JPH0619066A - Method for photographic development - Google Patents

Abstract

PURPOSE:To conduct development without silver contamination by using a developer contg. a specified carboxylic acid derivative. CONSTITUTION:A developer contg. at least one between the carboxylic acid derivatives of sulfonated 2-mercaptobenzothiazole or 2-mercaptobenzimidazole is used. In this case, the six-membered ring of the derivative is replaced by at least one sulfonic group, and the sulfonic group or the carboxylic group may contain an alkali metal atom or an ammonium group. The dissolved silver is trapped by such a compd. to prevent the contamination of a photosensitive material with silver, the developer is not contaminated with silver for a long time, and the developer is excellently preserved for a long period. Accordingly, rapid development is performed, and the fixing rate is not lowered.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photographic processing method using a developing solution containing a novel acid, and in particular, silver stain is not generated even when the developing processing is carried out using a developing solution containing sulfite. The present invention relates to a photographic processing method.

[0002]

BACKGROUND OF THE INVENTION Black and white silver halide photographic light-sensitive materials are generally subjected to imagewise exposure, followed by photographic processing by four processes including development, fixing, washing with water and drying. Most of the development processing is so-called P which is a combination of hydroquinone and phenidone (meth).
Although it is processed with a Q (MQ) developing solution, since the development is carried out in an alkaline solution, a sulfite is contained in order to prevent oxidation of the developing agent and improve the storage stability. However, since this sulfite has a property of dissolving a silver salt, it dissolves the silver salt during the development processing, and the silver salt dissolved in the developer is reduced by the developing agent to form fine metallic silver on the photosensitive material. Will be deposited on the surface and cause silver stains. In particular, silver stain is a problem in high-temperature rapid processing using a carrier type automatic processor. Further, when the replenishment amount of the developing solution is small with respect to the processing amount of the light-sensitive material, the precipitation concentration becomes relatively high and the problem becomes serious.
In order to solve this problem, research has been conducted on a compound capable of improving the preservability without dissolving a silver salt, but the present situation has not been found yet. On the other hand, research has also been conducted on means capable of trapping dissolved silver salts to prevent precipitation. For example, the search for a silver sludge inhibitor has been widely conducted, and US Pat. No. 3,173,789 discloses 1-phenyl-5-mercaptotetrazole, and JP-A-52-36029 discloses disulfide compounds. No. 2 in the specification of 62-4703
-For mercaptobenzimidazole sulfonic acid,
In Japanese Patent Publication No. 62702/1987, 2-mercaptobenzothiazolesulfonic acid is reported. However, in the method using these, the developing speed is decreased, the fixing solution is brought into the fixing solution in the next step to decrease the fixing speed, and the compound reacts with the long-term storage of the developing solution to cause the action. It caused new problems such as the loss of effectiveness.

[0003]

SUMMARY OF THE INVENTION The present invention has been made to solve the above problems, and an object of the present invention is to provide a development processing method which does not cause silver stain. Another object of the present invention is to provide a development processing method which does not impair the fixability. Another object of the present invention is to provide a development processing method excellent in rapid processing property. Still another object of the present invention is to provide a development processing method for performing processing using a stable developing solution.

[0004]

The above object of the present invention is to process by using a developing solution containing at least one sulfonated 2-mercaptobenzothiazole or 2-mercaptobenzimidazole carboxylic acid derivative. It is achieved by a characteristic method of developing a black and white silver halide photographic light-sensitive material.

The present invention will be described in more detail below.

The developer used in the present invention contains at least one of sulfonated 2-mercaptobenzothiazole or 2-mercaptobenzimidazole carboxylic acid derivatives (hereinafter sometimes referred to as "the compound of the present invention").
Contains one.

In the present invention, the 6-membered ring of the carboxylic acid derivative of sulfonated 2-mercaptobenzothiazole or 2-mercaptobenzimidazole is substituted with at least one sulfonic acid group, and the sulfonic acid group or carboxylic acid group is It may contain a salt of an alkali metal atom or an ammonium group.

As the sulfonated carboxylic acid derivative of 2-mercaptobenzothiazole, a compound represented by the following general formula (I) is preferably used.

[0009]

[Chemical 1] In the formula, X is a hydrogen atom or a substituted or unsubstituted carbon atom 1
4 represents a lower alkyl group or a sulfonic acid group,
Represents a divalent linking group having 1 to 6 carbon atoms. M ₁ represents a hydrogen atom, an alkali metal atom or an ammonium group. Preferred alkali metal atoms in the present invention include sodium or potassium.

Specific examples of the carboxylic acid derivative of 2-mercaptobenzothiazole preferably used in the present invention are shown below, but the present invention is not limited thereto. Specific examples: (1) 3- (2- (5-sulfonic acid benzothiazolylthio)) propionic acid (2) 3- (2- (6-sulfonic acid benzothiazolylthio)) propionic acid (3) 3- (2- (5-Sulfonic acid-6-methylbenzothiazolylthio)) propionic acid (4) 3- (2- (5,7-disulfonic acid benzothiazolylthio)) propionic acid (5) 3- (2 -(5-Methyl-7-sulfonic acid benzothiazolylthio)) propionic acid (6) 3- (2- (5-sulfonic acid benzothiazolylthio)) acetic acid (7) 3- (2- (6-sulfone Acid benzothiazolylthio) acetic acid (8) 3- (2- (5-sulfonic acid-6-methylbenzothiazolylthio)) acetic acid (9) 3- (2- (5,7-disulfonic acid benzothiazolyl) (Luthio)) acetic acid (10) 3- (2- (5-me Lu-7-sulfonic acid benzothiazolylthio)) acetic acid (11) 3- (2- (5-sodium benzothiazolylthio) sodium propionate (12) 3- (2- (5-potassium sulfonate) Benzothiazolylthio)) potassium propionate (13) 3- (2- (6-ammonium ammonium benzothiazolylthio)) ammonium propionate

As the sulfonated 2-mercaptobenzimidazole carboxylic acid derivative, a compound represented by the following general formula (II) is preferably used.

[0012]

[Chemical 2] In the formula, X is a hydrogen atom or a substituted or unsubstituted carbon atom 1
4 represents a lower alkyl group or a sulfonic acid group,
Represents a divalent linking group having 1 to 6 carbon atoms. M ₂ represents a hydrogen atom, an alkali metal atom or an ammonium group. As the alkali metal atom, M in the general formula (I) is used.
_{The same as the one} shown in ₁ .

Specific examples of the carboxylic acid derivative of 2-mercaptobenzimidazole preferably used in the present invention are shown below, but the present invention is not limited thereto. Specific examples: (14) 3- (2- (5-sulfonic acid benzimidazolethio)) propionic acid (15) 3- (2- (6-sulfonic acid benzimidazolethio)) propionic acid (16) 3- (2 -(5-Sulfonic acid-6-methylbenzimidazolethio)) propionic acid (17) 3- (2- (5,7-disulfonic acid benzimidazolethio)) propionic acid (18) 3- (2- (5- Methyl-7-sulfonic acid benzimidazole thio)) propionic acid (19) 3- (2- (5-methyl-7-sulfonic acid benzimidazole thio)) acetic acid (20) 3- (2- (5-sodium sodium sulfonate) Benzimidazolethio)) sodium propionate (21) 3- (2- (5-potassium sulfonate potassium benzimidazolethio)) propionate (22) 3- (2- (6-sulfo Ammonium benzimidazole thio)) ammonium propionate

The amount of the compound of the present invention used is preferably 10 ^-5 to 10 ^-1 mol, more preferably 10 ^-4 to 10 ^-2 mol, per liter of the developing solution.

The compounds according to the invention are, for example, Teppema and S
The Journal of the American Chemical Society, reported by ebrella.
It can be easily obtained by sulfonation of a precursor synthesized according to the description of American Chemical Society 49, 1748 (1927).

The compound of the present invention has a function of trapping dissolved silver to prevent the generation of silver stains on the light-sensitive material, sustains the silver stain effect of the developer, and exhibits excellent long-term storage stability. Therefore, rapid development processing can be performed, and a reduction in fixing speed can be prevented. This is considered to be largely influenced by the properties of the compound of the present invention.
In the present invention, the effect of the present invention can be further enhanced by using a known mercapto compound in combination with the compound of the present invention.

In the present invention, the developing agent for the black and white developer is
Hydroquinone and its derivatives, metol and its derivatives,
Alternatively, it is used in combination with phenidone and its derivative. It is particularly useful to use a combination of hydroquinone and a phenidone derivative. As the antioxidant of the developing solution, for example, sulfites such as sodium sulfite, potassium sulfite, potassium metabisulfite and the like can be appropriately used. Sulfite ion is preferable when it is used in an amount of 0.25 mol / liter or more because the antioxidant effect is remarkably exhibited.

The developer contains a water softening agent such as ethylenediaminetetraacetic acid or nitriloacetic acid, potassium bromide or sodium chloride as an inorganic fog inhibitor, or benzotriazoles or benzimidazoles which are organic fog inhibitors. Etc. can be used. Further, glycols such as diethylene glycol and triethylene glycol and amines such as diethanolamine and triethanolamine can be used. Examples of the alkaline agent used in the developer include sodium hydroxide and potassium hydroxide, but the present invention is not limited thereto.

The developing solution may be a mixture of solid components, an organic aqueous solution containing glycol or amine, or a viscous liquid having a high viscosity in a semi-kneaded state. Further, it may be diluted at the time of use, or may be used as it is.

In the development processing of the present invention, the development temperature is
It can be set to a normal temperature range of 20-30 ° C,
It can also be set to a high temperature treatment range of 30 to 40 ° C. The processing time can be set in the normal range of 45 to 90 seconds or in the rapid processing range of 5 to 45 seconds.

The developing solution used in the present invention can be applied to a silver halide photographic light-sensitive material for printing light-sensitive materials or medical use. Here, an example of application to a silver halide photographic light-sensitive material for a printing light-sensitive material is given, but the present invention is not limited thereto.

The silver halide used in the silver halide photographic light-sensitive material is AgBr, AgCl, AgClB.
Any of r, AgClBrI, AgBrI, AgClBrI and the like can be mentioned. The silver halide can be sensitized with a noble metal salt such as a sulfur compound or a gold salt. Further, it is possible to add performance according to the application by using a doping technique. For example, the contrast may be increased with a rhodium salt or the like, or the high illuminance sensitivity may be increased with an iridium salt or the like. Further, reduction sensitization can be performed, and these methods can be combined to perform sensitization.

A silver halide photographic light-sensitive material can be formed by coating an emulsion prepared by dispersing the above silver halide in a hydrophilic colloid medium, for example, gelatin on a polyethylene terephthalate or triacetyl cellulose support. it can.

As the gelatin crosslinking agent, aldehydes such as glyoxal and mucochloric acid, cyanuric acid, aziridine or vinyl sulfonic acid can be used.

Other compounds such as antihalation dyes, safelight improving dyes, sensitizing dyes, antifoggants, matting agents, antistatic agents, and development regulators are appropriately added to the silver halide photographic light-sensitive material depending on the application and performance. Can be included.

[0026]

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

(Preparation of Photosensitive Material) For example, JP-A-63-23003
A bright room light-sensitive material sample for printing was prepared according to the specification of Japanese Patent Publication No. 5. An emulsion layer containing silver halide grains having an average grain size of 0.13 μm and AgCl ₉₉ Br ₁ and a non-photosensitive protective layer were coated on the front side of a support having antihalation on the back side. However, the emulsion layer should have a gelatin coverage of 2 g / m ² , the latex coverage should be 1.0 g / m ² , and the silver coverage should be 3.0 g / m ^2, and the emulsion protective layer should have a gelatin coverage. 1.0 g / m ² , the amount of latex applied was 0.5 g / m ² , and the dye for improving safelight property was 0.3 g / m ² so as to be applied. Cyanuric acid was used as a crosslinking agent for gelatin.

(Processing) The prepared photosensitive material sample was developed, fixed, washed with water and dried. As standard processing conditions, developing temperature is 38 ° C, developing time is 10 seconds, fixing temperature is 34 ° C,
The washing temperature was set to 25 ° C and the drying temperature was set to 40 ° C. As the developing solution, the compounds shown in Table 1 were added to the developing solution having the following composition.

Developer composition Ethylenediaminetetraacetic acid sodium salt 1 g Sodium sulfite 60 g Hydroquinone 20 g 1-Phenyl-3-pyrazolidone 0.5 g Potassium carbonate 38 g Potassium bromide 3 g 5-Methylbenzotriazole 0.5 g Compound (Table 1 6 × 10 ^-4 mol Water containing 10% diethylene glycol is added to make 1 liter. The pH was adjusted to 10.8 with sodium hydroxide.

(Evaluation) The resulting photosensitive material samples were evaluated for silver stain and storability, and the developing speed and fixing speed were measured.

Silver stain (development stain): Development tank capacity is 5
A 30 m ² film was processed using a liter roller transport automatic processor. 12 ml per 0.1 m ² of film for processing
Was carried out while replenishing each of the developer and 16 ml of the fixer. In order to examine the presence or absence of silver stain after the treatment, a 3.5 × 12 cm film piece was treated without being exposed and the stain on the film surface was visually observed. The development stain was evaluated on a scale of 5; the worst stain was ranked 1 and the stain-free spot was ranked 5.

Development speed: Expressed as relative sensitivity at a development time of 10 seconds. Minus means delay.

Fixing speed: The time (seconds) during which the light-sensitive material sample became transparent with the fixing solution after processing 30 m ² was measured and expressed as a relative speed.

Storability: The prepared developing solution was packed in a polyethylene packaging material and heat-treated at 60 ° C. for 20 days. After heat treatment,
A silver stain test was performed and a 5-grade evaluation was performed. The most severe stain was ranked 1 and the one without stain was ranked 5. The closer to rank 5, it means that the effect of preventing silver stain is not lost even when the developer is heated.

The results are shown in Table 1.

[0036]

[Table 1] Comparative compound A: 1-phenyl-5-mercaptotetrazole Comparative compound B: 2-mercaptobenzimidazole-5
-Sulfonic acid comparative compound C: 2-mercaptobenzthiazole-5-
Sulfonic acid Comparative compound D: Bisphenylacetic acid-2-disulfide

As is apparent from Table 1, in Tests 6 to 14 using the developer containing the compound of the present invention, there was almost no development stain, the developing rate and the fixing rate were not lowered, and the developing solution was stored. It was found that the property is also good.

[0038]

As described in detail above, according to the present invention, it is possible to provide a photographic development method capable of improving silver stain, being excellent in storage stability of a developing solution, and not impairing fixing property, and being capable of rapid processing. .

Claims (2)

[Claims] 1. A black-and-white silver halide photographic light-sensitive material, which is processed by using a developer containing at least one sulfonated 2-mercaptobenzothiazole or 2-mercaptobenzimidazole carboxylic acid derivative. Development processing method. 2. The sulfonated 2-mercaptobenzothiazole or 2-mercaptobenzimidazole carboxylic acid derivative according to claim 1, wherein at least one of the substituents of the 6-membered ring is a sulfonic acid group. The method for developing a black and white silver halide photographic light-sensitive material according to claim 1, wherein the group or the carboxylic acid group is a carboxylic acid derivative containing a salt of an alkali metal atom or an ammonium group.