JPH075645A - Solution and method for processing photographic sensitive material - Google Patents

Abstract

PURPOSE:To prevent the deposition and precipitation in the processing solution after a developing process and to the inside walls and rollers by incorporating at least one kind of specified compound. CONSTITUTION:The processing solution contains at least one kind of compound represented by the formula in which each of R1 and R2 is hydroxy, amino, acylamino, alkylsulfonylamino, alkoxy-carbonylamino, mercapto, or alkylthio; and X is an atomic group necessary to form a 5- or 6-membered ring together with the 3 C atoms each combined with O, R1, and R2. This processing solution is one of fixing, rinsing, and stabilizing solutions, and this fixing solution contains a boron compound in an amount of<0.01mol/l.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a processing solution and a processing method for silver halide photographic light-sensitive materials. More specifically, the present invention relates to a processing solution used in the steps after the developing step, in which precipitation and precipitation are prevented from occurring and a processing method.

[0002]

2. Description of the Related Art It is widely practiced to develop a silver halide light-sensitive material and then fix it with a fixing solution containing thiosulfate, and to add a water-soluble aluminum compound to the fixing solution to fix it. In the process, the silver halide light-sensitive material is subjected to a film hardening treatment, followed by a stabilization and / or water washing process,
It is well known to reduce the load in the drying process and improve the transportability, and it is widely used. In recent years, the processing system for silver halide light-sensitive materials has been required to reduce the replenishment amount from the standpoint of environmental protection, and as the processing amount has increased, rapid processing has progressed, resulting in an extremely high concentration of thiosulfate in the fixing solution. Has been raised to.

Generally, the water used in the processing step of the silver halide light-sensitive material is tap water or industrial water which is used without any special pretreatment and contains a considerably high concentration of calcium ion, magnesium ion and the like. There is. Further, the light-sensitive material also contains the same type of ions, which are eluted into the fixing solution. In addition, there is a similar carry-on from the developer in the previous step. As a result, a large amount of white suspended matter may be generated due to the carry-in of these ions, or a white precipitate may adhere to the fixing roller or the tank wall, and in some cases, the photosensitive material may be soiled. In addition, a slight amount of aluminum hydroxide may be produced by the alkaline component of the developing solution brought into the fixing solution, which may cause white precipitation.

To prevent this, boric acid has been added to a fixing solution or the like, but its effect is not sufficient, and rather it is mixed into waste water when brought into a subsequent washing step. It is not preferable in terms. A method of adding a polybasic acid such as citric acid or tartaric acid is also known, but the effect is not sufficient. There is also a method of adding salicylic acid, sulfosalicylic acid, or the like to a developing solution or a fixing solution, but it cannot be said to be a sufficient countermeasure.

The problems of precipitation and deposition similarly occur due to the influence of water used in the stabilization process and the washing process, or the liquid brought in from the fixing process. If such a precipitate occurs, it may be transferred to the light-sensitive material and cause a problem of surface stains, or the precipitate generated at the interface between the liquid and the air may pass through the vessel wall of the tank and enter the adjacent bath. Therefore, the solution was strongly desired.

[0006]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a processing solution which does not cause deposition or precipitation in the processing solution after the development step or on the wall or roller of an automatic processor in the processing step of a light-sensitive material. To do. It is a further object of the present invention to provide a processing method which does not cause precipitation or precipitation in the steps after the developing step by providing the above processing solution.

[0007]

The above objects have been achieved by the following processing solutions and processing methods for silver halide photosensitive materials. (1) A processing solution for a silver halide photographic light-sensitive material used in a processing step after development, which contains at least one compound represented by the following general formula (I). General formula (I)

[0008]

[Chemical 2]

In the formula, R ₁ and R ₂ each represent a hydroxy group, an amino group, an acylamino group, an alkylsulfonylamino group, an arylsulfonylamino group, an alkoxycarbonylamino group, a mercapto group or an alkylthio group. X represents an atomic group necessary for forming a 5- or 6-membered ring with two vinyl carbon atoms substituted by R ₁ and R ₂ and a carbonyl carbon atom. (2) A processing solution containing at least one of the compounds represented by the general formula (I) is a fixing solution, a bleach-fixing solution, a rinse solution,
The treatment liquid according to (1) above, which is either a washing liquid or a stabilizing liquid. (3) The processing liquid according to (1) above, which is a fixing liquid containing at least one compound represented by the general formula (I) and containing no boron compound in an amount of more than 0.01 mol / liter. (4) A treatment comprising exposing and developing a silver halide photographic light-sensitive material having at least one silver halide light-sensitive layer on a support and then containing at least one compound represented by the general formula (I). A method of processing a silver halide photographic light-sensitive material, which comprises processing with a liquid. The general formula (I) will be described in detail below.

In the formula, R ₁ and R ₂ are respectively a hydroxy group and an amino group (substituents are substituted with an alkyl group having 1 to 10 carbon atoms, such as a methyl group, an ethyl group, an n-butyl group or a hydroxyethyl group). Those having as a group), acylamino group (acetylamino group, benzoylamino group, etc.), alkylsulfonylamino group (methanesulfonylamino group, etc.), arylsulfonylamino group (benzenesulfonylamino group, p-toluenesulfonylamino group) Etc.), alkoxycarbonylamino group (methoxycarbonylamino group etc.), mercapto group,
Represents an alkylthio group (methylthio group, ethylthio group, etc.). Preferred examples of R ₁ and R ₂ include a hydroxy group, an amino group, an alkylsulfonylamino group and an arylsulfonylamino group.

X is composed of a carbon atom, an oxygen atom or a nitrogen atom, and X forms a 5- or 6-membered ring together with two vinyl carbons substituted by R ₁ and R ₂ and a carbonyl carbon. Specific examples of the X, -O -, - C- ( R 3)
_{(R 4) -, - C} (R 5) =, - C (= O) -, - N
(R ₆ )-, -N =, are combined. However, R ₃ , R ₄ , R ₅ , and R ₆ are hydrogen atoms and have 1 to 10 carbon atoms.
An optionally substituted alkyl group (including a hydroxy group, a carboxy group and a sulfo group as a substituent),
It represents an optionally substituted aryl group having 6 to 15 carbon atoms (such as an alkyl group, a halogen atom, a hydroxy group, a carboxy group and a sulfo group), a hydroxy group and a carboxyl group. Further, a saturated or unsaturated condensed ring may be formed on the 5- or 6-membered ring.

Examples of the 5- or 6-membered ring include a dihydrofuranone ring, a dihydropyrone ring, a pyranone ring, a cyclopentenone ring, a cyclohexenone ring, a pyrrolinone ring, a pyrazolinone ring, a pyridone ring, an azacyclohexenone ring, and a uracil ring. And preferred examples of the 5- or 6-membered ring include
Dihydrofuranone ring, cyclopentenone ring, cyclohexenone ring, pyrazolinone ring, azacyclohexenone ring,
The uracil ring can be mentioned. Specific examples of the compound of the present invention are shown below, but the present invention is not limited thereto.

[0013]

[Chemical 3]

[0014]

[Chemical 4]

[0015]

[Chemical 5]

[0016]

[Chemical 6]

[0017]

[Chemical 7]

Examples of these salts include salts of lithium, sodium, potassium, ammonium and the like.

Of these, ascorbic acid or erythorbic acid (stereoisomerism) (I-1) is preferable.
The amount added to the treatment liquid is not particularly limited, but practically, a value within the range of 0.1 g to 100 g, preferably 0.5 to 60 g, and more preferably 1 g to 30 g per liter of the treatment liquid is used. It is desirable for obtaining the effect of suppressing the formation of white precipitate. The treatment liquid of the present invention may contain only one type of compound represented by the general formula (I), or may contain two or more types.

In the processing step of the silver halide light-sensitive material, a fixing solution, a bleaching solution, a bleach-fixing solution, a stabilizing solution, a rinsing solution (between each processing such as developing and fixing, fixing and washing or stabilizing, etc.). The liquid used for the light-sensitive material), a washing liquid and a stabilizing liquid are mentioned, and the order of these steps is appropriately selected depending on the silver halide light-sensitive material. The processing solution of the present invention may be used in any step as long as it is a step after the developing step, but is preferably used in a fixing solution and a bleach-fixing solution.
More preferably, it is used as a fixing solution. The processing liquid of the present invention may be used for manual processing in which independent processing tanks are arranged, or may be used for automatic processing using an automatic processor. The effect of the present invention can be more exerted when an automatic processor is used.

The fixer used in the present invention is an aqueous solution containing thiosulfate, and has a pH of 3.8 or higher, preferably 4.2 to 4.2.
Has 7.0. Sodium thiosulfate as a fixing agent,
There are ammonium thiosulfate and the like, but ammonium thiosulfate is particularly preferable from the viewpoint of fixing speed. However, from the viewpoint of environmental protection in recent years, the use of sodium thiosulfate is desired. The amount of the fixing agent used can be appropriately changed,
Generally, it is about 0.1 to about 6 mol / liter. The fixer contains a water-soluble aluminum salt that acts as a hardening agent, and examples thereof include aluminum chloride, aluminum sulfate, and potassium alum. For the fixing solution, tartaric acid, citric acid, succinic acid, malic acid, gluconic acid and salts thereof, or derivatives thereof can be used alone or in combination of two or more kinds. It is effective that these compounds are contained in an amount of 0.005 mol or more per liter of the fixing solution, and particularly 0.01 mol / liter to 0.03 mol / liter is particularly effective. If desired, a preservative (eg, sulfite or bisulfite), a pH buffer (eg, acetic acid), a pH adjuster (eg, sulfuric acid), a chelating agent having a water softening ability, or JP-A-62-62 The compound described in -78551 may be included. Further, a compound such as boric acid or borax is usually used for the purpose of preventing the precipitation of the water-soluble aluminum salt, but the fixing solution of the present invention does not need to do so, and even if used, 0.01 It is preferably not more than mol / liter.

The bleaching solution of the present invention includes a processing solution containing a known compound such as a trivalent iron or tetravalent cobalt compound, a peracid, a quinone or a nitroso compound as an oxidizing agent. The bleach-fixing solution of the present invention combines the functions of the bleaching solution and the fixing solution into one solution, and examples thereof include a solution having the above-mentioned fixing solution component and bleaching solution component together.

The stabilizing solution of the present invention contains acids such as phosphoric acid and acetic acid and salts thereof, organic acids such as tartaric acid, citric acid, malic acid and succinic acid and salts thereof, and water-softening ability of aminopolycarboxylic acids. Examples of the treatment liquid include a chelating agent having an aldehyde, an aldehyde, a glycol such as diethylene glycol, an optical brightener, and the like, alone or in a mixture.

Although tap water or distilled water may be used as it is for the rinse liquid and the washing liquid of the present invention, sulfite, phosphate, E
It may contain a chelating agent such as DTA, DTPA and TTHA, and an organic acid such as citric acid, tartaric acid and acetic acid.

In the step of developing the silver halide light-sensitive material of the present invention, it is preferable to use a dihydroxybenzene type developing agent as a developing agent and a p-aminophenol type developing agent or a 3-pyrazolidone type developing agent as an auxiliary developing agent. Examples of the dihydroxybenzene-based developing agent used in the present invention include hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, methylhydroquinone, 2,5-dichlorohydroquinone,
There are 2,3-dibromohydroquinone, 2,5-dimethylhydroquinone and the like, and among them, hydroquinone is particularly preferable. 1-Phenyl-3- as an auxiliary developing agent
Examples of pyrazolidone or its derivative include 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone and 1-phenyl-4-methyl-4-.
Hydroxymethyl-3-pyrazolidone, 1-phenyl-
4,4-dihydroxylmethyl-3-pyrazolidone, 1
-Phenyl-5-methyl-3-pyrazolidone, 1-p-
Aminophenyl-4,4 dimethyl-3-pyrazolidone,
1-p-tolyl-4-methyl-4-hydroxymethyl-
3-pyrazolidone and the like. As p-aminophenol-based auxiliary developing agents, N-methyl-p-aminophenol, p-aminophenol, N- (β-hydroxyethyl) -p-aminophenol, N- (4-hydroxyphenyl) glycine, 2-methyl -P-aminopheno-
And p-benzylaminophenol, but N-methyl-p-aminophenol is preferred.

The dihydroxybenzene type developing agent is usually preferably used in an amount of 0.01 mol / liter to 1.5 mol / liter. It is more preferably 0.05 mol / liter to 1.2 mol / liter. When a combination of dihydroxybenzenes and 1-phenyl-3-pyrazolidones or p-aminophenols is used, the latter is usually added in an amount of 0.0005 mol / liter to 0.2 mol / liter, preferably 0.001 mol / liter. Mol / l
It is preferably used in an amount of 0.1 mol / l.

Examples of sulfite preservatives used in the developing solution include sodium sulfite, potassium sulfite, lithium sulfite, sodium bisulfite, potassium metabisulfite, and formaldehyde sodium bisulfite. Sulfite is used at 0.2 mol / liter or more. It is preferably 0.3 mol / liter or more. The upper limit of the concentration of the developer is preferably 2.5 mol / liter.
The pH of the developer used in the developing treatment of the present invention is preferably in the range of 9 to 13. More preferably pH 9.
The range is from 7 to 12.0. Alkali agents used to set the pH include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate and the like. In addition, a pH buffering agent such as silicate, sodium triphosphate and potassium triphosphate can be used in the developer of the present invention. The concentration of the buffer is preferably 0.3 mol / liter or more. It is not preferable to use a pH buffering agent such as boric acid or borax from the viewpoint of environmental protection.

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, and indazoles such as 5-nitroindazole. Antifoggants such as benztriazole-based compounds such as compounds based on sodium, 2-mercaptobenzimidazole-5-sulfonate, and 5-methylbenztriazole may be included in Research Disclosure No. 17
Volume 6, No. 17643, Item XXI (December Issue, 197)
8 years) may be included. Also, U.S. Pat. No. 4,269,929 and JP-A-61-26775.
The amine compounds described in No. 9 and US Pat. No. 5,039,591 may be contained. Further, a color tone agent, a surface active agent, a hardener, etc. may be contained if necessary.

In the developer of the present invention, a silver stain preventing agent, for example, the compounds described in JP-A-56-24347 can be used. The developer of the present invention includes European Patent Publication 1
36582, British Patent No. 958678, U.S. Pat. No. 3,232,761, and development acceleration of amino compounds such as alkanolamines described in JP-A-56-106244,
It can be used for the purpose of increasing the contrast.

In the processing method of the present invention, after development, fixing step, bleaching, fixing step, bleach-fixing step and the like, treatment with washing water or a stabilizing solution is carried out, followed by drying. Replenishment amount of 3 liters or less per 1 m ^{2 of} silver halide light-sensitive material (zero, that is, including washing with water)
It is also possible to treat with washing water or stabilizing solution of That is, not only water saving processing becomes possible, but also piping for installing the automatic processing machine can be eliminated. As a method of reducing the replenishment amount of wash water, a multi-stage countercurrent method (for example, two-stage,
3 stages, etc.) are known. When this multi-stage countercurrent method is applied to the present invention, the photosensitive material after fixing is processed in a gradually cleaning direction, that is, the processing solution which is not contaminated with the fixing solution is sequentially processed, so that the efficiency is further improved. Washed with water.

In the above water-saving treatment or pipe-less treatment, it is preferable to provide washing water or a stabilizing solution with a deterrent means. When washing with a small amount of washing water in the method of the present invention, it is also preferable to adopt a constitution of a washing step as described in JP-A-63-143548. Further, some or all of the overflow from the washing or stabilizing bath caused by supplementing the washing or stabilizing bath with antifungal means by the method of the present invention according to the treatment is disclosed in JP-A-60-2351.
As described in No. 33, it can also be used for a processing solution having a fixing ability which is a processing step before that.

The washed (or stabilized) light-sensitive material is squeezed out of washing water, that is, dried through a squeeze roller. The drying is performed at about 40 ° C to 100 ° C, and the drying time is appropriately changed depending on the surrounding conditions, but is usually about 4
Seconds to 3 minutes, particularly preferably 40 to 80 ° C for about 5
Seconds to 1 minute.

The processing solution and processing method of the present invention can be used for processing all kinds of silver halide photographic light-sensitive materials. As the halogen composition of the silver halide emulsion used in the present invention, a suitable one can be selected from compositions such as silver chloride, silver chlorobromide, silver chloroiodobromide, and silver iodobromide. . The silver halide grains in the photographic emulsion used in the present invention can have a relatively wide grain size distribution, but preferably have a narrow grain size distribution,
In particular with respect to the weight or number of silver halide grains
The size of particles occupying 0% is ± 40% of the average particle size.
It is preferably within the range. (In general, such an emulsion is called a monodisperse emulsion.) The silver halide grains in a photographic emulsion may have a regular crystal such as a cube or an octahedron, or may be spherical or Research Disclosure. 22534 (Ja
n. 1983), tabular silver halide grains having a high aspect ratio can be used. Further, it may have a composite form of these crystal forms. The silver halide grains may have a uniform inner layer and a surface layer, or may have different layers. In addition, Japanese Patent Publication No. 41-20
Two or more kinds of silver halide emulsions, such as the internal latent image type silver halide emulsion grains and the surface latent image type emulsion grains described in No. 68, may be mixed and used. The silver halide emulsion used in the present invention includes a cadmium salt, a sulfite salt, in the process of forming silver halide grains or physical ripening.
A lead salt, a thallium salt, an iridium salt, a complex salt thereof or the like may coexist. As the silver halide emulsion, a so-called unripened emulsion (primitive emulsion) which is not chemically sensitized can be used, but it may be chemically sensitized. For chemical sensitization, H. Frieser, “Die Grundlagen der Photo
graphischen Prozesse mit Silver halogeniden `` Akad
The method described in emische Verlagsgesswlschaft, (1968) and the like can be used. That is, a sulfur sensitizing method using a compound containing sulfur capable of reacting with active gelatin or silver (for example, thiosulfates, thioureas, mercapto compounds, rhodanins), a reducing substance (for example, primary tin salt, amines, Reduction sensitization method using hydrazine derivative, formamidinesulfinic acid, silane compound, noble metal sensitization method using noble metal compound (eg, gold compound, complex salt of Group VIII metal of platinum, iridium, palladium, etc.) Etc. can be implemented alone or in combination.

The photosensitive silver halide emulsion of the present invention may be spectrally sensitized by a sensitizing dye to blue light, green light, red light or infrared light having a relatively long wavelength. As a sensitizing dye,
Cyanine dye, merocyanine dye, complex cyanine dye, complex merocyanine dye, holopolar cyanine dye, styryl dye, hemicyanine dye,
Oxonol dyes, hemioxonol dyes and the like can be used. Examples of useful sensitizing dyes used in the present invention include Research Disclosure Item 17643 IV-A (December 1978, p-23), Item 1831.
Paragraph X (August 1979, p-437) describes or is cited. These sensitizing dyes may be used alone, or may be used in combination,
Combinations of sensitizing dyes are often used especially for the purpose of supersensitization. Along with the sensitizing dye, a dye having no spectral sensitizing effect by itself or a substance which does not substantially absorb visible light and exhibits supersensitization may be contained in the emulsion.
Useful sensitizing dyes, combinations of dyes exhibiting supersensitization and substances exhibiting supersensitization are described in Research Disclosure (R
esearch Disclosure) 176, 17643 (published December 1978), page 23, IV, section J.

The silver halide light-sensitive material according to the present invention may contain a water-soluble dye as a filter dye in the hydrophilic colloid layer or for various purposes such as an anti-irradiation dye. Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Of these, oxonol dyes, hemioxonol dyes and merocyanine dyes are useful. Specific examples of dyes that can be used are West German Patent 616,007 and British Patent 584,6.
No. 09, No. 1, 117, 429, Japanese Patent Publication No. 26-777.
No. 7, No. 39-22069, No. 54-38129,
JP-A-48-85130, JP-A-49-99620, JP-A-49-114420, JP-A-49-129537, PB
Report 74175, Photographic Abstract (Photogr. Abstr.) 128 ('21) and the like.

As the binder or protective colloid that can be used in the emulsion layer or intermediate layer of the light-sensitive material of the present invention, it is advantageous to use gelatin, but other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein, cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, and cellulose sulfates, sodium alginate, sugar derivatives such as starch, polyvinyl alcohol, It is possible to use various synthetic hydrophilic polymer substances such as polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, and other single or copolymers. it can. Gelatin includes lime-processed gelatin, acid-processed gelatin, and Bulletin of the Society of Scientific Photographic Japan (Bull. SOC. SCI. Pho
To. Japan) No. 16, page 30 (1966), an enzyme-treated gelatin may be used, or a hydrolyzed product or an enzymatically decomposed product of gelatin may also be used.

The photographic emulsion used in the present invention may contain various compounds for the purpose of preventing fog during the production process of the light-sensitive material, during storage or during photographic processing, or for stabilizing photographic performance. Azoles,
For example, benzothiazolium salt, nitroimidazoles,
Nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles ( In particular, 1-phenyl-5-mercaptotetrazole, etc., mercaptopyrimidines, mercaptotriazines, thioketo compounds such as oxazolinethione, azaindenes, such as triazaindenes, tetraazaindenes (especially 4-hydroxy-substituted (1 , 3, 3a,
7) Tetraazaindenes), pentaazaindenes, etc., and many compounds known as antifoggants or stabilizers such as benzenesulfonic acid amide can be added. Among these, benzotriazoles (for example, 5-methylbenzotriazole) are particularly preferable. Further, these compounds may be contained in the treatment liquid.

The photographic light-sensitive material of the present invention may contain an inorganic or organic hardener in the photographic emulsion layer or other hydrophilic colloid layer. For example, chromium salts (chromium alum, chromium nad acetate), aldehydes (formaldehyde, glyoxal, glutaraldehyde, etc.), N-methylol compounds (dimethylolurea, methyloldimethylhydantoin, etc.), dioxane derivatives (2,3-dihydroxydioxane, etc.), Active vinyl compounds (1, 3, 5
-Triacryloyl-hexahydro-s-triazine etc.), mucohalogen acids (mucochloric acid, mucophenoxycycloric acid etc.) and the like can be used alone or in combination.

In the photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material produced by using the present invention, coating aids, antistatic agents, slipperiness improvement, emulsion dispersion, adhesion prevention and photographic property improvement (for example, development acceleration) , Contrast enhancement, sensitization), and various other surfactants may be included. For example, saponin (steroidal), alkylene oxide derivative (eg polyethylene glycol, polyethylene glycol /
Polypropylene glycol condensates, polyethylene glycol alkyl ethers or polyethylene glycol alkyl aryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycol alkylamines or amides, silicone polyethylene oxide adducts), glycidol derivatives ( For example, alkenyl succinic acid polyglyceride, alkylphenol polyglyceride), polyhydric alcohol fatty acid esters, sugar alkyl esters and other nonionic surfactants, alkyl carboxylates, alkyl sulfonates, alkylbenzene sulfonates, alkyls. Naphthalene sulfonate, alkyl sulfates, allylic phosphates, N-acyl-N-ants Carboxy groups, sulfo groups, phospho groups, sulfuric acid ester groups, phosphoric acid ester groups, etc. such as tauric acid, sulfosuccinic acid esters, sulfoalkyl polyoxyethylene alkyl phenyl ethers, polyoxyethylene alkyl phosphoric acid esters, etc. Anionic surfactants containing acidic groups, amino acids, aminoalkyl sulfonic acids, aminoalkyl sulfuric acid or phosphoric acid esters, alkyl betaines, amphoteric surfactants such as amine oxides, alkylamine salts, aliphatic or aromatic Cationic surfactants such as quaternary ammonium salts, heterocyclic quaternary ammonium salts such as pyridium and imidazolium, and phosphonium or sulfonium salts containing an aliphatic or heterocyclic ring can be used.

The photographic light-sensitive material used in the present invention may contain a dispersion of a water-insoluble or sparingly soluble synthetic polymer in a photographic emulsion layer or other hydrophilic colloid layer for the purpose of improving dimensional stability. For example, alkyl (methacrylate,
Alkoxyalkyl (meth) acrylate, glycidyl (meth) acrylate, (meth) acrylamide, vinyl ester (eg vinyl acetate), acrylonitrile,
Olefin, styrene, etc., alone or in combination, or in combination with acrylic acid, methacrylic acid, α, β-unsaturated dicarboxylic acid, hydroxylalkyl (meth) acrylate, sulfoalkyl (meth) acrylate, styrenesulfonic acid, etc. A polymer used as a monomer component can be used.

The support used in the light-sensitive material of the present invention is a flexible support of paper or synthetic paper laminated with α-olefin polymer (eg polyethylene, polypropylene, ethylene / butene copolymer). , Metal, etc. are included. Among them, polyethylene terephthalate is particularly preferable. As the undercoat layer to be used in the present invention, the undercoat layer described in JP-A-9-3972 in an organic solvent system containing polyhydroxybenzenes, JP-A-49-1111.
No. 8, No. 52-10491, etc., and the aqueous latex undercoating layer. The surface of the undercoat layer can be chemically or physically treated. Examples of the treatment include chemical treatment, mechanical treatment, corona discharge treatment, and other surface activation treatments. The present invention is for printing, X-
It can be applied to various light-sensitive materials for ray, general negative including color, general positive, and direct positive.

[0042]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited thereto.

Example 1 <Preparation of emulsion> 1 liquid water 1.0 liter gelatin 20 g sodium chloride 20 g 1,3-dimethylimidazoline-2-thione 20 mg sodium benzenesulfonate 8 mg 2 liquid water 400 ml silver nitrate 100 g 3 liquid water 400 ml chloride Sodium 27.5 g Potassium bromide 21.0 g Potassium hexachloroiridium (III) 15 ml (0.001% aqueous solution) Ammonium hexabromorhodium (III) 1.5 ml (0.001% aqueous solution) 38 ° C, pH 4.5 Add 2 and 3 liquids to the 1 liquid kept at the same time with stirring for 10 minutes to obtain 0.16 μm
Nuclear particles were obtained. Then, the following 4 liquid and 5 liquid were added over 10 minutes. Further, 0.15 g of potassium iodide was added to complete grain formation. 4-Liquid Water 400 ml Silver Nitrate 100 g 5-Liquid Water 400 ml Sodium Chloride 27.1 g Potassium Bromide 21 g Hexacyanoferrate (III) Potassium 5 ml (0.001% aqueous solution) Then, washed by water according to the conventional method and added with 30 g of gelatin. .

The pH was adjusted to 5.3 and the pAg was adjusted to 7.5,
2.6 mg of sodium thiosulfate, 1.0 mg of triphenylphosphine selenide and 6.2 mg of chloroauric acid were added, 4 mg of sodium benzenethiosulfonate and 1 mg of sodium benzenesulfinate were added to obtain the optimum concentration at 55 ° C. Chemically sensitized to obtain. 4-hydroxy-6 as a stabilizer
-Methyl-1,3,3a, 7-tetraazaindene 20
0 mg and phenoxyethanol as a preservative were added. Finally, the average particle size containing silver chloride of 70 mol% was 0.20 μm.
A silver iodochlorobromide cubic grain emulsion was obtained. (Coefficient of variation 9%)

Preparation of coating sample An ortho sensitizing dye (compound below) was added to the above emulsion at 5 × 10 5.
Ortho sensitization was performed by adding ^-4 mol / mol Ag. Further, as antifoggants, hydroquinone, 1-phenyl-5-
2.5 g and 50 mg of mercaptotetrazole were added per 1 mol of Ag, polyethyl acrylate latex was added as a plasticizer in a gelatin binder ratio of 25%, and 2-bis (vinylsulfonylacetamide) ethane was added as a hardening agent in an amount of 86 mg / m ^2. Further, colloidal silica was added at a gelatin binder ratio of 40% and coated on a polyester support so that the silver content was 3.0 g / m ² .

[0046]

[Chemical 8]

A protective layer lower layer and a protective layer upper layer having the following compositions were simultaneously coated thereon. <Lower layer of protective layer> Gelatin 0.25 g / m ² Sodium benzenethiosulfonate 4 mg / m ² 1,5-Dihydroxy-2-benzaldehyde 25 mg / m ² Polyethyl acrylate latex 125 mg / m ²

<Upper layer of protective layer> Gelatin 0.25 g / m ² Silica matting agent having an average of 2.5 μm 50 mg / m ² compound (gelatin dispersion) 30 mg / m ² Colloidal silica having a particle size of 10 to ²⁰ μm 30 mg / m ² compound 5 mg / m ² sodium dodecylbenzenesulfonate 22 mg / m ²

[0049]

[Chemical 9]

The support used in this example has a back layer and a back protective layer having the following compositions. <Back layer> Gelatin 3.0 g / m ² Sodium dodecylbenzene sulfonate 80 mg / m ² compound 70 mg / m ² compound 85 mg / m ² compound 90 mg / m ² 1,3-divinylsulfone-2-propanol 60 mg / m ² SnO ₂ / Sb (weight ratio 90/10, average particle size 0.20μ) 200 mg / m ²

[0051]

[Chemical 10]

<Back protective layer> Gelatin 0.5 g / m ² Polymethylmethacrylate 30 mg / m ² (particle size 4.7 μm) Sodium dodecylbenzene sulfonate 20 mg / m ^{2 The} above compound (gelatin dispersion) 100 mg / m ² Compound 2 mg / m ²

The following developing solution and fixing solution were set in a plate-making automatic developing machine FG-680A manufactured by Fuji Photo Film Co., Ltd., and the developing time was 20 seconds, the fixing time was 18 seconds, and the developing temperature was 38.
A running test was carried out using the above silver halide light-sensitive material under the conditions of a temperature of 37 ° C., a fixing temperature of 37 ° C., and an amount of washing water of 5 liters / minute. Forty rounds of a half-exposure large-size paper-sized photosensitive material were processed by treating 40 sheets per day, operating for 6 days, and resting for 1 day. The replenishment amount was 100 ml of the developing solution and 120 ml of the fixing solution per one sheet of Daizen paper.

Next, the composition of the developer is shown below. Potassium hydroxide 35.0 g Diethylenetriamine-pentaacetic acid 2.0 g Potassium carbonate 12.0 g Sodium metabisulfite 40.0 g Potassium bromide 3.0 g Hydroquinone 25.0 g 5-Methylbenzotriazole 0.08 g 4-Hydroxymethyl-4- Methyl-1-phenyl-3-pyrazolidone 0.45 g 2,3,5,6,7,8-hexahydro-2-thioxo-4- (1H) -quinazolinone 0.04 g 2-mercaptobenzimidazole-5-sulfonic acid Sodium erythorbate 0.15 g Sodium erythorbate 3.0 g Potassium hydroxide is added, and water is added to make 1 liter. The pH is adjusted to 10.5. 1 liter

<Fixing Solution of the Present Invention> Ammonium thiosulfate 150 g Sodium sulfite 5 g Sodium metabisulfite 20 g Sodium acetate trihydrate 18 g Ethylenediaminetetraacetic acid diNa salt 0.05 g Aluminum sulfate aqueous solution (27 wt / wt%) 25 g Compound I -1 3g Water added 1 liter pH 4.8

Comparative Example Fixing Solution-1 Ammonium thiosulfate 150 g Sodium sulfite 5 g Sodium metabisulfite 20 g Sodium acetate trihydrate 18 g Ethylenediaminetetraacetic acid diNa salt 0.05 g Aluminum sulfate aqueous solution (27 wt / wt%) 25 g Bor Acid 7g Water added 1 liter pH 4.8

<Comparative Fixing Solution-2> Ammonium thiosulfate 180 g Sodium sulfite 5 g Sodium metabisulfite 20 g Sodium acetate trihydrate 8 g Ethylenediaminetetraacetic acid diNa salt 0.05 g Aluminum sulfate aqueous solution (27 wt / wt%) 25 g Water In addition 1 liter pH 4.8

As a result, even after 4 rounds of treatment, when the fixing solution containing the compound I-10 of the present invention was used, no precipitation or deposition of deposits was observed on the walls of the fixing tank or the washing tank or on the surfaces of the rollers. I couldn't see it at all. Similarly, no precipitation was observed in the fixer of Comparative Example-1. However, when this fixer was used, the boric acid concentration in the wash water was about 1 to 5 ppm when it was brought into the wash tank. Is not preferable. When the fixing solution of Comparative Example-2 was used, a white precipitate was clearly observed on the vessel walls and rollers of the fixing tank and the washing tank, the guide plate of the crossover portion, and the like. Further, similar effects were obtained when I-3 and I-17 were used instead of the compound I-1 of the present invention.

Example 2 <Preparation of emulsion> 30 g of gelatin and 6 g of potassium bromide were added to 1 liter of water, and an aqueous solution of silver nitrate (5 g as silver nitrate) and potassium iodide of 0. An aqueous potassium bromide solution containing 15 g was added by the double jet method over 1 minute. Further, an aqueous solution of silver nitrate (145 g as silver nitrate) and an aqueous solution of potassium bromide containing 4.2 g of potassium iodide were added by the double jet method. The rate of addition at this time is such that the flow rate at the end of addition is 5
The flow rate was accelerated so that it doubled. After completion of the addition, soluble salts were removed at 35 ° C. by a sedimentation method, the temperature was raised to 40 ° C., and 75 g of gelatin was added to adjust the pH to 6.7. The obtained emulsion was tabular grains having a projected area diameter of 0.98 μm and an average thickness of 0.138 μm, and the silver iodide content was 3
It was mol%. This emulsion was chemically sensitized by combining gold and sulfur sensitization.

<Preparation of photographic material> As a surface protective layer, in addition to gelatin, polyacrylamide having an average molecular weight of 5000, sodium polystyrene sulfonate, polymethylmethacrylate fine particles (average particle size 3.0 μm), polyethylene oxide, and a hardener. An aqueous gelatin solution containing the above was used. Anhydro-5,5-dichloro-9-ethyl-3,3'-di (3-sulfopropyl) oxacarbocyanine hydroxide sodium salt was added to the above emulsion as a sensitizing dye at a ratio of 500 mg / 1 mol Ag and iodine. Potassium iodide was added at a rate of 200 mg / 1 mol Ag. Furthermore, as stabilizers, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene and 2,6-bis (hydroxyamino) -4-diethylamino-1,
3,5-triazine and nitrone, trimethylolpropane as a dry antifoggant, a coating aid, and a film hardener are added to prepare a coating solution, which is coated and dried simultaneously on both sides of a polyethylene terephthalate support simultaneously with a surface protective layer. , Made photographic material. The coated silver amount of this photographic material is 2 g / m ² per side.

The following developing solution and fixing solution were set in an FPM-9000 type automatic developing machine manufactured by Fuji Photo Film Co., Ltd.
A running test was carried out using the above silver halide light-sensitive material under the conditions of a developing time of 24 seconds, a fixing time of 25 seconds, a developing temperature of 35 ° C., a fixing temperature of 35 ° C. and a washing water amount of 5 liters / minute.
Thirty sheets of half-exposed light-sensitive material having a size of 4 cuts were processed per day, and in the same manner as in Example 1, a cycle of operating for 6 days and resting for 1 day was repeated 4 times. The replenishing amount was 50 ml of the developing solution and 60 ml of the fixing solution per one sheet of 4-cut size.

<Development Replenisher> Potassium sulfite 44.2 g Potassium metabisulfite 12.6 g Hydroquinone 30.0 g 1-Phenyl-3-pyrazolidone 1.5 g Diethylenetriamine pentaacetic acid 1.0 g Potassium hydroxide 29.0 g 5-Methylbenz Triazole 0.06 g 5-Nitroindazole 0.2 g Glacial acetic acid 7.5 g Glutaraldehyde 5.0 g Diethylene glycol 20.0 g Potassium hydroxide is added and water is added to 1 liter to pH.
To 10.30. To this developing replenisher, 3 g / liter of potassium bromide and 4 ml / liter of glacial acetic acid were added as a starter, and this was used as a developing solution (mother liquor).

<Fixing Solution of the Present Invention> Ammonium thiosulfate 125 g Sodium thiosulfate 25 g Sodium sulfite 18 g Acetic acid (90%) 19 g Ethylenediaminetetraacetic acid diNa salt 0.25 g Ammonia water (27%) 8 g Aluminum sulfate aqueous solution (27 wt / wt%) 27 g Tartaric acid 3.5 g Compound I-1 4 g Water was added to 1 liter pH 4.8

Comparative Example Fixing Solution-3 Ammonium thiosulfate 125 g Sodium thiosulfate 25 g Sodium sulfite 18 g Acetic acid (90%) 19 g Ethylenediaminetetraacetic acid diNa salt 0.25 g Ammonia water (27%) 8 g Aluminum sulfate aqueous solution (27 wt / wt%) 27g Tartaric acid 3.5g Add water 1 liter pH 4.8

As a result, even after four rounds of treatment, when the fixing solution containing the compound I-1 of the present invention was used, the fixing walls of the fixing tank and the washing tank and the rollers were washed in the same manner as in Example-1. No precipitation or deposit was observed on the surface. Similarly, in the fixer of Comparative Example 3, no precipitation was observed, but the boric acid concentration in the wash water was about 1 to 5 ppm, which is not preferable from the viewpoint of environmental protection.

[0066]

The compound of the present invention is used for the steps after the development treatment,
Above all, when added to the fixer, it can suppress the formation of precipitates due to alkaline earth metals in water and aluminum salts used as hardeners, and at the same time, it is mixed with waste water of the washing water like boric acid. Does not cause a problem for the environment.

Claims (4)

[Claims] 1. A processing solution for a silver halide photographic light-sensitive material, which contains at least one compound represented by the following general formula (I) and is used in a processing step after development. General formula (I) In the formula, R ₁ and R ₂ are each a hydroxy group, an amino group,
It represents an acylamino group, an alkylsulfonylamino group, an arylsulfonylamino group, an alkoxycarbonylamino group, a mercapto group or an alkylthio group. X is R
₁ represents a group of atoms necessary for forming a 5- or 6-membered ring together with two vinyl carbon atoms substituted by R ₁ and R ₂ and a carbonyl carbon atom. 2. A processing solution containing at least one compound represented by the general formula (I) is a fixing solution, a bleach-fixing solution,
The treatment liquid according to claim 1, which is one of a rinse liquid, a water washing liquid, and a stabilizing liquid. 3. A fixing solution containing at least one compound represented by the general formula (I) and containing no boron compound in an amount of more than 0.01 mol / liter.
The treatment liquid described. 4. A silver halide photographic light-sensitive material having at least one silver halide light-sensitive layer on a support is exposed,
A method for processing a silver halide photographic light-sensitive material, which comprises developing and then processing with a processing solution containing at least one compound represented by the general formula (I).