JPH05197089A - Processing agent for photography - Google Patents

Abstract

PURPOSE:To obtain a powdery processing agent easy in transportation and preservation, excellent in uniformity and solubility of components in a processing agent packaging material, high in granule strength, free from the scattering of powder by disintegrating, suitable to an automatic preparation and replenishing mechanism of an automatic developing device free from the residue of powdery agent, low in environmental contamination and miniaturized. CONSTITUTION:The subject processing agent for photography is obtained by granulating and molding two or more kinds of a powdery chemicals after mixing and the av. particle diameter ratio of the total mixed powdery chemicals is (1:1)-(1:50). And when the weight ratio of at least one kind of mixed chemicals to the total mixed chemicals is <=1/200, the drastic effectiveness is attained.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a processing agent for silver halide photographic light-sensitive materials, and more particularly to an improved powdery processing agent.

[0002]

BACKGROUND OF THE INVENTION Photographic processing agents are roughly classified into liquid type and powder type, and an automatic processor is used to process a large amount of photographic light-sensitive material with high accuracy. A replenisher is automatically replenished in a processing tank in order to compensate for liquid fatigue depending on the amount and / or time.

In order to replenish the replenishing treatment agent to the treatment tank, in the liquid type, the replenishing agent may be supplied to the treatment tank as it is, or may be diluted with water and then supplied from the replenishment tank to the treatment tank by a pump. In the case of powder type treatment agent, it is put directly into the treatment tank and stirred for a certain period of time, or the one dissolved in hot water beforehand is replenished to the treatment tank, and the powder type is inferior to the liquid type in terms of workability. ,
Furthermore, powder is scattered during preparation, which causes problems in the working environment.
Further, it is difficult to make the composition of the treating agent uniform especially when a small amount of the additive component is contained, and it is necessary to take special measures in manufacturing, which causes a problem of cost increase.

On the other hand, the powder type treating agent can be greatly reduced in size and weight as compared with the liquid type treating agent and is very advantageous for transportation and storage. Has been done. For example, a powder type treating agent divided into several components and formed into a layer is put in an airtight bag and vacuum packed. It was devised so that the components that react when they contact each other in the same pack are separated, but since it powders at the same time as opening, it can be incorporated into an automatic processor.
Or, when it is applied to an automatic replenishing mechanism of the side-by-side type, there are problems such as powder scattering to the surroundings, adhesion of powder, and remaining, and there is a problem of powder scattering to the surroundings by manual work.

Further, in recent years, there has been a strong demand for downsizing of an automatic processor and a solution adjusting replenishing device due to a demand for space saving, and the replenishing device can be downsized by performing replenishment while dissolving and preparing a processing agent little by little. Although the method is preferable, the above-mentioned powder type powder processing agent does not have a uniform composition in the package, and when it is replenished while dissolving little by little, the stability of photographic performance cannot be obtained. In addition, the solubility is insufficient, the preparation time is long, and the dissolution replenishing device cannot be sufficiently downsized.

Further, the powder is scattered at the time of opening, adheres and remains in the dissolution replenishing device, and the performance becomes unstable due to the inclusion of 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 No.
In 3-39735 and 3-39739, it has been attempted to granulate the treatment agent powder, but the technology for homogenizing the treatment agent has not been improved, and the components of each treatment agent packaging material kit are Uniformity and processing agent Uniformity and solubility of the components in the packaging material, high granular strength, no scattering of powder due to disintegration, no dust remaining in the package, less environmental pollution, miniaturized automatic development The powder processing agent suitable for the automatic liquid replenishing mechanism in the machine has not been obtained.

[0009]

In view of the above problems, the object of the present invention is to facilitate transportation and storage, to provide excellent uniformity and solubility of the components in the packaging material for treating agent, and to have high granule strength, resulting from disintegration. It is an object of the present invention to provide a powder processing agent which is suitable for an automatic liquid preparation replenishing mechanism in a downsized automatic developing machine in which the powder does not scatter and the powder in the package does not remain and which causes little environmental pollution.

[0010]

The above object of the present invention is to provide a photographic processing agent which is obtained by mixing two or more kinds of powdery medicines and then granulating and molding the mixture, and the average particle diameter ratio of all the mixed powdery medicines. But,
This is achieved by a photographic processing agent characterized by being in the range of 1: 1 to 1:50.

Further, the effect of the present invention is remarkable when the weight ratio of the mixed drug of at least one kind to the total amount of the mixed drug is 1/200 or less.

The present invention will be specifically described below.

In order to form the granules according to the present invention, it is preferable to use a generally used granulation aid, and an additive such as crystallization water, a small amount of water, water-soluble or alkali- or acid-soluble polymer is used. .. Specifically, gelatin, pectin, polyacrylic acid, polyvinyl alcohol, polyvinylpyrrolidone, vinyl acetate copolymer, polyethylene oxide, sodium carboxymethyl cellulose, hydroxypropyl cellulose, methyl cellulose, ethyl cellulose, alginic acid, xanthate gum, gum arabic, tragacanth gum. , Karaya gum, carrageenan, methyl vinyl ether, maleic anhydride copolymer,
Polyoxyethylene stearyl ether, polyoxyethylene alkyl ether such as polyoxyethylene ethyl ether, polyoxyethylene alkylphenol ether such as polyoxyethylene octylphenol ether and polyoxyethylene nonylphenol ether, or the water-soluble property described in Japanese Patent Application No. 2-203165. It is possible to use one kind selected from the binders or a combination of two or more kinds.

The granulation method applied in the present invention includes rolling granulation method, extrusion granulation method, compression granulation method, crushing granulation method,
The stirring granulation method, the spray drying method, the dissolution solidification method and the like can be used alone or in combination, but the extrusion granulation method and the compression granulation method are particularly preferable.

The particle size and shape of the granulated product suitable for the present invention vary depending on the desired characteristics, but generally the solubility desired for the photographic processing agent and the amount of residual powder in the waste packaging material after preparation are adjusted. Or, considering the durability against breakage of granulated material due to vibration during transportation, in the case of granules, the spherical equivalent particle size is 0.5 mm to 50 mm.
The shape is preferably cylindrical, spherical, cubic, rectangular parallelepiped, etc., more preferably spherical or cylindrical.

Similarly in the case of tablets, a diameter of about 2 mm to 5 cm is preferable although it depends on the desired characteristics. Further, when it is desired to improve the solubility, a flat tablet having a reduced tablet thickness, a flat tablet having a further reduced central portion thickness, a hollow donut tablet and the like are also useful. On the contrary, the diameter may be further increased for the purpose of slow dissolution, and can be adjusted arbitrarily.

The surface condition (smoothness, porosity, etc.) may be changed to control the solubility.

It is also possible to have a plurality of shapes in order to give different solubilities to a plurality of granules or to adjust the solubilities of materials having different solubilities. Further, it may be a multi-layer granulated product having different compositions on the surface and inside. 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. 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 contains the following developing agents. As a black and white developing agent, dihydroxybenzenes (for example, hydroquinone, chlorohydroquinone,
Bromohydroquinone, isopropylhydroquinone,
Methyl hydroquinone, 2,3-dichlorohydroquinone,
2,5-Dimethylhydroquinone, potassium hydroquinone monosulfonate, sodium hydroquinone monosulfonate, 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-pyrazolidone, 1-phenyl-5-methyl-
3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, 1-phenyl-4,4-dihydroxymethyl-3-pyrazolidone, etc.), aminophenols such as o-aminophenol, p-amino Phenol, N-methyl
-o-aminophenol, N-methyl-p-aminophenol,
2,4-diaminophenol, etc., 1-aryl-3-aminovirazolines (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-methanesulfonamide ethylaniline,
4-amino-3-methyl-N-ethyl-N-β-methoxyethylaniline and the like).

Other LFA Mason Photographic Process
ing Chemistry (Focal Press. 1966), 226-229
Pages, those described in JP-A-48-64933, etc. may be used.

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

In addition to the developer, if necessary, preservatives (eg, sulfurous acid, bisulfite, etc.), buffers (eg, carbonate, boric acid, borate, alkanolamine, etc.), alkaline agents (eg, hydroxide). , Carbonates, etc., solubilizers (eg polyethylene glycols, esters thereof, etc.), pH adjusters (eg organic acids such as acetic acid), sensitizers (eg quaternary ammonium salts etc.), development acceleration Agents, hardeners (for example, dialdehydes such as glutaraldehyde), surfactants and the like can be contained. The developer further includes an antifoggant (for example, a halide such as potassium bromide and sodium bromide, benzotriazole, benzothiazole, tetrazolethiazole, etc.), a chelating agent (for example, ethylenediaminetetraacetic acid, an alkali metal salt thereof, Polyphosphate, nitriloacetate, etc.) can be included.

The following fixing agents are preferable.

The fixing agent preferably contains thiosulfate. The thiosulfate is supplied as a solid, specifically as a lithium, potassium, sodium, ammonium salt or the like, and these are used after being dissolved. Of these, sodium and ammonium salts are preferably supplied,
The fixing solution is used by dissolving it, and more preferably, by supplying it as an ammonium salt and dissolving it, a fixing solution having a high fixing rate can be obtained. The concentration of thiosulfate is preferably 0.1 to 5 mol / l, more preferable concentration is 0.5 to 2 mol / l, and further preferable concentration is 0.7 to 1.8 mol / l.

The fixing agent 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. Is. As the sulfite, solid lithium, potassium, sodium, ammonium salt or the like is used, and it is used by dissolving with the solid thiosulfate.

The fixing agent preferably contains citric acid, tartaric acid, malic acid, succinic acid, and phenylacetic acid as 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 hydrogen tartrate, potassium tartarate,
Lithium, potassium, sodium, ammonium salts represented by potassium tartrate, sodium hydrogen tartrate, sodium tartrate, ammonium hydrogen tartrate, potassium ammonium tartrate, sodium potassium tartrate, sodium malate, ammonium malate, sodium succinate, ammonium succinate, etc. Etc. are mentioned as a preferable thing, and these can be used 1 type or in combination of 2 or more types.

Of the above compounds, more preferred are citric acid, isocitric acid, malic acid, phenylacetic acid and salts thereof.

The above-mentioned citric acid, tartaric acid, malic acid, succinic acid, etc. are supplied as solids and are used by dissolving them in an aqueous solvent. The preferable 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.

The fixing agent includes various acids in addition to the above compounds.
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 surface active agent include anionic surface active agents such as sulfuric acid ester compounds and sulphonated compounds, nonionic surface active agents such as polyethylene glycol type and ester type surfactants, JP-A-57-6840 (the title of the invention: " Amphoteric surfactants described in "Fixing Solution for Photographs" and the like are included.

Examples of the wetting agent include alkanolamine and alkylene glycol.

As the fixing accelerator, for example, JP-B-45-357.
No. 54, JP-B Nos. 58-122535 and 58-122536, thiourea derivatives, alcohols having a triple bond in the molecule, thioethers described in US Pat. No. 4,126,459 and the like.

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

[0040]

【Example】

Example 1 Preparation of a black and white photographic developer (use liquid 1000 liter prescription) Comparative Example of the present invention Developer a Developer low amount Average particle size Recipe A; Polyethylene glycol having a molecular weight of 600 500 g −-5-nitroindazole 20 g 150 μ 150 μ Hydroquinone 1800g 50μ 50μ 1-Phenyl-4,4-dimethyl-3-pyrazolidinone 43g 70μ 70μ Ethylenediaminetetraacetic acid disodium salt 150g 30μ 30μ Formula B; KBr 900g 150μ 2000μ Potassium carbonate 6000g 150μ 150μ Potassium sulfite 5000g 150μ 200μ Potassium hydrogen carbonate 300g 150μ 150μ 1-Phenyl-5-mercaptotetrazole 2g 20μ 20μ 5-Methylbenzotriazole 14g 30μ 30μ Water 500g --- After uniformly mixing the formulation A, use a pressure granulator to produce granules with a diameter of 3 mm and a length of 3 mm. Obtained.

Subsequently, a rotary granulator was used to obtain spherical granules. Using a rotary sizing machine, add a small amount of a mixture of the spherical granules obtained by the prescription A and the prescription B to the granules of the A, and then dry the granules. The agent (a) was obtained.

Comparative Example A granulated developer (B) was obtained in the same manner as in the present invention except that the particle size of KBr in the formulation B was changed from that in the present invention.

(Evaluation) The obtained granular developer (a),
(B) Both the disintegration property and the solubility of the granules were good.

147 g of each of the obtained granule developers of (a) and (b) were sampled from arbitrary 10 places,
Dilute each with water, make up to 1000 ml, and use the developer (a)-
1-10 and (b) -1-10 were adjusted.

Konica Corporation photosensitive material for printing RHG10
0E is exposed according to a conventional method, and the above developer (A) -1 to 10,
(B) -1 to 10 were developed at 28 ° C. for 30 seconds, fixed, washed with water and dried by a conventional method, and then the sensitivity was measured. Sensitivity was expressed as relative sensitivity when (a) -1 was set to 100.

Developer 1 2 3 4 5 6 7 8 9 10 Average σr (a) 100 98 102 105 96 98 101 99 103 97 99.9 2.7 (b) 102 115 78 98 105 89 105 103 93 96 98.4 9.7 σr is standard Deviation% The results of the above table show that the developer (a) has a small variation in sensitivity depending on the sampling location, has excellent sensitivity stability for each processing agent packaging material kit, and is of the type that is replenished while adjusting the dissolution little by little. It can be seen that the treatment agent is suitable for the dissolution adjusting and replenishing device.

Example 2 Preparation of a developer for black and white photography (use liquid 1000 liter formulation) Comparative example of the present invention Developer C developer Ni content average particle size formulation C; polyethylene glycol 500 molecular weight 500 g--hydroquinone 2000 g 50 μ 50 μ 1 -Phenyl-4,4-dimethyl-3-pyrazolidinone 60g 70μ 70μ Ethylenediaminetetraacetic acid disodium salt 200g 30μ 30μ KBr 350g 150μ 2000μ Potassium sulfite 3300g 60μ 60μ Potassium carbonate 1500g 150μ 150μ 5-Methylbenzotriazole 60g 30μ 30μ Water 500g Formula C Is thoroughly kneaded and the diameter is 3m using a pressure granulator.
Granules with m and length of 3 mm were obtained.

Subsequently, using a rotary sizing machine, the particles were made spherical and dried to obtain a granular developer (c).

Comparative Example A granulated developer (d) was obtained in the same manner as in the present invention except that the particle size of KBr in the formulation C was changed from that in the present invention.

(Evaluation) The obtained granular developer (C),
In both (2), the disintegration property and solubility of the granules were good.

80 g of each of the obtained granule developers (c) and (d) were sampled from arbitrary 10 locations,
Dilute each with water, make up to 1000 ml, and use the developer (C)-
1-10 and (d) -1-10 were adjusted.

Konica Corporation photosensitive material for printing RSD10
0E is exposed according to a conventional method, and the above developer (C) -1 to 10,
(D) Development was carried out at 38 ° C. for 20 seconds with each of (1) to 10 and fixing, washing with water and drying were carried out by a conventional method, and then the sensitivity was measured. The sensitivity was expressed as relative sensitivity when the sensitivity of (C) -1 was set to 100.

The obtained results are as follows.

Developer 1 2 3 4 5 6 7 8 9 10 Average σr (c) 100 97 107 104 97 98 105 92 111 95 100.6 5.6 (d) 101 92 112 106 97 93 107 83 117 95 100.2 9.8 σr is standard The result similar to that of Example 1 was obtained from this result indicating the deviation%.

[0055]

EFFECTS OF THE INVENTION According to the present invention, it is easy to transport and store, has excellent uniformity and solubility of the components in the treating agent packaging material, has high granule strength and does not scatter powder due to disintegration, and is a powder agent in the packaging. It was possible to provide a powder processing agent suitable for an automatic liquid preparation replenishing mechanism in a miniaturized automatic developing machine with little residue and little environmental pollution.

Claims (2)

[Claims] 1. A photographic processing agent which is granulated and molded after mixing two or more powdery chemicals, wherein the average particle diameter ratio of all the powdery chemicals mixed is 1: 1 to 1: 1. Photographic processing agent characterized by being in the range of 50. 2. A photographic processing agent which is granulated and molded after mixing two or more kinds of powdered medicines, wherein at least one kind of the mixed medicines is weighted with respect to the total amount of the mixed medicines. In ratio
2. The photographic processing agent according to claim 1, which is 1/200 or less.