JP3298030B2 - Fixing solution for processing silver halide photographic materials - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fixing solution for processing a silver halide photographic light-sensitive material, and more particularly, to a high fixing speed which is excellent in desilvering property in a processing step of rapid and low replenishment of a silver halide photographic light-sensitive material. The present invention relates to a fixing solution for processing a silver halide photographic material capable of providing a fixing method.

[0002]

2. Description of the Related Art In recent years, it has been desired to rapidly process a photosensitive material. For example, in the case of a photosensitive material for X-ray photography, it can be processed in a so-called dry-to-dry process in 30 seconds, mainly for an ortho system. In such a case, the time allotted to the fixing process is about 5 to 10 seconds, and the extremely short fixing process imposes a heavy load and deteriorates the finished image quality.

For example, residual color failures caused by delay in elution of the sensitizing dye from the photographic material, poor fixing caused by a slow fixing speed, so-called poor desilvering, insoluble matters in the processing solution adhere to the surface of the photosensitive material. This is a so-called processing stain or the like caused by the above.

Further, thiosulfate is used as a desilvering agent in the fixing solution. It is known that the concentration of thiosulfate is increased for rapid processing. As a result, the water washability deteriorates and the amount of residual thiosulfate increases, which adversely affects the storage stability of the image.

[0005] In recent years, it has been desired to reduce the amount of waste photographic processing liquid in order to reduce the environmental pollution load, and it has been considered to reduce the amount of replenishment. However, since the reduction in the amount of replenishment promotes deterioration of the finished image quality, as an accelerator for the fixing process, for example, JP-A-45-35754, JP-B-58-122535,
No. 58-122536, thiourea derivatives, alcohols having a triple bond in the molecule, thioethers described in U.S. Pat.No.4,126,459 are disclosed but are not sufficient, especially when the fixing time is 10 seconds or less. Reduction of the replenishment amount resulted in deterioration of residual silver and residual color.

Accordingly, it has been desired to develop a fixing solution for processing silver halide photographic light-sensitive materials with low replenishment and rapid processing, free of residual silver and residual color.

[0007]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a high quality image free of residual silver and residual color even when a large amount of film is rapidly and continuously processed by an automatic processor with a reduced replenishing amount. An object of the present invention is to provide a fixer for processing a silver halide photographic material which can be obtained.

[0008]

SUMMARY OF THE INVENTION The above object of the present invention can be achieved by one of the following configurations or.

A fixing solution for processing a silver halide photographic light-sensitive material, comprising at least one kind of the compound represented by the general formula [1] or a salt thereof.

[0010]

[0011] Less of the sugars selected from the compound group
Silver halide photography characterized by containing both
Fixing solution for photosensitive material processing.

Hereinafter, the present invention will be described specifically.

First, the compound represented by the general formula [1 ] will be described.

[0014]

Embedded image

In the formula, R and R ₁ represent a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an alkenyl group, an acyl group or an alkynyl group, or an optionally substituted amino group -N <(R ₂ )
(R ₃ ), wherein R ₂ and R ₃ represent a hydrogen atom or an aliphatic residue, and represent an alkyl group, an alkenyl group, an acyl group or an alkynyl group having 1 to 30 carbon atoms which may be substituted; A substituted or unsubstituted alkyl group of Formulas 1 to 3 is preferable. When R ₂ and R ₃ form a ring,
The ring is preferably a 5-membered to 7-membered ring.
Examples include a morpholine ring. X is carbon number 1
5 represents an unsubstituted linking group, methylene group, ethylene
Group, propylene group and the like. m is 0 or 1 to 5
Represents an integer.

In the formula, M is a hydrogen atom, an alkali metal atom (eg, lithium, sodium, potassium, etc.), NH
₄ ⁺ , organic base (eg, conjugate acid such as triethylamine, 1,8-diazabicyclo [5.4.0] -7-undecene), quaternary ammonium (eg, (C ₂ H ₅ ) ₄ N ⁺ , (C ₄ H ₉ ) ₄ N ^+, etc.), ₄ P ⁺ 4 quaternary phosphonium (e.g. _{(C 4 H 9), C} 6 H 5 CH 2 P + (CH 3) 3 , etc.) is preferred.

M is an amidino group, -C (= S) -N <
(R ₄ ) (R ₅ ) or -S- (CH ₂ ) _m -N <(R ₆ ) (R ₇ ). R ₄ , R ₅ , R ₆ and R ₇ have the same meanings as R ₂ and R ₃ .

The substituents of the aliphatic residues represented by R, R ₁ , R ₂ and R ₃ include a carboxyl group, a hydroxyl group,
Sulfo group, carbamoyl group, sulfamoyl group, amino group, mercapto group, cyano group, ester group, sulfonyl group, alkoxy group, alkylthio group, alkoxysulfonyl group, acylamino group, sulfonylamino group, acyloxy group, acyl group and the like are preferable, These substituents may be further substituted.

Examples of the salt of the compound represented by the general formula [1] include hydrochloride, sulfate, oxalate, P-toluenesulfonate and methanesulfonate.

[0020]

[0021]

Next, the saccharide according to the present invention will be described.
Sugars Many consist monosaccharides, polysaccharides represented by the general formula C _n H _2n O _n. The monosaccharides generally refer to aldehydes or ketones of polyhydric alcohols and their reduced derivatives, oxidized derivatives, dehydrated derivatives, and further broad derivatives such as amino sugars and thio sugars. Polysaccharides refer to two or more dehydration condensation products of the aforementioned monosaccharides.

Among these saccharides, more preferred are aldoses having a reducing aldehyde group and derivatives thereof, which are selected from the above-mentioned compounds . In addition, these optical isomers can be used similarly.

The compounds represented by the general formula (1) below, and Specific examples of the saccharides, the present invention is not limited to these compounds.

[0025]

Embedded image

[0026]

Embedded image

[0027]

Embedded image

[0028]

Embedded image

3-1 D-okilose 3-2 L-arabinose 3-3 D-ribose 3-4 D-deoxyribose 3-5 D-glucose 3-6 D-galactose 3-7 D-mannose 3-8 L -Sol hose 3-9 D-tagatose 3-10 L-fucose 3-11 L-rhamnose 3-12 D-mannoheptulose 3-13 Sedheptulose 3-14 D-erythrose 3-15 Glycosan (1,5 ) α (1,2) 3-16 glycosen-1,2 3-17 D-glucal 3-19 D-glyconic acid 3-20 glycosamine 3-21 galactosamine 3-22 chitin (poly-N-acetyl-D-glucocumin ) 3-23 6-amino-6-deoxy-D-glucose 3-24 3-amino-3-deoxy-D-ribose 3-25 picrosin 3-26 D-apiose 3-27 3-deoxyapiose 3-28 D-thioglucose 3-29 thiomethylribose 3-30 α-lactose 3-31 α-mal Tooth 3-32 D-trehalose 3-33 Maltotriose

The amount of the compound of the present invention to be added is preferably 0.01 to 100 g / l, particularly preferably 0.1 to 50 g / l, per liter of the fixing solution. As the fixing agent of the present invention, sodium thiosulfate, potassium thiosulfate, and ammonium thiosulfate are preferable, and ammonium thiosulfate is particularly preferable.

The concentration of thiosulfate as a fixing solution is preferably 0.1 to 5 mol / l, more preferably 0.1 mol / l.
3 to 2 mol / l, more preferably 0.5 to 1.
5 mol / l.

The fixing solution of the present invention contains a sulfite as a preservative, and the concentration of the sulfite is 0.2 mol / L or less when the thiosulfate and the sulfite are dissolved and mixed in water, and is preferably not more than 0.2 mol / liter. It is 0.1 mol / liter or less. As the sulfite, potassium, sodium, ammonium salts and the like are used, and the fixing solution preferably contains citric acid, tartaric acid, malic acid, succinic acid, phenylacetic acid, and optical isomers thereof. As salts of, for example, potassium citrate, lithium citrate, sodium citrate, ammonium citrate, lithium hydrogen tartrate, potassium hydrogen tartrate, potassium tartrate, sodium hydrogen tartrate, sodium tartrate, ammonium hydrogen tartrate, ammonium potassium tartrate, sodium tartrate Preferred examples include lithium, potassium, sodium, ammonium salts and the like represented by potassium, sodium malate, ammonium malate, sodium succinate, ammonium succinate, and the like. Only together can be used.

Among the above compounds, more preferred are citric acid, isocitric acid, malic acid, phenylacetic acid and salts thereof.

The citric acid, tartaric acid, malic acid, succinic acid and the like are supplied as solids and used after being dissolved in an aqueous solvent. The preferred content in the fixing solution after dissolution is 0.05 mol / liter or more, and the most preferred content is 0.2 to
0.6 mol / liter.

The fixing solution of the present invention may contain a hardener. Hardening agents preferably used are aluminum compounds, such as aluminum sulfate and potassium alum.

The pH of the fixing solution is preferably from 3.8 to 5.8, particularly preferably from 4.5 to 5.1. It should be noted that the higher the pH, the better the fixability, but the worse the dryness.

Preferred processing conditions for the fixing solution of the present invention are a fixing time of 5 to 20 seconds and a processing temperature of 15 to 45 ° C., particularly preferably 25 to 38 ° C.

A surfactant may be added to the fixing solution of the present invention. Preferred surfactants include, for example, anionic surfactants such as sulfated and sulfonated compounds, nonionic surfactants such as polyethylene glycol-based and ester-based surfactants, and amphoteric surfactants described in JP-A-57-6840. No.

In the fixing solution, in addition to the above compounds, various acids,
Additives such as salts, chelating agents and wetting agents can be included.

Examples of the acid include salts of inorganic acids such as sulfuric acid, hydrochloric acid, nitric acid and boric acid, and organic acids such as formic acid, propionic acid, oxalic acid and malic acid.

Examples of the salt include salts of these acids such as lithium, potassium, sodium and ammonium.

Examples of the chelating agent include aminopolycarboxylic acids such as nitrilotriacetic acid and ethylenediaminetetraacetic acid, and salts thereof.

Examples of the wetting agent include alkanolamine and alkylene glycol.

Among the above additives, acids and salts such as sulfuric acid, boric acid and aminopolycarboxylic acids are preferred. The preferred amount of the additive is 0.5 to 20 g / liter.

The fixing processing agent of the present invention can be used for various black-and-white silver halide photographic materials such as X-ray, printing plate making, black and white general use, film for laser light source, CRT photographing, duplication, and II indirect photosensitive material. Applicable to material.

The developer contains the following developing agent. Examples of black-and-white developing agents include dihydroxybenzenes (eg, hydroquinone, chlorohydroquinone, bromohydroquinone, dichlorohydroquinone, isopropylhydroquinone, methylhydroquinone, 2,3-dichlorohydroquinone, methoxyhydroquinone, 2,5-dimethylhydroquinone, hydroquinone monosulfonic acid) Potassium, sodium hydroquinone monosulfonate), 3-pyrazolidones (for example, 1-
Phenyl-3-pyrazolidone, 1-phenyl-4-methyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-ethyl-3-pyrazolidone, 1-phenyl-
5-methyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, 1-phenyl-4,4-dihydroxymethyl-3-pyrazolidone, 1-p-tolyl-3-pyrazolidone, 1-phenyl-2-acetyl-4,4-dimethyl-3-pyrazolidone, 1- (2-benzothiazole) -3-pyrazolidone, 3-
Acetoxy-1-phenyl-3-pyrazolidone, etc.), aminophenols (eg, o-aminophenol, p-aminophenol, N-methyl-o-aminophenol, N-methyl-p-
Aminophenol, 2,4 diaminophenol, etc.), 1-allyl-3-aminopyrazolines (eg, 1- (p-hydroxyphenyl) -3-aminopyrazoline, 1- (p-methylaminophenyl) -3 -Aminopyrazoline, 1- (p-amino-m-methylphenyl) -3-aminopyrazoline, etc.), ascorbic acid, pyrazolones (eg, 4-aminopyrazolone) and the like, or a mixture thereof.

In addition, LFA Mason Photographic Proce
ssing Chemistry (Focal Press, 1966) 226-229
Page, JP-A-48-64933 and the like.

In the developing solution, if necessary, a preservative (eg, sulfite, bisulfite, etc.), a buffer (eg, carbonate, boric acid, borate, alkanolamine, etc.), an alkali agent ( Eg, carbonates), dissolution aids (eg, polyethylene glycols and esters thereof), pH adjusters (eg, organic acids such as citric acid),
A sensitizer (for example, a quaternary ammonium salt), a development accelerator, a hardener (for example, dialdehydes such as glutaraldehyde), a surfactant and the like can be contained. Further, as an antifogging agent, an azole organic antifogging agent (for example, indazole type, imidazole type, benzimidazole type, triazole type, benzotriazo type, tetrazole type, thiadiazole type), calcium ions mixed in tap water used in the treatment liquid And sodium hexametaphosphate, calcium hexametaphosphate, polyphosphate and the like.

The replenishment amount of the developing solution is 50 per m ² of the photosensitive material.
0 to 200 cc is preferred.

The development time is 5 to 45 seconds, preferably 8 to 30 seconds.
Seconds. The development temperature is preferably from 25 to 50 ° C, more preferably from 30 to 40 ° C.

Drying is usually performed at 35 to 100 ° C., preferably 40 to 8 ° C.
A drying zone in which hot air of 0 ° C. is blown or heating means by far-infrared rays may be provided in the automatic developing machine.

The automatic developing machine has the above-mentioned developing, fixing,
An automatic developing machine (JP-A-3-264953) having a function of applying water or a rinsing solution of an acidic solution or water having no fixing ability to the photosensitive material during each washing step may be used. Further, the automatic developing machine may have a built-in device capable of adjusting a developing solution and a fixing solution.

The silver halide grains used in the emulsion may be normal grains or twin grains. The average grain size of the tabular silver halide grains is preferably from 0.3 to 3.0 μm, particularly preferably from 0.5 to 1.5 μm. .

Tabular silver halide grains have an average value (called average aspect ratio) of grain diameter / thickness (called as aspect ratio) of 1 to 5, preferably 1.5 to 4, particularly preferably 2 to 4. 3.

The average thickness of the tabular silver halide grains is 0.5
μm or less, particularly preferably 0.3 μm or less.

In the present invention, the diameter of a silver halide grain is defined as the diameter of a circle having an area equal to the projected area of the grain from observation of an electron micrograph of the silver halide grain.

The thickness of a silver halide grain is defined as the minimum of the distance between two parallel planes constituting a tabular silver halide grain.

The thickness of the tabular silver halide grains can be determined from an electron micrograph with a shadow of the silver halide grains or an electron micrograph of a sample tomogram obtained by coating a silver halide emulsion on a support and drying. .

To determine the average aspect ratio, the minimum
Measure 100 samples. In the silver halide emulsion of the present invention, the effect is obtained when the ratio of tabular silver halide grains to all photosensitive silver halide grains is 50% or more.

The silver halide emulsion may be a single emulsion or a mixture of two or more emulsions. The emulsion to be mixed may be the emulsions according to the present invention, or may be normal crystals or twin grains having an aspect ratio of less than 2.

The tabular silver halide emulsions are preferably monodisperse emulsions. The average grain size is preferably within ± 20% of the center of the silver halide grains, and more than 50% by weight of the silver halide grains. Particularly preferably used.

The tabular silver halide emulsion may have any halogen composition such as silver chloride, silver bromide, silver chlorobromide, silver iodobromide, and silver chloroiodobromide. Silver iodobromide is preferred, and the average silver iodide content is 0 to 5.0 mol%, particularly preferably 0.1 to 3.0 mol%.

The tabular silver halide emulsion of the present invention comprises:
The halogen composition may be uniform in the grains and silver iodide may be localized, but those localized in the center are also preferably used.

The method for producing tabular silver halide emulsions is described, for example, in JP-A-58-113926, JP-A-59-113927 and JP-A-58-113934.
No. 62-1855, European Patent Nos. 219,849, 219,85
No. 0 etc. can be referred to. Further, a method for producing a monodisperse tabular silver halide emulsion is described in JP-A-61-664.
No. 3 publication can be referred to.

As a method for producing a tabular silver iodobromide emulsion having a high aspect ratio, an aqueous silver nitrate solution or an aqueous silver nitrate solution and an aqueous halide solution are simultaneously added to an aqueous gelatin solution having a pBr of 2 or less to generate seed crystals. And then grown by the double jet method.

The size of the tabular silver halide grains can be controlled by the temperature during grain formation and the rate of addition of the silver salt and the aqueous halide solution. The aspect ratio can be controlled by the seed crystal preparation method, thickness, pAg and pH during growth, halogen composition, ripening time and temperature, and the like.

The average silver iodide content of the tabular silver halide emulsion can be controlled by changing the composition of the aqueous halide solution to be added, that is, the ratio of bromide to iodide.

For the tabular silver halide grains, a silver halide solvent such as ammonia, thioether, thiourea or the like can be used, if necessary, during production. The grains may be grown by supplying an aqueous solution containing silver ions and an aqueous solution containing halogen ions, or may be supplied as fine particles of silver halide. In this case, silver iodide, silver iodobromide, silver bromide, silver chlorobromide, silver chloride, a solution containing a halogen ion, a solution containing a silver ion, or the like can be supplied.

As for the distribution of halogen, core / shell type or double structure type grains having a silver halide composition whose surface is different from the inside of the grains are preferably used. Regarding core / shell type particles, JP-A-59-177535 and JP-A-57-178447
The particles can be prepared by the methods described in JP-A Nos. 60-35726 and 60-147727.

The emulsion may be subjected to a water washing method such as a Nudel washing method or a flocculation sedimentation method to remove soluble salts. As a preferred washing method, for example,
As a particularly preferred desalting method, a method using an aromatic hydrocarbon aldehyde resin containing a sulfo group described in 35-16086, or a method using G3, G8 or the like as an aggregating polymer agent described in JP-A-63-158644 is used. No.

The chemical sensitization method includes so-called sulfur sensitization,
Sensitization with a selenium compound, sensitization with a tellurium compound, gold sensitization, sensitization with a noble metal of Group VIII of the periodic table (for example, Pd, Pt, Ir, and the like), and a sensitization method using a combination thereof can be used. Among them, a combination of gold sensitization and sulfur sensitization or a combination of gold sensitization and a selenium compound is preferable. It is also preferable to carry out in combination with reduction sensitization.

It is preferable to supply iodine ions at the time of chemical sensitization or at the end of the chemical sensitization in terms of sensitivity and dye adsorption. Particularly, a method of adding silver iodide in the form of fine grains is preferable.

It is also preferable to carry out the chemical sensitization in the presence of a compound having adsorptivity to silver halide. As the compounds, azoles, diazoles, triazoles, tetrazoles, indazoles, thiazoles, pyrimidines, azaindenes, and particularly compounds having a mercapto group and compounds having a benzene ring are preferable.

The silver halide photographic light-sensitive material according to the present invention is subjected to a reduction treatment, that is, a so-called reduction sensitization method, in which a reducing compound is added, and a silver ripening state called pAg = 1 to 7, which is called silver ripening, is passed. Method, called high pH aging
It may be applied to the silver halide emulsion by a method of passing a high pH state of H = 8 to 11 or the like. Further, these two or more methods can be used in combination.

The method of adding a reducing compound is preferable because the degree of reduction sensitization can be finely adjusted. As the reducing compound, any of inorganic or organic compounds may be used. Thiourea dioxide, stannous salts, amines and polyamines, hydrazine derivatives, formamidine sulfinic acid, silane compounds, borane compounds, ascorbic acid and its derivatives, sulfurous acid And the like. Particularly preferred are thiourea dioxide, stannous chloride and dimethylamine borane. The amount of these reducing compounds to be added varies depending on the reducibility of the compounds, the type of silver halide, and emulsion production conditions such as dissolution conditions, but is 1 × 10 ⁻⁸ per mol of silver halide.
A range of １1 × 10 ^-2 mol is suitable. These reducing compounds are dissolved in an organic solvent such as water or alcohols, and added during the growth of silver halide grains.

The silver halide photographic material is spectrally sensitized using a known spectral sensitizing dye.

The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes,
Holobola cyanine dyes, hemicyanine dyes, styril dyes and hemioxonol dyes are included. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes and complex merocyanine emulsions.

In the silver halide emulsion, various photographic additives can be used before and after physical ripening or chemical ripening. Known additives include, for example, Research Disclosure No. 17643 (December 1978), No. 1
8716 (November 1979) and No. 308119 (December 1989). The types of compounds and the locations described in these three research disclosures are listed below.

Additive RD-17643 RD-18716 RD-308119 Page Classification Page Classification Page Classification Chemical sensitizer 23 III 648 Upper right 996 III Sensitizing dye 23 IV 648-649 996-8 III Desensitizing dye 23 IV 998 B Dye 25-26 VIII 649-650 1003 VIII Development accelerator 29 XXI 648 Upper right Fog inhibitor / stabilizer 24 IV 649 Upper right 1006-7 VI Brightener 24 V 998 V Surfactant 26-7 XI 650 Right 1005-6 XI Antistatic agent 27 XII 650 right 1006-7 XIII plasticizer 27 XII 650 right 1006 XII sliding agent 27 XII matting agent 28 XVI 650 right 1008-9 XVI binder 26 XXII 1009-4 XXII support 28 XVII 1009 XVII according to the present invention Examples of the support that can be used for the light-sensitive material include the aforementioned RD-17643, page 28, and RD-308119, page 100.
What is described on page 9 is mentioned.

A suitable support is a plastic film or the like, and the surface of the support may be provided with an undercoat layer, or subjected to corona discharge, ultraviolet irradiation or the like in order to improve the adhesion of the coating layer.

[0081]

EXAMPLES The present invention will be described below in detail with reference to examples, but embodiments of the present invention are not limited thereto.

Example 1 Preparation of one kind emulsion While controlling at 60 ° C., pAg = 8 and pH = 2.0, a single jet of silver iodobromide containing 1 mol% of silver iodide having an average grain size of 0.3 μm was conducted by a double jet method. Dispersed cubic particles were prepared.

The resulting reaction solution was desalted at 40 ° C. using an aqueous solution of Demol N manufactured by Kao Atlas Co. and an aqueous solution of magnesium sulfate, and then re-dispersed by adding an aqueous solution of gelatin to obtain a seed emulsion.

Growth from Seed Emulsion 1 Using the seed emulsion described above, grains were grown as follows. First, the seed emulsion is dispersed in an aqueous gelatin solution maintained at 40 ° C.
The pH was adjusted to 9.7 with aqueous ammonia and acetic acid.

An aqueous solution of ammonium nitrate ion and an aqueous solution of potassium bromide and potassium iodide were added to this solution by a double jet method. During the addition, pAg was controlled to 7.3, pH was controlled to 9.7, and a layer having a silver iodide content of 15 mol% was formed. Next, an aqueous solution of ammonium silver nitrate and an aqueous solution of potassium bromide were added by a double jet method. The pAg was kept at 9.0 until 95% of the target particle size, and the pH was continuously changed from 9.0 to 8.0. Thereafter, the pAg was adjusted to 11.0, and the particles were grown to a target particle size while maintaining the pH at 8.0. Subsequently, the pH was lowered to 6.0 with acetic acid, and
Anhydrous dichloro-9-ethyl-3,3'-di- (3-sulfopropyl) oxacarbocyanine sodium salt (desensitizing dye GD-
1) was added at 400 mg / mol AgX, desalted using an aqueous solution of Demol N manufactured by Kao Atlas Co., and an aqueous solution of magnesium sulfate, and then redispersed by adding a gelatin solution.

According to this method, the average silver iodide content was 1.0 mol, and the vertices were rounded at the top, and the average grain size was 0.40 μm and 0.65 μm.
μm, 1.00 μm, coefficient of variation (δ / r) 0.17, 0.1
(A), (B),
(C) was prepared.

Preparation of Seed Emulsion 2 Including hydrogen peroxide-treated gelatin stirred vigorously at 40 ° C.
An equimolar aqueous potassium bromide solution containing a silver nitrate aqueous solution and hydrogen peroxide-treated gelatin is added to the 05N aqueous potassium bromide solution by the double jet method, and the mixture is heated at 25 ° C over 30 minutes from 1.5 minutes later.
After the temperature of the solution was lowered to 80 ml, 80 ml of aqueous ammonia (28%) was added per mole of silver nitrate, and stirring was continued for 5 minutes.

Thereafter, the pH was adjusted to 6.0 with acetic acid, desalted using an aqueous solution of Demol N manufactured by Kao Atlas Co. and an aqueous solution of magnesium sulfate, and then redispersed by adding an aqueous solution of gelatin.

The obtained seed emulsion was spherical grains having an average particle size of 0.23 μm and a coefficient of variation of 0.28.

Growth from Seed Emulsion 2 Using the seed emulsion described above, grains were grown as follows. An aqueous solution of potassium bromide and potassium iodide and an aqueous solution of silver nitrate were added by double jet method to an aqueous solution containing ossein gelatin and propyloxy-polyethyleneoxydisuccinate disodium salt vigorously stirred at 75 ° C. PH =
5.8, pAg = 9.0. After the addition was completed, the pH was adjusted to 6.0, and GD-1 was added at 400 mg / mol AgX. After further desalination using Kao Atlas Demol N aqueous solution at 40 ° C,
An aqueous gelatin solution was added and redispersed.

According to this method, a tabular silver iodobromide emulsion (D) having an average silver iodide content of 0.5 mol%, a projected area diameter of 0.96 μm, a coefficient of variation of 0.25, and an aspect ratio (projected area diameter / grain thickness) of 4.0 was obtained. Was prepared.

Preparation of Samples The obtained emulsions (A), (B), (C) and (D) were each subjected to GD-1 and 55,5′-di- (butoxycarbonyl) -1,55 ° C. at 55 ° C.
Anhydrous sodium salt of 1'-diethyl-3,3'-di- (4-sulfobutyl) benzimidazolocarbocyanine (weight ratio of 200: 1) (A) was 975 mg per mole of silver halide,
600 mg of (B), 390 mg of (C) and 500 mg of (D) were added.

After 10 minutes, chloroauric acid, sodium thiosulfate,
Ammonium thiocyanate was added for chemical ripening.
Fifteen minutes before the completion of ripening, 200 mg of potassium iodide was added per mol of silver halide, and then 4-hydroxy-6-methyl-
1,3,3a, 7-Tetrazaindene was added in an amount of 3 × 10 ^-2 mol per mol of silver halide and dispersed in an aqueous solution containing 70 g of gelatin.

Of the four types of ripened emulsions, (A)
(B) and (C) were mixed at a weight ratio of 15:65:20 to obtain Emulsion-I, and (D) alone was used as Emulsion-II.

To Emulsion-I and Emulsion-II, additives as shown in JP-A-2-301744, page 95, line 16 to page 96, line 20 were added.

Further, 1.2 g of a dye emulsified dispersion shown below was added to prepare an emulsion coating solution.

Preparation of Dye Emulsified Dispersion 10 kg of the following dye was dissolved at 55 ° C. in a solvent consisting of 28 liters of tricresyl phosphate and 85 liters of ethyl acetate.
This is called an oil-based solvent. On the other hand, a 9.3% gelatin aqueous solution containing 1.35 kg of an anionic surfactant (AS) is called an aqueous solvent.

Next, the oil-based solvent and the aqueous-based solvent were placed in a dispersion vessel, and dispersed while maintaining the liquid temperature at 40 ° C.

[0099]

Embedded image

The additives used for the protective layer are as follows. The amount of addition is indicated by the amount per liter of the coating solution.

Coating solution for protective layer Lime-treated inert gelatin 68 g Acid-treated gelatin 2 g Sodium-i-amyl-n-decylsulfosuccinate 0.3 g Polymethyl methacrylate (matting agent having an area average particle size of 5.0 μm) 1.1 g Silicon dioxide particles (Mat agent having an area average particle diameter of 3.0 μm) 0.5 g Ludox AM (Colloidal silica manufactured by DuPont) 30 g 40% aqueous solution of glyoxal (hardener) 1.5 ml (CH ₂ = CHSO ₂ CH ₂ ) ₂ O (hardener) 500mg

[0102]

Embedded image

The emulsion layer had a silver equivalent of 1.7 g per side.
/ M ^2, 2.5 g / m ² as a weight with a gelatin protective layer at a speed per minute 90m by two slide hopper type coater so that the 0.99 g / m ² as a weight with gelatin, glycidyl methacrylate - methyl acrylate Emulsion on a 175 μm polyethylene terephthalate base coated with an aqueous dispersion of a copolymer obtained by diluting a butyl methacrylate copolymer (50:10:40 wt%) to a concentration of 10 wt% as a subbing liquid A layer and a protective layer were simultaneously coated on both sides and dried in 2 minutes and 15 seconds to obtain a sample film.

Preparation of developer (1 liter formulation) Potassium sulfite 70 g Trisodium hydroxyethylethylenediaminetriacetate 8 g 1,4-dihydroxybenzene 35 g Boric acid 10 g 5-methylbenzotriazole 0.04 g 1-phenyl-5-mercaptotetrazole 0.01 g Meta-weight Sodium sulfite 5 g Acetic acid (90%) 13 g Triethylene glycol 15 g 1-Phenyl-3-pyrazolidone 1.2 g 5-Nitroindazole 0.2 g Glutaraldehyde 4 g 5-Nitrobenzimidazole 1 g Dissolve in 1 liter of water and use sodium hydroxide. pH 10.5
Solution.

Preparation of starter solution Potassium bromide 300 g Glacial acetic acid 144 g Preparation of fixing solution of the present invention Sodium thiosulfate pentahydrate 4.5 g Amonium thiosulfate 150 g Exemplary compounds Amount shown in Tables 1 and 3 Disodium ethylenediaminetetraacetate 0.5 g Anhydrous Sodium sulfite 8g Potassium acetate 16g Aluminum sulfate 10-18 water salt 10g Sulfuric acid (50wt%) 5g Citric acid 1g Boric acid 7g Glacial acetic acid 5g An aqueous solution of 1 liter was prepared with glacial acetic acid to obtain a solution of pH 4.4.

<Processability Test> The processing performance of the fixing solution using the fixing accelerator of the present invention was evaluated in terms of residual silver and residual color.

Evaluation of Residual Color Using an automatic developing machine SRX-503, the above-mentioned developing solution, starter and fixing solution (exemplary compounds were added as fixing promoters as shown in Table 1) were used to determine the running equilibrium as follows. Made the state. First, 16.5 liters of the developing solution was filled in a developing tank, and 330 cc of a starter was added. At this time, the pH of the liquid in the developing tank was 10.38. After the fixer was also filled in the processing tank, the photosensitive material prepared above was exposed to light so as to obtain an optical density of 1.1, and processed for a processing time of 30 seconds.

The developing conditions were as follows: a developing temperature of 37 ° C., a fixing temperature of 36 ° C., a developing replenishment amount of 20 cc / quarter, and a fixing replenishing amount of 20 cc.
Performed in cc / quarter cuts. As the replenisher, the above-described developer and fixer were used. The pH of the thus-developed developer in a running equilibrium state was 10.38, and the pH of the fixer was 4.7.

Next, the unexposed light-sensitive material was subjected to development processing, and the remaining color was evaluated according to the following evaluation criteria.

Evaluation Criteria 5: No residual color contamination 4: Slight residual color contamination 3: Some residual color contamination, but no practical problem 2: Many residual color contamination, but limit of practical range 1: Remaining color contamination Evaluation of Residual Silver in Practical Use Unexposed film was processed in the same manner as above to obtain a sample for evaluating residual silver. Evaluation of residual silver was performed by the following method.

Residual silver evaluation solution (2.6 × 10 5 sodium sulfide)
^-3 mol / liter aqueous solution) is dropped one by one at five places on the residual silver evaluation film. After leaving for 3 minutes, wipe off the solution well and leave for 15 hours at room temperature and normal humidity.
Using a 65 (manufactured by Konica Corporation) spectral filter 436 ± 10 nm interference filter, measure the blue light transmission density of the lower part of the residual silver and the part where the residual silver does not drip, and use the difference as a guide for residual silver. . That is, the larger the difference, the higher the residual silver concentration in the processed film. Tables 1 and 3 show these results.
Shown in

[0112]

[Table 1]

[0113]

[0114]

[Table 3]

As is clear from Tables 1 and 3 , the treatment using the fixing accelerator of the present invention gave excellent results in fixing performance such as residual silver and residual color as compared with the comparative sample. Further, it can be seen that a plurality of the fixing accelerators of the present invention may be used in combination.

[0116]

According to the present invention, even if a large amount of film is rapidly and continuously processed by an automatic processor with a reduced replenishing amount,
A fixing solution for processing a silver halide photographic light-sensitive material capable of obtaining an image of excellent quality without residual silver or residual color can be provided.

Claims (2)

(57) [Claims] 1. A fixing solution for processing a silver halide photographic light-sensitive material, which comprises at least one of a compound represented by the following general formula [1] or a salt thereof. Embedded image [In the formula, R and R ₁ represent a hydrogen atom or an alkyl group, alkenyl group, acyl group or alkynyl group having 1 to 30 carbon atoms or an optionally substituted amino group -N <(R ₂ ) (R ₃ ) ,
R ₂ and R ₃ represent a hydrogen atom or an aliphatic residue, and R ₂ and R ₃
And may form a ring. X represents an unsubstituted linking group having 1 to 5 carbon atoms, and m represents an integer of 0 or 1 to 5. M represents a hydrogen atom, an alkali metal atom, or an ammonium group. ] 2. A fixing solution for processing a silver halide photographic light-sensitive material, which comprises at least one of the following sugars selected from the group of compounds : Compound group: D-okilose, L-arabinose, D-ribault
, D-deoxyribose, D-glucose, D-galactose
, D-mannose, L-sol hose, D-tagatose, L-f
Course, L-Rhamnose, D-Mannoheptulose, Sed
Heptulose, D-erythrose, glycosan (1,5) α
(1,2), glycosen-1,2, D-glucal, D-glycone
Acid, glycosamine, galactosamine, chitin (poly-N-A
(Cetyl-D-glucocumin), 6-amino-6-deoxy-D-glu
Course, 3-amino-3-deoxy-D-ribose, picrosi
, D-apiose, 3-deoxyapiose, D-thioglu
Course, thiomethylribose, α-lactose, α-mal
Tooth, D-trehalose, maltotriose