JPH04299337A - Developer for silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To provide the developer for silver halide photographic sensitive materials which prevents the liquid contamination by silver sludge and has excellent preservable stability. CONSTITUTION:This developer for silver halide photographic sensitive materials contains respectively at least one of the compds. expressed by formula I and formula II. In the formula I, A denotes a bivalent group; B denotes -SO3<->, -COO<->, -OHO, -SO2NHR1 or -CONHR1; R1 denotes H, 1 to 3C alkyl group. In the formula II, R2, R3 denote an alkyl group, aryl group.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for developing silver halide photographic materials, and more particularly to a developer used therein.

0002

BACKGROUND OF THE INVENTION It is generally known that a developer used for developing silver halide photographic materials contains a sulfite salt for the purpose of increasing the storage stability of the developer. In some cases, a developer containing a compound having a strong dissolving action on silver halide, such as thiosulfate, is also used, such as a developer for silver salt diffusion transfer or a one-bath development fixer.

[0003] When a photosensitive material is processed with a developer containing a compound having a dissolving action on silver halide, such as sulfite or thiosulfate, a large amount of silver complexes are easily reduced and accumulated as silver sludge. be done. In particular, when photosensitive materials are continuously processed using an automatic developer, silver sludge not only floats, but also adheres to rollers, belts, etc., and reflects light called silver stain on the roller streaks on the photosensitive material. This causes stains caused by precipitated silver that appear yellow or brown. 2-Mercapto-1,3,4-thiadiazoles (British Patent No. 940) are used as silver sludge and liquid stain preventive agents.
169 specification) 2-mercapto-1,3,4-oxadiazoles or 1-phenyl-5-mercaptotetrazole (US Patent No. 3,173,789)
,D. L-6,8-dithioctanoic acid (U.S. Pat. No. 3,
318,701), o-mercaptobenzoic acid (
British Patent No. 1,144,481), aliphatic mercaptocarboxylic acid (US Pat. No. 3,628,955), L-thiazolidine-4-carboxylic acid (J. Photo
ogr. Sci. , 13, 233 (1965)), disulfide compounds (JP-A-52-36029),
2-benzoxazolethiol, 2-benzimidazolethiol (Photogr.Sci.Eng., 2
0,220 (1976)), acetylene glycols (
2-Mercaptobenzothiazole-5-sulfonic acid (JP-A-56-724)
No. 41 Specification) etc. are known.

However, these compounds have been used as anti-sludge agents in developing solutions that have a dissolving effect on silver halide, especially those containing high concentrations of sulfite (for example, 0.2 mol/l or more). In some cases, the sludge prevention effect is lost due to air oxidation, the sludge prevention effect is weak and a large amount must be used, it has a negative effect on photographic properties such as desensitization, softening, and development suppression, or it is expensive. There was a problem that it was difficult to say that it was completely satisfactory because it had an unpleasant odor.

Furthermore, when the compound of formula 3 described below is added to a developer containing a high concentration of sulfite, it has a very good sludge prevention effect, but has the disadvantage of poor storage stability and yellow fogging. It turns out.

[0006]

[Problems to be Solved by the Invention] Therefore, it is an object of the present invention to develop photosensitive materials using an automatic processor using a developer having a dissolving action on silver halide, especially a stable developer containing a high concentration of sulfite. To provide a developer capable of preventing liquid stains caused by silver sludge and stains on rollers and belts of a developing machine when processing materials, and capable of obtaining photographic images with excellent finished quality free of silver stains. Another object of the present invention is to provide a developer having good storage stability.

Another object of the present invention is to provide a method for processing silver halide black-and-white photographic materials with a developer that does not have the above-mentioned problems and prevents the generation of silver sludge.

[0008]

[Means for Solving the Problems] The above object of the present invention is to add at least one of the compounds represented by the following chemical formula 3 and at least one of the compounds represented by the chemical formula 4 to a developer for silver halide photographic light-sensitive materials. This was achieved by containing.

[0009]

[Chemical formula 3]

In the formula, M represents a hydrogen atom, an alkali metal atom or NH4, A represents an organic divalent group, and B represents -
SO3 M', -COOM', -SO2 NHR1,
-CONHR1 or -OH, M' represents a hydrogen atom, an alkali metal atom or NH4, and R1 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.

[0011]

[C4]

R2 and R3 represent an optionally substituted alkyl group or aryl group.

Specific examples of the compounds represented by the above formula 3 are shown in Table 1. However, only A and B are shown.

[0014]

[Table 1]

These compounds are known, and reference may be made to, for example, JP-A-58-105231 and JP-A-59-9661. The amount of the compound represented by formula 3 to be added is in the range of about 0.005 to about 5 g, preferably about 0.01 to about 2 g per liter of developer. Next, specific examples of the compound represented by Chemical Formula 4 are shown in Table 2.

[0016]

[Table 2]

The amount of the compound represented by formula 4 added is 0.01 to 5.0 g, preferably 0.1 to 1.0 g, per liter of developer.
It is in the range of 0g.

The development process of the present invention is carried out using conventional black and white photographic developing agents such as hydroquinone, alkylhydroquinone (such as t-butylhydroquinone, methylhydroquinone, dimethylhydroquinone), catechol, birazole, chlorohydroquinone, dichlorohydroquinone, alkoxyhydroquinone (such as methoxy or ethoxyhydroquinone), aminophenol developing agents (e.g. N-methyl-p-aminophenol, 2,4-diaminophenol, ascorbic acid developing agent, N-methyl-p-aminophenol sulfate, pyrazolones (
4-aminopyrazolone), 3-pyrazolidone developing agents (e.g. 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-5-methyl-3-pyrazolidone, 1- Phenyl-4-methyl-3-pyrazolidone, 1,5-diphenyl-3-pyrazolidone, 1-p-tolyl-3-pyrazolidone, 1-phenyl-2-acetyl-4,4-dimethyl-
3-pyrazolidone, 1-p-hydroxyphenyl-4,
4-dimethyl-3-pyrazolidone, 1-(2-benzothiazolyl)-3-pyrazolidone, 3-acetoxy-1-
An alkaline aqueous solution containing phenyl-3-pyrazolidone) or the like alone or in combination is preferable. In particular, combinations of hydroquinone and 3-pyrazolidones or hydroquinone and aminophenols are useful for high-temperature and rapid processing. However, it may be a so-called activator type developer that does not substantially contain a developing agent.

The developer containing the compounds represented by Chemical Formulas 3 and 4 used in the present invention exhibits a particularly remarkable sludge-preventing effect when it contains a large amount of sulfite ions. Specifically, at this time, sulfite ions are contained in an amount of 0.1 mol or more, preferably 0.2 mol to 1.0 mol, per 1 liter of the developer. As the sulfite that provides sulfite ions, specifically, alkali metal sulfites such as sodium sulfite, potassium sulfite, and potassium metasulfite can be used.

Silver sludge generated in the developer is particularly likely to deposit on rollers and belts in the developer, and silver sludge adhering to the rollers and belts tends to contaminate photosensitive materials. Therefore, the present invention is particularly useful when processing with an automatic processor. As such an automatic developing machine,
For example, the opposed roller method (for example, PAKO's Pakor
ol Super G24-2, Fuji Photo Film Co., Ltd. G-14LFG-24SQ, RN, etc.), staggered roller method (for example, Eastman Kodak Co. K
odalith Processor, M6 Pr
(e.g., Fuji Photo Film Co., Ltd. RU), belt conveyance method (e.g., Log-E-tronics LD)
-241D, etc.) Others (duPont Cron
alith 24L, etc.).

[0021] The developer may contain other buffering agents (for example, carbonates, boric acid, borates, alkanolamines), if necessary.
Alkaline agents (e.g. hydroxides, carbonates), solubilizing agents (
(e.g., polyethylene glycols, esters thereof), pH adjusters (e.g., organic acids such as acetic acid), sensitizers (e.g., quaternary ammonium salts), development accelerators, surfactants, hardeners, etc. can be done.

The developer further contains an antifoggant (for example, a benzotriazole such as 5-nitroindazole, 5-nitro-benzimidazole, 5-methyl-benzotriazole, 5-nitrobenzotriazole, benzothiazole, 1-phenyl chelating agents (e.g. ethylenediaminetetraacetic acid, alkali metal salts thereof, polyphosphates, nitriloacetic acid); salt).

The pH of the developer is selected to be sufficient to provide the desired density and contrast, but is preferably in the range of about 8-13. The developer processing temperature and time are interrelated and determined in relation to the total processing time, which is generally 10 seconds to 3 minutes at about 20-40°C;
For high temperature rapid processing, the temperature is about 25-45°C.

In the present invention, the components of the developer need only contain the components necessary for use, and the form before processing before preparing the solution for use may be, for example, a mixture of solid components or a concentrate. , solution, emulsion or suspension. For example, it may be a developer in which the components of the developer are divided into several parts and made into the same form or different forms, or it may be in the form of a powder or liquid preparation prepared by preparing these parts in advance. The liquid preparation can be dissolved in water or diluted with water to prepare a liquid for use, if necessary.

The light-sensitive material processed by the method of the present invention may be used for any purpose, but is preferably a black-and-white light-sensitive material, such as an X-ray light-sensitive material, a micro-sensitive material, an Alice light-sensitive material, or a photographic light-sensitive material. Applicable to photosensitive materials, black and white photosensitive materials for general amateurs, etc. Photosensitive silver halides include silver chloride, silver chlorobromide, silver chloroiodobromide, silver bromide, and silver iodobromide. Further, the photosensitive material used in the present invention may be either a negative type or a direct positive type.

A silver halide photographic material applicable to the method of the present invention comprises a support and at least one silver halide emulsion layer coated thereon. Further, the silver halide emulsion layer can be coated not only on one side of the support but also on both sides. Of course, a back layer, an antihalation layer, an intermediate layer, a top layer (for example, a protective layer), etc. can be included if necessary. Silver halide emulsions are silver halide dispersed in hydrophilic colloids such as gelatin, modified gelatin, colloidal albumin, casein, carboxymethylcellulose, hydroxyethylcellulose, sodium alginate, polyvinyl alcohol, polyvinylpyrrolidone, or mixtures thereof. It is. Silver halide emulsions are usually prepared by combining a water-soluble silver salt (for example, silver nitrate) and a water-soluble halide salt by a method well known in the art (for example, a single jet method, a double jet method, a controlled jet method, etc.). It is produced by mixing in the presence of a hydrophilic colloid, followed by physical ripening and chemical ripening such as gold sensitization and/or sulfur sensitization.

Silver halide emulsions are treated with spectral sensitizers (for example, cyanine dyes, mixtures thereof for merocyanine dyes), stabilizers (for example, 4-
hydroxy-6-methyl-1,3,3a,7-tetrazaindene), sensitizers (e.g., U.S. Pat. No. 3,619,
No. 198), antifoggants (e.g. benzotriazole, 5-nitrobenzimidazole, 1-phenyl-5-mercaptotetrazole), hardeners (e.g. formalin, glyoxal, mucochloric acid, 2- Hydroxy-4,6-dichloro-s-triazine), coating aids (for example, saponin, sodium lauryl sulfate, dodecylphenol polyethylene oxide ether, hexadecyltrimethylammonium bromide), etc. can be added. The silver halide emulsion produced in this way is coated on a support such as baryta paper, resin coated paper, cellulose acetate film, polyethylene terephthalate film, etc. by dipping method, air knife method, bead method, extrusion doctor method, double-sided coating method, etc. It is applied and dried by

[0028]

EXAMPLES Next, the present invention will be explained in detail with reference to examples, but the present invention is of course not limited to these.

Example 1 The following developing solutions (A) to (F) were prepared. Both pH
It was 10.65. Developer (A) Sodium sulfite
67g hydroquinone
23g1-phenyl-3-pyrazolidone
0.4g potassium hydroxide
11g sodium carbonate (monohydrate)
11g potassium bromide
Add 3.0g water
Let it be 1 liter. pH
10.65

Developing solution (B) 300 mg of (I-2) was added to developer (A).

Developing solution (C) 300 mg of (I-3) was added to developer (A).

Developer (D) 3 each of (I-2) and (II-2) was added to developer (A).
00mg added.

[0033] The following fixer was used. ammonium thiosulfate
200.0g sodium sulfate (anhydrous)
20.0g boric acid

8.0g ethylenediaminetetraacetic acid disodium
0.1g aluminum sulfate
15.0g sulfuric acid

2.0g glacial acetic acid
22.0g
add water
1.0l (adjust pH to 4.2)

Next, the developer (A) prepared in this way
The following experiments were conducted for ~(D). 22 liters of the developing solution was put into a roller conveyance type automatic developing machine, and a bright room film DCL-F manufactured by Mitsubishi Paper Mills Co., Ltd. was processed so that 20% of the area was blackened. Development temperature was 38℃, development time was 20℃.
Done in seconds, large paper size (20 inches x 24 inches)!
The developer was replenished at a rate of 100 ml each time one sheet was developed. In one day, 100 large sheets of film were processed for 5 hours. This treatment operation was continued for one week, and the sludge adhering to the film was evaluated as ◯, △, or ×. ○ marks are in good condition, △ marks are slightly dirty, ×
The marks get quite dirty.

Next, the prepared untreated developing solutions (A) to (
D) was left at 50° C. for one week to check its storage stability, and the film was processed with these developers to determine the degree of yellow fogging. Those with no abnormalities were marked with ○, those with a slight yellowish tinge were marked with △, and those with a distinct yellowish appearance were marked with ×. These judgments were made by stacking 10 transparent parts of the film. These results are shown in Table 3.

[0036]

[Table 3] [Table 3] Example 2 As shown in Table 4, using the exemplified compounds of chemical formulas 3 and 4, (
Developers E) to (L) were prepared. Addition amount is 30 each
It is 0 mg/l. The evaluation method is the same as in Example 1. These results are shown in Table 4.

[0035]

[Table 4]

As shown in Tables 3 and 4, it can be seen that the developer solution containing the exemplified compounds of Chemical Formulas 3 and 4 has good sludge prevention performance and good storage stability.

[0037]

Effects of the Invention According to the present invention, silver sludge generated in a developer containing a silver halide solvent such as sulfite can be very effectively prevented by using the compounds of chemical formulas 3 and 4 in combination, respectively. Moreover, storage stability can be improved.

Claims (1)

[Claims] 1. A developer for a silver halide photographic light-sensitive material, comprising at least one compound represented by the following chemical formula 1 and at least one compound represented by the following chemical formula 2. [Formula 1] In the formula, M represents a hydrogen atom, an alkali metal atom, or NH4, A represents an organic divalent group, and B represents -SO3 M
', -COOM', -SO2 NHR1, -CONH
R1 represents -OH, M' represents a hydrogen atom, an alkali metal atom or NH4, and R1 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. embedded image R2 and R3 represent an optionally substituted alkyl group or aryl group.