JPH0614182B2 - Silver halide color-Stabilizing solution for rinsing water for photographic light-sensitive materials - Google Patents

Description

Detailed Description of the Invention [Conventional field]

The present invention relates to a water-washing alternative stabilizing solution used for processing a silver halide color photographic light-sensitive material (hereinafter abbreviated as light-sensitive material), and more particularly to a water-washing alternative stabilizing solution which prevents stain generation in an unexposed area due to continuous processing.

[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 the cost for washing water due to an increase in the price of crude oil 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 multistage countercurrent stabilization treatment technique as described in JP-A-57-8543 and JP-A-58-1
A treatment technique using a water-washing alternative stabilizing solution containing a bismuth complex salt as described in Japanese Patent No. 34636 has been proposed. However, in the treatment using the stabilizing solution as a substitute for washing with water, the total amount of the replenishing solution to the stabilizing tank solution is 6 times the stable tank capacity.
~ 7 times more than continuous processing for a long time,
The present inventors have found that color stains occur on the processed light-sensitive material and are noticeable as stains. Above all, there is a problem that color contamination, that is, stain is conspicuous in the unexposed portion, and particularly in color paper, since the unexposed portion is a white background, even slight contamination causes a serious defect. It has also been found that the generation of such stains deteriorates the storage durability particularly when the dye image is stored, especially under the irradiation of light.

[Object of the Invention]

Therefore, an object of the present invention is to provide a technical means for preventing the unexposed portion of a photosensitive material from being contaminated when continuously processed by using an alternative stabilizing solution for washing and having no adverse effect on other performances. It is in. Still another object is to provide a technical means for preventing deterioration of storage stability of a dye image, particularly deterioration of photofading, when continuously processed using a water-washing alternative stabilizing solution.

[Summary of Invention]

The above-mentioned object of the present invention comprises a fluorescent whitening agent represented by the following general formula [I] in an amount of 0.05 to 100 g /, and a polymer or copolymer having a pyrrolidone nucleus, and having a pH of 5.5 to 10.0. It is achieved by a water-washing alternative stabilizing solution for silver halide color photographic light-sensitive materials, which is characterized by being in the range. General formula [I] In the formula, R ₁ , R ₂ , R ₃ , R ₄ R ₅ and R ₆ each represent a hydrogen atom, an alkyl group or an aryl group. R ₃ and R ₄ and R ₅ and R ₆ may combine with each other to form a heterocycle. M represents a hydrogen atom, an alkali metal atom or an ammonium group. The present inventors also provide, as a preferred embodiment of the present invention,
It has been found that the effects of the present invention are more remarkable when the stabilizing solution for washing with water according to the present invention contains an ammonium compound. The water-washing alternative stabilizer according to the present invention is used in a step subsequent to a processing step with a processing solution having a fixing ability after color development, and the effect of the present invention is particularly exerted when used in a development processing in which substantially no water-washing processing is performed. It is remarkable, and it is advantageous to apply it to such development processing. Further, it is preferable that the stabilizing solution for washing with water of the present invention contains a mildew-proofing agent because the effects of the present invention can be exerted for a long period of time.

[Constitution of the invention]

The present invention will be further described below. In the conventional washing process after development, bleaching and fixing processes, a large amount of washing water is used to remove the processing solution composition (color developing agent, benzyl alcohol,
Bleach, thiosulfate, etc.) or their reactants, oxidants, etc. were all washed away. Therefore, in the treatment with the washing substitute alternative stabilizing solution without the washing treatment, all of these components are eluted and accumulated in the stabilizing solution.
In particular, when the replenishment amount of the stabilizing solution as a substitute for water washing is small, the accumulated concentration of the substance to be washed increases. Furthermore, since the liquid replacement ratio of the washing-replacement stabilizing solution is reduced, the solution is stored for a long time, and the oxidation of the substance in the washing-replacement stabilizing solution increases.
Because of the coloring components of these substances, the stabilizing solution for washing alternative is considerably colored, and the adsorption of these coloring components to the photosensitive material in the stabilizing solution for washing alternative causes contamination of the unexposed portion of the photosensitive material. It is presumed that. In the present invention, among the optical brighteners, a compound represented by the general formula [I] is added in a specified amount and a polymer or copolymer having a pyrrolidone nucleus is added to a stabilizing solution for washing with water to adjust the pH.
It is based on the finding that it is possible to prevent the contamination that occurs during long-term continuous processing and the deterioration of the storage stability of the dye image due to the range of 5.5 to 10.0,
The fact that this can prevent the problems peculiar to the substitute solution for washing with water is surprising and has never been known. Next, the compound used in the present invention will be described. In the general formula [I] of the present invention, R ₁ , R ₂ , R ₃ , R ₄ ,
The alkyl group and aryl group represented by R ₅ and R ₆ may each have a substituent, and the aryl group is preferably a phenyl group, and the substituent is a hydroxyl group, a sulfo group or a sulfoamino group. And carboxamino groups are preferred. The heterocycle formed by connecting R ₃ and R ₄ and R ₅ and R ₆ is preferably a heterocycle containing an oxygen atom, and examples thereof include a morpholino group. The alkali metal atom represented by M is, for example, a sodium atom or a potassium atom. Specific preferred compounds represented by the general formula [I] are shown below, but the invention is not limited thereto. (I-1) (I-2) (I-3) (I-4) (I-5) (I-6) (I-7) (I-8) (I-9) (I-10) The fluorescent whitening agent represented by the general formula [I] used in the present invention is synthesized by a usual method described in, for example, “Fluorescent Whitening Agent” (published in August 1976), page 8 edited by Chemical Industry Association. can do. The above-mentioned optical brightening agent used in the present invention more effectively achieves the object of the present invention when the maximum fluorescence wavelength λmax of the fluorescence spectrum is 433 to 440 nm. The amount of the fluorescent whitening agent added to the stabilizing solution as a substitute for washing with water is 1
The range is 0.05 to 100 g, but more preferably 0.1 to 20
g, and most preferably 0.2 to 10 g. The polymer or copolymer having a pyrrolidone nucleus in the molecular structure used in the present invention (hereinafter, referred to as a polymer or copolymer having a pyrrolidone nucleus) has a main chain or a side chain of the polymer with a pyrrolidone nucleus. All of the polymerizable polymers substituted by an arbitrary number are contained in the position of, and may be a homopolymer thereof or a copolymer obtained by polymerizing two or more kinds of copolymerization components. In the latter case, a polymer as a copolymerization component having a monomer unit having pyrrolidone (pyrrolidone nucleus unit) in the molecular structure has a pyrrolidone nucleus unit in the molecular structure that is copolymerized with the polymer as the copolymer component. Not included 20% or more in the copolymer obtained by copolymerizing with another polymer, especially 30%
The above is preferably included. Incidentally, as the other polymer having no pyrrolidone nucleus unit in the molecular structure to be copolymerized with the polymer as the copolymerization component having the pyrrolidone nucleus unit in the molecular structure, as long as a hydrophilic copolymer can be obtained. Anything can be used. Polymers or copolymers with a pyrrolidone nucleus have an average molecular weight
It is preferably 1,000 to 70,000, and typical examples thereof include the following. [Exemplified compound] [1] Poly-N-vinyl-2-pyrrolidone (* Note 1) [2] Poly-N- (2-acryloyloxy) ethyl-2-pyrrolidone [3] Poly-N-glycidyl-2- Pyrrolidone [4] Poly-N-allyl-2-pyrrolidone [5] Poly-N, N-dimethyl-N- [3 (1-pyrrolidonyl) -2-hydroxy] propyl-amino-N′-acryloylimine [6] Copoly-N-vinyl-2-pyrrolidone / N-acryloylmorpholine (molar ratio 4
2:58) [7] Copoly-N-vinyl-2-pyrrolidone / N-acryloylpiperidine (molar ratio 3
5:65) [8] Poly-N-vinyl-2-pyrrolidone / N-methacryloyl-
2-Methylimidazole (molar ratio 55:45)

[9] Copoly-N- (2-acryloyloxy) -ethyl-2-pi
Loridone / acrylic acid diethylamide (molar ratio 60:
40) [10] Copoly-N- (2-methacryloyloxy) ethyl-2
-Pyrrolidone / sodium acrylate (mol
Ratio 75:25) [11] Copoly-N- (3-acryloyloxy) propyl-2
-Pyrrolidone / Methyl methacrylate (mol
Ratio 65:35) [12] Copoly-N, N-dimethyl-N- [3- (2-pyrrolidone
) -2-Hydroxy] -propylamine-N′-acryloyl
Ruimin / ethyl acrylate
 (Molar ratio 70:30) [13] Copoly-N-vinyl-2-pyrrolidone / vinyl acetate (Molar ratio 70:30) [14] Copoly-N-vinyl-2-pyrrolidone / methacrylic acid
Chill (molar ratio 70:30) [15] Copoly-N-vinyl-2-pyrrolidone / styrene (Molar ratio 80:20) [16] Copoly-N-vinyl-2-pyrrolidone / acrylic acid acrylate
Mido / N-vinyl-2-methylimidazole (molar ratio 50:30:
20) [17] Copoly-N-vinyl-2-pyrrolidone / N- (1,1-dimethyl)
(3-oxy) -butyl-acrylamide (molar ratio 70:30) [18] copoly-N-allyl-2-pyrrolidone / vinyl acetate (molar ratio 64:36) [19] copoly-N-biryl-2- Pyrrolidone / 4-vinylpyri
Gin (molar ratio 60:40) [20] Copoly-N-vinyl-2-pyrrolidone / acrylic acid
Chill / acrylic acid monoethanolamine acid
(Molar ratio 50: 45: 5) [21] Copoly-N-vinyl-2-pyrrolidone / piperidinoma
Raremic acid piperidine acid
Ratio 53:47) [22] Copoly-N-vinylpyrrolidone / 4-vinylpyridino
-N-methyl iodide (molar ratio 4
2:58) [23] Copoly-N-vinylpyrrolidone / thio maleic acid
Urea half ammonium salt
 (Molar ratio 60:40) * Note 1 Exemplified compound [1] is general aniline and
・ Film Corp (General Aniline and Film Corp)
From PVP K-15, PVP K-17, PVP K-30, PVP K-60, PVP K-90
Product Name Mata Mfg. Co., Ltd.
engngesellschaft) to Kollidon 12, Kollidon 17, Ko
Redon 25, Kollidon 30, Kollidon 90, Rubiscol K-1
7, Rubisroll K-30, and Rubiscol K-90
It is commercially available. The polymer or copolymer having a pyrrolidone nucleus is described above.
As a part of it is commercially available, it can be easily obtained.
And John Willie and Sons Incorporated
Issued by John Wilery and Sons, Inc. (1961)
Tabry Earl Sorenson, T W
Prepared by W.R.Sorenson, T.W.Campbell
Eve Method of Polymer Chemistry (Prepa
those listed in (rative Methods of Polymer Chemistry)
It can be easily synthesized according to the method. Further, for the purpose of the present invention, a compound having the above pyrrolidone nucleus
Among the compounds, a particularly preferable compound is the exemplified compound [1].
It Polymers or copolymers with a pyrrolidone nucleus can be used alone
May be used or two or more kinds may be used in combination, and the amount used
Is in the range of 0.01 to 100 g per wash washing alternative stabilizing solution,
It is preferably in the range of 0.05 to 10 g. The polymer or
The copolymer may be added to the stabilizing tank solution as an alternative to washing with water.
A stable tank solution that is added to the tank replenisher to replace the washing with water.
May be used in the form of replenishment with
You may. Antifungal agent preferably used in the alternative treatment solution for washing with water of the present invention
Is salicylic acid, sorbic acid, dehydroacetic acid, hydroxy
Cibenzoic acid compounds, alkylphenol compounds, chi
Azole compounds, pyridine compounds, guanidine compounds
Compound, carbamate compound, morpholine compound, four
Phosphonium compounds, ammonium compounds, urea
Compounds, isoxazole compounds, propanolami
Compounds, sulfamide derivatives and amino acid compounds
Is. The hydroxybenzoic acid compound is hydroxybenzoic acid.
Acid and hydroxybenzoic acid ester compounds
Chill ester, ethyl ester, propyl ester,
There are chill esters and the like, but preferably hydroxybenzoic
Acid n-butyl ester, isobutyl ester, propyl
Esters, more preferably the hydroxybenzoic acid
It is a mixture of three acid esters. The alkylphenol compound has an alkyl group of C1-6.
It is a compound having an alkyl group of
Kuha ortho phenylphenol and ortho cyclohexyl
It is ruphenol. A thiazole-based compound has a 5-membered ring with a nitrogen atom and a sulfur source.
A compound having a child, preferably 1,2-benziso
Thiazolin-3-one, 2-methyl-4-isothiazoline
3-one, 2-octyl-4-isothiazolin-3-o
5-chloro-2-methyl-4-isothiazoline 3-
On, 2- (4-thiazolyl) benzimidazole
It Pyridine compounds are specifically 2,6-dimethylpyrididinium
1,2,4,6-trimethylpyridine, sodium-2-
Pyridine thiol-1-oxide, etc., but preferred
Kuha Sodium-2-pyridinethiol-1-oxide
Is. The guanidine compounds are specifically cyclohexidine and
Lihexamethylene Biguanidine Hydrochloride, Dodecyl Guani
Gin hydrochloride, etc., preferably dodecylguanidine
And its salts. The carbamate compound is specifically methyl-1- (butyrate).
Lucabamoyl) -2-benzimidazole carbamay
And methyl imidazole carbamate. The morpholine compound is specifically 4- (2-nitrobutyrate).
) Morpholine, 4- (3-nitrobutyl) morpholine
Etc. Quaternary phosphonium compounds are tetraalkylphosphonium
There are various salts, such as tetra-alkoxyphosphonium salt, but
More preferably, it is a tetraalkylphosphonium salt.
A physically preferred compound is tri-n-butyl-tetradecyl.
Ruphosphonium chloride and tri-phenyl-nitro
Phenylphosphonium chloride. The quaternary ammonium compound is specifically benzalkonium
Salt, benzethonium salt, tetraalkylammonium
There are salts, alkylpyridinium salts, and the like. More specifically,
Dodecyldimethylbenzyl ammonium chloride, do
Decyl dimethyl ammonium chloride, lauryl pyri
For example, dinium chloride. The urea compound is specifically N- (3,4-dichlorophene).
Nyl) -N '-(4-chlorophenyl) urea, N- (3
-Trifluoromethyl-4-chlorophenyl) -N'-
(4-chlorophenyl) urea and the like. The isoxazole-based compound is specifically 3-hydroxy-
5-methyl-isoxazole and the like. Propanolamine-based compounds include n-propanols
There are isopropanols, specifically DL-2-ben
Dilamino-1-propanol, 3-diethylamino-
1-propanol, 2-dimethylamino-2-methyl-
1-propanol, 3-amino-1-propanol, a
Dopropanolamine, diisopropanolamine,
N, N-dimethyl-isopronolamine and the like. The sulfamide derivative is specifically fluorinated sulfamide.
De, 4-chloro-3,5-dinitrobenzene sulfami
De, sulfanilamide, acetosulfamine, sulf
Pyridine, sulfaguanidine, sulfathiazo
Le, sulfadiazine, sulfamelazine, sulfame
Tadine, sulfisoxazole, homosulfami
, Sulfisomidine, sulfaguanidine, sulfa
Methizole, sulfapyrazine, phthalisosulfaty
Examples include azole and succinylsulfathiazole. The amino acid compound is specifically N-lauryl-β-ara.
There is nin. Among the above antifungal agents, the antifungal agent is preferably used in the present invention.
Compounds are pyridine compounds, guanidine compounds and
And thiazole compounds. The amount of antifungal agent added to the stabilizing solution for washing is 1
Used in the range of 0.002 to 50 g, preferably 0.0
Used in the range of 05-10g. It is desirable to add it to the stabilizing solution as a substitute for washing used in the present invention.
Ammonia compounds are ammons of various inorganic or organic compounds.
Although it is supplied by a nickel salt,
Monium, ammonium bromide, ammonium carbonate, chloride
Ammonium, ammonium hypophosphite, ammonium phosphate
Ni, Ammonium phosphite, Ammofluoroborate
Aluminum, ammonium arsenate, ammonium hydrogen carbonate, fluorine
Ammonium hydrogen fluoride, ammonium hydrogen sulfate, sulfuric acid
Ammonium, ammonium iodide, ammonium nitrate,
Ammonium pentaborate, ammonium acetate, adibic acid
Ammonium, ammonium laurate tricarboxylate,
Ammonium benzoate, ammonium carbamate,
Ammonium enoate, diethyldithiocarbamate
Monium, ammonium formate, ammonium malate
, Ammonium hydrogen oxalate, ammonium hydrogen phthalate
Um, ammonium hydrogen tartrate, ammonium thiosulfate
System, ammonium sulfite, ethylenediaminetetraacetic acid
Monium, 1-hydroxyethylidene-1,1-diphos
Ammonium phonate, ammonium lactate, Ann malate
Monium, ammonium maleate, ammonium oxalate
Um, ammonium phthalate, ammoniu picrate
Gamma, pyrrolidine ammonium dithiocarbamate, sali
Ammonium citrate, ammonium succinate, sulfa
Ammonium nitrate, ammonium tartrate, thioglycol
Ammonium phosphate, 2,4,6-trinitropheno
Lumonium and the like. These are two or more even for single use
May be used together. 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. In the present invention, the stabilizing solution as a substitute for washing with water is a key to iron ions.
Contains a chelating agent with a rate stability constant of 8 or more
From the viewpoint of the effect of the present invention, it is preferable. Here, the chelate stability constant is L.G.Sillen / A.E.Marte.
ll, "Stability Constants of Metal-ion Complexes",
The Chemical Society, London (1964) S.Chabere K ・ A.E.Ma
rtell, "Organic Sequestering Agents", Wiley (1959)
It means a commonly known constant such as. If the chelate stability constant for iron ions is 8 or more,
As a chelating agent, an organic carboxylic acid chelating agent,
Machine phosphoric acid chelating agent, inorganic phosphoric acid chelating agent, polyhydric acid
Roxy compounds and the like can be mentioned. In addition, with the above iron ion
Is a ferric ion (Fe³⁺) Is meant. Sharpness with chelate stability of 8 or more with ferric ion
The following compounds can be mentioned as specific examples of the compound for the adhesive agent.
However, the present invention is not limited to these. Ie ethylene
Diamine diorthohydroxy cyphenylacetic acid, diamino
Propane tetraacetic acid, nitrilotriacetic acid, hydroxyethyl ether
Tolylenediamine triacetic acid, Dihydroxyethylglycine,
Ethylenediaminediacetic acid, ethylenediaminedipropio
Acid, iminodiacetic acid, diethylenetriaminepentaacetic acid,
Droxyethyliminodiacetic acid, diaminopropanol tetra
Acetic acid, transcyclohexanediaminetetraacetic acid, ethyl
Diamine tetraacetic acid, glycol ether diamine tetraacetic acid
Acid, ethylenediamine tetrakis methitylene phosphon
Acid, nitrilotrimethylenephosphonic acid, 1-hydroxy
Ethylidene-1,1-diphosphonic acid, 1,1-diphosphonic acid
Noethane-2-carboxylic acid, 2-phosphonobutane-1,
2,4-tricarboxylic acid, 1-hydroxy-1-phospho
Nopropane-1,2,3-tricarboxylic acid, catechol
-3,5-disulfonic acid, sodium pyrophosphate, tet
Sodium lapolyphosphate and sodium hexametaphosphate
And A-PO is particularly preferable.₃M₂(In the formula, M
Is hydrogen atom, sodium atom, potassium atom, ammonium
Represents a cation such as um, and A represents an inorganic or organic group.
You ), For example, 2-phosphonob
Tan-1,2,4-tricarboxylic acid, 1,1-diphospho
Noethane-2-carphonic acid, pyrophosphoric acid, tetrapoly
Sodium phosphate, sodium hexametaphosphate, porili
Sodium acid salt, nitrilotrimethylenephosphonic acid,
Tolylenediamine tetraphosphonic acid, diethylene triamid
-Pentaphosphonic acid, 1-hydroxypropylidene-
1,1-diphosphonic acid, 1-aminoethylidene-1,1
-Diphosphonic acid, 1-hydroxyethylidene-1,1-
Diphosphonic acid and salts thereof. The amount of the above chelating agent to be used is 1 per washing washing alternative stabilizing solution,
Good results in the range of 0.01-50g, preferably 0.05-20g
Is obtained. In the present invention, the stabilizing solution as a substitute for washing with water is used together with the chelating agent.
It is preferable to use a metal salt for storage of images.
Yes. Such metal salts include Mg, Bi, Ba, Ca, Ce, Co, I
Metal salt of n, Mn, Ni, Pb, Sn, Zn, Ti, Zr, Al or Sr
, Halides, hydroxides, sulfates, carbonates
Inorganic salts such as salts, phosphates and acetates, or water-soluble chelating agents
Can be supplied as The amount used is 1 x 10 per stabilizer.^-Four
~ 1-10^-2It is in the molar range. Other commonly known stabilizing bath additives include, for example:
Surfactants, organic sulfur compounds, onium salts, formalis
There are hardeners such as tin and chromium, but these compounds are
It is necessary to maintain the pH of the stabilizing solution for washing with water in the present invention.
In addition, the stability of storage of color photographic images and the occurrence of precipitation
What kind of compound, etc.
Can be used in combination and addition amount
Absent. The pH of the stabilizing solution for washing with water in the present invention is in the range of 5.5 to 10.0.
And more preferably in the range of pH 6.3 to 9.5, especially
It is preferably in the range of 7.0 to 9.0. An alternative to washing with water
The pH adjuster that can be contained in the constant solution is generally known.
You can use any of the alkaline or acid agents
It In the present invention, the replenishing amount of the washing substitute stabilizer to the washing substitute stabilizer is
When the amount is small, the effect is great and the replenishment amount is processed.
1 to 50 of the amount brought in from the previous bath per unit area of material
In the double range, especially in the range of 2 to 20 times, the effect of the present invention
It is remarkable. For example 100 cm²The amount of hitting is 0.5 m
In some cases, the replenishment amount is preferably 1 m to 10 m. The treatment temperature for the treatment with the stabilizing solution as a substitute for water washing is 15 to 60 ° C.
It is preferably in the range of 20 ° C to 45 ° C. Also, processing time is fast
From the viewpoint of rapid processing, the shorter the time, the better, but usually 20
Seconds to 10 minutes, most preferably 1 to 3 minutes, multiple tanks
In the case of stabilization treatment, the treatment is performed in as short a time as in the former tank, and the latter tank
The longer the treatment time, the better. Especially in the front tank 20-50
It is desirable to process sequentially with increasing processing times of%. The stabilization treatment using the washing alternative stabilizer of the present invention is a photosensitive material.
The dye is treated with a fixing solution, and then the
Directly without the need for washing with water.
It is preferable to manage. It is treated with a processing solution that has fixing ability, and then
One bath development bleach-fix,
Bleach-fixing or directly after fixing, a stabilizing solution for washing with water of the present invention
It means that the washing process is basically
1-bath development bleach-fix, bleach-fix or
Short silver recovery for silver recovery between fixing bath and stabilizing bath
This means that a bath, rinse, etc. may be provided. Shi
However, a treatment bath with a fixing ability and a stabilizing solution instead of a water-washing solution are used.
It is desirable not to provide anything between the stabilization treatment steps. Washing alternative stabilization according to the present invention in the washing alternative stabilization process
When the multi-tank counter current method is used for the liquid supply,
If it is used, supply it to the post-bath and let it overflow from the pre-bath.
Is preferred. Of course, it can also be processed in a single tank. water
A method of adding the above compound to be contained in the wash substitute stabilizing solution, and
Then, add it as a concentrated liquid to the stabilizing tank for washing instead of water,
Or, use the stabilizing solution for washing substitute supplied to the stabilizing tank for washing substitute.
Add the above compound and supply it to a stable replacement solution for washing.
There are various methods such as whether to supply liquid, but what kind of addition method
You may add by the method. The substitute solution for washing with water according to the present invention is suitable for color development, desilvering and desilvering.
And a light-sensitive material that can obtain a dye image by fixing processing, especially with reflected light
It is effective for light-sensitive materials of the type that sees images. Advantageously suitable
Color negative paper and color paper can be used as photosensitive materials.
Examples include dipaper and reverse color paper. For color development of a light-sensitive material to which the washing substitute solution of the present invention is applied
Aromatic primary amine color developing agents are used,
Widely used in medicine in various color photographic processes
Known publicly known ones are included. For these developers
Is aminophenol type and p-phenylenediamine type
Derivatives are included. These compounds are more stable than free
Generally in the form of a salt, for example in the form of the hydrochloride or sulphate
used. Further, these compounds are generally used in color developers.
1 about 0.1 to about 30 g, preferably color development
Used at a concentration of about 1 to about 15 g for Image Liquid 1. Aminophenol-based developers include, for example, o-aminophen.
Nole, p-aminophenol, 5-amino-2-oxy
Citoluene, 2-amino-3-oxytoluene, 2-o
Xy-3-amino-1,4-dimethylbenzene and the like are included.
Get caught A particularly useful aromatic primary amine color developer is N, N-di
An alkyl-p-phenylenediamine compound,
The alkyl and phenyl groups can be replaced by any
You may stay. Of these, particularly useful compounds include N-
N-diethyl-p-phenylenediamine hydrochloride, N-me
Cyl-p-phenylenediamine hydrochloride, N, N-dimethyl
-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
Phosphorus-p-toluene sulfonate etc.
it can. 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, alcal 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. Processing solution having fixing ability used for desilvering and fixing processing
Examples of the fixing agent include thiosulfate (JP-A-57-185
435), thiocyanate (UK patent 565135)
Description, described in JP-A-54-137143), halogen
Compound (described in JP-A-52-130639), thioether
(Belgium patent 626970 specification), thiourea (English
National patent No. 1189416 description) etc. can be used
It Among these fixing agents, the effect of the present invention is more effective
It is thiosulfate that acts on. Also has fixing ability
The effect of the present invention is particularly noticeable when the processing solution is a bleach-fixing solution.
As a bleaching agent, ferric organic acid complex salt of organic acid (Japanese Patent Publication Sho
54-38895 publication, special table Sho 55-500704 publication, special
(Kaisho 56-52748 and 59-149358)
Can be used. Furthermore, a processing liquid having a fixing ability is used for the purpose of fixing treatment.
When it is a physical solution,
For bleach, you can use any bleach
Red blood salt, iron chloride (described in British Patent No. 736881,
Japanese Patent Publication No. 56-44424) Persulfate (German Patent No. 2141199)
Description), hydrogen peroxide (Japanese Patent Publication No. 58-11617)
No. 58-11618), organic acid ferric iron complex salt
57-70533, 58-43454, Japanese Patent Application
58-40633 specification description) etc. can be used. Even if silver is recovered from the water-washing alternative stabilizing solution of the present invention by a known method.
Good. For example, electrolysis method (French Patent 2,299,667
), Precipitation method (described in JP-A-52-73037, German Patent 2,
331,220), ion exchange method (JP-A-51-1711)
No. 4 publication, German patent 2,548,237 specification) and gold
There is a genus substitution method (described in British Patent 1,353,805)
It can be used effectively. A particularly effective treatment process applying the wash-stabilizing alternative of the present invention
Examples thereof include the following (1) and (2). (1) Color development-bleach-fixing-water washing alternative stabilizing treatment (2) Color development-bleaching-fixing-water washing alternative stabilizing treatment (Example) The present invention will be specifically described below with reference to Examples.
This does not limit the embodiments of the present invention.
Yes. Example 1 An experiment was conducted with the following color paper, processing solution and processing steps.
It was. [Color paper] Polyethylene coated paper The following layers on the support
From the above to produce a light-sensitive material. The average molecular weight of polyethylene coated paper is 10
200 parts by weight of polyethylene with a density of 0.90 and a density of 0.95
2,000, mixed with 20 parts by weight of polyethylene with a density of 0.80
Add 6.8% by weight of anatase type titanium oxide to the product and press
Weight 170g / m by extrusion coating method²High quality paper table
A 0.035 mm thick coating layer is formed on the front surface, and
A coating layer with a thickness of 0.040 mm is made of only chilen
Was used. On the polyethylene-coated surface of this support surface,
After pretreatment by Rona discharge, each layer is applied in sequence.
It was First layer: Blue-sensitive halo consisting of silver chlorobromide emulsion containing 80 mol% of silver bromide
Silver genide emulsion layer, the emulsion being based on 1 mol of silver halide
Containing 350 g of gelatin, the following per mol of silver halide
Structural sensitizing dye2.5 x 10^-3Sensitized with mol (isopro
Pill alcohol), dissolved in dibutyl phthalate
2,5-di-tert-butylhydroquinone 200 dispersed
mg / m²And α- [4- (1-beta) as a yellow coupler.
Benzyl-2-phenyl-3,5-dioxo-1,2,4-tria
Zolidyl)] α-bivalyl-2-chloro-5- [γ-
(2,4-di-tert-amylphenoxy) butyramide]
2 × 10 acetanilide per mol of silver halide^-1Mo
Including silver, silver amount 330mg / m²Is applied so that Second layer: di-tert-octane dissolved and dispersed in dibutyl phthalate
Chill hydroquinone 300mg / m², As a UV absorber 2-
(2'-hydroxy-3 ', 5'-di-tert-butylphen
Phenyl) benzotriazole 2- (2'-hydroxy-
5'-tert-butylphenyl) benzotriazole, 2
-(2'-hydroxy-3'-tert-butyl-5'-me
Tylphenyl) -5-chlorobenzotriazole and
2- (2'-hydroxy-3 ', 5'-di-tert-butyl
Ruphenyl) -5-chloro-benzotriazole mixture
Thing 200mg / m²2000mg / m gelatin in the gelatin layer containing²
Is applied so that Third layer: green-sensitive halo consisting of silver chlorobromide emulsion containing 85 mol% of silver bromide
Silver genide emulsion layer, the emulsion being based on 1 mol of silver halide
Containing 450 g of gelatin, the following per mol of silver halide
Structural sensitizing dye2.5 x 10^-1Sensitized with mol dibutyl phthalate
And were mixed with triclenzel phosphate mixed 2: 1.
2,5-di-tert-butylhydroxy solution dissolved and dispersed in an agent
Non 150 mg / m²And 1- (2,4,6 as magenta coupler
-Trichlorophenyl) -3- (2-chloro-5-oct
Tadecenyl succinimidoanilino) -5-pyrazolone
1.5 × 10 per mol of silver halide^-1Contains mol, silver
Amount 300mg / m²Is applied so that In addition, oxidation protection
2,2,4-Trimethyl-6-lauryloxy-
0.7 mole of 7-tert-octyl chroman per mole of coupler.
3 mol was contained. Fourth layer: di-tert-o dissolved and dispersed in dioctyl phthalate
Cutyl hydroquinone 30mg / m²And as an ultraviolet absorber
2- (2'-hydroxy-3 ', 5'-di-tert-butyl
Ruphenyl) benzotriazole, 2- (2'-hydro)
Xy-5'-tert-butylphenyl) benzotriazo
2- (2'-hydroxy-3'-tert-butyl-
5'-methylphenyl) -5-chlorobenzotriazo
And 2- (2'-hydroxy 3 ', 5'-tert-but
Mixture of tylphenyl) -5-chloro-benzotriazole
Compound (2: 1.5: 1.5: 2) 500 mg / m²The gelatin layer that contains
The amount of ratin is 2000 mg / m²Is applied so that Fifth layer: Red-sensitive halo consisting of silver chlorobromide emulsion containing 85 mol% of silver bromide
Silver genide emulsion layer, the emulsion being based on 1 mol of silver halide
Containing 500 g of gelatin, the following per mol of silver halide
Structural sensitizing dye2.5 x 10^-3Sensitized with mol dibutyl phthalate
2,5-di-tert-butylhydrol dissolved and dispersed in
Quinone mg / m²And 2,4-dichloro- as a cyan coupler
-3-methyl-6- [γ- (2,4-diamylphenoxy) butyrate
Lamido] phenol is 3.5 per mol of silver halide
× 10^-1Molar content, silver amount 300mg / m²Is applied to
ing. 6th layer: Gelatin layer with a gelatin content of 1400mg / m²Applied so that
Has been done. Halogenation used for each photosensitive emulsion layer (first, third and fifth layers)
The silver emulsion is prepared by the method described in Japanese Examined Patent Publication No. 46-7772.
Prepared with sodium thiosulfate pentahydrate
Chemically sensitized, 4-hydroxy-6-methyl as stabilizer
-1,3,3a, 7-Tetrazaindene, Bis (bi) as a hardener
Nylsulfonylmethyl) ether and as a coating aid
It contained saponin. After exposing the color paper produced by the above method, the following treatment
Continuous treatment was performed depending on the process and the treatment liquid. 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 minutes Treatment liquid composition <Color development tank liquid><Color development replenisher><Bleaching and fixing tank liquid><Bleach-fix replenisher A><Bleach-fix replenisher B><Stabilizing tank replacement solution and replenisher>The above-mentioned color developing tank solution and bleach-fixing tank in the automatic processor
Liquid and washing alternatives Stable tank liquid filled with color paper
The color development replenisher above every 3 minutes
Bleach-fix fixer replenishers A and B and wash wash substitute stable replenisher
A running test was performed while replenishing through. Replenishment
Liquid is 1 m of color paper²Each color development replenisher
190m, bleach-fix as a replenishment amount to the bleach-fix tank
Replenisher A and B 50m each, as the amount of replenishment to the stabilizing bath
Then, 250m of stable replenisher for washing instead of water was added. In addition, the stabilization processing bath of the automatic processor is
The first tank to the third tank is a stable tank, and the final tank is supplemented.
Fill and overflow from the last tank to the previous tank
Inflow, and this overflow liquid again
The multi-tank counter-current direction was used to flow into the tank. The total replenishment amount of the stabilizing solution for washing is 10 times the stable tank capacity.
The continuous treatment was carried out. After continuous treatment, first tank to third tank
Collect 13 pieces of each stabilizing solution for washing with water, one for each
Add the compounds shown in Table 1 and add H₂SO_FourAnd pH adjusted to 7.5 with KOH
Prepared, and using the treatment liquid after these continuous treatments,
The photosensitive material produced above was processed by the process.
Also, as a comparative sample, change to a stabilizing solution instead of washing with water and wash with running water.
A product (NO.14) treated with No. 14 was produced. The white background of the unexposed area of the processed sample was visually observed.
It was In addition, the spectral reflection density of 440 nm on the white background of the unexposed area was changed.
It was measured with an analyzer (manufactured by Hitachi, Ltd.). In addition, the magenta color of the sample obtained after processing
The light-resistant sample with a xenon arc lamp
The optical density of the dye image before and after the lightfastness test
Measured with a green light from a total (PDA-65, manufactured by Konishi Rokusha Kogyo Co., Ltd.)
Then, the fading rate was obtained. The results are shown in Table-1. Incidentally, among the compounds shown in Table-1, comparative fluorescent whitening agent [1]
The structures of [4] to [4] are shown below. Comparative optical brightener [1]Comparative optical brightener [2]Comparative optical brightener [3]Comparative optical brightener [4] From Table-1, among the known stilbene optical brighteners,
Only the compounds of the invention proved to be highly effective and highly preferred.
It Further, for the purpose of the present invention, a heavy compound having a pyrrolidone nucleus is used.
It is essential to use a combination or copolymer together
I understand. Example-2 One washing stabilizing alternative liquid after the continuous treatment of Example-1 22
Collect each of the 11 pieces as shown in Table-2
After adding the addition compounds shown in the table, the pH values shown in Table 2 were obtained.
The pH was adjusted, and the remaining 11 were each added without adding the compound.
The pH was adjusted in the same manner as the above liquid. H for pH adjustment₂SO_FourAlso
Was a diluted solution of KOH. Each of the adjusted pH
The same procedure as in Example 1 was carried out using a stabilizing solution as a substitute for washing with water.
Then, the spectral reflection density value (440 nm) was measured. Table of results
-2.As is clear from Table-2, the pH of the stabilizing solution for washing with water is 5.5.
The present invention is effective in the range of ~ 10, and this pH range is preferred.
It is preferably 6.3 to 9.5, and most preferably 7.0 to 9.0.
It Example-3 Formulation of a stabilizing agent for washing with water of Example-1 as a stabilizing agent for washing with water
1.0 g of the exemplified compound (I-7) of the present invention and the exemplified compound
[I] (General Aniline & Film Co., Ltd.)
PVP K-17) manufactured by K.K.
Other than that, the photosensitive material processing step and processing solution of Example-1 were carried out.
In the same manner as in Example-1, continuous treatment was performed. That conclusion
Very good results for unexposed white background and image storability
Got Next, 5-chloro--2-
Methyl-4-isothiazolin-3-one and 2-methyl-4-iso
Remove the antifungal agent of thiazolin-3-one and ammonia water
Then, continuous processing was performed in the same manner. As a result, continuous processing
Algae-like substance floats in the tank liquid after 3 weeks,
Mitsube white background is a mildew-proofing agent and ammonia water as an alternative to the washing of the present invention.
It was found to be slightly inferior to that contained in the constant solution.

【The invention's effect】

According to the present invention, contamination of an unexposed portion of a light-sensitive material that occurs when continuous processing is performed using a washing alternative stabilizing solution is improved without adversely affecting other performances, and continuous processing is performed using a washing alternative stabilizing solution. If the storage stability of the dye image deteriorates,
In particular, deterioration of photofading property is improved.

Claims (4)

[Claims] 1. A fluorescent brightening agent represented by the following general formula [I] is contained in an amount of 0.05 to 100 g /, and a polymer or copolymer having a pyrrolidone nucleus is contained, and the pH is in the range of 5.5 to 10.0. A stabilizing solution for washing with water for silver halide color photographic light-sensitive materials, which is characterized in that General formula [I] [In the formula, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ each represent a hydrogen atom, an alkyl group or an aryl group. And R ₃ and R ₄ and R ₅
R ₆ may combine with each other to form a heterocycle. M represents a hydrogen atom, an alkali metal atom or an ammonium group. ] 2. A water-washing alternative stabilizer for silver halide color photographic light-sensitive materials according to claim 1, wherein said water-washing alternative stabilizer for silver halide color photographic light-sensitive materials contains an ammonium compound. . 3. A silver halide color photographic light-sensitive material wash-replacement alternative stabilizing solution is used in a step subsequent to a processing solution having fixing ability after color development, and is used in a development processing in which substantially no water-washing processing is carried out. A water washing substitute stabilizer for a silver halide color photographic light-sensitive material according to claim 1 or 2. 4. The silver halide according to claim 1, 2 or 3 wherein the water-washing alternative stabilizing solution for a silver halide color photographic light-sensitive material contains a mildew-proofing agent. A stabilizing solution that is an alternative to water washing for color photographic light-sensitive materials.