JPH0353244A - Developing solution for silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To prevent the contamination by silver sludge and the contamination of the rollers and belts of an automatic developing machine at the time of processing the photosensitive material by using the developing machine by incorporating a specific compd. into a developing soln. CONSTITUTION:The compd. expressed by formula I is incorporated into the developing soln. In formula I, A and B denote a mercapto group, hydroxyl group and hydroxyalkyl group, etc.; R1 and R2 denote hydrogen; -X-Y group; X denotes a bivalent group; Y denotes a carboxyl group, hydroxyl group. The amt. of this compd. to be added is in an about 0.005 to 5g range per 1l developing soln. The contamination by silver sludge and the contamination of the rollers and belts of the automatic developing machine are prevented in the case of processing of the photosensitive material by using the developing machine.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a method for developing silver halide photographic materials, and particularly to a developer used therein.

(Prior Art) It is well known that a developer used for developing silver halide photographic materials generally contains a sulfite salt for the purpose of improving 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.

When a photosensitive material is processed with a developer containing a compound that has a dissolving effect on silver halide, such as sulfite or thiosulfate, a large amount of silver complex is eluted into the developer, and the eluted silver complex is easily removed. It is reduced and accumulated as silver sludge. In particular, when photosensitive materials are continuously processed using automatic processors, silver sludge not only floats, but also adheres to rollers, belts, etc., and reflects light on the photosensitive materials, called roller streaks, called silver stains. As a result, stains caused by precipitated silver that appear yellow or brown-gold occur.

2-Merkab} as an agent to prevent silver sludge and liquid stains
-1. 3. 4-Thiadiazoles (British Patent No. 9)
No. 40169 BJI Honor), 2-Merkabuto-1.3.
4-oxadiazoles or 1-7 enyl-5-mercabutotetrazole (U.S. Pat. No. 13,173,789)
D. L. -6,8-dithiooctanoic acid (U.S. Patent No. 3,318,701), 0-mercabutobenzoic acid (British Patent No. 1144481 [Male
Cao), aliphatic mercaptocarboxylic acid (US special wr brother 3,
6 2 8, 9 5 5), L-thi 77"lidi 7-4--jJk bolic acid (J. Photogr. S
ci. , 13.233rl965)), disulfide compound C% 1987-36029), 2-penzoxazolethiol, 2-penzimidazolethiol (Photogr. Sci. Eng.. 20
, 220 (1976)), Acetylene Glycols C%lltJ No. 55-95947 Akira #IW), 2
-Mercaptopenzothiazole-5 sulfonic acid ← JP-A-56-72441 8) etc. are known.

However, when these compounds are used as sludge inhibitors in a developer having a dissolving action on silver halide, especially a developer containing a high concentration of sulfite (e.g. 0.2 mol/t or more), air The sludge prevention effect may be lost due to oxidation, the sludge prevention effect may be weak and a large amount must be used, it may have negative effects on photographic properties such as desensitization, softening, and development suppression, or it may be expensive.
There was a problem that it was difficult to say that it was completely satisfactory because it had an unpleasant odor.

(Problems to be Solved by the Invention) Therefore, an object of the present invention is to use a developing solution having a dissolving action on silver halide, particularly a stable developing solution containing a high concentration of &t salt, for use in an automatic developing machine. The purpose of the present invention is to provide a developing solution that prevents liquid stains caused by silver sludge and stains on the rollers and belts of a developing machine when processing photosensitive materials, and that can obtain photographic images with excellent finished quality and no silver stains. .

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.

(O Means for Solving the Problems) The above object of the present invention was achieved by containing a compound represented by the following general formula [I] in a developer for silver halide photographic light-sensitive materials.

In formula C, A and B are a mercabuto group and a hydroxy group. R
1 and 2 represent a hydrogen atom or a -X-Y group, and X is 2
Y represents a carboxyl group or a hydroxyl group. ) Specific examples of the compound represented by the general formula (1) are shown below. However, only A and B are shown.

These compounds are publicly known, for example,
Reference may be made to No. 05231 and No. 59-9661 of the same.

The proof of addition of the compound represented by the general formula CI) is as follows: developer solution 1
Approximately o. oos ~ approx. 52, good case < approx. 0.01 ~
The range is approximately 22.

The developer processing solution of this invention is a conventional developing agent for black and white photography, such as hydroquinone, alkylnohydroquinone (e.g. t-butylnohydroquinone, methylhydroquinone,
dimethylhydroquinone), catechol, pyrazole, chlorohydroquinone, dichlorohydroquinone, alkoxynohydroquinone (e.g. methoxy or ethoxynohydroquinone), aminone enol developing crude drugs (e.g. N-methyl-p-aminoneenol, 2,4-diaminophenol), Ascorbic acid developer bath, N-methyl-p-aminophenol sulfate, virazolones (e.g. 4-aminovirazolone), 3-virazolidone developing agents (e.g. 1-7enyl-3-virazolidone, 1-
Phenyl-4,4-dimethyl-3-birasolidone, 1-
7enyl-5-methyl-3-hira7” IJ don,
1-7enyl-4-methyl-3-virazolidone, 1.5
-di7enyl-3-virazolidone, 1-p-}lilu 3
-Vyrazolidone, 1-phenyl-2-acetyl 4.4
-dimethyl-3-pi5zo)done, 1-p-hydroxyphenyl-4,4-dimethyl-3-virazolidone, 1-(
Preferably, it is an alkaline water bath solution containing 2-benzothiazolyl)-3-virazolidone, 31-a7Fx-1-phenyl-3-virazolidone), etc. alone or in combination.

In particular, a combination of hydroquinone and 3-virazolidones or a combination of hydroquinone and aminophenols is useful for rapid treatment at Ooto.

However, f. which does not substantially contain a developing agent. 'fJ actipator type developer may be used.

The developer containing the compound represented by the general formula [1] used in the present invention exhibits a remarkable sludge-preventing effect especially when it contains polysulfite ion gold. At this time, specifically, the developing solution contains 0.1 mol or more, preferably 0.2 mol to 1.0 mol, of sulfite ions per ton of developer. As a sulfite that gives sulfite ions,
Specifically, alkali metal sulfites such as sodium sulfite, potassium sulfite, and potassium metabisulfite can be used.

The silver sludge generated in the developer tends to deposit on the rollers and belts in the developing machine, and the silver sludge that adheres to the rollers and belts tends to stain the photosensitive material. Therefore, this method is particularly effective when processing with an automatic maintenance gutter.

As such an automatic developing machine, for example, a one-type facing roller type (
For example, P.A. KO company Pakorol Super 02
4-2, Fuji Photo Film Co., Ltd. G-14L%PG-24
SQ, RN, etc.), staggered roller one type (e.g. East
man Kodak Kodalith Processes
sor, M6 Processor, g±Photo Film Co., Ltd. RU), belt conveyance method (e.g. Log-
E-tronics LD-241D etc.) 0)
Ilb (dupont company coronalith
24L, etc.) There is an egg.

The developer may contain other buffering agents (e.g., carbonates, boric acid, borates, alkanolamines), alkaline agents (
(e.g. hydroxides, carbonates), solvent aids (e.g. polyethylene glycols, esters thereof), p}1 regulators (e.g. organic acids such as acetic acid), sensitizers (e.g.
Quaternary ammonium salts), development accelerators, interfacial activators, hardening agents, etc. can be added.

The developer further contains antifoggants (for example, penzotriazoles such as 5-1 ditroindazole, 5-nitropenzimidazole, 5-methyl-benzotriazole, 5-1 ditrobenzotriazole, penzothiazole, l).
Tetrazole such as -7enyl-5-mercabutotetetrazole, thiazole or British W license 1t, 2ac+,
2ss), chelating agents (e.g., ethylenediaminetetraacetic acid, alkali metal salts thereof,
Polyphosphate, nitriloacetate) f: Can be contained.

The p value of the developer prepared in this way is selected to be sufficient to provide the desired density and contrast.
Desirably, it is in the range of about 8-12.

Processing temperature and time are interrelated and determined in relation to the total processing time, generally at about 20-50°C.
0 seconds to 3 minutes, but in the case of high temperature rapid processing, it takes about 30 seconds to 3 minutes.
The temperature is 60°C.

In the present invention, the components of the developing solution may contain any necessary components at the time of use, and the form before processing before preparing the working solution for use may be, for example, a mixture of solid components, a concentrate, or a solution. , emulsion or suspension.

For example, it may be a developer that is divided into several parts and made into the same form or different forms. good.

The preparation can be dissolved in water or diluted with water to prepare a working solution, if necessary.

On the other hand, the fixing solution is an aqueous solution containing thiosulfate and a water-bathable aluminum compound, and preferably has a pH of about 3.8 to 5.5.
(20°C). In the method of the present invention, a stopping step may be provided after development, but the stopping step is generally omitted in roller conveyance type automatic developing machines. Therefore, the developer is brought into the fixer K, and the pH of the fixer increases. Therefore, the pH of the constant N group is about 3.8 to 5.0.
It is desirable to adjust the temperature to (20°C).

The fixing agent is a thiosulfate salt such as ammonium thiosulfate or sodium thiosulfate, and ammonium thiosulfate is particularly preferred from the viewpoint of fixing speed. The amount of the fixing agent used can be changed as appropriate, and is generally about 0.1 to 5 mol/t. Water-soluble aluminum salt, which mainly acts as a hardening agent in the fixing solution, generally improves the hardness of the acidic hardening fixer. It is a compound known as a film agent, such as aluminum chloride, aluminum sulfate, and potassium alum.

According to the method of the invention, the developed and fixed photographic material is washed and dried. Washing with water is carried out to almost completely remove the silver salt dissolved during fixing, and is preferably carried out at about 5 to 50° C. for 10 seconds to 3 minutes. Drying is carried out at approximately 30-80°C,
Although the drying time can be changed as appropriate depending on the surrounding conditions, it is usually about 5 seconds to 3 minutes and 30 seconds.

The photosensitive material processed by the method of the present invention may be used for any purpose, but preferably black and white photosensitive materials, such as X-ray photosensitive materials, micro photosensitive materials, Anrith photosensitive materials, and phototypesetting photosensitive materials. Applicable to photosensitive materials, general amateur black and white photosensitive materials, etc. The silver halide in the photosensitive layer is silver chloride, silver chloride,
These include silver chloroiodobromide, silver oxide, and silver iodobromide. The photosensitive material used in the present invention may be of either negative type or 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, if necessary, pack layer, anti-halation layer, etc.
It can have an intermediate layer and a top layer (eg, a protective layer).

Silver halide emulsions are silver halide emulsions dispersed in hydrophilic colloids such as gelatin, modified gelatin, colloidal albumin, casein, carboxymethylcellulose, hydroxyethylcellulose, alginate, polyvinyl alcohol, polyvinylpyrrolidone, or mixtures thereof. This is what I did. Silver halide emulsions are commonly used in the industry. A water-soluble silver salt (e.g., silver nitrate) and a bathable halide are mixed in the presence of water and a hydrophilic colloid using known methods (e.g., single-jet method, double-jet method, controlled-jet method, etc.). It is produced through physical ripening and chemical ripening such as gold sensitization and/or sulfur sensitization. Silver halide emulsions may contain spectral sensitizers (e.g. cyanine dyes, merocyanine dyes or mixtures thereof), stabilizers (e.g.
-Hydroxy-6-methyl-1. 3. 3a, 7-
tetrazaindene), sensitizers (e.g., U.S. Pat.
619,198), anti-capri agents (e.g., t}f, pen/-} IJ azole, 5-nitrobenzydazole, polyethylene oxide),
Hardeners (e.g. formalin, glyoxal, mucochloric acid, 2-hydroxy-4,6-dichloro-S-triazine), coating aids (e.g. sabonin, sodium lauryl sulfate, dodecylphenol polyethylene oxide ether, hexadecyl trimethyl Ammonium bromide) etc. can be added. The silver halide emulsion produced in this manner is coated on a support such as Paraita paper, resin-coated paper, cellulose acetate film, or polyethylene terephthalate film using the dihupping method, air knife method, pead method, extrusion doctor method, double-sided coating method, etc. It is coated [dry] by etc.

(Example) Next, the present invention will be explained in detail by giving examples, but of course it is not limited to these.

Example 1 The following developing solutions (A) to (F) were prepared. Both pH
It was 10.65.

Development (A) Development (B) Exemplary compound (1) k500η was added to developer (A).

Developer (C) Exemplified compound (2) was added to developer (A) in an amount of 500η.

Developer solution CD) 500η of exemplified compound (6) was added to developer (A).

Phenomenon ゛63ξ(E) As a comparative compound, in the general formula [I], A=8H, B=N
H C 6H 5 compound fr. Added 500η.

Development i (F) As a comparative compound, A=SH, B=N(
Added 5009 of C2H5)2 compound.

1. The following fixer was used.

Ammonium thiosulfate 200. Of Sodium Sulfite (Anhydrous) 20. Boric acid
8.02 Ethylenediaminetetraacetic acid disodium 0.12
Aluminum sulfate 15. Ofsulfuric acid
2, of glacial acetic acid 22. Add water 1. Ot(p}1 is adjusted to 4.2) Next, the following experiments were conducted on the developers (A) to (F) prepared in this manner.

Currently 13! Liquid 221 was put into a roller conveyance type automatic developing machine, and silver chlorobromide (silver chloride 5
0 mol%) black and white photographic film with emulsion layer gold (@ amount 4
, 51/n? ) After exposing the f image, it was fed into the above-mentioned developing machine and developed. The development temperature was 38℃, the development time was 20 seconds, and the large paper size (20 inches x 24 inches) 1
Each time a sheet was developed, the developer was automatically replenished at a rate of 100.

I developed 100 sheets of paper-sized film in one day for five hours, and continued this process for a week.

In developing i (liquid A) to which the compound of the general formula CD of the present invention is not added, while developing the first 100 films,
The developing solution, which was initially colorless and transparent, soon began to dissolve, and deposits of silver sludge began to be observed.

Striped silver stains began to appear on the film. During the one-week treatment, this stain became very bad.

There was severe turbidity and silver sludge deposits in the developer, and there was also severe silver staining on the rollers of the automatic processor. The silver stains on the film became more severe as the number of treatments increased.

Damage that appeared to have been caused by contact with the sludge adhering to the rollers was also observed on the surface of the encased film.

In developer solutions [E] and [F] containing comparative compound gold,
Almost no silver sludge was observed even after one week of development, but immediately after the developer was prepared,
Compared to the characteristics, there was severe desensitization and softening, and a decrease in the maximum density.

On the other hand, developing solutions [B] and [C
] and [D], no silver sludge was observed even after one week of development, and transparency was maintained.

Furthermore, when compared with the photographic properties using developer [A], there was no inferiority in the photographic properties, and the photographic properties were good.

Example 2 The following developer solution CP) was prepared.

Developer [P] Add 30% each of Exemplified Compounds (1) to (10) to Developer [P].
10 types of developer with 0my added.

A test was conducted according to the conditions of Example 1, except that a black and white photographic film (silver i3.!M/m'') having a silver chloride emulsion layer on polyethylene terephthalate was used.

Although significant silver sludge was generated in the developer [Pl], no silver sludge was observed in any of the developers [Q] to [Z], and the photographic properties showed no abnormality.

(Effects of the Invention) The present invention improves the photographic properties of silver sludge produced in a developer containing a silver halide solvent such as sulfite by using a mercab compound of the general formula [I]. li - can prevent very good fertility without causing any damage.

Claims (1)

[Scope of Claims] 1. A developer for silver halide photographic materials, which contains a compound represented by the following general formula [I]. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, A and B are mercapto group, hydroxyl group,
Represents a hydroxyalkyl group, ▲ mathematical formula, chemical formula, table, etc. ▼ group. R_1 and R_2 are hydrogen atoms, -X
-Y group, where X is a divalent group and Y is a carboxyl group or a hydroxyl group. )