JPH05158195A - Processing composition for photography and processing method - Google Patents

Abstract

PURPOSE:To provide the processing composition for photography wherein precipitate and sludge are not generated even by mixture of metallic ions by incorporating at least one kind of specified compound and to obtain a processing method with the same used therein. CONSTITUTION:The processing composition contains at least one kind of compound shown in a formula. However, in the formula, Z shows a non-metallic atom group necessary to form a heterocycle. R shows hydrogen atom or substituent. (n) shows integer of 1-10. Q1-Q3 show hydrogen atom, aliphatic group, aromatic group or heterocyclic group. However, at least one of Q1-Q3 shows hydroxyl group, carboxyl group, sulfo group, etc., or aliphatic group and aromatic group which are substituted with hydroxamic acid. W shows bivalent bonding group containing alkylene group and/or arylene group.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a processing composition containing a novel chelating agent for masking metal ions harmful to development processing of a silver halide photographic light-sensitive material and a processing method using the same. ..

[0002]

2. Description of the Related Art Generally, a silver halide black-and-white photographic light-sensitive material is processed by a processing step such as black-and-white development, fixing and washing after exposure to give a silver halide color photographic light-sensitive material (hereinafter
It is called color photosensitive material. ) Is subjected to processing steps such as color development, desilvering, washing with water and stabilization after exposure.
After exposing the silver halide color reversal light-sensitive material, black and white development,
After the reversal processing, processing is performed by processing steps such as color development, desilvering, washing with water and stabilization.

In the color developing step in color development, the exposed silver halide grains are reduced to silver by the color developing agent, and the produced oxidation product of the color developing agent reacts with the coupler to form an image dye. . In the subsequent desilvering step, the developed silver produced in the developing step is oxidized to a silver salt by a bleaching agent having an oxidizing action (bleaching), and further, with a fixing agent which forms soluble silver, it is exposed to light with the unused silver halide. Removed from layer (fixed). Bleaching and fixing may be performed as independent bleaching and fixing steps, or may be performed simultaneously as a bleach-fixing step. For details of these processing steps and their composition,
James, "The Theory of P" (4th Edition) (James, "The Theory of P
hotographic Process "4'th edition" (1977),
Research Disclosure No. 17643 28-2
Page 9, Ibid. No. 18716, 651 Left column-Right column, Ibid. No. 3
07105, pp. 880-881. In addition to the above basic processing steps, various auxiliary steps are added for the purpose of maintaining the photographic and physical qualities of the dye image or maintaining the stability of processing. For example, a washing process, a stabilizing process, a hardening process, a stopping process and the like can be mentioned.

The above-mentioned processing steps are generally carried out by an automatic processor. From a large-scale developing station equipped with a large-sized automatic developing machine, a small-sized automatic developing machine called a minilab has recently been installed in a store. Photo processing has been carried out in various places up to the photo shop, and along with this, there have been cases in which the processing performance deteriorates. One of the major causes is the mixing of metal ions into the treatment liquid. Different metal ions enter the processing liquid through different routes. For example, calcium, magnesium, and iron ions in some cases, and calcium contained in gelatin of the light-sensitive material are mixed into the processing solution through the water used for preparing the processing solution. Also, the iron chelate used in the bleach-fixing solution splashes and mixes into the developer in the pre-bath, or the solution impregnated in the film is brought in, so that the ions contained in the pre-bath are brought in. There is also. The influence of the mixed ions differs depending on the ions and the treatment liquid.
The calcium and magnesium ions mixed in the developer are
Reacts with the carbonate used as a buffering agent to generate precipitates and sludge, clogging of the filter of the circulation system of the developing machine,
It causes problems such as film processing stains. In addition, when a transition metal salt such as iron ion is mixed in the developer, decomposition of a para-phenylenediamine color developing agent, a black-and-white developing agent such as hydroquinone or monol, or a preservative such as hydroxylamine or sulfite is caused. Through, a remarkable deterioration in photographic property occurs.

Also in the bleaching solution, if a transition metal such as iron ion is mixed in the bleaching solution using hydrogen peroxide or persulfate,
After all, the stability of the solution is remarkably reduced, and problems such as poor bleaching occur. Even in a bleaching solution using a ferric aminopolycarboxylic acid complex salt as a bleaching agent, the bleaching agent decomposes and forms a precipitate with iron ions and the like especially under heat aging. Also in the fixer, in the commonly used fixer of thiosulfate, the incorporation of transition metal salts causes a decrease in stability, resulting in turbidity in the solution,
Sludge is generated. As a result, due to the clogging of the filter of the automatic developing machine, the circulation flow rate decreases, fixing failure occurs, and processing stains occur on the film. Such a phenomenon in the fixer also occurs in the wash water following the fixer, and particularly when the wash water amount is reduced, the liquid exchange rate in the tank decreases, the decomposition of thiosulfate called sulfuration and the precipitation of silver sulfide occur. Generation problems are extremely likely to occur. When such a state is exhibited, fatal stains often occur on the film surface. In a stable solution prepared by using hard water containing a large amount of calcium and magnesium, bacteria are generated using these as nutrient sources, and the solution becomes cloudy,
Causes film stains. In addition, when transition metal-based ions such as iron ions are mixed, these ions remain in the film, which deteriorates the preservability of the processed film. As described above, since the mixing of metal ions into the treatment liquid causes various adverse effects, an effective ion masking agent has been strongly desired.

As a method for solving the above-mentioned problems, a chelating agent which masks metal ions has been used. For example,
Aminopolycarboxylic acids described in JP-B Nos. 48-30496 and 44-30232 (for example, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, etc.), or JP-A-56-97347 and JP-B-56-3935.
9 and organic phosphonic acids described in West German Patent No. 2,227,639, or JP-A Nos. 52-102726, 5;
3-42730, 54-12127, 55-
Phosphonocarboxylic acids described in JP-A-126241 and JP-A-55-69595, and others, JP-A-58-195845.
No. 58-203440 and Japanese Patent Publication No. 53-4090.
Examples thereof include compounds described in No. 0 and the like. Although some of these compounds have been put to practical use, their performance has not been fully satisfactory. For example, ethylenediaminetetraacetic acid has a large hiding power for calcium ions, but when it is added to a developer, it accelerates the decomposition of the developer and the preservative of the developer in the presence of iron ions, resulting in a decrease in image density and an increase in fog. This causes deterioration of photographic quality. Further, for example, alkylidene diphosphonic acid does not cause such an adverse effect even in the presence of iron ions, but a processing solution prepared with hard water containing a large amount of calcium produces solids and causes a failure of the developing machine. Such a problem has occurred. Especially in recent years, the replenishing amount of the photographic processing liquid has been decreasing more and more in response to the increasing social demand for environmental protection.
Along with this, the retention time of the treatment liquid in the treatment machine becomes longer, and thus the deterioration of the storage stability becomes a greater problem than ever before. Therefore, it has been desired to develop an excellent new chelating agent that effectively hides the metal ions accumulated in the treatment liquid without causing any harmful effects.

[0007]

SUMMARY OF THE INVENTION A first object of the present invention is to provide a photographic processing composition which does not cause precipitation or sludge even when a metal ion is mixed therein, and a processing method using the same. A second object of the present invention is to provide a stable treatment composition and a treatment using the same, which does not reduce the active ingredient in the treatment liquid or produce a component having a photographic adverse effect even by mixing metal ions. Is to provide a method.

[0008]

The above object was achieved by the following method. That is, a processing composition containing at least one compound represented by the following general formula (I) and a method for processing a silver halide light-sensitive material using the same.

[0009]

[Chemical 2]

(In the formula, Z represents a nonmetallic atom group necessary for forming a heterocycle. R represents a hydrogen atom or a substituent. N represents an integer of 1 to 10. Q ₁ and Q ₂ and Q ₃ each represent a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group, provided that at least one of Q ₁ , Q ₂ and Q ₃ is a hydroxy group, a carboxy group, a sulfo group,
It represents an aliphatic group, aromatic group or heterocyclic group substituted with a phosphono group, a sulfonamide group, a sulfamoyl group, a carbonamido group, a carbamoyl group or a hydroxamic acid group. W represents a divalent linking group containing an alkylene group and / or an arylene group. )

First, the compound represented by formula (I) will be described in detail below. The aliphatic group represented by Q ₁ , Q ₂ and Q ₃ is a linear, branched or cyclic alkyl group, alkenyl group or alkynyl group having 1 carbon atom.
Nos. 10 to 10 are preferred. The aliphatic group is more preferably an alkyl group, further preferably an alkyl group having 1 to 4 carbon atoms, and particularly preferably a methyl group or an ethyl group.

The aromatic group represented by Q ₁ , Q ₂ and Q ₃ is a monocyclic or bicyclic aryl group, and examples thereof include a phenyl group and a naphthyl group, and a phenyl group is more preferable.

The heterocycle formed by Z and Q ₁ , Q ₂ , Q
_The heterocyclic group represented by 3 is a 3- to 10-membered saturated or unsaturated heterocyclic ring containing at least one of N, O or S atoms, which may be a single ring, A condensed ring may be formed with an aromatic ring or a heterocycle. The heterocycle is preferably a 5- or 6-membered unsaturated heterocycle. Examples of the heterocycle include pyridine, pyrazine,
Pyrimidine, pyridazine, triazine, tetrazine, thiophene, furan, pyran, pyrrole, imidazole,
Pyrazole, thiazole, isothiazole, oxazole, isoxazole, oxadiazole, thiadiazole, thianthrene, isobenzofuran, chromene, xanthene, phenoxathiin, indolizine, isoindole, indole, triazole, triazolium,
Tetrazole, quinolidine, isoquinoline, quinoline,
Examples include phthalazine, naphthyridine, quinoxaline, quinazoline, cinnoline, carbazole, carboline, phenanthridine, acridine, pteridine, phenanthroline, phenazine, phenothiazine, phenoxazine, chroman, pyrroline, pyrazoline, indoline and isoindoline. Preferably, it is a monocyclic heterocycle, pyridine, pyrazine, pyrimidine, pyridazine,
Examples thereof include thiophene, furan, pyrrole, imidazole, triazole, tetrazole, pyrazole, thiazole, isothiazole, oxazole, isoxazole, thiadiazole and oxadiazole. A nitrogen-containing monocyclic heterocycle is more preferable, and pyridine, pyrazine, pyrimidine, pyridazine, pyrrole, imidazole, triazole, tetrazole, and pyrazole are particularly preferable.

The substituent represented by R is an alkyl group (eg, methyl group, ethyl group), aralkyl group (eg, phenylmethyl group), alkenyl group (eg, allyl group), alkynyl group, alkoxy group (eg, methoxy group). , Ethoxy group), aryl group (eg phenyl group, p
-Methylphenyl group), an amino group (for example, a dimethylamino group), an acylamino group (for example, an acetylamino group),
Sulfonylamino group (eg methanesulfonylamino group), ureido group, urethane group, aryloxy group (eg phenyloxy group), sulfamoyl group (eg methylsulfamoyl group), carbamoyl group (eg carbamoyl group, methylcarbamoyl group), Alkylthio group (methylthio group), arylthio group (eg phenylthio group), sulfonyl group (eg methanesulfonyl group),
Sulfinyl group (eg methanesulfinyl group), hydroxy group, halogen atom (eg chlorine atom, bromine atom,
Fluorine atom), cyano group, sulfo group, carboxy group, phosphono group, aryloxycarbonyl group (eg phenyloxycarbonyl group), acyl group (eg acetyl group, benzoyl group), alkoxycarbonyl group (eg methoxycarbonyl group), acyloxy Examples thereof include a group (for example, acetoxy group), a carbonamido group, a sulfonamide group, a nitro group, a hydroxamic acid group and the like, and if possible, a dissociation product or a salt thereof. When the above substituent has a carbon atom, it preferably has 1 to 4 carbon atoms.

Of the above-mentioned substituents, a carboxy group, a phosphono group, a sulfo group, a hydroxy group, an alkoxy group, an amino group, a sulfamoyl group, a carbamoyl group, an alkylthio group, a carbonamido group and a sulfonamide group are more preferable. Is a carboxy group, a phosphono group, a sulfo group, and a hydroxy group. A carboxy group, a phosphono group and a sulfo group are more preferable, and a carboxy group is particularly preferable. When n = 2 to 10, R may be the same or different.

The aliphatic group, aromatic group and heterocyclic group represented by Q ₁ , Q ₂ and Q ₃ are hydroxy group, carboxy group, sulfo group, phosphono group, sulfonamide group, sulfamoyl group and carbonamido group. In addition to the carbamoyl group or the hydroxamic acid group, it may have a substituent again, and as the substituent, those enumerated as the substituents represented by R can be applied. The substituent for Q ₁ , Q ₂ and Q ₃ is preferably a hydroxy group, a carboxy group, a sulfo group or a phosphono group, more preferably a carboxy group. The divalent linking group represented by W is preferably represented by the following general formula (W). Formula ^{(W) - (W 1 -D} ) m -W 2 - wherein, W ¹ and W ² may be different even in the same straight-chain or branched alkylene group having 2 to 8 carbon atoms (Including a cycloalkylene group having 5 to 10 carbon atoms), 5 to 5 carbon atoms
It represents a cycloalkylene group having 10 carbon atoms, an arylene group having 6 to 10 carbon atoms or an aralkylene group having 7 to 10 carbon atoms. D
Represents -O-, -S-, -N (Rw)-, or a divalent nitrogen-containing heterocyclic group. Rw is a hydrogen atom or -COOM ₁ ,-
PO ₃ M ₂ M ₃ , -OH or -SO ₃ M ₄ alkyl group having 1 to 8 carbon atoms which may be substituted or 6 carbon atoms
10 represents an aryl group. M ₁ , M ₂ , M ₃ and M
Each ₄ represents a hydrogen atom or a cation. Examples of the cation include alkali metals (eg, lithium, sodium, potassium), ammonium (eg, ammonium, tetraethylammonium), pyridinium and the like. The linking group represented by W may have a substituent, and examples of the substituent include the substituent represented by R.

The divalent nitrogen-containing heterocyclic group is preferably a 5- or 6-membered ring in which the hetero atom is nitrogen, and is bonded to W ¹ and W ² at adjacent carbon atoms such as imidazolyl group. The thing is more preferable. As W ¹ and W ² , an alkylene group having 2 to 4 carbon atoms is preferable. m represents an integer of 0 to 3, and when m is 2 or 3, W ¹ -D may be the same or different. m is preferably 0 to 2, and 0
Or, 1 is more preferable, and 0 is particularly preferable. Specific examples of W include the following.

[0018]

[Chemical 3]

[0019]

[Chemical 4] Among the compounds represented by the general formula (I), compounds represented by the following general formulas (II), (III), (IV), (V) or (VI) are preferable. General formula (II)

[0020]

[Chemical 5]

In the formula, Z, R, n and W have the same meanings as in formula (I). L ₁ , L ₂ and L ₃ represent an alkylene group or an arylene group. A ₁ , A ₂ and A ₃ represent a carboxy group, a phosphono group, a hydroxy group, a sulfo group, an alkoxy group, an alkylthio group, a sulfonamide group, a sulfamoyl group, an amino group, a carbonamido group, a carbamoyl group or a hydroxamic acid group. .. General formula (III)

[0022]

[Chemical 6]

In the formula, Z, R, n and W have the same meanings as in formula (I). Z ₁ , R ₁ and n ₁ have the same meanings as Z, R and n in formula (I), respectively. L _2, L ₃ has the same meaning as L _2, L ₃ in the general formula (II). A _2, A ₃ has the same meaning as A _2, A ₃ in the general formula (II). General formula (IV)

[0024]

[Chemical 7]

In the formula, Z, R, n and W have the same meanings as in formula (I). Z ₂ , R ₂ and n ₂ have the same meanings as Z, R and n in formula (I), respectively. L _1, L ₃ has the same meaning as L _1, L ₃ in the general formula (II). A _1, A ₃ has the same meaning as A _1, A ₃ in the general formula (II). General formula (V)

[0026]

[Chemical 8]

In the formula, Z, R, n and W have the same meanings as in formula (I). Z ₁ and Z ₂ are synonymous with Z in the general formula (I), R ₁ and R ₂ are synonymous with R in the general formula (I), and n ₁ and n ₂ are the same as n in the general formula (I). Are synonymous. L ₃ has the same meaning as L ₃ in formula (II), and A
₃ has the same meaning as A ₃ in formula (II). General formula (VI)

[0028]

[Chemical 9]

In the formula, Z, R, n and W have the same meanings as in formula (I). Z ₁ , Z ₂ and Z ₃ are Z in the general formula (I).
R ₁ , R ₂ , and R ₃ have the same meanings as R in the general formula (I), and n ₁ , n ₂ , and n ₃ have the same meanings as n in the general formula (I).

In the general formulas (I) to (VI), R,
The substituents represented by R ₁ , R ₂ and R ₃ are preferably those substituted at the ortho position with respect to the nitrogen atom of the diamine moiety. L ₁ and L in the general formulas (II), (III), (IV) and (V)
_The alkylene group represented by ₂ and L ₃ may be linear or branched, and preferably has 1 to 6 carbon atoms. L ₁ , L ₂ and L ₃ may be the same or different. L ₁ , L ₂ and L ₃ may have a substituent, and examples thereof include the substituent of Q ₁ . L ₁ , L ₂ and L ₃ are preferably a methylene group or an ethylene group.
The arylene group represented by L ₁ , L ₂ and L ₃ is preferably an arylene group having a carbon number of 6 to 10, and examples thereof include a phenylene group and a naphthylene group, more preferably a phenylene group. Formulas (II), (III), (IV),
As A ₁ , A ₂ and A ₃ in (V) and (VI), a carboxy group, a phosphono group, a sulfo group and a hydroxy group are preferable, and a carboxy group, a phosphono group and a sulfo group are more preferable, and a carboxy group is particularly preferable. Groups are preferred. Of the compounds represented by the general formula (II), (III), (IV), (V) or (VI), more preferred are the general formula (II),
The compound represented by formula (III) or (IV), particularly the compound represented by formula (II) is preferable. Specific examples of the compound represented by formula (I) are shown below, but the invention is not limited thereto.

[0031]

[Chemical 10]

[0032]

[Chemical 11]

[0033]

[Chemical 12]

[0034]

[Chemical 13]

[0035]

[Chemical 14]

[0036]

[Chemical 15]

[0037]

[Chemical 16]

[0038]

[Chemical 17]

Next, representative synthetic examples of the compounds of the present invention are shown below.

[0040]

[Chemical 18]

That is, it can be obtained by substituting a halogen atom of a halogen-substituted heterocyclic derivative with a diamine derivative and reacting the obtained compound with a halogen-substituted compound. In the reaction of the halogen-substituted heterocyclic derivative and the diamine derivative, it is preferable to use an alkali and a catalyst. Examples of the alkali include potassium carbonate and sodium carbonate. Examples of the catalyst include copper powder, CuCl,
CuBr, CuI, CuO and the like can be mentioned.

The reaction may or may not use a solvent. When used, it is not limited as long as it does not participate in the reaction. Examples thereof include alcohols (methanol, ethanol, isopropanol, butanol, pentanol, etc.), dioxane, dimethylformamide and the like. A solvent is preferably used in the reaction with the halogen-substituted compound. When used, it is not limited as long as it does not participate in the reaction. For example, water, alcohol (for example, methanol, ethanol, isopropanol), dioxane and the like can be mentioned. This reaction preferably uses a base, and examples thereof include sodium hydroxide, potassium hydroxide, tertiary amines (eg triethylamine etc.), pyridine and the like. Synthesis example 1. Synthesis of Exemplified Compound 1

[0043]

[Chemical 19]

Synthesis of compound 1a 2-chloro-3-carboxypyridine 25.0 g
(0.159 mol), ethylenediamine 95.4 g
(1.59 mol), potassium carbonate 40.0 g (0.
289 mol), copper powder 0.3 g, methanol 100 ml
And was heated to reflux for 2 hours. The insoluble matter was filtered off, the filtrate was concentrated, and concentrated hydrochloric acid was added to adjust the pH to about 1.
The precipitated solid was collected by filtration, washed with cold water, and dried to give 33.2 g (0.114 mol) of pale yellow solid 1a.
Obtained. Yield 72% Synthesis of Compound 1 29.1 g (0.100 m) of Compound 1a synthesized above
ol), 25.6 g (0.22 g) of sodium chloroacetate
(0 mol) was dissolved in 50 ml of water, and 124 ml (0.620 mol) of 5N aqueous sodium hydroxide solution was gradually added to the mixture while heating and stirring at 50 ° C. After stirring at 50 ° C. for 4 hours, the reaction solution was filtered and the filtrate was concentrated to an internal volume of about 60 ml. Concentrated hydrochloric acid 3
2.5 g (0.320 mol) was added and the mixture was allowed to stand in the refrigerator overnight, then the precipitated solid was collected by filtration and washed with cold water,
16.1 g of white crystal 1 (0.
0542 mol) was obtained. Yield 54% Elemental analysis value C ₁₂ H ₁₅ N ₃ O ₆ H CN Calculated value (%) 5.09 48.49 14.14 Measured value (%) 5.18 48.32 14.03 Other compounds It can be synthesized in the same manner.

The compound of the present invention can be applied to any processing composition for processing a silver halide black and white light-sensitive material or a silver halide color light-sensitive material. For example, as a processing composition for a black-and-white photosensitive material, a general-purpose black-and-white developing solution,
Processing compositions for color light-sensitive materials such as infectious developer for squirrel film, fixer and washing water, color developer, bleaching solution, fixing solution, bleach-fixing solution, adjusting solution, stopping solution, hardening solution, washing with water. Examples thereof include water, a stabilizing solution, a rinsing solution, a fogging solution, and a toning solution, but are not limited thereto. The addition amount of the compound of the present invention varies depending on the treatment composition to be added, but it is used in the range of 10 mg to 50 g per liter of the treatment composition. More specifically, for example, when it is added to a black-and-white developing solution or a color developing solution, the amount is preferably 0.5 to 10 g, and particularly preferably 0.5 to 5 g, per liter of the processing liquid. When it is added to the bleaching solution, it is 0.1 to 20 g, and particularly preferably 0.1 to 5 g, per liter of the bleaching solution. When it is added to the fixing solution or the bleach-fixing solution, it is 1 to 40 g, and particularly preferably 1 to 20 g, per liter of the processing solution. When it is added to the stabilizing solution, it is 50 mg to 1 g, and particularly preferably 50 to 300 mg, per liter of the stabilizing solution.
The compound of the present invention may be used alone or in combination of two or more kinds. Further, various chelating agents can be used in combination as long as the effect of the compound of the present invention is not impaired. Preferred examples of chelating agents that can be used in combination include aminopolycarboxylic acids such as ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, and ethylenediamine-N, N, N ', N'. -Organophosphonic acids such as tetramethylenephosphonic acid or European Patent 345
Examples thereof include the hydrolyzate of the maleic anhydride polymer described in 172A1.

Hydroquinone type developing agents such as hydroquinone, bromohydroquinone, methylhydroquinone and 2,5-dichlorohydroquinone are preferable as the developing agent for the black and white developing solution. Further, as auxiliary developing agents, p-aminophenol type developing agents such as N-methyl-p-aminophenol and 1-phenyl-4-methyl-4-
A 3-pyrazolidone-based developing agent such as hydroxymethyl-3-pyrazolidone is preferably used in combination. Further, it is preferable to use a sulfite-based compound such as sodium sulfite, potassium sulfite, sodium bisulfite, potassium metabisulfite, or formaldehyde sodium bisulfite as a preservative. The pH of the developer is preferably in the range of 9 to 13, and alkaline agents used for setting the pH include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate and the like. In addition, a pH buffering agent such as boric acid, borax, silicate, sodium triphosphate or potassium triphosphate can be used in the developer. Further, development inhibitors such as potassium bromide and potassium iodide, organic solvents such as ethylene glycol, diethylene glycol, triethylene glycol, dimethylformamide, methyl cellosolve, hexylene glycol, ethanol and methanol, indazole compounds, benzimidazole. Antifoggants such as compounds based on compounds and benztriazole compounds may be included.
Development accelerators described in Volume 176, No. 17643, Item XXI (December, 1978) may be included. US Patent 4,
The amine compounds described in JP-A No. 269,929, JP-A-61-267759 and Japanese Patent Application No. 1-291818 may be contained. Further, if necessary, a color toning agent, a surfactant, a hardener and the like may be contained. Further, a silver stain preventing agent such as the compounds described in JP-A-56-24347 can be used in the developer. Also, European Patent Publication 1
36582, British Patent 958678, U.S. Pat. No. 3,232,761, and amino compounds such as alkanolamines described in JP-A-56-106244, which promote development.
It can be used for the purpose of increasing contrast.

The fixing solution for black and white is an aqueous solution of PH 4.2 to 7.0 containing thiosulfate as a fixing agent. Examples of thiosulfates include sodium thiosulfate and ammonium thiosulfate. In addition to thiosulfate, JP-A-57-15084
It is also preferable to use the mesoionic compound described in No. 2 in combination. Hardeners (eg, water-soluble aluminum salts); tartaric acid, citric acid, gluconic acid or their derivatives; preservatives (eg, sulfites, bisulfites), p
An H buffer (eg, acetic acid, boric acid) and a pH adjuster (eg, sulfuric acid) can be included.

The color developing solution is an alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component and having a pH of 9 to 12. As the color developing agent, aminophenol compounds are also useful, but p-phenylenediamine compounds are preferably used, and typical examples thereof include 3-methyl-4-amino-N, N-diethylaniline and 3 -Methyl-4-
Amino-N-ethyl-N-β-hydroxyethylaniline,
4-Amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl- Examples include β-methoxyethylaniline and their sulfates, hydrochlorides or p-toluenesulfonates. Color developers include pH buffering agents such as alkali metal carbonates, borates or phosphates; chloride salts, bromide salts, iodide salts, benzimidazoles, benzothiazoles or mercapto compounds. It is common to include an inhibitor or an antifoggant. If necessary, various preservatives such as hydroxylamine, diethylhydroxylamine and sulfite; organic solvents such as ethylene glycol and diethylene glycol; development acceleration such as benzyl alcohol, polyethylene glycol, quaternary ammonium salts and amines Agents; dye-forming couplers; competing couplers; auxiliary developing agents such as 1-phenyl-3-pyrazolidone; nucleating agents such as sodium boron hydride and hydrazine compounds; tackifiers; 4,4'-diamino-2, A fluorescent whitening agent such as a 2′-disulfostilbene compound; various surfactants such as an alkyl sulfonic acid, an aryl sulfonic acid, an aliphatic carboxylic acid, and an aromatic carboxylic acid can be added.

Examples of the bleaching agent used in the bleaching solution and the bleach-fixing solution include compounds of polyvalent metals such as iron (III); peracids; quinones; iron salts and the like. Typical bleaching agents include iron chloride; ferricyanide; dichromate; organic complex salts of iron (III) (eg ethylenediaminetetraacetic acid,
Metal complex salts of aminopolycarboxylic acids such as diethylenetriaminepentaacetic acid and 1,3-diaminopropanetetraacetic acid);
Persulfate and the like can be mentioned. A bleaching solution or a bleach-fixing solution using an aminopolycarboxylic acid iron (III) complex salt,
Used at a pH of 3.5-8. Known additives such as rehalogenating agents such as ammonium bromide and ammonium chloride; pH buffering agents such as ammonium nitrate; metal corrosion inhibitors such as ammonium sulfate may be added to the bleaching solution and bleach-fixing solution. it can. In addition to the above compounds, the bleaching solution and the bleach-fixing solution preferably contain an organic acid for the purpose of preventing bleach stain. Particularly preferable organic acid is a compound having an acid dissociation constant (pKa) of 2 to 5.5, and specifically, acetic acid, propionic acid and the like are preferable. Examples of the fixing agent used in the fixing solution and the bleach-fixing solution for color light-sensitive materials include thiosulfates, thiocyanates, thioether compounds, thioureas, and large amounts of iodide salts. Is most commonly used, with ammonium thiosulfate being the most widely used. Further, the combined use of thiosulfate and thiocyanate, thioether compounds, thiourea and the like is also preferable. Preservatives such as sulfites, bisulfites, carbonyl bisulfite adducts or sulfinic acid compounds described in European Patent 294769A are used in fixing solutions and bleach-fixing solutions; various fluorescent whitening agents; defoaming agents; Surfactant; polyvinylpyrrolidone; methanol; US Pat. No. 3,
893,858, West German Patent 1,290,812, JP-A-53-95,63
A bleaching accelerator such as a compound having a mercapto group or a disulfide group described in No. 0 may be contained.

Water washing and stabilizing solutions include water softeners such as inorganic phosphoric acid, polyaminocarboxylic acid and organic aminophosphonic acid; chlorine-based sterilization such as isothiazolone compounds, siabendazoles and sodium chlorinated isocyanurate. Agents; metal salts such as Mg salt, Al salt, Bi salt; surfactants; hardeners; germicides and the like. Examples of dye stabilizers that can be used in the stabilizing solution include aldehydes such as formalin and glutaraldehyde, N-methylol compounds such as dimethylolurea, hexamethylenetetramine, and aldehyde sulfite adducts. In addition, the stabilizing solution also contains a pH adjusting buffer such as boric acid or sodium hydroxide; 1-
A chelating agent such as hydroxyethylidene-1,1-diphosphonic acid and ethylenediaminetetraacetic acid; an antisulfurizing agent such as alkanolamine; an optical brightening agent; a mildewproofing agent and the like can be contained.

The photographic light-sensitive material which can be processed with the processing composition of the present invention includes a usual black-and-white silver halide photographic light-sensitive material (for example, black-and-white light-sensitive material for photographing, black-and-white light-sensitive material for X ray, black-and-white light sensitive material for printing). Material), a normal multilayer silver halide color photographic light-sensitive material (for example, a color negative film, a color reversal film, a color positive film,
Film color negative film, color photographic paper, reversal color photographic paper, direct positive color photographic paper), infrared light sensitive material for laser scanner, diffusion transfer photosensitive material (eg silver diffusion transfer photosensitive material, color diffusion transfer photosensitive material) And so on. The photographic light-sensitive material according to the present invention has various layer structures on one side or both sides depending on the purpose of the light-sensitive material (for example, a silver halide emulsion layer having sensitivity to red, green and blue, an undercoat layer, an antihalation layer, It may be a filter layer, an intermediate layer, a surface protective layer) or an array.

Support of photographic light-sensitive material according to the present invention; coating method; kind of silver halide used in silver halide emulsion layer, surface protective layer, etc. (eg, silver iodobromide, silver iodochlorobromide, odor) Silver halide, silver chlorobromide, silver chloride), its particle shape (eg, cubic, tabular, spherical), its particle size, its variation rate, its crystal structure (eg, core / shell structure, multiphase structure, homogeneous phase) Structure), its manufacturing method (for example, single jet method, double jet method), binder (for example, gelatin), hardener, antifoggant, metal doping agent, silver halide solvent, thickener, emulsion precipitation agent, size Stabilizer, anti-adhesion agent, stabilizer, anti-staining agent, dye image stabilizer, stain inhibitor, chemical sensitizer, spectral sensitizer, sensitivity enhancer, supersensitizer, nucleating agent, coupler ( For example, the pivaloyl acetanilide type and the Ben Ileacetanilide type yellow coupler, 5-pyrazolone type or pyrazoloazole type magenta coupler, phenol type or naphthol type cyan coupler, DIR coupler, bleaching accelerator releasing type coupler, competitive coupler, colored coupler), coupler dispersion method ( For example, oil-in-water dispersion method using a high boiling point solvent),
Plasticizer, antistatic agent, lubricant, coating aid, surface active agent,
Whitening agent, formalin scavenger, light scattering agent, matting agent, light absorbing agent, ultraviolet absorbing agent, filter dye, irradiation dye, development improving agent, matting agent, preservative (eg, 2-phenoxyethanol), anti-vibration agent. There is no particular limitation on the agent and the like, and for example, Product Licensing magazine, Volume 92, pp. 107-110 (19
December 71) and Research Disclosure (hereinafter referred to as RD) No. 176
43 (December 1978), RD magazine No. 18716 (1
997 November), RD magazine No. 307105 (1989)
(November, 2011) can be referred to.

[0053]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto. Example 1 The following processing solutions were prepared. (Color developer) Unit (g) Diethylenetriaminepentaacetic acid 1.0 Chelate compound (shown in Table 1) 0.01 mol Sodium sulfite 4.0 Potassium carbonate 30.0 Potassium bromide 1.4 Potassium iodide 1.5 mg Hydroxyl Amine sulphate 2.4 4- (N-ethyl-N-β-hydroxyethylamino) -2-methylaniline sulphate 4.5 Water added 1000 ml pH 10.05

Ferric chloride as ferric ion of 5 ppm and calcium nitrate as calcium ion of 150 ppm were added to the above color developing solutions to obtain samples 101 to 116. 5 liters of each of these samples is 10 cm long, 25 cm wide,
It was filled in a hard vinyl chloride container having a depth of 30 cm, and while the liquid in the container was continuously circulated at a rate of 3 liters per minute by a pump, the temperature was adjusted to 38 ° C. and a 30-day aging test was performed. This container is equipped with a floating lid that covers the liquid surface of 200 cm ^{2, and} the liquid surface area open to the air is 50 cm.
² Next, the multilayer color light-sensitive material sample 105 described in Example 1 of JP-A-2-89045 was cut to a width of 35 mm and subjected to wedge exposure of 5 CMS at a color temperature of 4800K. This was used as a color developer, which was used immediately after preparation (new solution) of Samples 101 to 116 and after the aging test, and was processed by the following processing steps. [Processing step] Processing time Processing temperature Color development 3 minutes 15 seconds 37.8 ° C Bleaching 50 seconds 38.0 ° C Settling 1 minute 40 seconds 38.0 ° C Washing (1) 30 seconds 38.0 ° C Washing (2 ) 20 seconds 38.0 ℃ Stability 20 seconds 38.0 ℃

(Bleach) Unit (g) 1,3-Propanediaminetetraacetate Iron (III) ammonium 0.55 mol Ammonium bromide 85 Ammonium nitrate 20 Glycolic acid 55 Water was added to 1000 ml pH 4.0

(Fixing Solution) Unit (g) Ethylenediaminetetraacetic acid diammonium salt 1.7 Ammonium sulfite 14.0 Ammonium thiosulfate aqueous solution (700 g / liter) 260.0 ml Water was added to 1000 ml pH 7.0

(Washing water) Tap water was used as an H-type strongly acidic cation exchange resin (Amberlite IR-produced by Rohm and Haas).
120B) and OH-type strongly basic anion exchange resin (Amberlite IRA-400) were passed through a mixed bed column to adjust the concentration of calcium and magnesium ions to 3
Treatment to less than mg / l, followed by 20 mg / l sodium isocyanurate dichloride and 15 sodium sulfate
0 mg / l was added. The pH of this solution is 6.5-
It was in the range of 7.5.

(Stabilizer) Unit (g) Water 900 ml Pyrazole 4.0 g Formalin (37% formaldehyde solution) 1.5 ml Polyoxyethylene-p-monononylphenyl ether 0.3 g (average degree of polymerization 10) Ethylenediaminetetraacetic acid diester Sodium 0.05g Add water 1000ml pH 5.8

At the exposure amount at which the B concentration measured with blue light (B light) becomes 2.5 when treated with a new liquid, the B concentration obtained with the liquid after the aging test is changed to the X-Rite 310 type photograph density. The difference ΔD _B with the new solution was determined by measuring with a tometer. Further, the residual ratio of the developing agent and hydroxylamine after aging was determined by analysis. Further, the color developing solution after aging was visually inspected for the occurrence of precipitation. The above results are shown in Table 1.

[0060]

[Table 1]

As is clear from Table 1, when the conventional chelating agent is added, the level of prevention of precipitation and securing of the liquid stability is insufficient, but the addition of the compound of the present invention causes a significant increase. You can see the effect.

Example 2 As a silver halide color light-sensitive material, among Sample No. 214 (multilayer color paper) described in Example 2 of JP-A-2-139544, a bisphenol compound of III-23 described in JP-A-2-139544 was used. Instead, III-10 was changed to the following compounds as yellow coupler (ExY), cyan coupler (ExC), image stabilizer (Cpd-8), solvent (Solv-6), and oxonol dye, respectively. Furthermore, the following compounds were used as antiseptics (antibacterial and antifungal agents). A multilayer color photographic paper B was prepared.

[0063]

[Chemical 20]

[0064]

[Chemical 21]

[0065]

[Chemical formula 22]

[0066]

[Chemical formula 23]

[0067]

[Chemical formula 24]

Next, the following processing solutions were prepared. [Color developer] Water 600 ml Potassium bromide 0.015 g Potassium chloride 3.1 g Triethanolamine 10.0 g Potassium carbonate 27 g Fluorescent brightener (WHITEX 4B, manufactured by Sumitomo Chemical Co., Ltd.) 1.0 g Preservative (disodium -N, N-bis (sulfonate ethyl) hydroxylamine) 45 mmol N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 5.0 g Water was added to 1000 ml. pH (25 ° C) 10.05

The above color developing solution was designated as Sample 201, and the compounds of the present invention and comparative compounds were added thereto in the amounts shown in Table 5 to be designated as Samples 202 to 208. 5 ppm of ferric ion and 150 ppm of calcium ion were added to each of these color developers, and the mixture was allowed to stand for 20 days at 38 ° C. in a beaker so that the aperture ratio was 0.10 cm ⁻¹ . Sensitometer (F product from Fuji Photo Film Co., Ltd.
WH type) was used to perform gradation exposure of a three-color separation filter for sensitometry. The exposure was performed so that the exposure amount was 250 CMS with the exposure time of 0.1 seconds. After the exposure, processing was performed according to the following steps using the (fresh solution) immediately after preparation of the solution prepared above and the aged color developing solution (aging solution). [Treatment process] Treatment process Temperature Time Color development 38 ° C 45 sec Bleach fixing 35 ° C 25 sec Rinse 35 ° C 20 sec Rinse 35 ° C 20 sec Rinse 35 ° C 20 sec Dry 80 ° C 60 sec

[Bleach-fixing solution] Water 400 ml Ammonium thiosulfate (700 g / l) 100 ml Sodium sulfite 17 g Ethylenediaminetetraacetic acid iron (III) ammonium 55 g Ethylenediaminetetraacetate disodium 5 g Ammonium bromide 40 g Water is added 1000 ml pH (25 ° C.) 6.8 [Rinse solution] Ion-exchanged water (calcium and magnesium are each 3 ppm or less)

With respect to the minimum density (Dmin) of yellow when processed with a fresh solution and the sensitivity (logarithm of exposure dose giving density 0.5) of magenta, the minimum density Dmin of yellow when processed with an aged solution. The amount of increase (ΔDmin) and the amount of change in magenta sensitivity (ΔS) were calculated. In addition, the residual amount of the main drug in the aged liquid was quantified by high performance liquid chromatography. Further, it was observed whether or not a precipitate was formed in the liquid over time.

[0072]

[Table 2]

As is clear from Table 2, according to the present invention, the values of ΔDmin and ΔS are small and the fluctuation of the photographic property is suppressed. Furthermore, the occurrence of precipitation is also greatly improved compared to the comparative example. In particular, among the conventional compounds, those having a large effect of preventing the formation of precipitates have poor preservative properties of the main drug, while those having a small amount of decomposition of the main drug have been insufficient in preventing the formation of precipitates. On the other hand, it can be seen that the compound represented by the general formula (I) of the present invention provides a stable developing solution without forming a precipitate.

Example 3 Sample No. 3 of the example of JP-A-3-174148. B
-6 was used to prepare a developing solution (B) in which the disodium ethylenediaminetetraacetate in the following developing solution (A) was replaced with the same molar amount of Exemplified Compound 3, and each developing solution was heated at 40 ° C.
When a running treatment was performed after 4 days of aging, improvement in precipitation was observed. Further, when the residual amount and pH of hydroquinone and potassium sulfite in the developer after the lapse of time were measured, it was found that the reduction of hydroquinone and potassium sulfite due to aerial oxidation was suppressed to a minimum, and the increase in pH was also suppressed. ,understood.

Developer (A) Hydroquinone 45.0 g N-methyl-p-aminophenol 1/2 sulfate 0.8 g Sodium hydroxide 18.0 g Potassium hydroxide 55.0 g 2-Sulfosalicylic acid 45.0 g Boric acid 25. 0 g Potassium sulfite 110.0 g Ethylenediaminetetraacetic acid disodium 1.0 g Potassium bromide 6.0 g 5-Methylbenztriazol 0.6 g n-Butyl-diethanolamine 15.0 g Water is added to make 1 liter (pH = 11.6)

[0076]

The treatment liquid containing the compound of the present invention suppresses the oxidation or decomposition of the components of the treatment liquid due to the action of metal ions, maintains the performance of the treatment liquid for a long period of time, and further There is no precipitation in the solution due to accumulation, and therefore there are no problems such as film stains and clogging of filters of automatic processors.

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[Procedure amendment]

[Submission date] August 13, 1992

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0016

[Correction method] Change

[Correction content]

The aliphatic group, aromatic group and heterocyclic group represented by Q ₁ , Q ₂ and Q ₃ are hydroxy group, carboxy group, sulfo group, phosphono group, sulfonamide group, sulfamoyl group and carbonamido group. In addition to the carbamoyl group or the hydroxamic acid group, it may have a substituent again, and as the substituent, those enumerated as the substituents represented by R can be applied. The substituent for Q ₁ , Q ₂ and Q ₃ is preferably a hydroxy group, a carboxy group, a sulfo group or a phosphono group, and more preferably a carboxy group. The divalent linking group represented by W is preferably represented by the following general formula (W). Formula _{^{(W) - (W 1 -D}} ) m -W 2 - wherein, ^{W 1} and ^{W 2} may be different even in the same straight-chain or branched alkylene group having 1 to 8 carbon atoms (Including cycloalkylene group having 5 to 10 carbon atoms), 6 to carbon atoms
It represents an arylene group having 10 or an aralkylene group having 7 to 10 carbon atoms and a divalent nitrogen-containing heterocyclic group. D is -O-,
-S-, -N (Rw)-, and a divalent nitrogen-containing heterocyclic group are represented. Rw is a hydrogen atom or -COOM ₁ , -PO ₃ M ₂
It represents an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 10 carbon atoms, which may be substituted with M ₃ , —OH or —SO ₃ M ₄ . M ₁ , M ₂ , M ₃ and M ₄ each represent a hydrogen atom or a cation. As a cation,
Examples thereof include alkali metals (eg, lithium, sodium, potassium), ammonium (eg, ammonium, tetraethylammonium), pyridinium and the like. The linking group represented by W may have a substituent, and examples of the substituent include the substituent represented by R.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0018

[Correction method] Change

[Correction content]

[0018]

[Chemical 3]

[Procedure 3]

[Document name to be amended] Statement

[Item name to be corrected] 0040

[Correction method] Change

[Correction content]

[0040]

[Chemical 18]

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0046

[Correction method] Change

[Correction content]

Hydroquinone type developing agents such as hydroquinone, bromohydroquinone, methylhydroquinone and 2,5-dichlorohydroquinone are preferable as the developing agent for the black and white developing solution. Further, as auxiliary developing agents, p-aminophenol type developing agents such as N-methyl-p-aminophenol and 1-phenyl-4-methyl-4-
A 3-pyrazolidone-based developing agent such as hydroxymethyl-3-pyrazolidone is preferably used in combination. Further, it is preferable to use a sulfite-based compound such as sodium sulfite, potassium sulfite, sodium bisulfite, potassium metabisulfite, or formaldehyde sodium bisulfite as a preservative. The pH of the developer is preferably in the range of 9 to 13, and alkaline agents used for setting the pH include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate and the like. In addition, a pH buffering agent such as boric acid, borax, silicate, sodium triphosphate or potassium triphosphate can be used in the developer.
Further, a development inhibitor such as potassium bromide or potassium iodide,
Ethylene glycol, diethylene glycol, triethylene glycol, dimethylformamide, methyl cellosolve, hexylene glycol, ethanol, organic solvents such as methanol, indazole-based compounds, benzimidazole-based compounds, may include antifoggants such as benztriazole-based compounds, Research Disc
Loss Volume 176, No. 17643, XXI
The development accelerator described in the paragraph (December issue, 1978) may be included. Further, the amine compounds described in U.S. Pat. No. 4,269,929, JP-A-61-267759 and Japanese Patent Application No. 1-291818 may be contained. Further, if necessary, a color toning agent, a surfactant, a hardener and the like may be contained. Further, a silver stain preventive agent, for example, JP-A-5-
The compounds described in 6-24347 can be used. Further, amino compounds such as alkanolamines described in European Patent Publication No. 136582, British Patent No. 958678, US Pat. No. 3,232,761, and Japanese Patent Laid-Open No. 56-106244 can be used for the purpose of promoting development and increasing contrast. ..

[Procedure Amendment 5]

[Document name to be amended] Statement

[Correction target item name] 0069

[Correction method] Change

[Correction content]

The above color developing solution was designated as Sample 201, and the compounds of the present invention and the comparative compound were added thereto in the amounts shown in Table 2 to be designated as Samples 202 to 208. 5 ppm of ferric ion and 150 ppm of calcium ion were added to each of these color developers, and the mixture was allowed to stand for 20 days at 38 ° C. in a beaker so that the aperture ratio was 0.10 cm ⁻¹ . A sensitometer (FWH type manufactured by Fuji Photo Film Co., Ltd.) was used for the multi-layer color photographic printing paper B, and gradation exposure of a three-color separation filter for sensitometry was applied. The exposure was performed so that the exposure amount was 250 CMS with the exposure time of 0.1 seconds. After the exposure, processing was performed according to the following steps using the (fresh solution) immediately after preparation of the solution prepared above and the aged color developing solution (aging solution).

Claims (2)

[Claims] 1. A photographic processing composition comprising at least one compound represented by the following general formula (I). General formula (I): (In the formula, Z represents a non-metal atom group necessary for forming a heterocycle. R represents a hydrogen atom or a substituent. N represents 1
Represents an integer of 1 to 10. Q ₁ , Q ₂ and Q ₃ each represent a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group. However, at least one of Q ₁ , Q ₂ and Q ₃ is
Hydroxy group, carboxy group, sulfo group, phosphono group,
It represents an aliphatic group, aromatic group or heterocyclic group substituted with a sulfonamide group, a sulfamoyl group, a carbonamido group, a carbamoyl group or a hydroxamic acid group. W is
It represents a divalent linking group containing an alkylene group and / or an arylene group. ) 2. A silver halide photographic light-sensitive material, characterized in that the silver halide photographic light-sensitive material is treated with a processing liquid containing at least one compound represented by the general formula (I). Processing method.