JPH06175299A - Photographic processing composition and processing method - Google Patents

Abstract

PURPOSE:To provide a photographic processing soln. which effectively masks metal ions without deteriorating photographic properties. CONSTITUTION:This photographic processing compsn. for a silver halide photographic sensitive material contains a compd. represented by the formula or a salt thereof. In the formula, R1 is H, unsubstd alkyl or-L2-A2, R2, is H or-L3-A3, each of L,-L, is alkylene, each of A1-A3 is carboxy, phosphono, sulfo or hydroxy, W is >=2C alkylene and (n) is an integer of 2-6.

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 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 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), Research Disclosure No. 17643, pages 28-29, No. 187.
16 651 left column to right column, same No. 307105 880
Pp. 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, washing step, stabilization step, hardening step,
Stopping process etc. are included.

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 varies depending on the ions and the treatment liquid. Calcium and magnesium ions mixed in the developing solution react with a carbonate used as a buffering agent to generate precipitates and sludges, which causes problems such as clogging of the filter in the circulation system of the developing machine and stains on the processing film. 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 bleaching failure 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.

[0008] In a stable solution prepared by using hard water containing a large amount of calcium and magnesium, bacteria are generated by using these as a nutrient source to cause turbidity in the solution and film stain. 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 is used and various compounds have been proposed. For example, Japanese Patent Publication No. 48-30496,
44-30232, JP-A-4-313752, JP-A-4-268552, and JP-A-4-62545 (for example, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, ethylenediamine-N,
N'-disuccinic acid, etc.) or JP-A-56-9734.
7, Japanese Patent Publication No. 56-39359 and West German Patent No. 2,2.
27,639, organic phosphonic acids, or JP-A Nos. 52-102726, 53-42730, and 54.
-112127, 55-126241, 55-
Phosphonocarboxylic acids described in Japanese Patent No. 695956, and others, JP-A-58-195845 and 58-20344.
Examples thereof include compounds described in No. 0 and JP-B-53-40900. Some of these have been proposed as treatment compositions that are easily biodegradable. A processing composition that is easily biodegradable is preferable from the viewpoint of environmental protection in recent years in which it is desired to render the photographic processing waste liquid generated from photographic processing harmless.

However, the performance of these known compounds has not been fully satisfactory. For example, although ethylenediaminetetraacetic acid has a large hiding power for calcium ions, when it is added to the 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. Will deteriorate the photographic quality of. In addition, for example, ethylenediamine-N, N'-disuccinic acid and alkylidene diphosphonic acid, even in the presence of iron ions,
Although such an adverse effect is not caused, there is the above-mentioned problem that a processing liquid prepared with hard water containing a large amount of calcium produces solids and causes a failure of the developing machine.

Particularly in recent years, the replenishing amount of the photographic processing liquid has been decreasing more and more due to the increasing social demand for environmental protection, and the retention time of the processing liquid in the processing machine becomes longer accordingly. Therefore, the deterioration of the storability is a serious problem more than ever before. Therefore, it has been desired to develop a technique for effectively concealing metal ions accumulated in the treatment liquid without causing any harmful effect.

[0012]

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.

[0013]

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)

[0014]

[Chemical 2]

(Wherein R₁Is a hydrogen atom,
Kill group or -L₂-A₂Represents R ₂Is a hydrogen atom or
Is -L₃-A₃Represents L₁, L₂And L₃Is that
Represents an alkylene group. A₁, A₂And A₃Is it
Carboxy group, phosphono group, sulfo group or hydro group
Represents a xy group. W is an alkylene group having 2 or more carbon atoms
Represent. n represents an integer of 2 to 6. )

First, the compound represented by formula (I) or a salt thereof will be described in detail below. The unsubstituted alkyl group represented by R ₁ may be linear, branched or cyclic, and is preferably linear or branched. 1 as the number of carbons
Nos. 1 to 6 are preferable, and Nos. 1 to 3 are more preferable.

The alkylene group of L ₁ , L ₂ and L ₃ may be linear, branched or cyclic, and is preferably a linear alkylene group. The alkylene group of L ₁ , L ₂ and L ₃ may have a substituent, and as the substituent, an alkenyl group (eg allyl), an alkynyl group, an alkoxy group (eg methoxy, ethoxy), an aryl group ( For example, phenyl, p-methylphenyl), acylamino group (eg acetylamino), sulfonylamino group (eg methanesulfonylamino), ureido group, alkoxycarbonylamino group (eg methoxycarbonylamino), aryloxycarbonylamino group (eg phenoxycarbonyl). Amino), aryloxy groups (eg phenyloxy), sulfamoyl groups (eg methylsulfamoyl), carbamoyl groups (eg carbamoyl, methylcarbamoyl), alkylthio groups (eg methylthio, carboxymethylthio), arylthio groups. O group (eg phenylthio), sulfonyl group (eg methanesulfonyl), sulfinyl group (eg methanesulfinyl), hydroxy group, halogen atom (eg chlorine atom, bromine atom, fluorine), cyano group, sulfo group, carboxy group, phosphono group , Aryloxycarbonyl groups (eg phenyloxycarbonyl), acyl groups (eg acetyl, benzoyl), alkoxycarbonyl groups (eg methoxycarbonyl), acyloxy groups (eg acetoxy), nitro groups, hydroxamic acid groups and the like. Among them, alkoxy group, sulfo group, carboxy group,
A hydroxy group and a phosphono group are preferable, and a carboxy group is particularly preferable. The alkylene group of L ₁ , L ₂ and L ₃ preferably has 1 to 6 carbon atoms, and a particularly preferred group is a methylene group or an ethylene group. L ₁ , L
Specific examples of the alkylene groups of ₂ and L ₃ include the following.

[0018]

[Chemical 3]

A ₁ , A ₂ and A ₃ are preferably carboxy groups or phosphono groups, with carboxy groups being particularly preferred. R ₁ is preferably a hydrogen atom. R ₂ is -L ₃
-A ₃ is preferable. The alkylene group having 2 or more carbon atoms for W may be linear, branched or cyclic, and preferably,
It is a linear alkylene group. The alkylene group of W may have a substituent, and as the substituent, those mentioned as the substituents which the alkylene group represented by L ₁ , L ₂ and L ₃ may have are applied. it can. Of these, an alkoxy group, a carboxy group and a hydroxy group are preferable, and a carboxy group and a hydroxy group are more preferable. The alkylene group of W has preferably 2 to 6 carbon atoms, more preferably 2 or 3 carbon atoms, and particularly preferably an ethylene group. n represents an integer of 2 to 6, in which case W may be the same or different. n is preferably 2 or 3, and more preferably 2. Specific examples of the compound represented by formula (I) are shown below, but the invention is not limited thereto.

[0020]

[Chemical 4]

[0021]

[Chemical 5]

The compound represented by the general formula (I) is an ammonium salt (eg ammonium salt, tetraethylammonium salt), an alkali metal salt (eg lithium salt, sodium salt, potassium salt) or an acid salt (eg hydrochloride salt, sulfuric acid). Salt, oxalate). The compounds of the present invention are disclosed in JP-A-59-70652 and 63-146998.
Can be synthesized by the synthetic method described in No. etc. and a method similar thereto.

Next, representative synthetic examples of the compounds of the present invention are shown below. Synthesis example 1. Synthesis of Compound 1 28.0 g (0.240 mol) of sodium chloroacetate
Is dissolved in 50 ml of water, and while stirring at room temperature, 2
-(2-aminoethoxy) ethanol 10.5 g (0.
10 mol) was slowly added dropwise. Then, 24.0 g (0.240 mol) of 40% sodium hydroxide aqueous solution was added to p
The solution was slowly added dropwise so as to maintain H9 to 10. After completion of dropping, the mixture was stirred at 50 ° C. for 2 hours. After cooling to room temperature, concentrated hydrochloric acid (24.3 g, 0.24 mol) was added, and the mixture was concentrated under reduced pressure until the reaction liquid became about 50 ml. After desalting by gel filtration column chromatography, the eluent was concentrated and acetone was added to precipitate a white solid. The target product 1 is obtained by filtering the solid and drying it under reduced pressure.
7.9 g (0.0357 mol) was obtained. Yield 36% 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 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 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 per liter of the processing solution,
Particularly preferably, it is 0.5 to 5 g. Use in black-and-white developers and color developers has the effect of preventing the occurrence of sedimentation and sludge, and prevents the decomposition of developing agents and preservatives to prevent changes in photographic properties such as sensitivity and gradation. There is an effect to do. When added to the bleaching solution, it is added in an amount of 0.1 to 1 liter of the bleaching solution.
It is 20 g, and particularly preferably 0.1 to 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 for the black and white developer. 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 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 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 or 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 bactericides 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. Azoles such as 1,2,4-triazole and 1,4-bis (1,2,4
The combined use of an azolylmethylamine derivative such as -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 by 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 photographing, black-and-white light-sensitive material for X ray, black-and-white light sensitive material 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; 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 (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, bleach 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.

[0037]

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 (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 as ferric ion of 5 ppm and calcium nitrate as calcium ion of 150 ppm were added to the above color developing solutions to prepare samples 101 to 113. 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 113 and after a 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 / liter) 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 Solution) Unit (g) sodium p-toluenesulfinate 0.03 polyoxyethylene-p-monononylphenyl ether (average degree of polymerization: 10) 0.2 ethylenediaminetetraacetic acid disodium salt 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) 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. Furthermore, the color developing solution after aging was visually examined for the presence or absence of precipitation. The above results are shown in Table 1.

[0043]

[Table 1]

[0044]

[Chemical 6]

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

Example 2 The fixer of Example 1 was prepared by adding the compounds 1, 2, 3, 6 of the present invention,
Samples 201 to 208 were prepared by adding 7, 8, 9 or 25 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, 3, 6 and
Samples 302 to 309 were prepared by adding 7, 8, 9 or 25 at a rate of 100 mg / 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 is processed at 45 ° C. and 70% RH.
After 1 week under the moist heat condition, the increase in magenta stain (ΔDmin) before and after the aging was determined. Table 2 shows the obtained results.
Shown in.

[0048]

[Table 2]

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

Example 4 The surface of a paper support laminated on both sides with polyethylene was subjected to a corona discharge treatment, followed by providing a gelatin subbing layer containing sodium dodecylbenzenesulfonate, and further coating various photographic constituent layers to prepare a A multilayer color photographic paper 001 having the layer structure shown was produced. The coating liquid was prepared as follows. Preparation of first layer coating solution Yellow coupler (ExY) 158.0 g, color image stabilizer (Cpd-1) 15.0 g, color image stabilizer (Cpd-2)
7.5 g, color image stabilizer (Cpd-3) 16.0 g, solvent (Solv-1) 25 g, solvent (Solv-2) 25
g and 180 cc of ethyl acetate, and the solution is 10%
An emulsified dispersion A was prepared by emulsifying and dispersing in 1000 g of a 10% gelatin aqueous solution containing 60 cc of sodium dodecylbenzenesulfonate and 10 g of citric acid. On the other hand, silver chlorobromide emulsion A (cubic, 3: 7 mixture of large size emulsion A having an average grain size of 0.88 μm and small size emulsion A having a grain size of 0.70 μm (silver molar ratio). The variation coefficient of grain size distribution is , 0.08 and 0.10 respectively, and silver bromide 0.
3 mol% localized on a part of the particle surface) was prepared.
In this emulsion, blue-sensitive sensitizing dyes A and B shown below were added to the large-sized emulsion A per mol of silver of 2.0 ×, respectively.
10 ⁻⁴ mol, and 2.5 × 10 ⁻⁴ mol was added to each of the small-sized emulsions A. The chemical ripening of this emulsion was carried out by adding a sulfur sensitizer and a gold sensitizer. The above emulsified dispersion A and this silver chlorobromide emulsion A were mixed and dissolved to prepare a coating solution for the first layer having the composition described below. The emulsion coating amount indicates the silver amount conversion coating amount.

The coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer. As the gelatin hardening agent for each layer, 1-oxy-3,5-dichloro-s-triazine sodium salt was used. Also, Cpd-14 and Cp are added to each layer.
The total amount of d-15 was 25.0 mg / m ² and 50 mg / m ² , respectively.
It was added so as to be m ² . The following spectral sensitizing dyes were used for the silver chlorobromide emulsion of each photosensitive emulsion layer. [Blue sensitive emulsion layer]

[0052]

[Chemical 7]

(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〕

[0054]

[Chemical 8]

(4.0 × 10 ⁻⁴ mol for large size emulsion and 5.6 × 10 ⁻⁴ mol for small size emulsion per mol of silver halide)

[0056]

[Chemical 9]

(7.0 × 10 ⁻⁵ mol for large size emulsion and 1.0 × 10 ⁻⁵ mol for small size emulsion per mol of silver halide) [Red-sensitive emulsion layer] ]

[0058]

[Chemical 10]

(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.

[0060]

[Chemical 11]

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 8.5 x 10 ^-5 mol, 7.7 x 10 ^-4 mol and 2.5 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.

[0062]

[Chemical 12]

(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. Support Polyethylene laminated paper [Polyethylene on the first layer side contains white pigment (TiO ₂ ) and bluish dye (ultra-blue)]

First layer (blue-sensitive emulsion layer) Silver chlorobromide emulsion A 0.27 Gelatin 1.36 Yellow coupler (ExY) 0.79 Color image stabilizer (Cpd-1) 0.08 Color image stabilization Agent (Cpd-2) 0.04 Color image stabilizer (Cpd-3) 0.08 Solvent (Solv-1) 0.13 Solvent (Solv-2) 0.13 Second layer (color mixing prevention layer) Gelatin 1. 00 Color mixing inhibitor (Cpd-4) 0.06 Solvent (Solv-7) 0.03 Solvent (Solv-2) 0.25 Solvent (Solv-3) 0.25

Third Layer (Green Sensitive Emulsion Layer) Silver chlorobromide emulsion (cubic, 1: 3 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 mol The coefficient of variation of grain size distribution was 0.10 and 0.08, respectively, and 0.8 mol% of AgBr was locally contained in a part of the grain surface in each size emulsion.) 0.13 Gelatin 1.45 Magenta Coupler (ExM) 0.16 Color image stabilizer (Cpd-5) 0.15 Color image stabilizer (Cpd-2) 0.03 Color image stabilizer (Cpd-6) 0.01 Color image stabilizer (Cpd-) 7) 0.01 Color image stabilizer (Cpd-8) 0.08 Solvent (Solv-3) 0.50 Solvent (Solv-4) 0.15 Solvent (Solv-5) 0.15

Fourth Layer (Color Mixing Prevention Layer) Gelatin 0.70 Color mixing inhibitor (Cpd-4) 0.04 Solvent (Solv-7) 0.02 Solvent (Solv-2) 0.18 Solvent (Solv-3) 0.18 Fifth layer (red-sensitive emulsion layer) Silver chlorobromide emulsion (cubic, 1: 3 mixture of large size emulsion C having an average grain size of 0.50 μm and small size emulsion C of 0.41 μm (Ag mol The coefficient of variation of the grain size distribution is 0.09 and 0.11, and in each size emulsion 0.8 mol% of AgBr was locally contained in a part of the grain surface.) 0.20 Gelatin 0.85 Cyan Coupler (ExC) 0.33 Ultraviolet absorber (UV-2) 0.18 Color image stabilizer (Cpd-1) 0.30 Color image stabilizer (Cpd-9) 0.01 Color image stabilizer (Cpd-10) ) 0.01 color image stabilizer (Cpd-11) 0 01 solvent (Solv-6) 0.22 Color Image Stabilizer (Cpd-8) 0.01 Color Image Stabilizer (Cpd-6) 0.01 solvent (Solv-1) 0.01

Sixth Layer (Ultraviolet Absorbing Layer) Gelatin 0.55 Ultraviolet Absorber (UV-1) 0.38 Color Image Stabilizer (Cpd-12) 0.15 Color Image Stabilizer (Cpd-5) 0.02 Seventh layer (protective layer) Gelatin 1.13 Polyvinyl alcohol acrylic modified copolymer (modification degree 17%) 0.05 Liquid paraffin 0.02 Color image stabilizer (Cpd-13) 0.01

[0068]

[Chemical 13]

[0069]

[Chemical 14]

[0070]

[Chemical 15]

[0071]

[Chemical 16]

[0072]

[Chemical 17]

[0073]

[Chemical 18]

[0074]

[Chemical 19]

The following color developing 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, Sumitomo Chemical Co., Ltd.) 1.0 g Preservative (disodium -N, N-bis (sulphonatoethyl) hydroxylamine) 45 mmol N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulphate 5.0 g Water added 1000 ml pH (25 ° C) 10.05

The above color developing solution was designated as Sample 401, and the compounds of the present invention and comparative compounds were added thereto in the amounts shown in Table 3 to be designated as Samples 402 to 408. 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 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 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 below 3 ppm each)

With respect to the minimum density (Dmin) of yellow when processed with a fresh solution and the sensitivity (logarithm of exposure dose log E which gives a density of 0.5) of yellow, 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 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.

[0079]

[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.

Example 5 Sample No. 3 of the example of JP-A-3-174148. B
-6 is used to disperse disodium ethylenediaminetetraacetate in the following developer (A) in the same molar amount as exemplified compound 1 of the present invention.
When a developing solution (B) was prepared by substituting for each developing solution and each developing solution was aged at 40 ° C. for 4 days and then subjected to running treatment, 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 6 302 as defined in the OECD Chemicals Testing Guideline
Table 4 shows the results of the biodegradability test based on the B modified Zahn-Wellens method.

[0084]

[Table 4]

From the above results, it was confirmed that the compound of the present invention is excellent in biodegradability.

[0086]

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, so 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.

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)(In the formula, R₁Is a hydrogen atom, an unsubstituted alkyl group or-
L₂-A₂Represents R ₂Is a hydrogen atom or -L₃-A
₃Represents L₁, L₂And L₃Each is an arche
Represents a group. A₁, A₂And A₃Are each
Represents an oxy group, a phosphono group, a sulfo group or a hydroxy group
You W represents an alkylene group having 2 or more carbon atoms. n is
It represents an integer of 2 to 6. ) 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 the general formula (I) or a salt thereof according to claim 1. A method for processing a silver halide photographic light-sensitive material.