JP2920438B2 - Photographic processing agents - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel processing agent for a silver halide photographic light-sensitive material.

[0002]

2. Description of the Related Art Conventionally, a processing agent for a silver halide photographic light-sensitive material has been used in the form of a liquid or a powder. In the case of a liquid, it is used as it is or after being mixed with water at an arbitrary ratio. In the case of powder, it is used after dissolving it in water.

[0003] However, in the case of a liquid preparation, although the dissolving method is simple, since it contains water in advance, both its volume and weight are large, and there are safety problems such as transportation cost and liquid leakage. Also, when handling a large amount, the weight is burdensome for the user. On the other hand, in the case of the powder, the powder is easily scattered at the time of adjustment, although the compact is significantly superior to the liquid, which is a problem in the working environment.

[0004] In addition, both liquids and powders remain in the packaging material after the preparation of the liquids or powders, which poses a problem of environmental pollution at the time of disposal.

[0005] As a method for solving these problems, a method of granulating or tableting a treating agent has been studied in the art.

[0006] As a general method for granulation or tablet production, starch, polyvinyl alcohol, cellulose, gelatin, etc. are used to maintain the strength of granules or tablets. Are uniformly mixed, and then granulated by a method such as an extrusion granulation method or a mixing stirring granulation method, or formed into a tablet by pressure molding. After that, residual moisture is removed through a drying process to obtain a final product.

However, in a photographic processing agent, particularly a developer, the residual water greatly affects the storage stability, so that a particle forming method using water is not preferable. Although it is possible to reduce the amount of residual moisture by drying conditions, the strength of granules or tablets is degraded and powder is generated by destruction by vibration during transportation,
The same problems as dusts occur, and above all, the production cost increases significantly. In conventional granulation technology, it is common to mix a hydrophilic binder with water or a lower alcohol and add it to the powder to perform granulation, especially for photographic chemicals that have a large effect of moisture. A measure was desired.

[0008]

SUMMARY OF THE INVENTION In view of the above-mentioned problems, it is an object of the present invention to provide a method for dispersing powder in a liquid preparation and remaining powder in a waste packaging material while maintaining compactness of a powder treating agent. Reduce
It is an object of the present invention to provide a photographic processing agent which is excellent in environmental suitability, low in production cost and extremely excellent in storage stability.

[0009]

The object of the present invention is that the melting point is 30 ° C. or more,
A water-soluble or alkali-soluble polymer of 100 ° C or lower is heated and dissolved, and uniformly mixed in a powder mixture of components of a photographic processing agent, then granulated or tablet-formed, and then manufactured without passing through a drying process. This is achieved by a photographic processing agent.

Hereinafter, the present invention will be described specifically.

In the present invention, as described above, the water content in the granulated material can be greatly reduced only by cooling without passing through the drying step by granulating the photographic processing agent, so that the production cost is low and the storage is low. It is possible to produce granules having excellent properties.

The water-soluble or alkali-soluble polymer used in the present invention includes polyalkylene glycols such as polyethylene glycol, polyvinyl alcohol, and the like.
Polyvinylpyrrolidone, polyoxyethylene alkyl ethers such as polyoxyethylene cetyl ether and polyoxyethylene stearyl ether, polyoxyethylene alkyl phenol ethers such as polyoxyethylene octyl phenol ether and polyoxyethylene nonyl phenol ether or Japanese Patent Application No. 2-203165. It can be used by selecting from water-soluble binders.
The amount of the soluble polymer used in the present invention depends on the properties of the polymer to be used and the solubility and strength of the required granules or tablets (hereinafter referred to as granules). 1 to 50% by weight, preferably 5 to 30% by weight, based on the total amount of

The water-soluble polymer used is preferably solid at room temperature, and more preferably has a melting point of 30 ° C. to 60 ° C.

The granulation method applied in the present invention includes rolling granulation, extrusion granulation, compression granulation, pulverization granulation,
A stirring granulation method, a spray drying method, a solution coagulation method and the like can be used, but an extrusion granulation method and a compression granulation method are particularly preferable.

The particle size and shape of the granulated material suitable for the present invention vary depending on the desired properties. Generally, however, the solubility desired for the photographic processing agent and the amount of the residual powder in the waste packaging material after preparation are adjusted. Or, considering the durability against destruction of the granulated material due to vibration during transportation, in the case of granules, the particle size is about 0.1 mm to 10 mm,
It is preferably about 0.5 mm to 5 mm, and the shape is cylindrical, spherical, cubic, rectangular, or the like, and more preferably spherical or cylindrical. In the case of tablets, the diameter also varies depending on the desired properties, but a diameter of about 5 mm to 5 cm is preferable. When it is desired to improve the solubility, a plate-shaped tablet having a reduced tablet thickness, a tablet having a further reduced central portion of the plate-shaped tablet, a hollow donut-shaped tablet, and the like are also useful.
Conversely, the diameter may be further increased for the purpose of slow dissolution, and can be adjusted arbitrarily.

The surface state (smooth, porous, etc.) may be changed to control the solubility.

A plurality of granules can be formed in a plurality of shapes in order to impart different solubilities to the plurality of granules or match the solubilities of materials having different solubilities. Further, multilayer granules having different compositions on the surface and inside may be used.

The photographic processing agent used in the present invention is not particularly limited, and any known photographic processing agent can be applied.

[0019]

The present invention will be described in further detail with reference to specific examples.

<< Preparation of Photographic Material for Evaluation >> [Preparation Method of Emulsion (A)] A silver chlorobromide emulsion was prepared using the following solutions A, B and C.

<Solution A> Ossein gelatin 17g Polyisopropylene-polyethylene oxydisuccinate sodium salt 10% aqueous ethanol 5ml Distilled water 1280ml <Solution B> Silver nitrate 170g Distilled water 410ml <Solution C> Sodium chloride 45.0g Bromide Potassium 27.4 g Rhodium trichloride trihydrate 28 μg Polyisopropylene oxydisuccinate sodium salt 10% ethanol solution 3 ml Ossein gelatin 11 g Distilled water 407 ml After keeping solution A at 40 ° C, chlorinated so that the EAg value becomes 160 mV. Sodium was added.

Next, using a mixing stirrer described in JP-A-57-92523 and JP-A-57-92524, Solution B and Solution C were added by a double jet method. The addition flow rate is gradually increased so that the addition flow rate is proportional to the vertical surface area of the generated silver halide.
The addition was performed while keeping the g value constant. The EAg value was changed from 160 mV to 120 mV using a 3 ml / l aqueous sodium chloride solution 5 minutes after the start of the addition, and was maintained until the mixing was completed. To keep the EAg value constant, the EAg value was controlled using a 3 mol / l aqueous sodium chloride solution.

For the measurement of the EAg value, a metal silver electrode and a double junction type saturated Ag / AgCl reference electrode were used (the structure of the electrode was a double junction disclosed in Japanese Patent Application Laid-Open No. 57-197534). ). During addition, the emulsion was sampled, and it was confirmed by an electron microscope that no new grains were generated in the system.

During the addition, the system was controlled with a 3% aqueous solution of nitric acid so as to keep the pH of the system constant at 3.0. After the addition of the liquids B and C, the emulsion is aged for 10 minutes by Ostwald ripening, then desalted and washed with a conventional method, and then an aqueous solution of ossein gelatin is used.
Add 600 ml (containing 30 g of ossein gelatin) at 55 ° C / 30
After dispersion by stirring for minutes, the mixture was adjusted to 750 ml.

Emulsion (A) is subjected to gold-sulfur sensitization, and sensitizing dye A is added per mole of silver halide contained in the emulsion.
300 mg 4-hydroxy-6-methyl-1,3,3 as stabilizer
a, 7-Tetrazaindene was added, and sensitizing dye B was added in an amount of 100 mg per mol of silver halide contained in the emulsion.

[0026]

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Next, 800 mg of the following compound C was added per mol of silver halide, 300 mg of sodium p-dodecylbenzenesulfonate, 2 g of styrene-maleic acid copolymer, styrene-butyl acrylate-acrylic acid copolymer latex (Average particle size about 0.25μm) Add 15g, Ag amount
JP-A-59-199 so that 4.0 g / m ² and gelatin amount is 2.00 / m ²
No. 41 was coated on a polyethylene terephthalate film base which had been coated as described in Example (1). At that time as spreading agent so that gelatin amount 1.0 g / m ^2, bis- (2-
Ethylhexyl) sulfosuccinate ester 10 mg / m ^2, was added, and the protective layer formalin 15 mg / m ² comprising glyoxal 8 mg / m ² was coated on the emulsion layer as a hardening agent, to obtain a dried sample.

[0028]

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<< Adjustment of treatment agent >>

[0030]

[Developer composition] Formulation for 1L of working solution (Composition-A) 1. water-soluble polymer or other granulated binder as shown in Table 1. 2. 1.0 g of disodium ethylenediaminetetraacetate Sodium sulfite 24.4 g4. Phenidone 0.5 g5. Hydroquinone 15.0 g 6.5-methylbenztriazole 0.2 g 7.1-phenyl-5-mercaptotetrazole 0.02 g 8.5-nitroindazole 0.06 g (Composition-B) 10. Water-soluble polymer or other granulated binder. Sodium carbonate 9.2 g 12. Potassium bromide 9.0 g 13. Sodium sulfite 15.6 g 14.5-Nitroindazole 0.06 g 15. Sodium hydroxide 7.4 g

[0031]

[Composition of fixing solution] 1. Polyethylene glycol (molecular weight) Shown in Table 1. 5.0 g of sodium sulfite 4. Boric acid 13.0 g 4. Ammonium thiosulfate 135.0 g Citric acid 80.9 g Based on the above composition, add a water-soluble polymer or water as shown in Table 1 as a binder in a recipe for one batch of 1000 liters, and extrude a granulation method to 1 mm in diameter and 1.5 m in length.
m (both average values) were prepared. In addition, a part of a flat tablet having a diameter of 2 cm and a thickness of 5 mm was obtained by press molding (however, the thickness of the central portion was 2 mm in order to improve solubility). If necessary, vacuum drying was performed to reduce the water content in the granulated product to about 0.5%. The binder was added in a state of being heated and melted.

[Strength Test of Granules or Tablets] Each 100 g of the obtained sample was weighed, placed in a 5 × 5 × 15 cm plastic box, sealed, and then vibrated up and down 5 cm at a cycle of 100 times / 1 min. For 5 minutes. Thereafter, the sample was emptied from the box, and the amount of powder remaining in the box was visually checked. Those having little residual amount were evaluated as A rank, those adhering to almost the entire wall surface of the box were evaluated as E rank, and the intermediates were evaluated as B, C and D ranks.

[Storage Stability Test] Each sample was weighed in a required amount, sealed in an aluminum-coated policy, completely sealed, and then heat-treated at 40 ° C. for 10 days.

After the obtained sample was dissolved in water according to the standard formulation, the above silver halide photographic material was processed under the following conditions.

The photosensitive material for evaluation was exposed for 1 second with a tungsten light source using an optical wedge. The exposed sample was processed by an automatic processor using the developing solution shown in Table 1 under the following conditions.

Developing conditions Step Temperature (° C.) Time (second) Developing 28 15 Fixing 28 Approx. 15 Washing Normal temperature Approx. 12 Drying 50 10 The photographic performance of the sample obtained by the treatment is shown in Table 1. still,
Relative sensitivity is indicated by the logE value of the exposure that gives a density of 2.0,
Relative values are shown with the respective sensitivities without heat treatment as 100.

[0037]

[Table 1]

As can be seen from the results shown in Table 1, the strength of the granules produced by the usual method is remarkably poor, and the amount of residual powder in the waste packaging material is large or the storage stability is very poor.

If the melting point of the binder is less than 30 ° C., the stability of the granulated material is poor and the surface is viscous and sticks to the waste packaging material. Those exceeding 100 ° C. were not granulated and were discharged as powder from the manufacturing apparatus.

According to the present invention, good results were obtained without these problems.

Similar evaluations were made by the tablet molding method, but the results were the same.

[0042]

According to the present invention, while maintaining the compactness of the powder treatment agent, the scattering of powder in the liquid preparation and the amount of powder remaining in the waste packaging material are reduced, which is excellent in environmental suitability and storage stability. Significantly superior photographic processing agents could be provided.

Claims (1)

(57) [Claims] 1. A water-soluble or alkali-soluble polymer having a melting point of 30 ° C. or more and 100 ° C. or less is heated and dissolved, and uniformly mixed in a powder mixture of a photographic processing component, followed by granulation or tablet molding. A photographic processing agent which is manufactured without passing through a drying step thereafter.