JPS6230417B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to development processing of silver halide photographic materials, and more particularly to a method for accelerating development and increasing effective sensitivity during development processing. In the development process of silver halide photographic light-sensitive materials, it is desired to accelerate the development speed and increase the effective sensitivity of the light-sensitive material without deteriorating its graininess. Many development acceleration methods have been proposed for this purpose. Compounds added to the developer to accelerate development include polyalkylene oxide compounds, thioether compounds, ammonium,
Onium compounds of the phosphonium or sulfonium type as well as polyonium compounds are well known. However, many such development accelerators tend to increase fog after processing of photographic materials and also tend to coarsen the grains.
In addition, there are other products that have the disadvantages of poor solubility in alkaline developers and poor storage stability in solutions, but very few of these are in practical use, especially development accelerators for thioether compounds. Because it has a very high accelerating effect, it is effective in cases where all the silver halide present is developed, such as in color developing solutions for reversal color photosensitive materials.
When added to a normal developer, fog increases significantly even in a small amount, making it impossible to obtain an effective increase in sensitivity, and it is difficult to maintain a constant concentration of this compound in continuous processing, so it is hardly ever put into practical use. do not have. The first object of the present invention is to provide a method for developing silver halide light-sensitive materials using a new development accelerator that reduces fog, increases development speed, and effectively increases sensitivity. The second object is to provide a method for processing silver halide light-sensitive materials, which can always provide a constant low density fog and a desired constant sensitivity even during continuous processing in which the concentration of the accelerator varies. The third object is to provide a method for processing silver halide photographic materials that can increase effective sensitivity without deteriorating graininess. Fourth, we need a method for processing silver halide photographic materials that causes less environmental pollution and can provide low fog, effective increase in sensitivity, and high gamma without using highly polluting development accelerators such as benzyl alcohol. It is to provide. Fifth, silver halide photographic light-sensitive materials with low risk of low fog, increased sensitivity, and high gamma can be obtained without using development accelerators such as thiocyanates that may decompose and release cyanide. The purpose is to provide a processing method. As a result of studies, the present inventor has found that the object of the present invention is to develop the exposed silver halide photographic material with a developer containing a compound represented by the following general formula [] or before developing with a developer. It has been found that this can be achieved by treatment with a treatment liquid containing a compound represented by the following general formula []. General formula [] HO-A-S-B-OH [In the formula, A and B are substitutions having 2 to 4 carbon atoms,
The unsubstituted alkylene group and substituent represent a hydroxy group and/or a carboxy group. ) The compounds of the present invention are generally commercially available and can be easily obtained. Next, specific representative examples of the compounds of the present invention will be given. In the present invention, one or more compounds of the present invention are used by adding them to a developer or a so-called pretreatment solution preceding the developer. When added to the developer and pre-processing solution, the amount added is 1
0.001 to 100 g, particularly 0.1 to 10 g, is preferred. In general, when added to a black and white developer, a black and white first developer for reversal color film processing, and a color developing solution such as a color negative film or color paper, the amount is preferably 0.01 to 10 g per processing solution. In the case of a developing solution that develops all remaining AgX, such as color development called development, the amount is preferably 0.5 to 30 g per processing solution. Furthermore, when it is added to a pre-treatment liquid prior to the above-mentioned developer, the amount is preferably 0.01 to 30 g per treatment liquid. As the developer used in the present invention, as described above, a black and white developer and a color developer for color sensitive material processing are used. Furthermore, a pretreatment liquid prior to these is used. The developing solution used in the above black and white development is a normal black and white developer used in processing black and white silver halide photographic light-sensitive materials, and a black and white developer called black and white first development used in processing silver halide color photographic light sensitive materials for reversal. A developer can be used. This developer can contain various additives that are generally added to black and white developers. Typical additives include 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolone, 1
-Developing agents such as phenyl-3-pyrazolidone, metol, and hydroquinone, preservatives such as sulfites, accelerators consisting of alkalis such as sodium hydroxide, sodium carbonate, and potassium carbonate, potassium bromide, and 2-methylbenzimidazole. , inorganic or organic inhibitors such as methylbenzthiazole, nitrobenzoic acid, water softeners such as aminopolycarboxylic acids and organophosphates or polyphosphates,
Examples include surface overdevelopment inhibitors comprising trace amounts of iodide and mercapto compounds. Furthermore, the color developer used in the above color development step can be of any type used in color development processing of color photographic light-sensitive materials, and includes, for example, an aromatic primary amine color developing agent. An alkaline aqueous solution is preferably used in the present invention, and can contain a PH adjusting agent such as sodium hydroxide, sodium carbonate, potassium carbonate, sodium metaborate, sodium bicarbonate, or boric acid, or a PH buffering agent. In special cases, fogging agents such as tin chloride and borohydrides may be added, and benzyl alcohol and the like may also be included. As a color developing agent, for example, N-ethyl-N-methoxyethyl-
3-Methyl-p-phenylenediamine tosyl salt, 3-methyl-4-amino-N-ethyl-[2
-(2-methoxyethoxy)ethyl]aniline・
Tosyl salt, N,N-diethyl-p-phenylenediamine sulfate, 4-amino-N-ethyl-N-β
-Hydroxyethylaniline sulfate, 3-methyl-4-amino-N-ethyl-β-methanesulfamide ethylaniline sesquisulfate monohydrate, 3-methyl-4-amino-N-ethyl-
There are phenylene diamines such as N-β-hydroxyethylaniline sulfate. In addition, the developer using these compounds contains bromides, iodides, carbonates, bisulfites, known antifoggants, known development accelerators, etc.
It is also possible to contain solvents such as ethylene glycols. Furthermore, these color developing solutions can contain chelating agents such as phosphonobutanecarboxylic acid and alkoxydenediphosphonic acid. Furthermore, the pretreatment liquid that can be used in the present invention can have various compositions. The pretreatment liquid with the simplest composition is an aqueous solution in which the compound of the present invention is simply dissolved, but acids such as acetic acid and boric acid,
Aqueous solutions containing appropriate alkalis such as sodium hydroxide, or salts such as sodium sulfite, sodium acetate, sodium sulfate, sodium borate, sodium carbonate, and sodium bicarbonate can also be advantageously used as the pretreatment liquid. Any pH of the pretreatment liquid can be used, and any of them can bring about the effects of the present invention, but if the pH is too high, stains may occur. In the pretreatment liquid, if necessary, a suspending agent consisting of a chelate compound such as 1-hydroxyethylidene-1,1-diphosphonic acid or phosphonocarboxylic acid,
Hardening agents made of various compounds including alum and aldehyde, PH buffering agents, fixing agents of halogen salts, antioxidants such as sulfites, hydroxylamine, hydrazine, swelling agents such as sodium sulfate and magnesium sulfate. It is possible to contain inhibitors, surfactants, etc. Although it is preferable that the pretreatment liquid and the developer be treated directly in succession, a buffer liquid (acid or alkali) for washing with water or stopping treatment may be interposed between the two liquids. In such cases, the same development accelerating effect can be obtained when the compound of the present invention is added to the pretreatment liquid. The pH of the developer can be used within the range of 8.5 to 14.0, with 9.0 to 12.5 being particularly preferred. The pH of the pretreatment liquid is 1.0~
The pH of the pretreatment liquid can be used within the range of 14, but since the desired pH of the pretreatment liquid varies depending on the compound used, it is necessary to find the optimum pH for each by experiment. However, generally the processing is carried out at temperatures of 20°C to 60°C, preferably 30°C to 52°C. Next, silver halide photosensitive materials that can be used in the present invention will be described. A silver halide photosensitive material consists of a support (for example, a glass plate, polyethylene terephthalate film, cellulose acetate film, baryta paper, polymer-coated paper, etc.) and at least one silver halide emulsion layer coated thereon. The silver halide emulsion layer may be coated on both sides of the support, and may have a back layer, an antihalation layer, an intermediate layer, a filter layer, a surface protection layer, etc., if necessary. Silver halide emulsions are made by combining silver halides such as silver chloride, silver iodide, silver bromide, silver chlorobromide, silver iodobromide, and silver chloroiorobromide with hydrophilic colloids (e.g., gelatin, modified gelatin, casein, carboxylic acid, etc.). methylcellulose, polyvinyl alcohol, polyvinylpyrrolidone, etc.). A silver halide emulsion is prepared by combining a water-soluble silver salt (for example, silver nitrate) and a water-soluble halide with water and a hydrophilic colloid by a method commonly used in the industry (for example, single-jet method, double-jet method, etc.). It is produced by mixing in the presence of a chemical compound, physically ripening it, and if necessary chemically ripening it with a sulfur compound, a gold compound, etc. Silver halide emulsions may contain spectral sensitizers (cyanine dyes,
merocyanine dye, etc.), stabilizers (e.g., 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene, benzotriazole, 5-nitrobenzimidazole, etc.), hardening agents (e.g., formalin, glyoxal, -Hydroxy-4,6
-dichloro-S-triazine, mucochloric acid, etc.), coating aids (eg, saponin, sodium lauryl sulfate, polyethylene oxide, etc.), color couplers, polymer latex, etc. can be added. Development processing using a developer containing the compound of the present invention is applicable to black and white negative film, black and white reversal film, color reversal film, black and white aviation film, color negative film, color reversal film, color paper, color positive film, and color reversal film for motion pictures. It can also be applied to the processing of any silver halide color photographic materials such as color reversal films for TVs. The details of the present invention will be explained below with reference to Examples, but the embodiments of the present invention are not limited thereto. Example 1 1-Hydroxy-2- was added as a cyan coupler to a red-sensitive silver iodobromide emulsion (silver iodide 7 mol%).
N-γ-(2,4-di-t-amylphenoxybutyl)naphthamide was emulsified and mixed, and 1-(2' ,4′,6′-trichlorophenol)3″-[2″-chloro-3″-(2″,4″-di-t-
amylphenoxyacetamide)anilino]-5-
Pyrazolone was emulsified and mixed, and α-benzoyl-[2-chloro-5-α-
(Dodecyloxycarbonyl)propyloxycarbonyl]acetanilide was emulsified and mixed and sequentially applied onto resin coated paper to prepare a reversal color paper photographic material for photographing. For emulsification of each coupler, dibutyl phthalate and tricresyl phosphate were used as coupler solvents, sorbitan monolaurate and sodium dodecylbenzenesulfonate were used as emulsifiers, and 1-(p-nonylphenoxytrifluoride) was used as an emulsifier. Sodium oxyethylene)butane-4-sulfonate and lauric acid ester of sucrose were added as coating aids. Furthermore, a filter layer of yellow colloidal silver containing potassium iodide is placed between the green-sensitive emulsion layer and the blue-sensitive emulsion layer in the sample, and di-t-amylhydroquinone is dispersed between the green-sensitive emulsion layer and the red-sensitive emulsion layer. An intermediate layer consisting of gelatin impregnated therein and a protective layer mainly consisting of gelatin are provided on the blue-sensitive emulsion layer. This silver halide color photographic light-sensitive material was exposed to light according to the sensitometric method, and then processed at a temperature of 38° C. using the following processing solution according to the processing steps. Processing process first development (black and white development) 38℃ 2 minutes stop bath 38℃ 30 seconds water wash 38℃ 30 seconds color development 38℃ 2 minutes water wash 38℃ 30 seconds bleach-fix solution 38℃ 3 minutes water wash 38℃ 2 minutes Stabilizing bath 38℃ 30 seconds Total 11 minutes [Processing solution composition] First developer (black and white development) Sodium tetrapolyphosphate 3.0g Sodium hydrogen sulfite 5.0g 1-phenyl-3-pyrazolidone 0.7g Anhydrous sodium sulfite 60.0g Hydroquinone 8.0g Sodium carbonate monohydrate 53.0g Potassium bromide 3.0g Potassium iodide (0.1%) 44.0ml Diethylene glycol 20.0ml Polyethylene glycol #400 5.0g Caustic soda 2.8g Add water 1 (PH; 9.59) Stop solution Sodium acetate 30g Glacial acetic acid 8ml Add water 1 (PH; 4.0) Color developer Benzyl alcohol 12ml Sodium tetrabolyphosphate 3.0g Anhydrous sodium sulfite 7.5g Potassium carbonate 32.0g Potassium bromide 0.3g Potassium iodide (0.1%) 90.0ml Caustic soda 2.3 g 3-methyl-4-amino-N-ethyl-N-β
-Methanesulfonamide ethylaniline 11.0g Kodatsu RA-1 0.2g Ethylene glycol 20ml Add water 1 (PH; 10.75) Bleach-fix solution Bisthiourea 3.0g Ammonium bromide 50.0g Aqueous ammonia (28%) 30.0ml Ethylenediaminetetraacetic acid Iron() ammonium monohydrate 45g Ethylenediaminetetraacetic acid disodium 2
Aqueous salt 2g Anhydrous sodium sulfite 10g Ammonium thiosulfate 160.0ml Glacial acetic acid 6.9ml Add water 1 (PH; 6.4) Stabilizing solution Sodium succinate 20g Fluorescent brightener 1.5g Add water 1 (PH; 4.0) Development processing Comparative development was carried out by adding the following to the black and white developer. 1 to the black and white developer 1 No addition of compound 2 Comparative compound (known development accelerator) KSCN
2.0g 3 Exemplified Compound (1) 0.15g 4 Exemplified Compound (3) 0.15g The photographic properties obtained are shown in Table 1.

[Table] As shown in Table 1, it can be seen that when processed with developer (1) that does not contain any accelerator, fog is extremely high and gamma is low, making it impossible to obtain effective sensitivity. . In addition, when processing with a developer containing a known thiocyanate as an accelerator, such as developer (2), the effect of accelerating development was certainly observed, but fog was high, Dmax was low, and gamma was not satisfactory. However, developer solutions (3) to (4) containing compounds according to the invention
It can be seen that the development promotion effect is extremely excellent, the fog is low, and the maximum density is high, which is ideal, and the gamma value also shows a desirable high value. In addition, the granularity of the coloring dye after processing is also affected by the black and white developer (1) or
It turns out that it is better than (2). It was also found that the dye storage properties of the coloring dyes were similarly excellent. In addition to this example, the benzyl alcohol accelerator was removed from the color developer, and instead 1 g of the compound of the present invention was added to each separate developer and developed in the same manner as in this example. As a result, when the compound of the present invention is used, the photographic performance is significantly higher than that with benzyl alcohol even without benzyl alcohol. It was found that it also showed an excellent promoting effect. Example 2 After pretreatment by corona discharge on a paper support coated on the surface with a polyethylene layer containing anatase titanium oxide as white pigment,
Color photographic paper was made by applying each of the following layers in sequence. First layer: A silver chlorobromide photographic emulsion containing 5 mol% silver chloride was optically treated with anhydro-5-methyl-5'-methoxy-3-3'-di-(3-sulfopropyl) selenacyanine hydroxide. This was sensitized with 2,5-di-t-butylhydroquinone and α-[4-(1-benzyl-2-phenyl-3,5-dioxo-) as a yellow coupler.
1,2,4-triazolidyl)]-α-pivalyl-2-chloro-5-[γ-(2,4-di-t
―amylphenoxy)butyramide] to which a protective dispersion of acetanilide was added.
The coating was applied so that it was 0.35 g/m ² . Second layer; di-t-octylhydroquinone and 2-(2'-hydroxy-
3′-5′-di-t-butylphenyl)benztriazole, 2-(2′-hydroxy-5′-t-butylphenyl)benztriazole, 2-
(2'-Hydroxy-3'-t-butyl-5'-methylphenyl)-5-chlorobenztriazole and 2-(2'-hydroxy-3',5'-di-t-butylphenyl)-5-chlorobenz A gelatin solution to which a protect dispersion containing a mixture of triazoles was added was applied as an intermediate layer. Third layer: A silver chlorobromide photographic emulsion containing 15 mol% silver chloride was mixed with anhydro-9-ethyl-5,5'-diphenyl-3,3'-di-(3-sulfopropyl).
Optically sensitized with oxacarbocyanine hydroxide, 2,5-di-t-butylhydroquinone, 2,2,4-trimethyl-6-lauryloxy-7-t-octylcoumaron and 1-( 2,4,6-trichlorophenyl)-3-(2-chloro-5-octadecenylsuccinimidoanilino)-5-
A Flotect dispersion of pyrazolone was added to the coating to give a silver content of 0.4 g/m ² . Fourth layer: The same liquid as the second layer was applied as an intermediate layer. Fifth layer: Silver chlorobromide photographic emulsion containing 15 mol% of silver chloride was mixed with anhydro-2-[3-ethyl-5-
(1-ethyl-4(1H)-quinolilidene)ethylidene-4-oxo-thiazolidin-2-ylidene]methyl[-3-(3-sulfopropyl)
Optical sensitization was performed using benzoxazolium hydroxide, and 2,5-di-t-butylhydroquinone and 2,4 as a cyan coupler were added to this.
-dichloro-3-methyl-6-[γ-(2,4
-Diamylphenoxy)butyramide] to which a protective dispersion of phenol was added,
The coating was applied so that it was 0.27 g/m ² . Sixth layer: A gelatin solution was applied as a protective layer. The silver halide photographic emulsions used in each of the above-mentioned photosensitive layers were prepared by the method described in Japanese Patent Publication No. 46-7772, each chemically sensitized with sodium thiosulfate, and 4-hydroxy-
6-Methyl-1,3,3a,7-tetrazaindene was added. In addition, the coating liquid for all layers includes
Saponin was added as a coating aid, and bis(vinylsulfonylmethyl)ether was added as a hardening agent. The color photographic paper produced as described above was exposed to a light wedge according to the sensitometric method, and then processed at a temperature of 33° C. using the following processing solution in the following order. Processing process Color development 33℃ 3 minutes 30 seconds Bleach fixing 33℃ 1 minute 30 seconds Washing with water 30℃ 3 minutes Drying 75-85℃ Total 8 minutes Color developer Fluorescent brightener (Note 1) 2g Hydroxylamine sulfate 3g 1-hydroxyethylidene-1,1-diphosphonic acid 1.5g 3-methyl-4-amino-N-ethyl-N-
(β-methanesulfonamidoethyl)aniline sulfate 5g Potassium carbonate 30g Potassium sulfite (50% solution) 4ml Potassium bromide 0.6g Potassium chloride 0.5g Potassium hydroxide 2.5g Add water 1 (PH; 10.20) (Note 1) ) Tinopal MSP as a fluorescent brightener
(trade name: Ciba Geigy, Switzerland) Ethylene diamine-tetraacetic acid 40 g Ammonium sulfite (50% solution) 30 ml Ammonium thiosulfate (70% solution) 140 ml Aqueous ammonia (28% solution) 30 ml Ethylene diamine-tetraacetic acid ( )sodium
70g of water was added 1 (PH; 6.80) During the development process, the following materials were added to the color developing solution and comparative development was carried out. 1 to color developer 1 No compound added 2 Comparative compound (known development accelerator) HOCH ₂ CH ₂ SCH 2 CH ₂ SCH _{2 CH 2 OH} 1.0g 3 Exemplary compound (1) 1.0g 4 Exemplary compound (3) 1.5 g 5 Exemplary Compound (2) 0.5g The photographic properties obtained are shown in Table 2.

[Table] As can be seen from the results in Table 2, the developer without the addition of a development accelerator has low fog, but the maximum density is extremely low and gamma is also low, meaning that no effective accelerating effect can be obtained at all. Furthermore, it can be seen that the developing solution (2) containing a thioether compound, which is a known accelerator, exhibits undesirable characteristics such as extremely high fog and low maximum density, making it impossible to obtain effective sensitivity.
In comparison, it can be seen that the developers (3) to (5) containing the compounds of the present invention have a desirably high maximum density, very low fog, and a high gamma, exhibiting a desirable accelerating effect. Preferred embodiments of the present invention are shown below. Embodiment Item (1) The processing method according to the claims, characterized in that the silver halide photographic light-sensitive material is a silver halide color photographic light-sensitive material. Embodiment (2) The processing method according to claim or embodiment (1), wherein the developer is a color developer containing a color developing agent. Embodiment (3) The treatment method according to the claims, characterized in that the compound is HO--CH ₂ CH ₂ --S--CH ₂ CH ₂ OH.

Claims (1)

[Scope of Claims] 1. The exposed silver halide photographic light-sensitive material is treated with a developer containing a compound represented by the following general formula [], or prior to development processing with a developer, a compound represented by the following general formula [] is used. 1. A method for processing a silver halide photographic material, the method comprising processing a silver halide photographic material with a processing solution containing a compound containing a compound. General formula [] HO-A-S-B-OH [wherein A and B are an alkylene group having 2 to 4 carbon atoms (the alkylene group may be substituted with a hydroxy group and/or a carboxy group). ). ]