JP3030581B2 - Photographic processing agents - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photographic processing agent, and more particularly to a granular processing agent.

[0002]

BACKGROUND OF THE INVENTION Conventionally, photographic processing agents are roughly classified into a liquid type and a powder type, and automatic developing machines have been used to process a large amount of photographic light-sensitive materials with high precision. In the case of the type, it is only necessary to supply the replenisher to the processing tank in order to compensate for the liquid fatigue according to the processing amount and / or the aging. Or, it is replenished in the hot water in advance in the processing tank, the powder type is inferior to the liquid type in terms of workability, the powder is scattered at the time of liquid preparation, there is a problem in the work environment, and especially When a small amount of an additive component is contained, it is difficult to make the composition of the treatment agent uniform, which requires special measures in production, and raises the cost.

[0003] On the other hand, the powder type processing agent can be significantly reduced in size and weight as compared with the liquid type processing agent, and is very advantageous for transportation and storage. Have been. For example, a powder-type treating agent divided into several components and formed into a layer is placed in an airtight bag and vacuum-packed. In the same pack, the components that react when they come into contact with each other are devised so that they are separated.However, since they are powdered as soon as they are opened, they can be incorporated into automatic developing machines.
Alternatively, when the method is applied to an automatic replenishment mechanism of a side-by-side type, there are problems such as scattering of powder to the surroundings, adhesion and remaining of the powder, and a problem of scattering of powder to the surroundings manually.

In recent years, there has been a strong demand for miniaturization of automatic developing machines and liquid replenishing devices due to the demand for space saving. The replenishing device is miniaturized by replenishing while dissolving and preparing the processing agent little by little. Although the method is preferable, in the case of the above-mentioned powder type powder processing agent, when the replenishment is carried out while dissolving little by little because the composition in the package is not uniform, photographic performance stability cannot be obtained. In addition, the solubility is insufficient, and it takes a long time to prepare a solution, and thus the size of the dissolution replenisher cannot be sufficiently reduced.

Further, when the powder is opened, the powder is scattered, adheres and remains in the dissolution replenishing device, and the performance becomes unstable due to the mixing of the oxide of the adhered powder component during long-term running. Further, the treating agent powder remains on the inner surface of the package, which causes a problem of environmental pollution when the packaging material is discarded.

In order to solve such a problem, Japanese Patent Laid-Open Publication No.
No. 39735 and No. 3-39739 attempt to granulate the powder processing agent, but there is the generation of disintegrated powder due to vibration during transportation, etc. However, it is not enough to make the granulation, and it is necessary to devise pressure granulation at a high pressure to increase the collapse strength.

On the other hand, when the disintegration strength is increased, the solubility is deteriorated. In particular, in the case of a treating agent containing a poorly water-soluble additive, a granule treating agent having sufficient solubility and sufficient disintegration strength has not been obtained. .

[0008]

SUMMARY OF THE INVENTION In view of the above-mentioned problems, an object of the present invention is to provide an easy-to-transport, easy-to-store, high-solubility, and high-grain strength suitable for a miniaturized automatic liquid replenishment mechanism. Another object of the present invention is to provide a powder treating agent which is free from powder scattering due to disintegration, has no dust remaining in the package, and has low environmental pollution.

[0009]

The object of the present invention is to provide a granulated or tablet-like photographic processing agent obtained by mixing and granulating two or more kinds of powdery drugs used as a photographic processing agent. The granulation has a layer structure of two or more layers, and the outermost layer contains at least one additive that improves the solubility of at least one additive contained in the inner layer and the outermost layer in water. Photographic processing agents.

In a preferred embodiment, the granulated material contains a poorly water-soluble additive in the outermost layer in an amount of 0.01 to 1.0% of the total weight of the treating agent. Here, poor water solubility means 0.1% in water at room temperature
It means that it has the following solubility.

Hereinafter, the present invention will be described specifically.

In order to form the granules according to the present invention, generally used granulation auxiliaries can be used, and the water of crystallization, a small amount of water, a water-soluble or alkali- or acid-soluble polymer as an additive can be used. Used. Specifically, gelatin, pectin, polyacrylic acid, polyvinyl alcohol, polyvinyl pyrrolidone, vinyl acetate copolymer, polyethylene oxide, sodium carboxymethylcellulose, hydroxypropylcellulose, methylcellulose, ethylcellulose, alginic acid, chitanic acid gum, gum arabic, tragacanth gum , Karaya gum, carrageenan, methyl vinyl ether, maleic anhydride copolymer,
Polyoxyethylene stearyl ether, polyoxyethylene ethyl ether and other polyoxyethylene alkyl ethers, polyoxyethylene octyl phenol ether and polyoxyethylene nonyl phenol ether and other polyoxyethylene alkyl phenol ethers or the water solubility described in Japanese Patent Application No. 2-203165. One type selected from binders or a combination of two or more types can be used.

The granulation method applied in the present invention includes rolling granulation, extrusion granulation, compression granulation, pulverization granulation, and the like.
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 the preparation are adjusted. Or, considering the durability against destruction of the granulated material due to vibration during transportation, in the case of granular, the spherical equivalent particle size is 0.5 mm to 50 m
m, preferably about 1 mm to 15 mm, and the shape is cylindrical, spherical, cubic, rectangular, or the like, and more preferably spherical or cylindrical.

[0015] In the case of a tablet, the diameter is also preferably about 2 mm to 5 cm, although it depends on the desired properties. 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. In this case, the inner layer is a developing agent, a preservative, a granulation aid such as a water-soluble polymer, and the outermost layer is an alkali agent, a development inhibitor, a granulation aid such as a water-soluble polymer, etc. Is preferred.

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

That is, it is a liquid containing the following developing agents. As black and white developing agents, dihydroxybenzenes (for example, hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, methylhydroquinone, 2,3-dichlorohydroquinone,
5-dimethylhydroquinone, potassium hydroquinone monosulfonate, sodium hydroquinone monosulfonate), 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-pyrazolidone, 1-phenyl-5-methyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl
-3-pyrazolidone, 1-phenyl-4,4-dihydroxymethyl
-3-pyrazolidone, etc.), aminophenols (eg, o
-Aminophenol, p-aminophenol, N-methyl-o-
Aminophenol, N-methyl-p-aminophenol, 2,4
1-aryl-3-aminopyrazolines (eg, 1- (p-hydroxyphenyl) -3-aminopyrazoline, 1- (p-methylaminophenyl) -3-aminopyrazoline, 1- (p-amino-m-methylphenyl) -3-
Aminopyrazoline, etc.) or a mixture thereof.

Further, as color developing agents, known primary aromatic amine developers such as phenylenediamines (eg, 4-amino-N, N-diethylaniline, 3-methyl-4-amino-N, N-diethylaniline) , 4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl
-N-β-hydroxyethylaniline, 3-methyl-4-amino-
N-ethyl-N-β-methanesulfonamidoethylaniline,
4-amino-3-methyl-N-ethyl-N-β-methoxyethylaniline).

[0021] In addition, the LFA Mason Photographic Process
ing Chemistry (Focal Press, 1966) 226-229
And those described in JP-A-48-64933 may be used.

These developing agents are generally used in an amount of about 0.1 to 80 g / l, preferably about 0.2 to 50 g / l.

In the developing solution, if necessary, a preservative (eg, sulfurous acid, bisulfite, etc.), a buffer (eg, carbonate, boric acid, borate, alkanolamine, etc.), an alkali agent (eg, hydroxide) , Carbonates, etc.), dissolution aids (eg, polyethylene glycols and esters thereof), pH adjusters (eg, organic acids such as acetic acid), sensitizers (eg, quaternary ammonium salts), development acceleration Agents, hardeners (eg, dialdehydes such as glutaraldehyde), surfactants, and the like. The developer further includes an antifoggant (for example, a halide such as potassium bromide or sodium bromide, benzotriazole, benzothiazole, or tetrazolethiazole), a chelating agent (for example, ethylenediaminetetraacetic acid, an alkali metal salt thereof, Polyphosphate, nitriloacetate, etc.).

The following fixing solutions are preferred.

The fixing solution preferably contains a thiosulfate. The thiosulfate is supplied as a solid, specifically, as a lithium, potassium, sodium, ammonium salt or the like, which is used after being dissolved. Among them, preferably supplied as sodium and ammonium salts,
It is used by dissolving, and more preferably, it is supplied as an ammonium salt and used by dissolving, whereby a fixing solution having a high fixing speed can be obtained. The concentration of thiosulfate is preferably 0.1 to 5 mol / l, more preferably 0.5 to 2 mol / l, and still more preferably 0.7 to 1.8 mol / l.

The fixing solution contains a sulfite, and the concentration of the sulfite is 0.2 mol / l or less, preferably 0.1 mol / l or less, when the thiosulfate and the sulfite are dissolved and mixed in an aqueous solvent. It is. As the sulfite, a solid lithium, potassium, sodium, ammonium salt or the like is used, which is dissolved and used together with the solid thiosulfate.

The fixing solution preferably contains citric acid, tartaric acid, malic acid, succinic acid, and phenylacetic acid includes citric acid, isocitric acid, malic acid, tartaric acid, succinic acid, and optical isomers thereof.

These salts include potassium citrate,
Lithium citrate, sodium citrate, ammonium citrate, lithium bitartrate, potassium bitartrate,
Lithium, potassium, sodium, ammonium salts represented by potassium tartrate, sodium bitartrate, sodium tartrate, ammonium hydrogen tartrate, ammonium potassium tartrate, sodium potassium tartrate, sodium malate, ammonium malate, sodium succinate, ammonium succinate, etc. And the like, and one or more of these can be used in combination. Among the above compounds, more preferred are citric acid, isocitric acid, malic acid, phenylacetic acid and salts thereof.

The citric acid, tartaric acid, malic acid, succinic acid and the like are supplied as solids and are used by dissolving in an aqueous solvent. The preferred content in the fixing solution after dissolution is 0.05 mol / l or more. The preferred content is 0.2 to 0.6 mol / l.

In the fixing solution, various acids,
Additives such as salts, chelating agents, surfactants, wetting agents and fixing accelerators can be included.

Examples of the acid include inorganic acids such as sulfuric acid, hydrochloric acid, nitric acid and boric acid, and organic acids such as formic acid, propionic acid, oxalic acid and malic acid.

Examples of the salt include salts of these acids such as lithium, potassium, sodium and ammonium.

Examples of the chelating agent include aminopolycarboxylic acids such as nitrilotriacetic acid and ethylenediaminetetraacetic acid, and salts thereof.

Examples of the surfactant include anionic surfactants such as sulfated and sulfonated compounds, nonionic surfactants such as polyethylene glycol-based and ester-based surfactants, and JP-A-57-6840 (the title of the invention; Amphoteric surfactants described in "Fixing solution for photography").

Examples of the wetting agent include alkanolamine and alkylene glycol.

Examples of the fixing accelerator include, for example, JP-B-45-357.
No. 54, Japanese Patent Publication Nos. 58-122535 and 58-122536, thiourea derivatives, alcohols having a triple bond in the molecule, and thioethers described in U.S. Pat. No. 4,126,459.

Among the above additives, acids and salts such as sulfuric acid, boric acid and aminopolycarboxylic acids are preferred. The preferred amount of the additive is 0.5 to 20 g / l.

[0038]

【Example】

Example 1 (Preparation of developer for black and white photography) Formulation A Polyethylene glycol (molecular weight 600) 140 g Sodium ethylenediaminetetraacetate 80 g Hydroquinone 1280 g Sodium sulfite 870 g Phenidone 43 g Formulation B Potassium bromide 384 g Sodium carbonate 790 g Sodium sulfite 2500 g Sodium hydroxide 630 g 1 -Phenyl-5-mercaptotetrazole 2g 5-Methylbenzotriazole 14g Formula C 5-Nitroindazole (poorly water-soluble additive) 10g Polyethylene glycol (molecular weight 600) 290g (Additive to improve water solubility of 5-nitroindazole) The polyethylene glycol of A and the remaining powder of formulation A were uniformly mixed and kneaded sufficiently to obtain a spherical granulated product having a diameter of about 7 mm using a compression granulator.

5-Nitroindazole is dissolved in the polyethylene glycol of the formula C, sufficiently kneaded with the homogeneous mixture of the formula B, and granulated by an extrusion granulator to obtain a diameter of 1 mm and a length of 3 mm.
Granules of the degree were obtained.

While adding the above granules little by little to the spherical granules obtained in Formula A, the granules obtained from Formulas B and C are further laminated on the surface of Formula A by using a rotary granulator, and further pressurized. After compression, the shape was adjusted to obtain a two-layer spherical granulated product (a) (diameter: 10 mm).

Example 2 Polyethylene glycol molecular weight 600 of formulation A of Example 1
Was replaced with polyethylene glycol having a molecular weight of 1,000, and heated and maintained so as to have a viscosity suitable for kneading. The remaining powder of Formula A and the mixture of Formula B of Example 1 were uniformly mixed and kneaded, followed by compression. A spherical granulated product having a diameter of 7 mm was obtained by a granulator.

The polyethylene glycol of Formula C of Example 1 was heated by changing polyethylene glycol having a molecular weight of 600 to polyethylene glycol having a molecular weight of 1,000, and a solution obtained by mixing and dissolving with a homogeneous mixture of other additives of Formula C was sprayed on the granules by a known method. After coating, the mixture was cooled to obtain a granulated product (b) having a diameter of about 10 mm.

COMPARATIVE EXAMPLE The polyethylene glycol of Formula A of Example 1 and the powder obtained by uniformly mixing the remaining powder of Formula A and all the powders of Formula B were thoroughly kneaded. 5-Nitroindazole was dissolved in the polyethylene glycol of the formula C, and the mixture was further uniformly kneaded with the mixture of the formulas A and B to obtain a granulated product (c) having a diameter of about 10 mm by a compression granulator. Evaluation was performed by the following method.

Evaluation of Disintegration Evaluation of the disintegration was carried out by filling the obtained granulated developer sample into a paper packaging material having an inner wall coated with polyethylene without voids and vibrating for 24 hours using a commercially available vibration tester. Thereafter, the amount of the fine powder formed by disintegration was visually evaluated on a 5-point scale.

5 is a good level with almost no fine powder, and 3 or less is not practical due to the situation of the fine powder adhering to the packaging material and the scattering of the fine powder at the time of adding and opening the packaging material.

Evaluation of Solubility in Water Evaluation of the solubility in water was carried out using the obtained granular developer sample 81.
g was dissolved in 1 l of water at 30 ° C. with stirring, and the time until complete dissolution was measured.

When the dissolution takes more than 5 minutes, the workability of the manual dissolution and the automatic liquid preparation mechanism is poor, which is not practical.

The results are shown below.

Results Granules Disintegrability Solubility in water (a) 43 minutes The present invention (b) 52 minutes 〃 (c) 4 10 minutes Comparative Example From the above results, the treating agent of the present invention is disintegratable and water-soluble. It can be seen that the solubility of both is excellent.

[0050]

Industrial Applicability According to the present invention, it is easy to transport and store, has good solubility suitable for a miniaturized automatic liquid replenishing mechanism, has high granule strength, does not disperse powder due to disintegration, and is packaged. A powder treatment agent with no residual powder inside and less environmental pollution could be provided.

Claims (2)

(57) [Claims] 1. Granules or tablets obtained by mixing and granulating two or more kinds of powdery drugs used as photographic processing agents
A Jo photographic processing agent, granulation product had two or more layers structure, improve the solubility in water of at least one additive contained in the inner layer and the outermost layer to the outermost layer A photographic processing agent comprising at least one additive to be added. 2. A photographic processing agent obtained by mixing and granulating two or more kinds of powdery chemicals used as a photographic processing agent, wherein the granulated material has a layer structure of at least two layers. And a sparingly water-soluble additive in the outermost layer in an amount of 0.
The photographic processing agent according to claim 1, wherein the photographic processing agent is contained in an amount of from 01 to 1.0%.