JPH0862812A - Method for processing silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE: To provide a method for processing a silver halide photographic sensitive material without using a large amt. of water unlike the conventional water washing method, excellent in picture stability after processing and without being limited by the supply and discharge of water in setting the place for an automatic developing machine. CONSTITUTION: A silver halide photographic sensitive material having at least one photosensitive silver halide emulsion layer on a substrate is processed as follows. Namely, the developed material is processed with a processing soln. contg. at least one kind of compd. shown by formula Z-SM and kept at pH 5-8 in place of the water washing after the developed material is processed with a processing soln. contg. a thiosulfate. In the formula, Z is a 6-membered ring including an N2 -contg. heterocyclic ring, the groups are replaced with substituents having at least one selected from the group consisting of hydroxyl, -SO3 M<1> group, -COOM<2> group (where each of M<1> and M<2> is hydrogen atom, an alkali metal atom or ammonium group), a substituted or unsubstituted amino group and a substituted or unsubstituted ammonio group, and M is hydrogen atom, an alkali metal atom or ammonium group and a substituted or unsubstituted amidino group.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method of processing a silver halide photographic light-sensitive material, and more particularly to a method of processing a silver halide photographic light-sensitive material having good image storage stability as an alternative to washing with water.

[0002]

2. Description of the Related Art Processing methods for silver halide photographic light-sensitive materials are generally carried out in the steps of developing, fixing, washing with water and drying.
Of these, a large amount of water is still used for the washing treatment. The use of water for washing treatment is not preferable from the viewpoint of effective utilization of water resources, and is also not preferable from the viewpoint of treating waste water after use.

Today, the use of automatic processors is common in photographic processing. It is also easy to use. In developing and fixing, since the amount of the processing liquid required to process a unit area is small, the used processing liquid can be collected in a small container. However, the amount of water treated per unit area in the washing process is large, and it cannot be collected in a small container. In addition, in order to supply these rinsing water, it must be connected to the tap water by an automatic processor, and for drainage, it must be connected to a drain pipe. This restriction is a major restriction on the installation location of the automatic processor.

In order to remove this restriction, when the washing process is performed using a small amount of water, the fixing solution composition contained in the light-sensitive material is not sufficiently washed in the light-sensitive material during the fixing process in the previous step. It remains, so-called insufficient washing with water, and the stability of the finished image during storage is extremely deteriorated. If the washing water is not sufficient, the image after storage will be fogged in the non-image area during storage of the processed image, especially when the image is stored under high humidity. I will end up.

[0005] A treatment method is expected which has an effect as an alternative to water washing by treating with a small amount of treatment liquid without using a large amount of water by the water washing treatment.

[0006]

In order to solve the above problems, an object of the present invention is to obtain a processing method with good image storage stability instead of washing treatment. A method for processing a silver halide photographic light-sensitive material that does not lose the pure black color of the image silver when it is stored under high humidity and discolors to brown, and does not cause fog in the non-image area. Especially. Another object of the present invention is to provide a method for processing a silver halide photographic light-sensitive material, which does not require a large amount of water-washing in the water-washing process and therefore can remove the restriction when installing an automatic processor.

[0007]

The above object of the present invention is to provide a method for processing a silver halide photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support,
After development, instead of washing with water after treatment with a treatment liquid containing thiosulfate, treatment with a treatment liquid having a pH of 5 to 8 containing at least one compound represented by the general formula [1] is used. It is achieved by the characteristic method of processing a silver halide photographic light-sensitive material.

The present invention will be specifically described below.

The treatment liquid of the present invention has a pH of 5 to 8, preferably pH 6 to 7, and particularly preferably pH 7. Further, although various kinds of contamination will be caused by the composition of the fixing solution which is the processing step immediately before that, a composition for removing this contamination may be included. Aminopolycarboxylic acids and other alkali salts may be used in order to prevent insolubilization of the aluminum compound, which is a hardener component contained in the fixing solution.

Further, it is possible to use an antibacterial agent together to prevent the generation of microorganisms by using the treatment liquid for a long period of time.

As the antifungal means, the ultraviolet irradiation method described in JP-A-60-263939, the method using a magnetic field described in JP-A-60-263940, and the ion exchange resin described in JP-A-61-131632 A method of using purified water to make pure water, JP-A-60-253807,
The methods using the antibacterial agents described in Nos. 60-295894, 61-63030, and 61-51396 can be used.

Furthermore, LEWest "Water Qality Criteri
a ”Photo Sci & Eng. Vol.9 No.6 (1965), MWBeach
“Microbiological Growths in Motion-Picture Proces
sing ”SMPTE Journal Vol.85, (1976), RODeegan,
“Photo Processing Wash Water Biocides” J. Imaging
Tech.Vol.10, No.6 (1984) and JP-A-57-8542 and 57-
58143, 58-105145, 57-132146, 58-18631
No. 57-97530, No. 57-157244, etc., and may be used in combination with antibacterial agents, antifungal agents, surfactants and the like.

Furthermore, RT Kreimen, J. Image, Tech1
0, (6) 242 (1984), isothiazoline compounds, Research Disclosure, Vol. 205, Item20526
(May, 1981), isothiazoline compounds described in Vol. 228, Item 22845 (April, 1983), isothiazoline compounds described in JP-A-61-51396. Compounds and the like can be used together as a bacteriostatic agent (Microbiocide).

Further, specific examples of the antifungal agent include phenol, 4-chlorophenol, pentachlorophenol, cresol, o-phenylphenol, chlorophene, dichlorophene, formaldehyde, glutaraldehyde, chloroacetamide, p-hydroxybenzoic acid. Acid ester, 2- (4-thiarizone) -benzimidazole, benzisothiazolin-3-one, dodecyl-benzyl-dimethylammonium chloride, N- (fluorodichloromethylthio) -phthalimide, 2,4,4'-trichloro-2 ′ -Hydroxydiphenyl ether and the like. Further, in addition to the silver image stabilizer, various surfactants can be added for the purpose of preventing unevenness of water droplets. As the surfactant, any of cation type, anion type, nonionic type and amphoteric type may be used. Specific examples of the surfactant include compounds described in "Surfactant Handbook" published by Engineering Book Co., Ltd.

Various compounds can be added to the above processing liquid for the purpose of stabilizing an image. For example, various buffers for adjusting the membrane pH (eg borate, metaborate, borax, phosphate, carbonate, potassium hydroxide, sodium hydroxide, aqueous ammonia, monocarboxylic acid, dicarboxylic acid, Typical examples include aldehydes such as polycarboxylic acids and the like) and folimarin. Other chelating agents, bactericides (thiazole-based, isothiazole-based, halogenated phenols, sulfanilamide,
Benzotriazole etc.), surfactant, optical brightener,
Various additives such as a hardening agent may be used, and two or more kinds of the same or different target compounds may be used in combination.

Further, as a film pH adjusting agent for the treatment liquid, ammonium chloride, ammonium nitrate, ammonium sulfate,
It is preferable to add various ammonium salts such as ammonium phosphate, ammonium sulfite and ammonium thiosulfate in order to improve the image storability.

The processing liquid method of the present invention can be applied to general-purpose light-sensitive materials (negative film and positive film for black-and-white photography, printing paper for black-and-white), and light-sensitive materials for plate making (lith film,
Examples thereof include a phototypesetting film, a phototypesetting printing paper), a photosensitive material for copying (microfilm, graph film), an X-ray photosensitive material and the like.

Next, the compound represented by the general formula [1] used in the present invention will be described in detail.

In the formula, Z is an alkyl group, an aromatic group or a heterocyclic group, and is a hydroxy group, --SO ₃ M ¹ group, --C
At least one selected from the group consisting of an OOM ² group (wherein M ¹ and M ² represent a hydrogen atom, an alkali metal atom, or an ammonium group), a substituted or unsubstituted amino group, or a substituted or unsubstituted ammonio group. Alternatively, it represents one substituted with a substituent having at least one selected from this group. M is a hydrogen atom, an alkali metal atom,
Represents a substituted or unsubstituted amidino group, which may form a hydrohalide or sulfonate.

The substituent having at least one selected from the above group is one having 20 or less carbon atoms, preferably a substituted or unsubstituted alkylthio group, a substituted or unsubstituted alkylamido group, a substituted or unsubstituted Is an alkylcarbamoyl group, a substituted or unsubstituted alkylsulfonamide group, or a substituted or unsubstituted alkylsulfamoyl group.

In the general formula [1], the nitrogen-containing heterocyclic group represented by Z is preferably a monocyclic or condensed ring having 1 to 32 carbon atoms, which is independently selected from nitrogen, oxygen and sulfur. It is a 6-membered ring having 1 to 6 heteroatoms in one ring, and may have a substituent in addition to the above.

In the general formula [1], the ammonio group preferably has 20 or less carbon atoms, and the substituent is a substituted or unsubstituted linear, branched, or cyclic alkyl group (eg, methyl group, ethyl group, benzyl group). Group, ethoxypropyl group,
(Eg, a cyclohexyl group), a substituted or unsubstituted phenyl group, or a naphthyl group.

The addition amount of the general formula [1] is 10 × 10 ^{-3 to} 6 × 10 ^-3 mol, preferably 2.0 × 10 ^-3 to 4.
It is 0 × 10 ^-3 mol.

Specific examples of the compounds represented by the general formula [1] are shown below, but the compounds are not limited to these compounds.

[0025]

Embedded image

The fixing solution of the present invention contains a thiosulfate, and examples of the thiosulfate include lithium, potassium, sodium and ammonium salts. Among them, a sodium salt or an ammonium salt, particularly an ammonium salt, has a high fixing speed. A fixer is obtained. Addition amount of thiosulfate is 1 for fixer
0.1-5 mol per liter, more preferably 0.5-2.
It is 0 mol, more preferably 0.7 to 1.8 mol. Most preferred is 0.8 to 1.5 moles.

The fixing solution of the present invention contains salts such as citric acid, tartaric acid, malic acid, succinic acid, and optical isomers thereof. As salts of citric acid, tartaric acid, malic acid, succinic acid, etc., lithium salts thereof, potassium salts, sodium salts, ammonium salts, etc., such as lithium hydrogen tartaric acid, potassium hydrogen, sodium hydrogen, ammonium hydrogen, potassium potassium tartaric acid, tartaric acid. Sodium potassium and the like may be used. Of these, more preferred are citric acid, isocitric acid, malic acid,
Succinic acid and salts thereof. Most preferably, malic acid and its salt.

The amount of these compounds used in the fixer is 0.06 to 1.5 mol, preferably 0.10 to 1.0 mol, and more preferably 0.20 to 0.60 mol, per liter of the fixer.

The fixing solution according to the present invention may contain additives such as various acids, salts, chelating agents, surfactants, wetting agents and fixing accelerators in addition to the above compounds. Examples of the acid include inorganic acids such as sulfuric acid, hydrochloric acid, nitric acid and boric acid, and organic acids such as formic acid, propionic acid and oxalic acid. Examples of the salt include salts of lithium, potassium, sodium, ammonium and the like. As the surface active agent, for example, an anionic surface active agent such as sulfate or sulfonate, a nonionic surface active agent such as polyethylene glycol or ester, or amphoteric surface active agent can be used. As the wetting agent, for example, alkanolamine, alkylene glycol, etc. may be used, and as the fixing accelerator, for example, thiourea derivative, alcohols having a triple bond in the molecule, thioethers, etc. may be used. The amount of these additives added is 0.5 to 20 g per liter of the fixing solution.

The pH of the fixing solution of the present invention is preferably 3.0 to 8.0, more preferably 4.5 to 7.0. The total processing time of the silver halide photographic light-sensitive material according to the present invention is Dry to D
It is processed by ry in the range of 20 to 60 seconds.

The silver halide photographic light-sensitive material used in the present invention preferably has at least one conductive layer on a support. As a method of forming a conductive layer,
There are a method of forming using a water-soluble conductive polymer, a hydrophobic polymer and a curing agent, and a method of forming using a metal oxide. Regarding these, for example, JP-A-3-265842, 5
The method described on page 15 can be used.

As the silver halide emulsion of the silver halide photographic light-sensitive material used in the present invention, silver chloride, silver bromide, silver chlorobromide, silver iodobromide, silver chloroiodobromide and the like can be used. Is preferably a silver chlorobromide emulsion or a silver chloroiodobromide emulsion containing 50 mol% or more of silver chloride. The average grain size of the silver halide grains is preferably 0.32 μm or less, particularly preferably 0.10 to 0.3.
2 μm.

The monodispersity is (standard deviation of particle size) /
Monodisperse particles having a coefficient of variation represented by (average particle size) × 100 of 15% or less are preferable. The amount of silver coated on the silver halide photographic light-sensitive material of the present invention is preferably 3.5 g or less per 1 m ² , and particularly preferably 1.5 to 3.3 g. The total amount of gelatin in the silver halide photographic light-sensitive material may be 6.0 g or less per m ² , preferably 1.5 to 5.5 g.

The emulsion used in the silver halide photographic light-sensitive material of the present invention can use various photographic additives in the steps before and after physical ripening or chemical ripening. Examples of the compound used in such a process include Research
Disclosure (RD) No.17643 (December 1978) Same No.187
Various compounds described in 16 (November, 1979) and No. 308119 (December, 1989) can be used. These three
The types and locations of the compounds listed in section (RD) are listed below.

Additive RD-17643 RD-18716 RD-308119 Page Classification Page Page Classification Chemical sensitizer 23 III 648 Upper right 996 III Sensitizing dye 23 IV 648-649 996-8 IVA Desensitizing dye 23 IV 998 IVB 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 Whitening agent 24 V 998 V Hardener 26 X 651 Left 1004 ~ 5 X Surfactant 26-27 XI 650 Right 1005-6 XI Plasticizer 27 XII 650 Right 1006 XII Sliding agent 27 XII Matting agent 28 XVI 650 Right 1008-9 XVI Binder 26 XXII 1003-4 IX Support 28 XVII 1009 XVII Halogen according to the invention Examples of the support used in the silver halide photographic light-sensitive material include those described in RD above. Suitable supports include polyethylene terephthalate film, polyolefin paper, etc. Provide an undercoat layer to improve the quality, or apply corona discharge or UV irradiation. It may be.

[0036]

EXAMPLES The present invention will be specifically described below with reference to examples.

Example 1 (Preparation of silver halide emulsion A) A silver chloroiodobromide emulsion comprising 90 mol% of silver chloride, 0.2 mol% of silver iodide and the rest of silver bromide was prepared by the simultaneous mixing method. . At the time of simultaneous mixing, K ₃ RhBr ₆ was added at 8.1 × 10 ⁻⁸ mol per mol of silver. The resulting emulsion was a cubic, monodisperse grain with a mean grain size of 0.20 μm (variation coefficient 9
%) Emulsion. Then, the emulsion was desalted with a modified gelatin described in JP-A-2-280139 (one in which the amino group in gelatin was substituted with henylcarbamyl, for example, G-8 in JP-A-2-280139). The EAg after desalting was 190 mv at 50 ° C.

The emulsion thus obtained was adjusted to pH 5.4 and EAg 120 mv, and then the temperature was adjusted to 60 ° C., and chloroauric acid was added at 2.2 × 1 per mol of silver.
After adding 0 ^-5 mol and stirring for 2 minutes, S ₈ is added to 1.5 mol per mol of silver.
× 10 ^-6 mol was added and chemical ripening was performed. At the end of ripening, the following was added per mol of silver.

4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene 7.5 × 10 ^-3 mol, 1-phenyl-5-mercaptotetrazole 3.5 × 10 ^-4 mol and gelatin 28.4 g An emulsion liquid was added.

(Preparation of silver halide photographic light-sensitive material) On one undercoat layer of a polyethylene terephthalate film having a thickness of 100 μm and subjected to the antistatic treatment described in Example 1 of JP-A-3-92175, the following formulation The silver halide emulsion of No. 1 was coated so that the amount of silver was 3.0 g / m ² and the amount of gelatin was 1.6 g / m ² .

Further, the following formulation 2 is provided as a protective layer on the upper layer.
Was coated so that the amount of gelatin would be 0.8 g / m ² . On the opposite undercoat layer, a backing layer of the following formulation 3 was coated so that the amount of gelatin would be 1.9 g / m ^2, and a protective layer of the following formulation 4 was 0.8 g / m ² on the upper layer.
^A sample was prepared by coating so as to be ² .

Formulation 1 (composition of silver halide emulsion layers)

[0043]

Embedded image

S-1 (sodium-iso-amyl-n-decylsulfosuccinate) 0.64 mg / m ² 2-mercapto-6-hydroxypurine 1.7 g / m ² EDTA 50 mg / m ² Formulation 2 (emulsion protective layer composition ) S-1 12 mg / m ² matting agent: monodisperse silica 22 mg / m ^{2 with an} average particle size of 3.5 μm 1,3-vinylsulfonyl-2-propanol 40 mg / m ²

[0045]

[Chemical 3]

[0046] Formulation 3 (backing layer composition) saponin ^{133mg / m 2 S-1 6mg} / m 2 Colloidal silica 100 mg / m ²

[0047]

[Chemical 4]

Formulation 4 (Composition of backing protective layer) Matting agent: Monodispersed polymethylmethacrylate having an average particle diameter of 5.0 μm 50 mg / m ² Sodium-di- (2-ethylhexyl) -sulfosuccinate 10 mg / m ² Samples obtained Was evaluated as follows. Automatic processor GR-2
6SR (manufactured by Konica Corp.) was processed under the following conditions using a developer and a fixer having the following compositions.

(Change in Fog Density of Unexposed Area of Treated Sample) After the sample was treated for 300 m ² while being replenished as described above, the sample exposed through the wedge was treated. The treated sample was divided into two equal parts, and one of them was allowed to stand for 3 days at 40 ° C and RH80% under the thermo-conditions for historical use. After that, the density was measured and the fog density of the unexposed area was compared with the other sample. .
Table 1 shows the values of the concentration increase.

Developer Composition (1 liter formulation) Compound A 0.2 mol Sodium sulfite 0.14 mol Dimezone S (1-phenyl-4-hydroxymethyl-4-methyl-3-pyrazolidone) 2.3 g Potassium carbonate 0.8 mol 5-methylbenzochilyl Azole 0.25g Potassium bromide 7.5g Compound B 0.7mmol Adjust pH to 10.3 with KOH.

Fixer composition (1 liter formulation) Sodium thiosulfate 1.0 mol Sodium sulfite 0.3 mol Sodium metabisulfite 0.15 mol Ethylenediaminetetraacetic acid disodium 0.1 mol Disodium malate 0.4 mol Glutaraldehyde 0.1 mol Add water as a working solution Make up to 1 liter and adjust the pH to 6.0 with sodium hydroxide and sulfuric acid.

(Processing conditions) (Process) (Temperature) (Time) Development 38 ° C 12 seconds Fixing 35 ° C 10 seconds Washing at room temperature 10 seconds Drying 40 ° C 12 seconds Total 44 seconds (each step time is so-called wading conveyance to the next step (Including time) Treatment liquid of the present invention: 2.0 × 10 ⁻³ mol of the compound of the general formula [1] is dissolved in water and finished to 1 liter with sodium hydroxide.
Adjust pH to 7.

The above developing solution and fixing solution were put in each processing tank of the automatic developing machine, and the processing in the water washing tank was carried out as follows.

(1) Pour water into the washing tank to carry out normal washing (2) Put water into the washing tank without supplying water (reserved water) (3) Put the treatment liquid of the present invention into the washing tank In this state, 500 sheets of 25.2 cm × 30.3 cm photographic printing paper were processed, and each solution was added to reduce the amount of each processing solution. Also,
The following compound (2-1) was used as a comparative compound.
The addition amount is the same as in the case of the treatment liquid of the present invention.

[0055]

[Chemical 5]

The treated sample was divided into two equal parts, and one of them was allowed to stand for 3 days at 40 ° C. and 80% RH under the thermo-conditions for historical use, and then the discoloration of the image area was compared with the other sample. Was evaluated by the following.

◯: No discoloration (remains black), Δ: Some discoloration is observed (usable) x: Brown discoloration (unusable) The results obtained are shown in Table 1. The compound in the table represents the compound added to the treatment liquid.

[0058]

[Table 1]

As is clear from Table 1, the image obtained by the treatment method in which the treatment liquid of the present invention is put in the washing tank is the same as the image obtained by ordinary washing, and water is put in the washing tank to prepare the water-supplying state. It can be seen that it is far superior to the image obtained in the non-reserved water state, and that it has sufficient image stability similar to the image obtained by the water washing method which has been generally performed so far.

Example 2 The same experiment and its evaluation as in Example 1 were conducted except that the treatment solution of the present invention was adjusted to pH 8.5 by adding sodium hydroxide. Table 2 shows the results.

[0061]

[Table 2]

As is clear from Table 2, the treatment liquid of the present invention
When the pH is 8 or more and 5 or less, the condition of the processed light-sensitive material is remarkably bad. On the other hand, the pH of the treatment liquid of the present invention
Then, it can be seen that sufficient image stability can be obtained.

[0063]

According to the present invention, after processing a silver halide photographic light-sensitive material, a silver halide photographic light-sensitive material is processed with a processing solution containing a thiosulfate and then washed with a large amount of water. Instead, the color tone of the image silver after processing by processing by the method of the present invention loses pure black and discolors to brown,
Furthermore, without generating fog in the non-image area, it is possible to obtain a stable image similar to the stability of the image obtained by washing with a large amount of water, which saves water resources, Further, since a large amount of water is not used, a water supply / drainage facility is not needed, and a processing method of a silver halide photographic light-sensitive material can be obtained without restrictions on the use place.

Claims (1)

[Claims] 1. A method of processing a silver halide photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support, which is followed by washing with water after processing with a processing solution containing thiosulfate. In place of the compound represented by the following general formula [1], and processing with a processing solution having a pH of 5-8. Formula (1) in Z-SM [wherein, Z is 6-membered ring containing a nitrogen-containing heterocyclic ring, these groups hydroxy group, -SO ₃ M ¹ group, -COOM ² group (wherein M ^1,
M ² represents a hydrogen atom, an alkali metal atom or an ammonium group), a substituted or unsubstituted amino group, or a substituted group having at least one selected from the group consisting of a substituted or unsubstituted ammonio group. Represents M
Represents a hydrogen atom, an alkali metal atom or an ammonium group, and a substituted or unsubstituted amidino group. ]