JPH06324437A - Developer composition for black and white silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To provide the stable developer compsn. for black and white silver halide photographic sensitive materials which does not generate silver staining and is excellent in rapid processability without impairing fixability. CONSTITUTION:The compd. expressed by the following formula is incorporated into the developer for black and white silver halide photographic sensitive materials. In the formula, R1 to R6 respectively denote hydrogen atoms, -SM1 groups, hydroxy groups, lower alkoxyl groups, -COOM2, groups, amino groups, or lower alkyl groups contg. -SO2M3 groups; at least one among R1 to R6 denote -SM1 groups. M1, M3, M3 respectively denote hydrogen atoms, alkaline metal atoms which may be the same or different.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel developer composition for black-and-white silver halide photographic light-sensitive material, and more particularly, a developer composition for black-and-white silver halide photographic light-sensitive material which does not cause silver stain even when subjected to rapid development processing. Regarding

[0002]

BACKGROUND OF THE INVENTION Black-and-white silver halide photographic light-sensitive materials are generally subjected to imagewise exposure, and then photographically processed by four processes including development, fixing, washing with water and drying. Most of the development processing is carried out with a developing solution containing a combination of hydroquinone and phenidone or methol, but since the development is carried out in an alkali, in order to prevent the oxidation of the developing agent and improve the storage stability, Contains sulfite. However, since this sulfite has a property of dissolving a silver salt, the silver salt is dissolved during the development process from the photographic light-sensitive material, and the silver salt dissolved in the developer is reduced to metallic silver to be deposited and exposed to light. It adheres to the surface of the material and causes silver stain. In particular, silver stain is a problem in high-temperature rapid processing using a carrier type automatic processor.

Further, when the replenishing amount of the developing solution is small with respect to the processing amount of the light-sensitive material, the precipitation concentration is relatively increased, which causes a serious problem. In order to solve this problem, a compound that can improve the storage stability without dissolving a silver salt has been studied, but it has not been found yet. On the other hand, research has also been conducted on means for trapping dissolved silver salts to prevent precipitation. For example, the search for silver sludge inhibitors has been widely conducted, see US Pat. No. 3,173,789.
1-phenyl-5-mercaptotetrazole derivatives, JP-A-52-36029 reports disulfide compounds, and JP-B-62-4702 reports 2-mercaptobenzimidazole sulfonic acid derivatives. However, in the method using these, the developing speed is lowered to be desensitized, or the developing solution is brought into the fixing solution in the next step to decrease the fixing speed, or the reaction is caused by long-term storage of the developing solution, It caused new problems such as the loss of action and effect.

[0004]

In order to solve the above problems, an object of the present invention is to provide a developer composition for black-and-white silver halide photographic light-sensitive material which does not cause silver stain and does not cause desensitization. To provide.

Another object of the present invention is to provide a developer composition for black-and-white silver halide photographic light-sensitive material which does not impair the fixability. Another object of the present invention is to provide a developer composition for black-and-white silver halide photographic light-sensitive materials which is excellent in rapid processability and is stable.

[0006]

The above object of the present invention is achieved by incorporating at least one of the compounds represented by the general formula [1] (Chemical Formula 1) into a developer for black and white silver halide photographic light-sensitive materials. To be done.

The present invention will be described in more detail below.

In the general formula [1], the lower alkyl group and lower alkoxy group represented by R _{1 to} R ₆ are groups each having 1 to 5 carbon atoms, and they may further have a substituent. Preferably, it is a group having 1 to 3 carbon atoms, and the amino group represented by R _{1 to} R ₆ represents a substituted or unsubstituted amino group, and a preferable substituent is a lower alkyl group. The ammonium group is a substituted or unsubstituted ammonium group, preferably an unsubstituted ammonium group.

R _{1 to} R ₆ are hydroxyl groups, --COO
It preferably contains M ₂ , an amino group, and a —SO ₃ M ₃ group.
At least one of R _{1 to} R ₆ is a —SM ₁ group.

The amount used is 10 per liter of developer.
^-5 to 10 ^-1 mol, and more preferably 10 ^-4 to 10 ^-2 . The pH of the developer is preferably 9.5 to 12.0, and the developer replenishment amount is 20
It is 0 ml / m ² or less, preferably 75 to 200 ml / m ² .

The processing time for Dry to Dry is 20 to 60 seconds, preferably 30 to 60 seconds.

Specific examples of the compound represented by the general formula [1] are shown below, but the invention is not limited thereto.

[0013]

[Chemical 2]

The compounds of the present invention are known compounds,
It is easily available.

The compound of the present invention has a function of trapping dissolved silver to prevent silver stain on the light-sensitive material, and has the effect of maintaining the silver stain preventive effect of the developing solution and exhibiting excellent long-term storage stability. Therefore, rapid development processing can be performed, and a reduction in fixing speed can be prevented.

The developing agents that can be used in the present invention include dihydroxybenzenes (for example, hydroquinone, chlorohydroquinone, promhydroquinone, 2,3-dichlorohydroquinone, methylhydroquinone, isopropylhydroquinone 2,5-dimethylhydroquinone, etc.), 3-pyrazolidones (eg 1-phenyl
-3-pyrazolidone, 1-phenyl-4-methyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-ethyl-3-virazolidone, 1-phenyl-5-methyl -
3-pyrazolidone), aminophenols (eg
o-aminophenol, p-aminophenol, N-methyl-o
-Aminophenol, N-methyl-p-aminophenol, 2,
4-diaminophenol etc.), pyrogallol, ascorbic acid, 1-aryl-3-pyrazolines (eg 1- (p-hydroxyphenyl) -3-aminopyrazoline, 1- (p-methylaminophenyl) -3-amino Pyrazoline, 1- (p-aminophenyl) -3-aminopyrazoline, 1- (p-amino-N-methylphenyl) -3-aminopyrazoline, etc.) can be used alone or in combination. However, it is preferable to use a combination of 3-pyrazolidones and dihydroxybenzenes or a combination of aminophenols and dihydroxybenzenes. The developing agent is usually preferably used in an amount of 0.01 to 1.4 mol / l.

In the present invention, examples of sulfites and metabisulfites used as preservatives include sodium sulfite, potassium sulfite, ammonium sulfite, and sodium metabisulfite. The sulfite is preferably 0.25 mol / l or more. It is particularly preferably 0.4 mol / l or more.

If necessary, the developer may contain an alkaline agent (sodium hydroxide, potassium hydroxide, etc.), a pH buffering agent (eg, carbonate, phosphate, borate, boric acid, acetic acid, citric acid, alkanol). Amines), solubilizers (eg polyethylene glycols, their esters, alkanolamines, etc.), sensitizers (eg nonionic surfactants containing polyoxyethylenes, quaternary ammonium compounds etc.), surfactants, Antifoaming agents, antifoggants (eg, silver bromide such as potassium bromide, sodium bromide, nitrobenzindazole, nitrobenzimidazole, benzotriazole, benzothiazole, tetrazoles, thiazoles, etc.), chelating agents (eg, Ethylenediaminetetraacetic acid or its alkali metal salts, nitrilo Acetates, such as polyphosphates), development accelerators (e.g. U.S. Pat. No. 2,304,025, JP-B-47-
The compounds described in JP-A-45541, etc.), a film hardening agent (eg, glutaraldehyde or its bisulfite adduct), or a defoaming agent can be added. The pH of the developer is preferably adjusted to 9.5-12.0.

The compound of the present invention is used in an activator processing solution containing a developing agent in a light-sensitive material, for example, an emulsion layer, and processing the light-sensitive material in an alkaline aqueous solution to perform development as a special form of development processing. Good. Such development processing is often used as one of the rapid processing methods for the light-sensitive material in combination with the silver salt stabilization processing with thiocyanate, and can be applied to such processing solutions. . In the case of such rapid processing, the effect of the present invention is particularly great.

As the fixing liquid, those having a generally used composition can be used. The fixer is generally an aqueous solution containing a fixer and others, and the pH is usually 3.8 to 5.8. As a fixing agent, sodium thiosulfate, potassium thiosulfate,
Use of thiosulfates such as ammonium thiosulfate, thiocyanates such as sodium thiocyanate, potassium thiocyanate and ammonium thiocyanate, as well as organic sulfur compounds capable of forming soluble stable silver complex salts, which are known as fixing agents. You can

A water-soluble aluminum salt acting as a hardening agent, for example, aluminum chloride, aluminum sulfate, potassium alum or the like can be added to the fixing solution.

If desired, the fixer contains a preservative (eg, sulfite, bisulfite), a pH buffer (eg, acetic acid), a pH adjuster (eg, sulfuric acid), and a chelating agent capable of softening water. And the like.

The developer may be a mixture of fixed components, an organic aqueous solution containing glycol or amine, or a viscous liquid with 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 black and white silver halide photographic light-sensitive material according to the present invention is preferably processed using an automatic processor.
At that time, the processing is performed while replenishing a fixed amount of developing solution proportional to the area of the photosensitive material. The development replenishment amount is 250 ml or less per 1 m ² in order to reduce the amount of waste liquid. It is preferably 75 ml or more and 200 ml or less per 1 m ² . 75 ml per 1 m ²
If the replenishment amount of the developing solution is less than the above, satisfactory photographic performance cannot be obtained due to desensitization, softening, and the like.

In the present invention, the total processing time (Dry to Dry) from when the leading edge of the film is inserted into the automatic developing machine to when it comes out of the drying zone when the processing is performed by using the automatic developing machine is demanded from the desire of shortening the developing time. It is preferably 20 to 60 seconds. The total processing time referred to here includes all process times required for processing a black and white silver halide photographic light-sensitive material, and specifically includes, for example, development, fixing, bleaching, washing with water, stabilization processing and drying necessary for processing. The time including all process times, that is, Dr
It's y to Dry time. If the total processing time is less than 20 seconds, satisfactory photographic performance cannot be obtained due to desensitization and softening. More preferably, the total processing time (Dry to Dry) is 30 to 60 seconds.

[0027]

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

Example 1 8 W / (m ² ·
After corona discharge with energy of (min), the antistatic liquid having the following constitution was applied at a rate of 30 m / min using a roll-fit coating pan and an air knife so as to have the following coating amount.

(Preparation of Support Having Conductive Layer) After corona discharge to 100 μm-thick polyethylene terephthalate subjected to subbing treatment, an antistatic liquid having the following constitution was applied at 70 m / min at the following coating amount. It was applied at high speed using a roll-fit coating pan and air knife.

Water-soluble conductive polymer P-6 0.6 g / m ² Hydrophobic polymer particles L-1 0.4 g / m ² Polyethylene oxide compound Ao-1 0.06 g / m ² Hardener E-8 0.2 g / m ² This was dried at 90 ° C. for 2 minutes and heat-treated at 140 ° C. for 90 seconds. A substrate was prepared by coating this conductive layer on one side.

[0031]

[Chemical 3]

(Preparation of silver halide emulsion) Silver chloroiodobromide (silver chloride 62 mol%, silver iodide 0.5 mol%) was prepared by the simultaneous mixing method.
Others were silver bromide) emulsions.

In the mixing step from the formation of 5% of the final reached average particle size to the final reached average particle size, potassium hexabromorhodiate and potassium hexachloroiridate are added in an amount of 8 × per mol of silver. 10 ⁻⁸ mol and 8 × 10 ⁻⁷ mol were added.

The obtained emulsion was desalted by a conventional flocculation method using a modified gelatin treated with phenyl isocyanate and then dispersed in gelatin to be used as an antifungal agent [A] or [B] below. And [C] are added and the average particle size is 0.30
An emulsion consisting of cubic monodisperse grains of 10 μm (coefficient of variation 10%) was obtained.

[0035]

[Chemical 4]

To this emulsion was added citric acid and sodium chloride and
After adding 1-phenyl-5-mercaptotetrazole, chloroauric acid and sodium thiosulfate were added and chemically aged at 60 ° C to reach maximum sensitivity, then 4-hydroxy-6-methyl-1,3,3
After ripening was stopped by adding 1 g of a, 7-tetrazaindene per 1 mol of silver, 600 mg of potassium bromide and 150 mg of a sensitizing dye having the following structure SD-1 were added per 1 mol of silver halide.

(Preparation of emulsion coating solution) To this emulsion, 4 g of hydroquinone per mol of silver halide, 15 g of polymer latex P1 having the following structure, 150 mg of inhibitor ST-1 and 2 g of 1N styrene-maleic acid polymer were used. Sodium hydroxide solution of 1.5 g of the following structure S-1 and saponin as a coating aid and 2,4-dichloro-6-hydroxy-1,3,5- as a hardening agent
The sodium salt of triazine was added.

(Preparation of Emulsion Protective Layer Coating Solution) For every 1 m ² , an aqueous solution containing 1.1 g of gelatin was added with 1 mg of formalin adduct of sodium bisulfite and 5.5 mg of 1-phenyl-4-hydroxymethyl-3-pyrazolidone. 15 mg each of monodispersed silica having an average particle size of 3 μm and an average particle size of 8 μm was added with the following structure S-2 as a coating aid and citric acid, and formalin was added as a hardening agent. Further, a fluorinated surfactant FA-33 was added so that the coating amount was 3 × 10 ^-6 mol / m ² .

(Preparation of coating solution for backing layer) An aqueous solution containing 2.3 g of gelatin per 1 m ² of 100 mg of the water-soluble dye compound III-1, 25 mg of III-3 and 100 m of III-3 described below.
g, polymer latex P-1 350 mg, styrene-maleic acid polymer 60 mg, colloidal silica 150 mg,
55 mg of a mixture of [A], [B] and [C], sodium dodecylbenzene sulfonate as a coating aid, glyoxal as a hardener and E-2 were added and stirred.

[0040]

[Chemical 5]

[0041]

[Chemical 6]

(Preparation of Backing Layer Protective Layer Coating Solution) 1
7m of S-2 was added to an aqueous solution containing 0.7g of gelatin per m ^2.
g, a dispersion of monodisperse polymethylmethacrylate having an average particle size of 5.5 μm, a mixture of [A], [B], and [C], and a styrene-maleic acid polymer are added and stirred, and glyoxal is further used as a hardening agent. And 2,4-dichloro-6-hydroxy-1,3,
The sodium salt of 5-triazine was added.

(Preparation of sample) 15 on one side of the polyethylene terephthalate film support having the above antistatic layer.
After corona discharge with an energy of W / (m ² · min), the backing layer coating solution and the backing layer protective film layer coating solution prepared as described above were applied to the side having the antistatic layer. Further, one side on the support was subjected to corona discharge with an energy of 15 W / (m ² · min), and then an emulsion layer and an emulsion protective film layer were coated. The emulsion layer was coated and dried so that the amount of silver was 4.0 mg / m ² and the amount of gelatin was 1.7 mg / m ² .

Then, using the following developing solution and fixing solution, development processing was carried out under the following conditions using a plate making automatic processor GQ.26SR (manufactured by Konica).

The film was processed without exposure.

<Processing Conditions> [Developer Formulation] Ethylenediaminetetraacetic acid disodium salt 2 g Diethylene glycol 25 g Potassium sulfite (55% W / V aqueous solution) 110 ml Potassium carbonate 55 g Hydroquinone 20 g 5-Methylbenzotriazole 200 mg General formula of the present invention [1 ] Or comparative compound (shown in Table 1) 1.0 × 10 ^-3 mol Potassium hydroxide Amount to bring the pH of the working solution to 10.5 Potassium bromide 5.0 g 1-Phenyl-3-pyrazolidone 750 mg Dissolve these in pure water Then, it was finished to 1 l and used.

[Fixing solution formulation] (Composition A) Ammonium thiosulfate (72.5% W / V aqueous solution) 230 ml Sodium sulfite 9.5 g Sodium acetate trihydrate 28 g Boric acid 6.7 g Sodium citrate dihydrate 2 g Acetic acid (90% W / W aqueous solution) Amount to adjust the pH of the used solution to 4.7 (Composition B) Pure water 17 ml Sulfuric acid (50% W / W aqueous solution) 2.5 g Aluminum sulfate (Al ₂ O ₃ equivalent content is 8.1% W / W aqueous solution) 21 g Fixing When the liquid was used, the above composition A and composition B were dissolved in this order in 500 ml of water, and the solution was made up to 1 l for use.

[Development Processing Conditions] Step Temperature Time Development 38 ° C. 12 seconds Fixing 35 ° C. 10 seconds Washing at room temperature 10 seconds Drying 50 ° C. 13 seconds Total 45 seconds Each step time includes a so-called wading conveyance time to the next step.

The replenisher using the same as the composition of the developer and fixer, the samples were 30 m ² performed while replenishing at the rate of developing 160 cc / m ² fixing 190 cc / m ^2. 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; rank 1 was the worst stain and rank 5 was the stain-free grade. When the rank is less than 3, it is in a practically unacceptable state.

Development speed: After exposure with a He-Ne laser for 10 ^-6 seconds, it was expressed as a relative sensitivity at the time of development processing under the above conditions.

Fixing speed: The time (seconds) during which the light-sensitive material sample became transparent with the fixing solution when 30 m ² was processed 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. Rank 3
If it is less than the above, it is not acceptable in practical use.

The results are shown in Table 1.

[0054]

[Table 1]

As is apparent from Table 1, in Tests 5 to 22 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.

[0056]

Industrial Applicability According to the present invention, it is possible to provide a developer composition capable of improving silver stain, having excellent storage stability of a developing solution, and not impairing fixability, and capable of rapid processing.

Claims (1)

[Claims] 1. A developer composition for black-and-white silver halide photographic light-sensitive material, which contains at least one compound represented by the following general formula [1]. [Chemical 1] (In the general formula [1], R _{1 to} R ₆ are each a hydrogen atom,
-SM ₁ group, hydroxyl group, lower alkoxy group, -CO
OM ₂ group, amino group, —SO ₃ M ₃ group or lower alkyl group, and at least one of R _{1 to} R ₆ represents a —SM ₁ group. M ₁ , M ₂ and M ₃ each represent a hydrogen atom, an alkali metal atom or an ammonium group, and may be the same or different. )