JPH07114154A - Photographic processing composition and processing method - Google Patents

Abstract

PURPOSE:To prevent the generation of precipitates, etc., by the infiltration of metallic ions and to obviate a decrease in the effective component in a processing soln. and the generation of a component having adverse photographic effect by incorporating a specified compd. or its salt. CONSTITUTION:This composition contains a compd. shown by the formula or its salt. In the formula R1 is a substituent such as hydrogen atom or alkyl (preferably 1-20C alkyl), X1...X3 are respectively hydrogen atom or -L1-A, L1...L7 are respectively bivalent aliphatic groups, bivalent aromatic groups or bivalent connecting groups consisting of their combination, A and A1...A3 are respectively -COOM, -OM, -SO3, M or -PO(OM)2, and M is hydrogen atom or cation. The oxidation or decomposition of the processing soln. due to metallic ion is suppressed by the processing soln. contg. the compd., and the performance of the soln. is maintained over a long period. Further, precipitates are not formed in the soln. even if metallic ions are accumulated.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a processing composition for 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 exposed and then processed by processing steps such as black-and-white development, fixing and washing with water to obtain a silver halide color photographic light-sensitive material (hereinafter
It is called a 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 development 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 (bleaching) into a silver salt by a bleaching agent (oxidizing agent) having an oxidizing action, and further unused by a fixing agent which forms soluble silver. Is removed from the photosensitive layer together with the silver halide of (fixing). 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 compositions, see "The Theory of Photographic Process" by James (Part 4).
Edition) (James, “The Theory of Photographic Process
"4'th edition" (1977) and the like.
In addition to the basic processing steps described above, various auxiliary steps are added for the purpose of maintaining the photographic and physical quality of the dye image, maintaining the stability of processing, and the like. 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 developing machine. From a large-scale developing station equipped with a large automatic developing machine, a small automatic developing machine called a minilab has recently been installed in a store. Photo processing has been carried out in various places up to a photo shop, and along with this, there have been cases where 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. In addition, 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 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.

Further, when a transition metal such as iron ion is mixed in a bleaching solution containing hydrogen peroxide or persulfate, the stability of the solution is remarkably lowered and problems such as poor bleaching occur. Also in the fixing solution, in a commonly used fixing solution of thiosulfate, the stability is lowered due to the incorporation of the transition metal salt, and the solution becomes turbid or sludge occurs. 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. This phenomenon in the fixer also occurs in the wash water that follows the fixer, and especially when the amount of wash water is reduced, the liquid exchange rate in the tank decreases, and decomposition of thiosulfate called sulfuration and 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 by using these as nutrient sources, causing turbidity in the solution and causing film stains. In addition, when transition metal-based ions such as iron ions are mixed, they remain in the film, which deteriorates the storability of the processed film. As described above, since the mixing of metal ions into the treatment liquid causes various adverse effects, an effective ionic 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,
Examples thereof include aminopolycarboxylic acids such as ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid, and organic phosphonic acids such as alkylidene diphosphonic acid. Although some of these compounds have been put into practical use,
Its performance was not entirely satisfactory. For example, although ethylenediaminetetraacetic acid has a large hiding power for calcium ions, when it is added to a developer, it accelerates the decomposition of the developer or the preservative of the developer in the presence of iron ions,
This causes deterioration of photographic properties such as a decrease in image density and an increase in fog. Further, for example, alkylidene diphosphonic acid does not cause such a bad effect even in the presence of iron ions, but a treatment liquid 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.

Particularly in recent years, the replenishing amount of the photographic processing liquid is decreasing more and more in response to the increasing social demand for environmental protection, and so-called water-saving processing is being performed. The residence time becomes longer, and thus the deterioration of the storage stability becomes a greater problem than ever before. Therefore, even in the water-saving treatment, there has been a demand for the development of a technique for effectively hiding the metal ions accumulated in the treatment liquid without causing any harmful effects.

Further, in recent years, from the viewpoint of environmental protection, it has been desired to render the photographic processing waste liquid generated from photographic processing harmless, and particularly to a processing composition which is easily biodegradable. As a chelating agent having biodegradability, N- (2-carboxymethoxyphenyl) iminodiacetic acid (West German Patent Publication No. 39125) is used.
51), β-alanine diacetate, glycine nipropionic acid (European Patent Publication No. 430000A), ethylenediamine-N, N′-disuccinic acid (JP-A-4-313752).
No.) etc. are disclosed. However, these chelating agents do not fully satisfy biodegradability and photographic processing performance, and in addition to the above-mentioned performance being insufficient,
It was found that molds and bacteria are generated in each treatment bath over time in water-saving treatments, etc., causing clogging of filters installed in the equipment and troubles due to adhesion of molds and bacteria aggregates to photosensitive materials. It was

[0009]

SUMMARY OF THE INVENTION It is, therefore, a first object of the present invention to provide a photographic processing composition which does not cause precipitation or sludge even when metal ions are mixed, 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 cause reduction of the active ingredient in the treatment liquid or generation of an ingredient exerting a photographically adverse effect even by mixing of metal ions. Is to provide a method.
A third object of the present invention is to provide a processing composition and a processing method using the same, in which the deterioration of image storability caused by the residual metal ions in the processing liquid components remaining in the processed photosensitive material is provided. Especially. The fourth object of the present invention is to
It is an object of the present invention to provide a treatment composition which does not cause an environmental problem of waste liquid and a treatment method using the same. A fifth object of the present invention is to provide a treatment composition which causes less generation of mold and bacteria and a treatment method using the same.

[0010]

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

[0011]

[Chemical 2]

(Where R₁Represents a hydrogen atom or a substituent
You X₁, X₂And X₃Is a hydrogen atom or -L₁
Represents -A. L₁, L₂, L₃, L_Four, L_Five, L₆Over
And L ₇Are divalent aliphatic groups, divalent aromatic groups or
It represents a divalent linking group consisting of a combination thereof.
A, A₁, A₂And A₃Are -COOM and -O respectively
M, -SO₃M or -PO (OM)₂And M is water
Represents an elementary atom or cation. )

First, the compound represented by formula (I) will be described in detail below. In the formula, the substituent represented by R ₁ is an alkyl group (preferably having 1 to 20 carbon atoms,
More preferably 1-4. For example, methyl, ethyl, iso
-Propyl), aralkyl group, (preferably having 7 to 7 carbon atoms)
23, more preferably 7 to 13. For example, phenylmethyl), an alkenyl group (preferably having 2 to 20 carbon atoms, more preferably 2 to 4 carbon atoms, for example, allyl), an alkoxy group (preferably having 1 to 20 carbon atoms, more preferably 1 to 4 carbon atoms, such as methoxy and ethoxy). , An aryl group (preferably having 6 to 20 carbon atoms, more preferably 6 to 13 carbon atoms, such as phenyl and p-methylphenyl), an acylamino group (preferably having 1 to 20 carbon atoms, more preferably 2 to 5 carbon atoms, such as acetylamino). , A sulfonylamino group (preferably having 1 to 20 carbon atoms, for example, methanesulfonylamino), a ureido group (preferably having 2 to 20 carbon atoms, such as methylureido), an alkoxycarbonylamino group, (preferably having 2 to 20 carbon atoms, for example. Methoxycarbonylamino), an aryloxy group (preferably having 6 to 20 carbon atoms. Luoxy), a sulfamoyl group (preferably having 0 to 20 carbon atoms, for example, methylsulfamoyl), a carbamoyl group (preferably having 1 to 20 carbon atoms, for example, carbamoyl and methylcarbamoyl), a mercapto group, an alkylthio group (preferably having 1 carbon atom). To 20, for example, methylthio, carboxylmethylthio), arylthio group (preferably having 6 to 20 carbon atoms, for example, phenylthio), sulfonyl group (preferably having 1 to 20 carbon atoms, for example, methanesulfonyl), sulfinyl group (preferably having 1 to carbon atoms). 20.
For example, methanesulfinyl), aryloxycarbonylamino group (preferably having 7 to 20 carbon atoms, for example, phenoxycarbonylamino), hydroxy group, cyano group, sulfo group, carboxyl group, phosphono group, aryloxycarbonyl group (preferably having 7 carbon atoms). -20. For example, phenyloxycarbonyl), an acyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 7, for example, acetyl, benzoyl), an alkoxycarbonyl group (preferably having 2 to 20 carbon atoms, more preferably 2 to 2 carbon atoms). 5. For example, methoxycarbonyl, an acyloxy group (preferably having 1 to 2 carbon atoms)
0. Examples thereof include acetoxy), nitro group, hydroxamic acid group, amino group, and heterocyclic group. Preferred as the substituent are an alkyl group, an alkoxy group, a sulfinyl group, a hydroxy group, a cyano group, a sulfo group, a carboxyl group, a phosphono group, an acyl group and a nitro group,
An alkyl group, an alkoxy group and a hydroxy group are particularly preferable. Moreover, these substituents may be further substituted.

L ₁ , L ₂ , L ₃ , L ₄ , L ₅ , L ₆ , L
_The divalent linking group represented by ₇ is a divalent aliphatic group, a divalent aromatic group, or a divalent linking group of a combination thereof. As the divalent aliphatic group, a linear, branched or cyclic alkylene group (preferably having 1 to 6 carbon atoms), an alkenylene group (preferably having 2 to 6 carbon atoms), an alkynylene group (preferably having 2 to 6 carbon atoms) ) Is mentioned. Also,
These divalent aliphatic groups may have a substituent,
For example, those mentioned as the substituents represented by R ₁ can be applied. ) The substituent is preferably a hydroxy group or a carboxyl group.

The divalent aliphatic group is preferably an alkylene group, more preferably a linear alkylene group. The linear alkylene group is particularly preferably a methylene group or an ethylene group.

Examples of the divalent aromatic group include a divalent aromatic hydrocarbon group (arylene group) and a divalent aromatic heterocyclic group. Divalent aromatic hydrocarbon group (arylene group)
May be monocyclic or bicyclic, and preferably has 6 to 20 carbon atoms.
And examples thereof include a phenylene group and a naphthylene group. The divalent aromatic heterocyclic group is a 3- to 10-membered group containing at least one of a nitrogen atom, an oxygen atom or a sulfur atom, and even if it is a single ring, it is further combined with another aromatic ring or heterocycle. You may form a condensed ring. The divalent aromatic heterocyclic group is preferably a 5- or 6-membered one containing at least one nitrogen atom as a hetero atom, and examples thereof include the following.

[0017]

[Chemical 3]

The divalent aromatic group is preferably an arylene group (preferably having 6 to 20 carbon atoms), more preferably a phenylene group or a naphthylene group, and particularly preferably a phenylene group. The divalent aromatic group may have a substituent, and for example, those exemplified as the substituent represented by R ₁ can be applied.

L ₁ , L ₂ , L ₃ , L ₄ , L ₅ , L ₆ , L
₇ may be a combination of a divalent aliphatic group and a divalent aromatic group, and examples thereof include the following.

[0020]

[Chemical 4]

The divalent linking group represented by L ₂ , L ₃ and L ₄ is preferably a divalent aliphatic group, and L ₁ ,
L ₅ , L ₆ and L ₇ are preferably a divalent aliphatic group or a divalent aromatic. More preferably L ₁ , L ₂ , L ₃ ,
The divalent linking group represented by L ₄ , L ₅ , L ₆ and L ₇ is a divalent aliphatic group.

A, A ₁ , A ₂ and A ₃ are each -C
OOM, -OM, represents a -SO ₃ M or -PO (OM) _2. A, A ₁ , A ₂ and A ₃ may be the same or different. A, A ₁ , A ₂ and A ₃
Of the groups represented by, preferably —COOM, —OM
And more preferably -COOM.

M represents a hydrogen atom or a cation, and as the cation, ammonium (for example, ammonium,
Tetraethylammonium), alkali metals (eg lithium, potassium, sodium), pyridinium and the like can be mentioned. The compound represented by the general formula (I) is an ammonium salt (for example, ammonium salt, tetraethylammonium salt), an alkali metal salt (for example, lithium salt, sodium salt, potassium salt) or an acidic salt (for example, hydrochloride, sulfate, oxalate). Acid salt).

When the compound is isolated, the number of ammonium, alkali metal or acid contained in the compound is preferably 0 to 6 (eg, monosodium salt, disodium salt, trisodium salt).

Of the compounds represented by the general formula (I), compounds in which X ₁ , X ₂ and X ₃ are hydrogen atoms are preferable. Specific examples of the compound represented by formula (I) are shown below, but the invention is not limited thereto.

[0026]

[Chemical 5]

[0027]

[Chemical 6]

[0028]

[Chemical 7]

[0029]

[Chemical 8]

[0030]

[Chemical 9]

The compound represented by the above general formula (I) is
For example, it can be synthesized according to the scheme shown below.

[0032]

[Chemical 10]

Triamine derivative (1) and halogen-substituted alkylenecarboxylic acid (other than --OM, --SO ₃ M, --P)
A secondary amine-substituted triamine derivative (2) can be synthesized by reacting with O (OM) ₂ ), and by treatment with an acid (for example, hydrochloric acid, sulfuric acid, etc.),
The H-form (3) of the desired compound (carboxylic acid, alcohol, sulfonic acid, phosphonic acid) can be obtained. Further, when further substitution is desired, the target product (4) can be obtained by adding a halogen-substituted alkylenecarboxylic acid or the like in an excess amount as compared with the above case. However, it is generally desirable to set the reaction temperature higher than that during the synthesis of the secondary amine (2), and to extend the reaction time.

The reaction was monitored by NMR, and if the raw material (halogen-substituted alkylenecarboxylic acid, etc.) disappeared before the reaction was completed, additional reaction was carried out at any time. Another synthetic method is known as a method of introducing methylenecarboxylic acid. The Strecker method can also be used (synthesis method of (5)).

Next, representative synthetic examples of the compounds of the present invention are shown below. The compound of the present invention is described in “Bretan of the Chemical Society of Japan”, Vol. 50, 34.
Pages 13-3414 (1977) (BULLETIN OF THECHE
MICAL SOCIETY OF JAPAN VOL.50 3413-341
4 (1977)) 2- (aminomethyl) -2-methyl-1,3-propanediamine-N, N ′, N ″ -triacetic acid (2- (aminomethyl) -2-methyl
-1,3-propanediamine-N, N ', N "-triaceti
acid), "Buretan of the Chemical Society of Japan," Vol. 41, 838-843 (1968) (BULLETIN OF THE CHEMICAL SOCIETY O
F JAPAN VOL.41 838-843 (1968)) 1,2,3-triaminopropane-N, N, N ',
N ', N ", N" -hexaacetic acid (1,2,3-Triaminopropane-N, N, N',
N ′, N ″, N ″ -hexaacetic acid) can be synthesized by a synthetic method and a method similar thereto.

Synthesis Example 1 Synthesis of Compound 2 1,1,1-tris (hydroxymethyl) ethane 126
g (1.05 mol) and 550 ml of pyridine were placed in a 2-liter three-necked flask, and the internal temperature was cooled to 10 ° C. with an ice bath while stirring well. Benzenesulfonyl chloride 664 g (3.76 mol) was added dropwise thereto over 2 hours and a half. After stirring at room temperature for 24 hours, this reaction solution was slowly added dropwise to a mixed solution of 1 liter of water, 2 liters of methanol and 800 ml of concentrated hydrochloric acid. The white precipitate thus deposited was washed 4 times with water, then with 300 ml of methanol and dried. 556 g (yield 98%) of 1,1,1-tris (benzenesulfonyloxymethyl) ethane was obtained. Next, 500 g (0.925 mol) of the obtained 1,1,1-tris (benzenesulfonyloxymethyl) ethane, 513 g (2.75 mol) of potassium phthalimide and 610 ml of xylene were placed in a three-necked flask and heated in an oil bath at 170 ° C. Heated and stirred. After 3 hours, the solvent was distilled off under reduced pressure and the residue was recrystallized from acetic acid. 261 g of 1,1,1-tris (phthalimidomethyl) ethane (yield 51%) was obtained.

An aqueous solution prepared by dissolving 261 g of the obtained 1,1,1-tris (phthalimidomethyl) ethane and 344 g of potassium hydroxide in 1 liter of water was placed in a three-necked flask and heated under reflux for 2 hours in an oil bath.

By distilling the reaction solution under atmospheric pressure while continuing to add water, 1,1,1-tris (aminomethyl) ethane azeotroped with water was obtained. Concentrated hydrochloric acid is added to the distillate to make pH 1
Adjusted to ~ 2 and concentrated under reduced pressure. Concentration was stopped before drying, and methanol was added to precipitate crystals. After filtration, washing with methanol and drying, 56 g of 1,1,1-tris (aminomethyl) ethane trihydrochloride (yield 48
%) Was obtained.

10.1 g (4.47 × 10 ^-2 mo) of 1,1,1-tris (aminomethyl) ethane trihydrochloride obtained.
l), 16.4 g of sodium chloroacetate (1.41 × 1)
(0 ⁻¹ mol) and 30 ml of water were placed in a three-necked flask, and the mixture was heated and stirred at 50 ° C. in a water bath. The pH was maintained at 9 to 10 while 54 mol (0.27 mol) of a 5N sodium hydroxide aqueous solution was added dropwise to this solution. After reacting for 5 hours, the solution was adjusted to pH 2 by adding concentrated hydrochloric acid, and the volume was about 30 ml.
It was concentrated under reduced pressure until. To this, 100 ml of ethanol was added and left overnight in the refrigerator.

The precipitated crystals were collected by filtration and recrystallized with concentrated hydrochloric acid. 4.7 g (yield 26%) of the target compound 2 was obtained. Melting point 125-130 ° C (decomposition)

Synthesis Example 2 Synthesis of Compound 8 17.8 g (0.20) of 1,2,3-triaminopropane
mol), 94.2 g (1.0 mol) of chloroacetic acid and 70 ml of water were placed in a three-necked flask, and the mixture was heated and stirred at 40 ° C. in a hot water bath for 20 hours while adding a sodium hydroxide aqueous solution and keeping the pH at 9-11. Then, 5 ml of 10N sodium hydroxide aqueous solution was further added, and the mixture was stirred at 50 ° C. for 1 hour. After cooling, 6.8 g (0.1
7 mol) and 43.6 g (0.89 mo) of sodium cyanide
l) was added, and 70 ml of an aqueous solution containing 0.10 mol of formaldehyde was added dropwise over 5 hours while maintaining the temperature at 25 ° C.

Thereafter, about 70 ml of the solvent was distilled off under reduced pressure at 60 ° C., 100 ml of water was added, and 100 ml of water was again distilled off under reduced pressure under the same conditions. After cooling the residue to 25 ° C., 70 ml of an aqueous solution containing 0.10 mol of formaldehyde was slowly added dropwise with stirring. Then, the solvent was distilled off again under reduced pressure at 60 ° C. in an amount of about 70 ml. This operation was repeated 8 times. The total amount of formaldehyde added was 0.80 mol. The reaction solution was adjusted to pH 1 with 6N hydrochloric acid and left in a refrigerator overnight to obtain a white precipitate. This precipitate was collected by filtration and the filtrate was concentrated to obtain a further precipitate. Both precipitates were combined, washed with water and dried under reduced pressure overnight. Target compound 8 71
g (yield 78%) was obtained. Melting point 230 ° C to 233 ° C (decomposition) Other compounds can be similarly synthesized.

The compound of the present invention can be applied to any processing composition for processing a silver halide black and white light-sensitive material and 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 squirrel film infectious developers, fixers and washing water, are color developers, bleaching solutions, fixing solutions, bleach-fixing solutions, adjusting solutions, stopping solutions, hardening solutions, washing solutions. 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 preferable amount is 0.5 to 10 g, and particularly preferably 0.5 to 5 g, per liter of the processing liquid. When used in black-and-white developers and color developers, it prevents the occurrence of precipitation and sludge, and also prevents the decomposition of developing agents and preservatives to prevent fluctuations in photographic properties such as sensitivity and gradation. There are effects. When added to the bleaching solution, it is added in an amount of 0.1 per 1 liter of the bleaching solution.
-20 g, particularly preferably 0.1-5 g.
Use in a bleaching solution has effects such as stability of the solution and improvement of bleaching failure. 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. The use in a fixing solution or a bleach-fixing solution has effects such as improvement of solution stability, prevention of turbidity of liquid and generation of sludge, and prevention of generation of stain in a non-image area after processing. When it is added to a washing solution or a stabilizing solution, it is 50 mg to 1 g per 1 liter of the treating solution, particularly preferably 50 to 3
It is 00 mg. Use in a washing solution or a stabilizing solution is effective in preventing turbidity of the solution, preventing deterioration of the storage stability of the obtained dye image, and preventing stain in the non-image area after processing.

The compounds of the present invention may be used alone or
You may use it in combination of 2 or more types. 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 compounds of the chelating agent that can be used in combination include ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid, transcyclohexanediaminetetraacetic acid, 1,2-diaminopropanetetraacetic acid, 1,3-diaminopropanetetraacetic acid,
Glycol ether diamine tetraacetic acid, iminodiacetic acid, methyliminodiacetic acid, carbamoylmethyliminodiacetic acid,
Hydroxyethyliminodiacetic acid, ethylenediamine-N
Aminopolycarboxylic acids such as-(β-hydroxyethyl) -N, N ', N'-triacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, nitrilo-N, N, N-trimethylenephosphonic acid, Ethylenediamine-N, N,
Examples thereof include organic phosphonic acids such as N ′, N′-tetramethylenephosphonic acid, and hydrolyzates of maleic anhydride polymers described in European Patent 345172A1.

Hydroquinone type developing agents such as hydroquinone, bromohydroquinone, methylhydroquinone and 2,5-dichlorohydroquinone are preferred as the developing agent in the black and white developing solution. N as an auxiliary developing agent
A p-aminophenol-based developing agent such as -methyl-p-aminophenol and a 3-pyrazolidone-based developing agent such as 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone are 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 black-and-white developing solution 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 benzotriazole and compounds based on Research Disclosure
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 JP-A-1-29418 may be contained. Further, a color tone agent, a surface active agent, a hardener, etc. may be contained if necessary. 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 the 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, 4-amino-N-ethyl-N-γ-hydroxypropylaniline, 4-amino-N-ethyl-N-δ-hydroxybutylaniline, 3- Methyl-4-amino-N-ethyl-N-β-methanesulfonamide ethylaniline, 3-methyl-4-amino
Examples include -N-ethyl-β-methoxyethylaniline and their sulfates, hydrochlorides or p-toluenesulfonates. Color developers include alkali metal carbonates (eg potassium carbonate), pH buffering agents such as borates or phosphates; chloride salts (eg potassium chloride), bromide salts (eg potassium bromide). , Iodide salts (eg,
It generally contains a development inhibitor such as potassium iodide), benzimidazoles, benzotriazoles, benzothiazoles or mercapto compounds, or an antifoggant. If necessary, various preservatives such as hydroxylamines such as hydroxylamine, diethylhydroxylamine, bis (sulfonateethyl) hydroxylamine, sulfites such as sodium sulfite, sodium bisulfite; ethylene glycol, diethylene glycol, etc. Organic solvents; development accelerators such as benzyl alcohol, polyethylene glycol, quaternary ammonium salts, amines; dye-forming couplers; competing couplers; auxiliary developing agents such as 1-phenyl-3-pyrazolidone; sodium boron hydride and hydrazine Nucleating agents such as compounds; viscosity-imparting agents; 4,4'-diamino-2,2'-
A fluorescent whitening agent such as a 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 are iron chloride; ferricyanide; dichromate;
Organic complex salts of iron (III) (for example, metal complex salts of aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, and 1,3-diaminopropanetetraacetic acid); and persulfates. The bleaching solution or the bleach-fixing solution using the aminopolycarboxylic acid iron (III) complex salt is used at a pH of 3.5 to 8. Known bleaching solutions and bleach-fixing solutions include rehalogenating agents such as ammonium bromide, sodium bromide, potassium bromide and ammonium chloride; pH buffering agents such as ammonium nitrate; metal corrosion inhibitors such as ammonium sulfate. Additives can be added. 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. A particularly preferred organic acid is a compound having an acid dissociation constant (pKa) of 2 to 5.5, specifically acetic acid,
Glycolic acid and propionic acid are preferred. Examples of the fixing agent used in the fixing solution or bleach-fixing solution for color light-sensitive materials include thiosulfates, thiocyanates, thioether compounds, thioureas, mesoionic compounds, and a large amount of iodide salts. , Thiosulfate is generally used, and ammonium thiosulfate is 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 No. 294769A can be used in fixers and bleach-fixers; various fluorescent brighteners; defoamers; Surfactants; polyvinylpyrrolidone; methanol; buffers such as imidazole; US Pat. No. 3,893,85
Bleaching accelerators such as compounds having a mercapto group or a disulfide group described in JP-A-8, West German Patent No. 1,290,812 and JP-A-53-95,630 may be contained.

The washing and stabilizing solutions include inorganic phosphoric acid, isothiazolone compounds, siabendazoles, chlorine-based bactericidal agents such as chlorinated sodium isocyanurate; Mg salt,
A metal salt such as an Al salt or a Bi salt; a surfactant; a hardener or the like can be contained. Further, the washing water and / or the stabilizing solution may contain various antibacterial agents and fungicides in order to prevent generation of water stains and molds generated in the processed light-sensitive material. Examples of these antibacterial agents and antifungal agents include thiazolylbenzimidazole compounds as disclosed in JP-A-57-157244 and JP-A-58-105145, or JP-A-54-27.
Nos. 424 and 57-8542, isothiazolone compounds, chlorophenol compounds represented by trichlorophenol, bromophenol compounds, organotin and organozinc compounds, or Thiocyanic acid- or isothiocyanic acid-based compounds, acid amide-based compounds, diazine or triazine-based compounds, thiourea-based compounds, benzotriazole alkylguanidine compounds, or quaternary compounds such as benzalkonium chloride Ammonium salts, antibiotics represented by penicillin, etc., Journal Antibacterial and Antifungus Agents (A. Antibact. Antifung. Agents) Voll. No. 5, p.
One or more general-purpose antifungal agents described in 207 to 223 (1983) may be used in combination. In addition, JP-A-48-83820
Various bactericides described in 1. can also be used.

Formaldehyde is generally used as the dye stabilizer which can be used in the stabilizing solution.
From the viewpoint of work environment safety, N-methylolazole, hexamethylenetetramine, formaldehyde bisulfite adduct, dimethylolurea, azolylmethylamine derivative and the like are preferable. Regarding these, JP-A-2-1533
No. 48, No. 4-270344, European Patent Publication No. 504.
No. 609A2. In particular, azoles such as 1,2,4-triazole and 1,4-bis (1,
The combined use of an azolylmethylamine derivative such as 2,4-triazol-1-ylmethyl) piperazine is preferable because of high image stability and low formaldehyde vapor pressure. In addition, the stabilizing solution may further contain a pH adjusting buffer such as boric acid and sodium hydroxide; an antisulfurizing agent such as alkanolamine; an optical brightening agent;

As the photographic light-sensitive material which can be processed with the processing composition of the present invention, a usual black-and-white silver halide photographic light-sensitive material (for example, black-and-white light-sensitive material for photography, black-and-white light-sensitive material for X ray, black-and-white light sensitivity for printing) can be used. 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 have a filter layer, an intermediate layer, a surface protective layer) or an arrangement.

Support of photographic light-sensitive material according to the present invention; coating method; type 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 (eg, single jet method, double jet method), binder (eg, gelatin), hardener, antifoggant, metal doping agent, silver halide solvent, thickener, emulsion precipitant, size Stabilizer, anti-adhesion agent, stabilizer, anti-staining agent, dye image stabilizer, anti-staining agent, chemical sensitizer, spectral sensitizer, sensitivity enhancer, supersensitizer, nucleating agent, coupler ( For example, pivaloyl acetanilide type and benz 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 (for example, 2-phenoxyethanol), anti-vibration agent. There is no particular limitation on the agent and the like, and for example, Product Licensing, Vol. 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, 2004), JP-A-4-34548, page 15, lower left column 1,
Line to page 20, lower right column, third line, ibid. 4-184432, page 7, right column, 32nd line to page 9, right column, 26th line, ibid. 4-274
No. 237, page 6, right column, line 30 to page 9, right column, line 49 can be referred to.

[0054]

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 Chelating agent (described in Table 1) 0.01 mol Sodium sulfite 4.0 Potassium carbonate 30.0 Potassium bromide 1.4 Potassium iodide 1.5 mg Hydroxylamine Sulfate 2.4- (N-ethyl-N-β-hydroxyethylamino) -2-methylaniline sulphate 4.5 Add water 1000 ml pH 10.05

Ferric chloride was added to the above color developing solution in an amount of 5 ppm as ferric ion and calcium nitrate was added in an amount of 150 ppm as calcium ion to prepare samples 101 to 115. 5 liters of each of these samples is 10 cm long, 25 cm wide,
A hard vinyl chloride container having a depth of 30 cm was filled, and the liquid in the container was continuously circulated at a rate of 3 liters per minute by a pump, and the temperature was adjusted to 38 ° C. to conduct a 30-day aging test. In addition, 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, a multilayer color light-sensitive material sample 101 described in Example 1 of JP-A-4-274236 was cut into 35 mm width,
A wedge exposure of 5 CMS was applied 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 115 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 secondary ammonium salt 1.7 Ammonium sulfite 14.0 Ammonium thiosulfate aqueous solution (700 g / l) 260.0 ml Water is 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 an OH-type strongly basic anion exchange resin (Amberlite IRA-400) are passed through a mixed bed column to adjust the concentration of calcium and magnesium ions to 3
Treatment to less than mg / liter, followed by sodium diisocyanurate dichloride 20 mg / liter and sodium sulfate 15
0 mg / l was added. The pH of this solution is 6.5
It was in the range of 7.5.

(Stabilizing liquid) Unit (g) sodium p-toluenesulfinate 0.03 polyoxyethylene-p-monononylphenyl ether (average degree of polymerization: 10) 0.2 chelating agent (described in Table 1) 0.05 1 , 2,4-Triazole 1.3 1,4-bis (1,2,4-triazol-1-ylmethyl) piperazine 0.75 Water was added to 1000 ml pH 8.5

At the exposure amount at which the B concentration measured with blue light (B light) was 2.5 when treated with a new liquid, the B concentration obtained with the liquid after the aging test was compared with 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. Furthermore, the color developing solution after aging was visually examined for the presence or absence of precipitation.

Also, the above-mentioned light-sensitive material is applied at a rate of 180 m / day for 5 times.
After daily treatment for 2 days, and after stopping for 2 days, the water in the final washing tank (washing tank) was collected to measure the viable cell count. Further, the antibacterial property was evaluated by the method described below for the photosensitive material which had been subjected to uniform exposure of 2854K500 CMS and then processed.

(Evaluation Method of Antifungal Property of Photosensitive Material) Aspergillus niger was used as a bacterium and was used as M-40Y.
(Sucrose 400 g, malt extract 20 g, yeast extract 5
g, 1 liter of water) was suspended in a 1/10 concentration liquid (nutrient medium), and then a sample cut into 35 mm × 40 mm was spotted with 0.03 ml at the center on the emulsion side. The spotted part has a circular shape with a diameter of about 2 mm. This was placed in a sterile plastic dish containing absorbent cotton containing sterilized water as a water source, covered with a lid, and then stored at 27 ° C. for 3 weeks. After 3 weeks, the average diameter of the reproductive range of the fungus spread in a circle from the center of the spot was measured and ranked as follows.

◯: No spread from the spot position. △: The breeding range is within a circle with a diameter of 1 cm. ×: The breeding range exceeds the circle with a diameter of 1 cm. The above results are shown in Table 1.

[0063]

[Table 1]

As is clear from Table 1, when the conventional chelating agent is added, there is a defect in any of the items, but according to the present invention, good results are obtained in all items. .

Example 2 The fixer of Example 1 was prepared by adding the compounds 1, 2, 4, 6 of the present invention,
Samples 201 to 210 were prepared by adding 7, 8, 9, 14, 16 or 21 at 3 g / liter, and further adding ferric ion corresponding to the carry-in from the bleaching solution in the prebath. These samples were aged at an aperture ratio of 0.1 cm ^-1 at 38 degrees for 30 days, and turbidity of the liquid was observed. The non-added ones showed remarkable turbidity after the passage of time, but the fixer containing the compound of the present invention maintained a transparent state, showing that no precipitate was generated.

Example 3 The stabilizing solution of Example 1 was used as it was as a comparative sample 301, whereas the exemplified compounds 1, 2, 4, 6 and
100 mg / each of 7, 8, 9, 14, 16 or 21
Samples 302 to 311 were prepared by adding at a rate of 1 liter. Using these stabilizers, a fresh liquid such as the color developer of Sample 101 of Example 1 was used in addition to the stabilizer, and the multilayer color light-sensitive material sample 101 was processed by the method described in Example 1. . The processed multilayer color light-sensitive material sample 101 was 4
After 1 week under humid heat condition of 5 ° C. and 70% RH, magenta stain increase (ΔDmin) before and after the aging was determined. The obtained results are shown in Table 2.

[0067]

[Table 2]

It can be seen that the stabilizing solution of the present invention containing the compound of the present invention suppresses the increase of stain and improves the image storability.

Example 4 A surface of a paper support laminated on both sides with polyethylene was subjected to a corona discharge treatment, and then a gelatin subbing layer containing sodium dodecylbenzenesulfonate was provided, and various photographic constituent layers were further coated to prepare the following. A multilayer color photographic paper 001 having the layer structure shown was produced. The coating liquid was prepared as follows. Fifth layer coating solution preparation Cyan coupler (ExC) 12.4 g, color image stabilizer (C
pd-9) 0.40 g, color image stabilizer (Cpd-8) 0.
40 g, ultraviolet absorber (UV-2) 7.0 g, color image stabilizer (Cpd-1) 9.5 g, color image stabilizer (Cpd-6)
0.40 g, color image stabilizer (Cpd-10) 0.40 g,
0.40 g of the color image stabilizer (Cpd-11) was added to the solvent (So
lv-1) 0.50 g, solvent (Solv-6) 7.4 g
And 27.2 cc of ethyl acetate, and this solution was added to 270 cc of 10% gelatin aqueous solution containing 8 cc of sodium dodecylbenzenesulfonate, and then emulsified and dispersed by an ultrasonic homogenizer to prepare an emulsified dispersion C. on the other hand,
Silver chlorobromide emulsion C (cube, average grain size 0.58 μm
7: 3 mixture of large size Emulsion C of 0.45 μm and small size Emulsion C of 0.45 μm (silver molar ratio). Coefficients of variation of the grain size distribution are 0.09 and 0.11, respectively, and 0.6 mol% of silver bromide for large-sized emulsion and 0.8 mol% of silver bromide for small-sized emulsion, respectively. Part of the silver halide grains, with the rest being silver chloride).
The chemical ripening of this emulsion was performed by adding a sulfur sensitizer and a gold sensitizer. The above emulsified dispersion C and this silver chlorobromide emulsion C were mixed and dissolved to prepare a coating solution for the fifth layer having the composition described below. The emulsion coating amount indicates the silver amount conversion coating amount.

Coating solutions other than the fifth layer were prepared in the same manner as the fifth layer coating solution. 1 as a gelatin hardening agent for each layer
-Oxy-3,5-dichloro-s-triazine sodium salt and 1,2-bis (vinylsulfonyl) ethane were used. The total amount of Cpd-14 and Cpd-15 in each layer, each was added to a 25.0 mg / m ² and 50 mg / m ^2. The following spectral sensitizing dyes were used for the silver chlorobromide emulsion of each photosensitive emulsion layer. [Blue sensitive emulsion layer]

[0071]

[Chemical 11]

(2.0 × 10 ⁻⁴ mol for large size emulsion and 2.5 × 10 ⁻⁴ mol for small size emulsion per mol of silver halide) [Green-sensitive emulsion] layer〕

[0073]

[Chemical 12]

(Per mol of silver halide, 4.0 × 10 ^-4 mol for large-sized emulsion, 5.6 × 10 ^-4 mol for small-sized emulsion)

[0075]

[Chemical 13]

(1 mol of silver halide: 7.0 × 10 ^-5 mol for a large-sized emulsion and 1.0 × 10 ^-4 mol for a small-sized emulsion) [Red-sensitive emulsion layer ]

[0077]

[Chemical 14]

(0.9 × 10 ⁻⁴ mol for large size emulsion and 1.1 × 10 ⁻⁴ mol for small size emulsion per mol of silver halide) Further, red-sensitive emulsion The following compound F was added to the layer in an amount of 2.6 × 10 ⁻³ mol per mol of silver halide.

[0079]

[Chemical 15]

1- (5-methylureidophenyl) is added to the blue-sensitive emulsion layer, the green-sensitive emulsion layer and the red-sensitive emulsion layer.
-5-Mercaptotetrazole was added in an amount of 3.4 x 10 ^-4 mol, 9.7 x 10 ^-4 mol and 5.5 x 10 ^-4 mol per mol of silver halide, respectively. Further, 4-hydroxy-6-methyl- was added to the blue-sensitive emulsion layer and the green-sensitive emulsion layer.
1,3,3a and 7-tetrazaindene were added in an amount of 1 × 10 ⁻⁴ mol and 2 × 10 ⁻⁴ mol, respectively, per mol of silver halide. Further, in order to prevent irradiation, the following dye (the amount in parentheses represents the coating amount) was added to the emulsion layer.

[0081]

[Chemical 16]

(Layer Structure) The composition of each layer is shown below. The numbers represent the coating amount (g / m ² ). The silver halide emulsion represents the coating amount in terms of silver. The coating pH was adjusted to 7.0 by adjusting the pH of the coating solution. Support polyethylene laminated paper [14 wt% white pigment (Ti
O ₂ ) and bluish dye (ultra-blue) are included]

First Layer (Yellow Coupler-Containing Blue Sensitive Emulsion Layer) Silver chlorobromide emulsion A (cubic, large size emulsion A having an average grain size of 0.8 μm and small size emulsion A having a grain size of 0.5 μm, 5: 5). The coefficient of variation of the mixture (Ag mole ratio) and the grain size distribution are 0.08 and 0.09, respectively. 0.27 gelatin 1.21 yellow coupler (ExY) 0.79 color image stabilizer (Cpd-1) 0.06 color image stabilizer (Cpd-2) 0.04 color Image stabilizer (Cpd-3) 0.08 Solvent (Solv-1) 0.10 Solvent (Solv-2) 0.10 Second layer (color mixing prevention layer) Gelatin 0.95 Color mixing inhibitor (Cpd-4) 0 0.08 solvent (Solv-7) 0.01 solvent ( OLV-2) 0.20 solvent (Solv-3) 0.25

Third layer (magenta coupler-containing green-sensitive emulsion layer) Silver chlorobromide emulsion (cubic, 6: 4 mixture of large size emulsion B having an average grain size of 0.55 μm and small size emulsion B of 0.39 μm) (Ag molar ratio). The variation coefficient of the grain size distribution is 0.10 and 0.08, respectively, 0.8 mol% of AgBr for the large size emulsion and 1.0 mol% of AgBr for the small size emulsion, respectively. 0.13 Gelatin 1.38 Magenta coupler (ExM) 0.16 Color image stabilizer (Cpd-5) 0.07 Color image 0.07 Stabilizer (Cpd-2) 0.03 Color image stabilizer (Cpd-6) 0.01 Color image stabilizer (Cpd-7) 0.01 Color image stabilizer (Cpd-8) 0.07 Solvent (Solv- 3) 0.30 solvent (So lv-5) 0.10 Solvent (Solv-8) 0.20 Solvent (Solv-9) 0.10

Fourth Layer (Color Mixing Prevention Layer) Gelatin 0.65 Color mixing inhibitor (Cpd-4) 0.06 Solvent (Solv-7) 0.01 Solvent (Solv-2) 0.15 Solvent (Solv-3) 0.18 Fifth layer (cyan coupler-containing red-sensitive emulsion layer) Silver chlorobromide emulsion (cubic, 7: 3 mixture of large size emulsion C having an average grain size of 0.58 μm and small size emulsion C of 0.45 μm) (Ag mole ratio) .The variation coefficient of grain size distribution is 0.09 and 0.11, AgBr 0.6 mol% for large size emulsion and AgBr 0.8 mol% for small size emulsion respectively. 0.20 gelatin 0.84 cyan coupler (ExC) 0.32 ultraviolet absorber (UV-2) 0.18 color image stabilizer (Cpd-1) .25 Color image stabilizer (Cpd-9) 0.01 Color image stabilizer (Cpd-10) 0.01 Color image stabilizer (Cpd-11) 0.01 Solvent (Solv-6) 0.19 Color image stable Agent (Cpd-8) 0.01 Color image stabilizer (Cpd-6) 0.01 Solvent (Solv-1) 0.01

Sixth Layer (Ultraviolet Absorbing Layer) Gelatin 0.53 Ultraviolet Absorber (UV-1) 0.38 Color Image Stabilizer (Cpd-12) 0.15 Seventh Layer (Protective Layer) Gelatin 1.12 Polyvinyl Acrylic-modified copolymer of alcohol (modification degree 17%) 0.07 Liquid paraffin 0.01 Color image stabilizer (Cpd-13) 0.01

[0087]

[Chemical 17]

[0088]

[Chemical 18]

[0089]

[Chemical 19]

[0090]

[Chemical 20]

[0091]

[Chemical 21]

[0092]

[Chemical formula 22]

[0093]

[Chemical formula 23]

[0094]

[Chemical formula 24]

[0095]

[Chemical 25]

[0096]

[Chemical formula 26]

The following color developing solutions were prepared. [Color developer] Water 800 ml Potassium bromide 0.03 g Potassium chloride 6.5 g 4,5-Dihydroxybenzene-1,3-disulfonic acid disodium salt 0.5 g Triethanolamine 12.0 g Potassium carbonate 27 g Sodium sulfite 0. 1 g Fluorescent brightener (WHITEX 4B, Sumitomo Chemical Co., Ltd.) 1.0 g Preservative (disodium-N, N-bis (sulfonate ethyl) hydroxylamine) 45 mmol N-ethyl-N- (β-methane Sulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 5.0 g Water was added to 1000 ml pH (25 ° C / adjusted with potassium hydroxide and sulfuric acid) 10.00

Samples 402 to 408 were prepared by adding the above-mentioned color developing solution to Sample 401, to which the compounds of the present invention and comparative compounds were added in the amounts shown in Table 3. Ferric ion 5 ppm and calcium ion 150 ppm were added to each of these color developing solutions, 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 . The above photographic paper 0
Photosensitometer 01 (FWH type manufactured by Fuji Photo Film Co., Ltd.)
Was used to provide gradation exposure of a three-color separation filter for sensitometry. Exposure is 250C with an exposure time of 0.1 seconds
The exposure amount was set to MS. After the exposure, processing was carried out in the small automatic developing machine according to the following steps using the (fresh solution) immediately after preparation of the solution prepared above and the color developing solution (aging solution) aged. [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 600 ml Ammonium thiosulfate (750 g / l) 93 ml Ammonium sulfite 40 g Ethylenediaminetetraacetic acid iron (III) ammonium 55 g Ethylenediaminetetraacetic acid 5 g Nitric acid (67%) 30 g Water is added 1000 ml pH (25 ° C / Adjusted with acetic acid and ammonia water) 5.8 [Rinse solution] Deionized water of sodium chlorinated isocyanurate (conductivity 5 μs / cm or less) 1000 ml pH 6.5

The minimum density of yellow (Dmin) when treated with a fresh solution and the sensitivity of magenta (logarithm of exposure dose giving density 0.5) to the minimum density of yellow Dmin when treated with an aged solution The amount of increase (ΔDmin) and the amount of change in magenta sensitivity (ΔS) were calculated. In addition, the remaining 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.

[0101]

[Table 3]

As is clear from Table 3, in the compounds of the present invention, the values of ΔDmin and ΔS are small, and the fluctuation of photographic properties is suppressed. Further, the occurrence of precipitation is also greatly improved as compared with the comparative compound. In particular, among the comparative compounds, those having a large effect of preventing the formation of precipitates were poor in the preservative property of the main drug, while those having a small amount of decomposition of the main drug were insufficient in preventing the formation of the precipitate. On the other hand, it can be seen that the compounds of the present invention provide a stable developing solution without forming a precipitate. In addition, treatment No. 40 using the compound of the present invention
The replenisher is set such that each component can be maintained for 6 to 408, 73 ml / m ² for the color developer replenishment rate for the bleach-fixing solution 60 ml / m ^2, rinsing with 3 tank countercurrent system 360 ml / When the photographic printing paper 001 was continuously processed at m ² until it was replenished with twice the tank capacity for color development, stable performance was obtained without generating a precipitate.

Example 5 Sample No. 1 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 8, and each developing solution was heated at 40 ° C.
When a running treatment was carried out 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 due to this 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 5-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-methylbenzotriazole 0.6 g n-butyl-diethanolamine 15.0 g water was added 1 liter pH 11.6

Example 6 Modification S stipulated in OECD chemical test guidelines
Table 4 shows the results of biodegradability tests based on the CAS method.

[0106]

[Table 4]

From the above results, it was confirmed that the compound of the present invention is excellent in biodegradability. As mentioned above,
The present invention can achieve both biodegradability, prevention of performance deterioration due to the action of metal ions, and prevention of generation of mold and bacteria.

[0108]

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 liquid due to accumulation, and there are few molds and bacteria. Therefore, there are no problems such as film stains and clogging of filters of automatic processors. In addition, the compound of the present invention is a biodegradable compound and contributes to environmental protection.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI technical display location // C07C 229/16 7537-4H

Claims (2)

[Claims] 1. A compound represented by the following general formula (I):
Or is characterized by containing at least one of its salts.
Photographic processing composition. General formula (I)(R in the formula₁Represents a hydrogen atom or a substituent. X₁, X
₂And X₃Is a hydrogen atom or -L₁Represents -A
You L₁, L₂, L₃, L_Four, L_Five, L₆And L ₇Haso
Divalent aliphatic group, divalent aromatic group or a combination thereof
It represents a divalent linking group consisting of a combination. A, A₁, A
₂And A₃Are -COOM, -OM, -SO respectively₃M
Or-PO (OM)₂Represents a hydrogen atom or
Indicates ON. ) 2. A silver halide photographic light-sensitive material which has been imagewise exposed is treated with a processing liquid containing at least one compound represented by formula (I) or a salt thereof according to claim 1. A method for processing a silver halide photographic light-sensitive material.