isothiazolin-3-one 0.02g 2-methyl-4-isothiazolin-3-one 0.02g ethylene glycol 1.0g 2-octyl-4- Isothiazolin- _3-one 0.01g 1-Hydroxyethylidene-1,1-diphosphonic acid (60% aqueous solution) 3.0g BiCl ₃ (45% aqueous solution) 0.65g Ammonia water (25% ammonium hydroxide aqueous solution) 4.0g Polyvinylpyrrolidone 0.3 g Nitrilotrimethylenephosphonic acid 0.5 g Water to 1 and sulfuric acid to pH 7.0. An automatic processor is filled with the above-mentioned color developing tank solution, bleach-fixing tank solution and stability tank solution, and while processing color paper, the above-mentioned color developing replenishing solution and bleach-fixing replenishing solutions A and B and stable replenishment are made every 3 minutes. The running test was carried out while replenishing the solution through the measuring cup. The replenishing amount is 190 ml per m ² of color paper for replenishing each color developing tank, 50 ml each for bleach-fixing replenishing solutions A and B as replenishing amounts for the bleach-fixing tank, and a stabilizing replacement replenishing liquid for washing as the replenishing amount for the stabilizing bath. Was replenished with 50 ml. The stabilization processing bath of the automatic processor is a stabilizing bath that is the first to third baths in the direction of the flow of the photosensitive material. Replenishment is performed from the final bath, and overflow is allowed to flow from the final bath to the previous stage. Further, a multi-tank countercurrent direction was adopted in which this overflow liquid was allowed to flow into the tank at the preceding stage. Sample No. 14 of Example-1 was treated halfway from the start of continuous treatment until the total replenishment amount of the stabilizing solution for washing with water reached 2.0 times the capacity of the stable tank, and the same experiment as in Example-1 was performed to perform residual thiol treatment. The sulfuric acid concentration and the magenta dye fading rate were obtained. Table of results
3 shows. From the results of Table-3, the present invention is effective when the thiosulfate contained in the processed light-sensitive material is 0.1 μg / cm ² or more, and particularly,
It can be seen that it is preferably 5 μg / cm ² or more, and most preferably 1.0 μg / cm ² . [Effects of the Invention] The method of the present invention does not require the use of washing water in the color developing treatment, and therefore does not require the energy cost of adjusting the temperature of the washing water, and the color developing treatment with a low pollution load can provide light exposure. Provide a color photographic image with improved fading of the magenta dye image when stored for long periods of time under irradiation.

 ─────────────────────────────────────────────────── --Continued from the front page (56) Reference JP-A-59-184345 (JP, A) JP-A-54-134621 (JP, A) JP-A-55-69141 (JP, A) JP-A-53- 17729 (JP, A) JP 56-159644 (JP, A) JP 54-145530 (JP, A) JP 59-195238 (JP, A) JP 61-141447 (JP, A) Japanese Patent Publication Sho 49-11572 (JP, B2)

Claims (4)

[Claims] 1. At least one selected from cyan couplers represented by the following general formulas [I], [II] and [III],
At least one selected from the compounds represented by the general formulas [IV] and [V], the general formulas [VI], [VII], [VIII],
When a silver halide color photographic light-sensitive material containing at least one selected from the compounds represented by [IX] and [X] is developed after imagewise exposure, a thiosulfate is used as a fixing agent and washed with water. Perform an alternative stabilization process,
A method of processing a silver halide color photographic light-sensitive material, characterized in that the processed light-sensitive material contains 0.1 μg / cm ² or more of thiosulfate. General formula [I] [In the formula, one of R and R ₁ is a hydrogen atom, the other is a linear or branched alkyl group having at least 2 to 12 carbon atoms, and X is a hydrogen atom or an aromatic primary amine color developing agent. It represents a group capable of splitting off by a coupling reaction with an oxidant, and R ₂ represents a ballast group. ] General formula [II] General formula (III) [In the formula, Y is -COR ₄ , -CONHCOR ₄ or -CONHSO ₂ R ₄ (R ₄ represents an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group or a heterocyclic group, and R ₅ represents a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group. Or represents a heterocyclic group, R ₄
And R ₅ may combine with each other to form a 5- or 6-membered ring. ), R ₃ represents a ballast group, and Z represents a hydrogen atom or a group capable of splitting off upon coupling with an oxidation product of an aromatic primary amine color developing agent. ] General formula [IV] [In the formula, X ₁ represents a hydrogen atom or —OZ ₁ . Z ₁ represents a hydrogen atom, a sulfonyl group, an acyl group, an alkoxycarbonyl group, a carbamoyl group, an alkyl group or an alkenyl group. R ₆ , R ₇ and R ₈ are each a hydrogen atom, a halogen atom, a cyano group, a sulfo group, an alkyl group, an alkenyl group,
Alkoxy group, an alkylthio group, an aryl group, -SO ₂ R ₉
Alternatively, it represents -COR ₉ . R ₉ represents a hydroxy group, an alkyl group, an alkoxy group, an aryloxy group or an amino group. ] General formula [V] [In the formula, R ₁₀ , R ₁₁ , R ₁₂ and R ₁₃ are each a hydrogen atom, an alkyl group, an aralkyl group, an aryl group, a halogen atom, an alkoxy group, an alkylthio group, an alkylsulfonyl group, a sulfo group, an arylsulfonyl group, an alkyl group. It represents a sulfinyl group, an arylsulfinyl group, an acylamino group, an acyloxy group, a carbamoyl group, an alkoxycarbonyl group, an acyl group, a sulfonamide group, a sulfamoyl group or a carboxy group. ] General formula [VI] General formula (VII) General formula [VIII] [In the formula, R ₁₄ represents a hydrogen atom, a halogen atom, an alkyl group,
It represents an aryl group or an alkoxy group. R ₁₅ to R ₂₂ may be the same or different and each represents a hydrogen atom or an alkyl group. Y ₁ represents a hydrogen atom, an acyl group, an alkoxycarbonyl group, a carbamoyl group or a sulfonyl group, and they may be the same or different. l represents an integer of 1, 2 or 3 and m represents an integer of 0 to 2. However, l + m is 4 or less. ] General formula [IX] [In the formula, R ₂₃ represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, and R ₂₄ , R ₂₅ , R ₂₇ and R ₂₈ are each a hydrogen atom,
It represents an alkyl group, an aryl group, an alkoxy group or an acylamino group, and R ₂₆ represents an alkyl group, an aryl group, a phenoxy group or an alkoxy group. Furthermore, R ₂₃ and R ₂₄ may be ring-closed to form a ring. ] General formula [X] [Wherein G represents a hydroxy group or an alkali-labile precursor thereof; each R ₂₉ is independently an alkyl group, an aryl group, or a heterocyclic group having a hetero atom selected from nitrogen, oxygen, sulfur and selenium. represents; represents R _30, R ₃₁ and R ₃₂ are each a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aryl group or an aryloxy group. ] 2. The method for processing a silver halide color photographic light-sensitive material according to claim 1, wherein the thiosulfate is ammonium thiosulfate. 3. The pH of the emulsion film surface of the processed light-sensitive material is
The method for processing a silver halide color photographic light-sensitive material according to claim 1 or 2, which is in the range of 2.5 to 9.0. 4. thiosulfate remaining in the processed light-sensitive material of Claims, wherein the first term to the third term, characterized in that in the range of 0.5μg / cm ² ~50μg / cm ² A method for processing a silver halide color photographic light-sensitive material.