JPH0365950A - Method for processing silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obviate the deterioration in the preservable property of the silver halide photographic sensitive material contg. at least one kind of specific compds. with time at or under a high temp. or high humidity by subjecting the photosensitive material to a development processing, fixing processing and washing and/or stabilizing processing within 45 seconds by using an automatic developing machine. CONSTITUTION:The silver halide photographic sensitive material contg. at least one kind of the compds. expressed by formula I in the silver halide emulsion layers and/or at least one layer of the hydrophilic colloidal layers adjacent to the silver halide emulsion layers is executed to the development processing, fixing processing and washing and/or stabilizing processing within 45 seconds by using the automatic developing machine. In the formula I, Z denotes a heterocycle having directly or indirectly at least one of the groups selected from -SO3M, -COOR<1>, -OH, and -NHR<2>; M denotes a hydrogen atom, alkaline metal or -NH4 group. The deterioration in the preservable property of the photosensitive material at or under the conditions of the high temp. or high humidity is obviated in this way.

Description

[Detailed Description of the Invention] [Industrial Field of Application] The present invention relates to a method for processing silver halide photographic materials,
More specifically, the present invention relates to a method for processing silver halide photographic materials that are suitable for ultra-rapid processing.

[Prior Art] In recent years, the consumption of silver halide photographic materials has continued to increase. As a result, the number of silver halide photographic materials to be processed has increased, and there is a demand for faster development, that is, to increase the amount of development processed within the same amount of time.

The above trend can be seen in the printing plate making field as well. That is, because the immediacy and number of times information is rapidly increasing, there is a need to shorten the delivery time and handle a larger amount of processing in printing plate-making work as well.

In order to satisfy such demands of the printing plate making industry, it was necessary to promote the simplification of the printing process and to further speed up the development process of the printing plate making film.

[Problems to be Solved by the Invention] However, when the developing process is further speeded up as described above, especially when the developing process, fixing process, washing with water and/or stabilizing process, and processing are performed within 45 seconds, ultra-quick processing is required. In processing, there is a drawback that the storage stability of photosensitive materials deteriorates markedly over time under high temperature or high humidity conditions, and there has been a demand for improvement of such drawbacks.

Therefore, an object of the present invention is to improve the deterioration of the storage stability of photosensitive materials over time under high temperature or high humidity conditions in ultra-rapid processing in which development processing, fixing processing, washing with water, and/or stabilization processing are performed within 45 seconds. An object of the present invention is to provide a method for processing a silver halide photographic material, which enables the processing of silver halide photographic materials.

[Means for Solving the Problems] In view of the above-mentioned problems, the present inventors have made extensive studies, and have found that the above-mentioned object of the present invention is to provide a silver halide emulsion layer and/or at least one adjacent to the silver halide emulsion layer. A silver halide photographic light-sensitive material containing at least one compound represented by the following formula [I] in one hydrophilic colloid layer is automatically developed.
The present inventors have discovered that this can be achieved by providing a method for processing silver halide photographic materials, which is characterized in that development processing, fixing processing, water washing and/or stabilization processing are performed within 45 seconds using a machine. .

General formula [I] In formula 1, Z is -S○3M, -COOR'-OH and -
Nl (represents a heterocyclic ring having at least one group selected from R2 directly or indirectly, R1 represents a hydrogen atom, an alkali metal or an alkyl group having 1 to 6 carbon atoms, R2 represents a hydrogen atom, C1-C6 alkyl group, -COR3-COOR3 or -5O2R
3, and R3 represents a hydrogen atom, a substituted or unsubstituted aliphatic group, or a substituted or unsubstituted aromatic group.

M represents a hydrogen atom, an alkali metal or an -NH4 group. ] The present invention will be explained in more detail below.

The processing time in the developing, fixing, washing and/or stabilizing processing of the present invention is 45 seconds or less, from when the leading edge of the film enters the developer to when it comes out of the fixing solution, washing solution and/or stabilizing solution. This means that the time is within 45 seconds, and this time includes the time for transfer from the developer to the fixer and the time for transfer from the fixer to the washing solution.

In the present invention, the object of the present invention can be achieved by increasing the processing line speed without shortening the length of the processing line.

The processing line speed of the automatic processor in the present invention is preferably 1,0001 m/min or more, and 2,000 mm/min.
More preferably, it is at least 1 minute.

The compound represented by the above formula [I] will be explained below. - As the compound represented by the formula [I], specifically, the compounds represented by the following formulas [I]-1 to [I]-3 are preferable.

(1)-1 [1) 2 [, Y]-3 s Specific examples of compounds represented by general formulas [I]-1 to [I]-3 are listed below, but it goes without saying that (1) -1 (N-2 (1)-3 CI )-1 The compound represented by the above general formula [I] is 5X per mole of silver halide contained in the silver halide photographic light-sensitive material.
In the range of 10-7 to 5 x 10-2 mol, especially 1
It is preferably contained in the silver halide photographic material in an amount of X 10-6 to 5X10-3 mol.

Further, the compound of general formula [I] is contained in at least one of the silver halide emulsion layer and/or a hydrophilic colloid layer adjacent to the emulsion layer, such as an emulsion protective layer or an undercoat layer. When it is contained in the layer, it is in the range of 1 mg to 5 g per 1f, especially 110l1 to 10
It is preferable to set it as the range of 00 mg.

The silver halide photographic light-sensitive material of the present invention is suitable as a light-sensitive material for printing, especially a light-sensitive material for printing that can obtain high contrast without using lithographic development, and is preferably represented by the following general formula [II]. It contains a tetrazolium compound and/or a hydrazone compound represented by the general formula [I[[ ].

- Formula [11] [In the formula, R1, R2 and R3 each represent a hydrogen atom or a substituent, and xe represents an anion. ] General formula [11] % formula % [In the formula, A represents an aliphatic group or an aromatic group, and B represents a formyl group, an acyl group, an alkyl or arylsulfonyl group, an alkyl or arylsulfinyl group, a carbamoyl group, an alkoxy or represents an aryloxycarbonyl group, a sulfinamoyl group, an alkoxysulfonyl group, a thioacyl group, a thiocarbamoyl group, or a heterocyclic group, and R1 and R2 are both hydrogen atoms, or one is a hydrogen atom and the other is a substituted or unsubstituted alkylsulfonyl group. group, or a substituted or unsubstituted arylsulfonyl group, or a substituted or unsubstituted acyl group. however,
B, R2 and the nitrogen atom to which they are bonded may form a hydrazone partial structure -N=C. ] Next, the compound of general formula [I[] will be explained.

- Preferred examples of substituents represented by R1 to R3 in the formula [IN are alkyl groups (e.g., polygroups such as methyl, ethyl, cyclopropyl, propyl, isopropyl, cyclobutyl, butyl, isobutyl, pentyl, cyclohexyl, etc.), amino groups , acylamino group (e.g. acetylamino group), hydroxyl group, alkoxy group (e.g. multiple groups such as methoxy, ethoxy, butoxy, butoxy, pentoxy), acyloxy group (e.g. acetyloxy group), halogen atom (e.g. fluorine, chlorine) , bromine, etc.), carbamoyl group, acylthio group (e.g. acetylthio group), alkoxycarbonyl group (e.g. ethoxycarbonyl group), carboxyl group, acyl group (e.g. acetyl group), cyan group, nitro group, mercapto group, sulfoxy group, amino Examples include groups such as sulfoxy groups.

Examples of the anion represented by Xe include halogen ions such as chloride ion, bromide ion, and iodide ion, acid groups of inorganic acids such as nitric acid, sulfuric acid, and perchloric acid, and monic acids such as sulfonic acid and carboxylic acid. Nuclides, anionic activators, specifically lower alkylbenzenesulfonic acid anions such as p-toluenesulfonic acid anions, higher alkylbenzenesulfonic acid anions such as p-dodecylbenzenesulfonic acid anions, and higher alkyl sulfates such as lauryl sulfate anions. Ester anions, boric acid anions such as tetraphenylboron, dialkyl sulfosuccinate anions such as di-2-ethylhexyl sulfosuccinate anions, polyether alcohol sulfate ester anions such as cedylboriethenoxysulfate anions, stearic acid anions, etc. Polymers such as higher aliphatic anions and polyacrylate anions with acid groups attached can be mentioned.

Specific examples of the compound represented by the general formula [n] used in the present invention are listed below, but the compound of the present invention is not limited to these.

(Exemplary Compound) IF-1-9 In the present invention, the above-mentioned tetrazolium compound is, for example, C'chemical Revie
It can be easily synthesized according to the method described in Vol. 55, pp. 335-483.

The tetrazolium compound represented by the above general formula [II] is used in an amount of about 1 mg or more to 10o, preferably about 10111 CI or more to about 2 g per mole of silver halide contained in the silver halide photographic light-sensitive material. Preferably.

The tetrazolium compounds represented by the general formula [II] used in the present invention may be used alone or in combination of two or more in an appropriate ratio.

Furthermore, the above-mentioned tetrazolium compounds and various tetrazolium compounds other than those mentioned above may be used in combination in appropriate proportions.

In the present invention, particularly favorable results can be obtained when an anion that binds to the above-mentioned tetrazolium compound and lowers the hydrophilicity of the tetrazolium compound is used in combination. Examples of such anions include acid groups of inorganic acids such as perchloric acid, acid groups of organic acids such as sulfonic acids and carboxylic acids, anionic activators, and specifically lower alkylbenzene sulfones such as o-toluenesulfonic acid anions. dialkylsulfosuccinate anions such as acid anions, p-dodecylbenzenesulfonic acid anions, alkylnaphthalenesulfonic acid anions, lauryl sulfate anions, tetraphenylborons, di,-2-ethylhexylsulfosuccinate anions, Examples include polyether alcohol pentate ester anions such as cetyl polyethenoxysulfate anions, stearate anions, and polyacrylate anions.

Such an anion may be added to the hydrophilic colloid layer after being mixed with the tetrazolium compound in advance, or
It can be added alone to silver halide emulsion layers or hydrophilic colloid layers containing or not containing tetrazolium.

Next, the compound represented by the general formula [1[[] will be explained.

In the general formula CI[[], the aliphatic group represented by A preferably has 1 to 30 carbon atoms, particularly 1 to 30 carbon atoms.
~20 straight chain, branched or cyclic alkyl groups. wherein the branched alkyl group has one or more heteO
It may be cyclized to form a saturated heterocycle containing atoms. Further, this alkyl group may have a substituent such as an aryl group, an alkoxy group, a sulfoxy group, a sulfonamide group, or a carbonamide group.

For example, t-butyl group, n-octyl group, t-octyl group, cyclohexyl group, pyrrolidyl group, imidazolyl group,
Examples include a tetrahydrofuryl group and a morpholino group.

- The aromatic group represented by A in formula [111] is a monocyclic or bicyclic aryl group or an unsaturated heterocyclic group. Here, the unsaturated heterocyclic group may be condensed with a monocyclic or bicyclic aryl group to form a heteroaryl group.

Examples include a benzene ring, a naphthalene ring, a pyridine ring, a pyrimidine ring, an imidazole ring, a virolazole ring, a quinoline ring, an inquinoline ring, a penzimidazole ring, a thiazole ring, and a benzothiazole ring, among which those containing a benzene ring are preferred.

Particularly preferred as A is an aryl group.

The aryl group or unsaturated heterocyclic group of A may have a substituent. Typical substituents include linear, branched or cyclic alkyl groups (preferably those with 1 to 20 carbon atoms)
, an aralkyl group (preferably an alkyl moiety with 1 carbon number)
-3 monocyclic or bicyclic ones>, alkoxy groups (preferably those having 1 to 20 carbon atoms), substituted amino M (preferably amino groups substituted with alkyl curvatures having 1 to 20 carbon atoms),
Examples thereof include an acylamino group (preferably having 2 to 30 carbon atoms), a sulfonamide group (preferably having 1 to 30 carbon atoms), and a ureido group (preferably having 1 to 30 carbon atoms).

- A in formula [1] may have a pallast group, which is commonly used in immobile photographic additives such as couplers, incorporated therein. A ballast group is a group having 8 or more carbon atoms and is relatively inert with respect to photographic properties, such as an alkyl group, an alkoxy group, a phenyl group, an alkylphenyl group, a phenoxy group, an alkylphenoxy group, etc. You can choose.

A in the general formula [1[[] may have a group incorporated therein that enhances adsorption to the silver halide grain surface. Examples of such adsorption groups include thiourea groups, heterocyclic thioamide groups, mercapto heterocyclic groups, and triazole groups, such as U.S. Pat.
JP 59-195233, JP 59-200231, JP 59-201045, JP 59-201046
No. 59-201047, No. 59-20104
No. 8, No. 59-201049, Patent Application No. 59-367
Examples thereof include groups described in No. 88, No. 60-11459, No. 60-19739, and the like.

B specifically represents a formyl group, an acyl group (acetyl group,
propionyl group, trifluoroacetyl group, chloroacetyl group, benzoyl group, 4-chlorobenzoyl group, bilboyl group, methoxalyl group, methyloxamoyl group, etc.)
, alkylsulfonyl groups (methanesulfonyl group, 2-chloroethanesulfonyl group, etc.), arylsulfonyl groups (
benzenesulfonyl group, etc.), alkylsulfinyl group (
methanesulfinyl group, etc.), arylsulfinyl group (
benzenesulfinyl group, etc.), carbamoyl group (methylcarbamoyl group, phenylcarbamoyl group, etc.), sulfamoyl group (dimethylsulfamoyl group, etc.), alkoxycarbonyl M (methoxycarbonyl group, methoxyethoxycarbonyl group, etc.), aryloxycarbonyl group (
phenoxycarbonyl group, etc.), sulf7moyl group (methylsulfamoyl group, etc.), alkoxysulfonyl group (methoxysulfonyl group, ethoxysulfonyl group, etc.), thioacyl group (methylthiocarbonyl group, etc.), thiocarbamoyl group, etc.) or heterocyclic group (Pyridine, etc.)

Particularly preferable B is a formyl group or an acyl group.

B in the general formula [1[[] is the partial structure of hydrazine together with R2 and the nitrogen atom to which these are condensed.
3 represents an alkyl group, an aryl group, or a heterocyclic group. R
4 represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group.

R+ and R2 are a hydrogen atom, an alkylsulfonyl group having 20 or less carbon atoms, and an arylsulfonyl group (preferably a phenylsulfonyl group or a Hammett substituent constant having a sum of −0
．． a phenylsulfonyl group substituted so that the number of carbon atoms is 5 or more, an acyl group having 20 or less carbon atoms (preferably a benzoyl group, or a benzoyl group substituted so that the sum of Hammett's substituent constants is -0.5 or more) or linear, branched or cyclic unsubstituted and substituted aliphatic acyl groups (substituents include, for example, halogen atoms, ether groups, sulfonamide groups, carbonamide groups, hydroxyl groups, carboxy groups, and sulfonic acid groups). >R+ and R2 are most preferably hydrogen atoms.

Specific examples of the hydrazine derivatives used in the present invention are shown below.

However, the present invention is not limited to the following compounds.

I[[-1 m-2 -4 l-5 1[[-6 -14 ■-15 ■-16 1F-7 I[[-8 -9 1[[-10 ■-17 ■-18 ■-19 ■-21 When a hydrazine derivative is contained in a photographic light-sensitive material, it is preferably contained in the silver halide emulsion layer, but other non-photosensitive hydrophilic colloids ff (e.g. protective layer, intermediate layer, filter layer, halation (e.g., a prevention layer).

Specifically, if the compound to be used is water-soluble, it can be prepared as an aqueous solution, or if it is poorly water-soluble, it can be prepared as a solution of water-miscible organic solvents such as alcohols, esters, or ketones, or as a hydrophilic colloid solution. It can be added to. When added to the silver halide emulsion layer, it may be added at any time from the start of chemical ripening to before coating, but it is preferably added between after the end of chemical ripening and before coating. In particular, it is preferable to add it to a coating solution prepared for coating.

The content of the hydrazine derivative is optimal depending on the grain size of the silver halide emulsion, the halogen composition, the method and degree of chemical sensitization, the relationship between the layer containing the compound and the silver halide emulsion layer, the type of antifogging compound, etc. It is desirable to select the amount of , and testing methods for its selection are well known to those skilled in the art.

Usually preferably from 10-gin moles to ixio-' moles, especially from 10-3 to 4 moles per mole of silver halide.
It is used in a range of X10-2 moles.

Further, the hydrazine derivative can be used by being mixed into the developer. In that case, the amount added is 51 per 11 of the developer.
1 g to 5 g, especially 10 mg to 1 g are suitable.

The silver halide used in the silver halide photographic material of the present invention is not particularly limited, but silver bromide, silver iodobromide, silver chloride, or silver chlorobromide is preferred. The composition of silver chlorobromide is preferably ACl/AQ Sr = 1001
It may be within the range of 0 to 2/98, but particularly preferably AOC deficiency/A (J Br = 100/O to 50150
The molar ratio of The composition of silver iodobromide is AgB+' /
AgT = 10010 to 90/10 is preferred. The average grain size of the silver halide grains is 0.10 μrp ~0,
40 μry is preferable, and particles with a narrow particle size distribution having a coefficient of variation expressed by (standard deviation of particle size)/(average particle size) x 100 of 15% or less are more preferable.

As the silver halide used in the present invention, various sensitizers, sensitizing dye stabilizers, etc. known in the photosensitive material industry can be used.

The silver halide is added into the hydrophilic colloid layer. The hydrophilic colloid particularly advantageously used in the present invention is gelatin, but hydrophilic colloids other than gelatin known in the photosensitive material industry can also be used.

These hydrophilic colloids can also be applied to layers that do not contain silver halide, such as antihalation layers, protective layers, intermediate layers, etc.

As the support used in the present invention, various supports known in the photosensitive material industry, such as polyester films, can be used.

The photosensitive material according to the present invention has a film thickness of about 17 m.
, that is, preferably 0.1 to 10μ, particularly preferably 0
．． Preferably, a protective gelatin layer of 8 to 2 μm is applied.

The hydrophilic colloid layer used in the present invention may optionally contain various photographic additives known in the art, such as gelatin plasticizers, hardeners, surfactants, image stabilizers, ultraviolet absorbers, and antistaining agents. , p-eye adjuster, nucleation inhibitor, antistatic agent, thickener, graininess improver, dye, mordant, brightener, development speed adjuster, matting agent, etc. within a range that does not impair the effects of the present invention. Can be used within.

The developing agent used in the development of the above-mentioned silver halide photographic light-sensitive material is 10 units.
theory of the Pho℃graphic
Process, Fourth Edition)
pages 291-334 and Journal of the American Chemical
the AlericanCheIIlical 5
73, page 3.100 (1951
) can be effectively used in the present invention.

These developers may be used alone or in combination of two or more types, but it is preferable to use two or more types in combination. In addition, in the developer used for development in the present invention, as a preservative,
For example, the use of sulfites such as sodium sulfite and potassium sulfite does not impair the effects of the present invention and can be cited as one of the features of the present invention. Furthermore, hydroxylamine and hydrazide compounds may be used as preservatives. In addition, adjusting the pH with caustic alkali, alkali carbonate, or amines used in general black and white developers and providing a buffer function, inorganic development inhibitors such as brompotali, organic development inhibitors such as benzotriazole, ethylenediaminetetraacetic acid, etc. metal ion scavengers, development accelerators such as methanol, ethanol, benzyl alcohol, polyalkylene oxide, sodium alkylarylsulfonate, natural saponins, surfactants such as sugars or alkyl esters of the above compounds, glutaraldehyde, formalin. , hardening agents such as glyoxal,
It is optional to add an ionic strength adjusting agent such as sodium Ta oxide.

For the above developer, amino compounds such as alkanolamines described in JP-A-56-106244 can be used.

In addition, F. A. Messon, “Photographic Brothecine Chemistry”, published by Focal Press (1
966), pages 226-229, U.S. Patent No. 2,193.
, No. 015, No. 2,592,364, Japanese Unexamined Patent Publication No. 48-6
Those described in No. 4933 may also be used.

In the present invention, "development time j" and "fixing time" respectively mean
The photosensitive material to be processed is in the developing solution in the developing tank of the automatic processor! The time from crushing to immersion in the next fixing solution, from immersion in the fixing tank solution to the next washing tank solution (stabilizing solution)
The time required for soaking.

Further, "washing time" refers to the time during which the product is immersed in the washing tank liquid.

In addition, "drying time" refers to the time the whitening machine is in the drying zone, which is usually equipped with a drying zone where hot air of 35°C to 100°C, preferably 40°C to 80°C is blown. means.

The developing temperature and time are usually about 25°C to 50°C for 20 seconds or less, preferably 30°C to 40°C for 6 seconds to 2
It takes 0 seconds.

The fixer is an aqueous solution containing thiosulfate and has a pH of 3.8 or higher, preferably 4.2 to 5.5.

Examples of the fixing agent include sodium thiosulfate and ammonium thiosulfate, which contain thiosulfate ions and ammonium ions as essential components, and ammonium thiosulfate is particularly preferred from the viewpoint of fixing speed. The amount of the fixing agent used can be varied as appropriate, and is generally about 0.1 to about 6 mol/2.

The fixer may also contain water-soluble aluminum salts that act as hardeners, such as aluminum chloride, ammonium sulfate, potassium alum, and the like.

Tartaric acid, citric acid, or their derivatives can be used alone or in combination of two or more kinds in the fixer.

It is effective to contain these compounds in an amount of 0.00 mol or more per 11 mol/l of the fixer, especially 0.01 mol/l to 0.03 mol/l.
Mol/fl is particularly useful.

Specific examples of the tartaric acid and citric acid include tartaric acid, potassium tartrate, sodium tartrate, potassium sodium tartrate, citric acid, sodium citrate, potassium citrate, lithium citrate, and ammonium citrate.

The fixing solution may optionally contain a preservative (e.g. sulfite, bisulfite), a 0-day buffering agent (e.g. acetic acid, nitric acid), a 9-day conditioner (e.g. sulfuric acid), a chelating agent with water softening ability, etc. It may contain compounds described in Japanese Patent Application No. 60-213562.

The fixing temperature and time are preferably 6 seconds to 1 minute at about 0°C to about 50°C, more preferably 6 seconds to 30 seconds at 30°C to 40°C, and even more preferably 6 seconds to 20 seconds at 30°C to 40°C. Seconds.

Where the automatic processor in the method of the present invention is replenished with a fixer concentrate together with water to dilute it as the light-sensitive material is processed, it is most preferred that the fixer concentrate is comprised of a single agent. is the same as for the developer.

The pH value for the fixer to exist stably as a single agent is 4.5 or higher, and more preferably +1) (4.65 or higher.If the pH is less than 4.5, the pH value is particularly high until the fixer is actually used. This is because thiosulfate decomposes and eventually becomes sulfurized if left for many years.Therefore, 0 mouth 4.5
In the above range, the generation of sulfur dioxide gas is small or non-existent, and the working environment is also improved. The upper limit for day 0 is not so strict, but if it is fixed at too high a temperature of 118, the pH of the membrane will be high even after washing with water, the membrane will swell, and the drying load will increase, so the limit is up to 7th grade. . In the case of a fixing solution that uses aluminum salt to harden the film, the limit is 0 days 5.5 from the viewpoint of preventing precipitation of the aluminum salt.

In the present invention, either the developing solution or the fixing solution may be a so-called working solution that does not require dilution water as described above (that is, it is replenished as an undiluted solution).

The amount of each concentrate supplied to the processing tank liquid and the mixing ratio with dilution water can be varied depending on the composition of the concentrate, but generally the ratio of concentrate to dilution water is 1:0 to 8. The total amount of each of the developer and fixer is preferably from 50n12 to 15001Q per 1f of photosensitive material.

In the present invention, the photosensitive material is subjected to water washing or stabilization treatment after being developed and fixed.

Any method known in the art can be applied to the washing or stabilization treatment, and water containing various additives known in the art can also be used as the washing water or stabilizing liquid. By using anti-mold water as washing water or stabilizing liquid, not only is it possible to save water by reducing the amount of replenishment to less than 32 ml per 1f of photosensitive material, but it also eliminates the need for piping for installing an automatic processor. It is possible to reduce the number of stock tanks. That is, the solution dilution water and washing water or stabilizing solution for the developer and fixer can be supplied from a common single layer stock tank, making it possible to further downsize the automatic developing machine.

When water treated with anti-mildew measures is used in combination with washing water or stabilizing liquid, the formation of lime scale can be effectively prevented.
It is possible to save 0 to 32 tons of water per unit, preferably 0 to 1 t.

Here, when the replenishment amount is O, there is no replenishment at all except for appropriately replenishing the amount of washing water in the washing tank that has decreased due to natural evaporation, etc. In other words, the so-called "reservoir water" is essentially not refilled. Refers to cases in which a processing method is used.

As a method of reducing the amount of replenishment, a multistage countercurrent system (for example, two stages, three stages, etc.) has been known for a long time. If this multi-stage countercurrent method is applied to the present invention, the photosensitive material in the fixer will be processed in a progressively cleaner direction, that is, in sequential contact with the processing solution that is not contaminated with the fixer, resulting in even more efficient processing. Washing is done. According to this, unstable thiosulfate salts and the like are appropriately removed, the possibility of discoloration and fading is further reduced, and a more significant stabilizing effect can be obtained. The amount of water used for washing is also much smaller compared to conventional methods.

When washing with a small amount of water, patent application 1729/1986
It is more preferable to provide a squeeze roller cleaning tank as described in No. 68.

Further, part or all of the overflow liquid from the washing or stabilizing bath, which is generated by replenishing the washing or stabilizing bath with anti-mold water depending on the treatment, is disclosed in Japanese Patent Application Laid-Open No. 60-23
As described in Japanese Patent Application No. 5133, it can also be used in a processing liquid having a fixing ability, which is a processing step before that. This is more preferable because the stock water can be saved and the amount of waste liquid can be reduced.

Anti-mildew methods include the ultraviolet irradiation method described in JP-A No. 263939, the method using a magnetic field described in JP-A No. 60-263940, and the use of ion exchange resin described in JP-A No. 61-131632. How to make pure water, patent application 1986-
No. 253807, No. 60-295894, No. 61-
The method using the antibacterial agent described in No. 63030 and No. 61-51396 can be used.

Furthermore, L.E. West, “Water Quality Criteria,” Photoscience and Engineering, Vol. 9, No. 6.

1965 (L, E, West “Water
Quality Criteria ” Photo
Sci & Eng, Vol, 9No, 6
(1965)), M.W. Peach, “Microbiological Growth in Motion Picture Processing”, Niss M.B.T.
E-Journal, Volume 85.

1916 (M, W, Beach″lyl iclob
iologicaGrowths in 1yloti
on-Picture Processing”S
MPTE Journal VOl, 85 (1
976) ), R.O.D.Gun "Photoprocessing Wash Water Biosize"
Journal of Imaging Technology No. 10
Volume, No. 6, 1984 (R, O, Deegan “P
hoto Processina Wash Wat
er31ocides” J, l waging
Tech, Vol. 10.

No. 6 (1984)) and JP-A-57-854
No. 2, No. 57-58143, No. 58-105145
Antibacterial agents, antifungal agents, surfactants, etc., which are described in publications such as No. 57-132146, No. 58-18631, No. 57-97530, and No. 57-157244, etc., may also be used in combination. can.

Furthermore, for the washing bath, R.T.
, Kreiman), “Journal of Imaging Technology,” Volume 10, No. 6, Page 242,
1984 (J, Iraaae, Te
ch 10. (6) 242 (1984)), Research Disclosure (RESEARCH [11SCLQSlJR
E) Volume 205, I ten 2052B (19
Isothiazoline compounds described in May 1981, Volume 228, Itea 22845 (198
Isothiazoline compounds described in 2013, April issue)
The compounds described in Japanese Patent Application No. 61-51396 and the like can also be used in combination as antibacterial agents (M1crobiocide).

Furthermore, specific examples of fungicides include phenol, 4-chlorophenol, pentachlorophenol, cresol, O
-Phenylphenol, chlorophene, dichlorophene, formaldehyde, geltaraldehyde, phosphoric acid, p-hydroxybenzoic acid ester, 2-(
4-thiazoline)-benzimidazole, benzisothiazolin-3-one, dodecyl-benzyl-dimethylammonium-chloride, N-(fluorodichloromethylthio)-phthalimide, 2.4.4'trichloro-2
'-Hydroxydiphenyl ether, etc.

The water treated with anti-mildew means and stored in the water stock tank is diluted with water for diluting the stock solutions of processing solutions such as the developer and fixer, and the amount added is preferably 0.01 to 10 g/4°, more preferably 0.01 to 10 g/4°.
It is 1 to 5 g/2.

Furthermore, in addition to the silver image stabilizer, various surfactants can be added to the washing water for the purpose of preventing water droplet unevenness. As the surfactant, any of cationic, anionic, nonionic, and amphoteric types may be used. Specific examples of surfactants include compounds described in "Surfactant Handbook" published by Kogaku Tosho ■.

Various compounds are added to the stabilizing bath for the purpose of stabilizing the image. for example! Adjust lp day (e.g. pH
3-8) various buffering agents (e.g. borate, metaborate, borax, phosphate, carbonate, potassium hydroxide, sodium hydroxide, aqueous ammonia, monocarboxylic acid, dicarboxylic acid, polycarbonate) Typical examples include aldehydes such as formalin (used in combination with carboxylic acids, etc.) and formalin. In addition, chelating agents, fungicides (thiazole,
Various additives such as isothiazole type, halogenated phenol, sulfanilamide, benzotriazole, etc.), surfactants, optical brighteners, and hardening agents may be used.
Two or more of the same or different desired compounds may be used in combination.

In addition, it is preferable to add various ammonium salts such as ammonium chloride, ammonium nitrate, ammonium sulfate, ammonium phosphate, ammonium sulfite, and thio1111M ammonium as a film conditioning agent for the processing solution in order to improve image storage stability.

The water washing or stabilization bath temperature and time using the above method is 0°C.
6 seconds to 1 minute at ~50°C is preferred, but 6 seconds to 1 minute at 15°C to 40°C
The heating time is more preferably from seconds to 30 seconds, and even more preferably from 6 seconds to 15 seconds at 15°C to 40°C.

In the method of the present invention, the developed, fixed and washed photographic material is preferably dried by squeezing out the washing water, that is, by using a squeeze roller method. Drying is approximately 0℃~
Drying is carried out at about 100°C, and the drying time can be changed appropriately depending on the surrounding conditions, but is usually about 5 seconds to 1 minute, but more preferably about 5 seconds to 30 seconds at 40°C to 80°C.

In the present invention, an even more excellent effect is exhibited in that the lower the swelling percentage of the photosensitive material, the shorter the drying time thereof.

According to the method of the present invention, the process of developing, fixing, washing and drying is carried out in a so-called dry-to-dry manner.
ory) processing time is within 100 seconds, preferably 60 seconds
It should be processed within seconds.

Here, "dry to dry" refers to the time from the moment the leading edge of the photosensitive material to be processed enters the film insertion area of the processor to the moment the leading edge emerges from the processor after being processed. .

[Example] The present invention will be described in more detail with reference to Examples below.

Example 1 [Method for Preparing Emulsion (A) 51] A silver chlorobromide emulsion was prepared using the following solutions of A solution, B solution, and C solution.

Solution A> Ossein gelatin 17g Polyisopropylene-polyethylene oxydisuccinic acid ester sodium salt 10% ethanol aqueous solution 5- Distilled water
1280. /<Solution B> Silver nitrate 170q Distilled water 4101 sentences <Solution C> Sodium chloride 45.0 Q Potassium bromide 27.4 Q Rhodium trichloride trihydrate 28μ Isobrobylene oxydisuccinate ester sodium salt 10% ethanol solution 3tR ossein gelatin 11 (1 distilled water
After keeping the 407d solution A at 40° C., sodium chloride was added so that the EAg value became 160 mV.

Next, solutions B and C were added by a double jet method using the mixing agitator described in JP-A-57-92523 and JP-A-57-92524.

As shown in Table 1, addition was carried out by gradually increasing the addition flow rate over a total addition time of 80 minutes while keeping the EAO value constant.

The EAil value was 3mj2 5 minutes after the start of addition from 160mV.
EAQ value 120m using sodium chloride aqueous solution of /2
This value was maintained until the completion of mixing.

In order to keep the EΔ9 value constant, EAQM was controlled using a 3 mol/2 aqueous sodium chloride solution.

Table 1 A metal silver electrode and a double junction saturated AQ/AIJ Cfl reference electrode were used to measure the EAO value (
The configuration of the M pole used a double junction disclosed in Japanese Patent Application Laid-open No. 197534/1983. ).

Further, an IT variable O-two tube metering pump was used to add solutions B and C.

Furthermore, by sampling the added milk preparations, we confirmed by observing with an electron microscope that no new particles were observed in the system.

During the addition, the pHfMI of the system was controlled to be kept constant at 3.0 using a 3% aqueous nitric acid solution.

After the addition of solutions B and C, the emulsion was subjected to Ostwald ripening for 10 minutes, and then desalted and washed with water using a conventional method. Then, an aqueous solution of ossein gelatin 6001Q (containing ossein gelatin 30a) was added to give 55 After dispersing by stirring at ℃ for 30 minutes, the volume was adjusted to 750 cc.

The obtained emulsion was subjected to total sulfur sensitization, and the following sensitizing dye A was added at 300% per mole of silver halide contained in the emulsion.
mg, 6-methyl-4-hydroxy-1, as stabilizer
3,3a,7-chitrazaindene was added and the following J! Emulsion (A) was prepared by adding 100 mg of J-sensitive dye B per mole of silver halide.

Sensitizing Dye A Sensitizing Dye B Sensitizing Dye B The dyes were coated on a polyethylene terephthalate film base subjected to the process described in Example (1) of Publication No. 59-19941. In this case, gelatin m 1.0 (l
Bis-(2-ethylhexyl)sulfosuccinate was added as a spreading agent at 10 mQ/1 to
”, the compound of general formula [I] was added as shown in Table 2 per mole of silver halide, and formalin 2 was added as a hardening agent.
Sample N was coated simultaneously with a protective layer containing 510/1”.
0.1-1 to 1-16 were produced.

Compound a Next, 800 mg of compound (I[-18) was added per 11 moles of halogenation, and further 1 g of p-dodecylbenzenesulfonic acid sodium 300II, 2 g of styrene-maleic acid copolymer polymer, and styrene-butyl acrylate-acrylic acid copolymer latex were added. (Average particle size approximately 0.25μl1)
15 (add l, AQ amount 4.OQ/f, gelatin amount 2
．． Each of the obtained samples NO, 1-1 to 1-16 was divided into two halves so that OOMf was obtained from JP-A-Sho-III (Table 2 expressed in 1/AfJ mol),
One side is left as it is, the other is at a temperature of 40℃ and a relative humidity of 80℃.
% for 3 days under high temperature and high humidity, wedge exposure was performed using a tungsten light source.

Each of the above-mentioned exposed samples was processed under the conditions shown in Table 2 in automatic development [1] using a developing solution and a fixing solution according to the following formulations.

[Development processing conditions] (Process) (Temperature) (Time) Development
35℃ 15 seconds fixation 34
Wash with water for about 15 seconds at room temperature Dry for about 12 seconds at 50℃ for 10 seconds Developer formulation (composition A) Pure water (ion-exchanged water > 150 vN engineered ethylene diamine tetraacetic acid disodium salt g diethylene glycol 0 Q subfiltration power') Rum ( 55% w/v aqueous solution)
100112 Carbonated potash/rum
50 (]Hydroquinone
is g5-methylbenzotriazole 200
mg1-Phenyl-5-mercaptotetrazole 0mg 4.5g to make 4 Potassium hydroxide 10 to 10 Potassium bromide (composition) Pure water (ion exchange water) 31g Diethylene glycol 50g Ethylenediaminetetraacetic acid disodium salt 5mg Acetic acid (90% aqueous solution) 0.3mQ
5-Nitroindazole 110mg1-
Phenyl-3-pyrazolidone 700 mg Butylamine diethanolamine 15 g When using a developer, the above compositions were dissolved in water 500112 in the order of the composition A1 and further processed.

Fixer formulation> (Composition A) Ammonium thiosulfate (72.5% W/V aqueous solution) 24
〇- Sodium sulfite 17g Sodium vinegar 3 water j3ii 6.51; 1 硼1
1i 6a Sodium citrate 2 water j3! 2! j Vinegar M (
90% w/w aqueous solution) 13.6d (composition) Pure water (ion exchange water) 17tffi
Sulfuric acid (50% V/W aqueous solution) 4.7g
Aluminum sulfate (Affi 20a, 1% w/w U) water '18N) 26.5 g When using the fixer, dissolve the above composition A in the order of composition A and composition in water 5001 and finish to 1. I used it. This fixer p
H was approximately 4.3.

The photographic properties of the processed samples are shown in Group 3.

In addition, gamma is expressed as tanθ of the linear part from optical density 0.2 to 1.5, and relative sensitivity is expressed as exposure 11 oaE vi te L giving density 2.0, test FI No. 1-1.
) Relative value with 3 days left as 100.

For fogging, the density of the unexposed film was measured.

Table 3 As is clear from Table 3, sample No. 1- according to the present invention
No. 3 to 1-16 show almost no change in contrast and fog values under high-temperature, high-humidity storage conditions even when processed in about 42 seconds from development to washing with water. That is, the method of the present invention suppressed a decrease in contrast and an increase in fog under high temperature and high humidity conditions.

Example 2 Silver nitrate aqueous solution, potassium bromide, potassium iodide aqueous solution,
Mixed by double jet method in the presence of ammonia while maintaining pA (+) at 7.9, average particle size 0.2 μm.
A monodispersed cubic silver iodobromide emulsion B (silver iodide 2 mol %, silver bromide 98 mol %) was prepared.

Separately, a silver nitrate aqueous solution and a potassium bromide aqueous solution were mixed in the presence of ammonia by a double jet method while maintaining I)/'l at 7.9 to form a monodisperse cubic silver bromide emulsion C with an average grain size of 0.35 μ square. I got it.

Emulsion B was further sulfur sensitized with sodium thiosulfate.

In addition, 5,5'-dichloro-3,3'-di(3-sulfopropyl)-9-ethyl-oxacarbocyanine sodium salt was used as a sensitizing dye in each emulsion A and B.
6 x 10-mol per mole of silver, respectively,
Spectral sensitization was performed by adding 4.5×10-mol.

Furthermore, 4-hydroxy-6-methyl-1,3 is used as a stabilizer.
,3a,7-chitrazaindene was added.

Emulsions B and C were mixed at a silver halide weight ratio of 6:4.

Furthermore, the hydrazine derivative represented by [I[[-3]] was added in an amount of 4×10 −3 mol per mol of silver.

Furthermore, alkylbenzene sulfonate as a surfactant,
After adding a vinyl sulfone hardener as a hardener and adjusting the pH of the emulsion to 5.8, the film thickness was 100 μm.
Coated silver fit onto polyethylene terephthalate support
Sample No. , 2-1 to 2-16 were prepared.

Table 4 IMA (represented by 1 mol) Each of the obtained samples NO, 2-1 to 2-16 was divided into two halves,
One was left as it was, and the other was left in a high temperature and high humidity environment of 40°C and 80% for 3 days, and then each was exposed to wedge light using a tungsten light source, and then developed with a developer having the following composition at 40°C for 10 seconds. The treatment was carried out for 110 seconds, washing with water for 9 seconds, and drying for 10 seconds.

Developer formulation> Hydroquinone 45.0 gN-
Methyl-p-aminophenol 1/2 sulfur M salt 0.8 g Sodium hydroxide 18.0 (1 hydrated potassium ss, o g5-sulfosalicyl 9 45.00 boron 11
25.0 g potassium sulfite
ilo, o g ethylenediaminetetraacetic acid II
j, disodium salt 1.0 g Potassium bromide 6.0 g 5-methylbenzotriazole 0.6 g N-butyljetanolamine 15.01; 1 Add water to 11
(+)H-12,0> The photographic characteristics of the sample obtained by processing are shown in Group 5.

Gamma, relative sensitivity (3 days of natural storage of sample No. 2-1 was set as 100), and fog in the table are as shown in Example 1 using a silver iodobromide emulsion. Even when processed with a forming developer, the sample according to the present invention can be used at high temperatures and
There was no change in contrast or fog when stored under high humidity, and the increase in relative sensitivity was suppressed.

Example 3 Sample N was prepared in the same manner as in Example 1 except that the compound represented by general formula (I) was added to the emulsion bowl as shown in Table 6.
Table 7 shows the results of fabricating and processing samples Nos. 013-1 to 3-14 and further evaluating them in the same manner as in Example 1.

table 6 1m! It/A (expressed in 1 mol) Similar to Example 1, the effects of the present invention were obtained.

[Effects of the Invention] As explained above in detail, the processing method of the present invention allows development processing, fixing processing, water washing and/or stabilization processing to be performed in 45 minutes.
In ultra-rapid processing that takes place within seconds, it is possible to improve the deterioration of the storage stability of photosensitive materials over time under high temperature or high humidity conditions.

Claims (2)

[Claims] (1) A silver halide photograph containing at least one compound represented by the following general formula [I] in a silver halide emulsion layer and/or at least one hydrophilic colloid layer adjacent to the silver halide emulsion layer. 1. A method for processing a silver halide photographic light-sensitive material, characterized in that the light-sensitive material is subjected to development processing, fixing processing, water washing and/or stabilization processing within 45 seconds using an automatic processor. General formula [I] ▲ Numerical formulas, chemical formulas, tables, etc. represents a ring, R^1 represents a hydrogen atom, an alkali metal or an alkyl group having 1 to 6 carbon atoms, R^2 represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, -COR^3, -COOR^3 or -SO_2R^3, where R^3 represents a hydrogen atom, a substituted or unsubstituted aliphatic group, or a substituted or unsubstituted aromatic group. M represents a hydrogen atom, an alkali metal or a -NH_4 group. ] (2) The processing method according to claim (1), wherein the automatic processor has a processing line speed of 1,000 mm/min or more.