JPH0635134A - Processing agent for black-and-white photography - Google Patents

Abstract

PURPOSE:To obtain the solid processing agent easy in conveyance and preservation, good in solubility, free of dissolution and deterioration in photographic performance during storage, and superior in aptitude to the environment. CONSTITUTION:This processing agent for the black-and-white photography contains polyhydroxybenzene and it comprises at least the solid developer containing polyhydroxybenzene adjusted to an average particle diameter of 10-500mum in advance a black-and-white photographic fixing agent containing a water-soluble aluminum compound adjusted to an average particle diameter of 10-500mum in advance.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a solid black and white photographic processing agent, and more particularly to a solid black and white photographic processing agent that does not deteriorate in solubility and photographic performance during storage.

[0002]

BACKGROUND OF THE INVENTION Conventionally, a processing agent for a silver halide photographic light-sensitive material has been a liquid agent or a powder agent. In the case of a liquid agent, it is used as it is, or a concentrated solution supplied with a kit is diluted with water. In the case of powder, it is used by dissolving it in water.

However, in the case of a liquid agent, although the dissolution method is simple, since a considerable amount of water is contained in advance, both volume and weight are large, transportation and storage costs are high, and there is a risk of liquid leakage. Therefore, there is a problem such as a change in performance during storage.

On the other hand, the powder is excellent in compactness with respect to the liquid, but is inferior in solubility to the liquid. Also,
Liquids and powders adhere to and remain on the packaging materials after use, causing environmental pollution problems when the packaging materials are discarded.

In order to solve these problems, as a fixing agent, Japanese Patent Laid-Open No. 3-39735 proposes to granulate a powder processing agent and make the particle diameter of raw materials 10 μm or less. Examples using a fixing agent for a color photographic light-sensitive material and a black and white fixing agent containing no water-soluble aluminum compound are described.

By the way, a water-soluble aluminum compound is generally used for a black-and-white photographic fixing agent for the purpose of hardening a light-sensitive material. The solid fixing agent containing a water-soluble aluminum compound may produce a sparingly soluble substance and cannot be completely dissolved during long-term storage or storage under high temperature and high humidity conditions for unknown reasons. In particular, when the water-soluble aluminum compound is used after being adjusted to have a particle size of 10 μm or less, it has been found that not only in the case of powder, but also in the case of a granulated product, solubility deterioration during storage becomes remarkable, It was found that the disclosed technical content does not provide a solid processing agent that can be used practically.

Further, in the same manner as the fixing agent, it is proposed in JP-A-2-09042 that the powder processing agent is granulated and the particle diameter of the raw material is 10 μm or less. An example using a developer for a photographic light-sensitive material is described.

By the way, in a black and white photographic developer containing polyhydroxybenzenes, even a solid developer is liable to undergo performance deterioration such as developability due to oxidative deterioration of the polyhydroxybenzenes, and in particular, it is crushed to 10 μm or less. When used as a powder, not only in the case of a powder, but also in the case of a granulated product, it was found that the preservability is remarkably deteriorated, and in the technical contents disclosed in the above publication, a solid developer that can be practically used is obtained. I knew I couldn't.

[0009]

In view of the above problems, the object of the present invention is easy transportation and storage, good solubility, no deterioration in solubility and photographic performance during storage, and further environmental friendliness. To provide an excellent solid processing agent.

[0010]

The above object of the present invention is a black-and-white photographic developer containing polyhydroxybenzenes, wherein at least the polyhydroxybenzenes among the raw materials of the developer have an average particle size of 10 to 500 μm. A solid black-and-white photographic developer characterized in that it is used in the form of a black and white photographic fixing agent, and a black and white photographic fixing agent containing a water-soluble aluminum compound. It is achieved by a solid black-and-white photographic fixing agent characterized by being used after being adjusted to ˜500 μm.

The developer preferably contains at least one developing agent selected from phenidones and methols.

The present invention will be specifically described below.

The solid of the solid processing agent used in the present invention means a general solid one, such as powder, granules, tablets,
It includes a paste or the like, and may be a mixture thereof.

As the method for dissolving the solid processing agent of the present invention, it may be carried out manually or mechanically as in the usual liquid preparation method. The replenishment tank may be inside the automatic processor or externally. May be there. As a method of supplying the treatment agent,
Any form may be used as long as each component of the treatment agent does not scatter, for example, a method of encapsulating a solid treatment agent with a water-soluble polymer film and directly adding it, packaging with paper surface-treated with polyethylene or the like, and scattering of powder agent. , There is a method of preventing the residue and adding it to the tank. Considering the solubility of the processing agent in water, the solid form is preferably granules or tablets, but the components of the photographic processing agent often include those which are poorly soluble in water. A sparingly soluble substance may precipitate in the liquid. In order to avoid this, there is a method of adding a solvent separately. To form granules or tablets,
It is preferable to use a commonly used granulation aid,
A water-soluble, alkali- or acid-soluble polymer is used. Specifically, gelatin, pectin, polyacrylic acid, polyacrylic acid salt, polyvinyl alcohol, polyvinylpyrrolidone, vinyl acetate copolymer, polyethylene oxide, sodium carboxymethyl cellulose, hydroxypropyl cellulose, methyl cellulose, ethyl cellulose, alginate, kitanic acid. Gum,
Gum arabic, tragacanth gum, karaya gum, carrageenan, methyl vinyl ether, maleic anhydride copolymer, polyoxyethylene alkyl ether such as polyoxyethylene ethyl ether and polyoxyethylene stearyl ether, polyoxyethylene octylphenol ether, polyoxyethylene nonylphenol ether, etc. The polyoxyethylene alkylphenol ether, or one or more selected from the water-soluble binders described in Japanese Patent Application No. 2-203165 can be used in combination.

Further, in order to increase the preservability of the treating agent in the kit, the treating agent may be enclosed in two or more separate forms in the kit.

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

The particle size and shape of the granulated product suitable for the present invention differ depending on the desired characteristics, but generally, the solubility desired for the photographic processing agent and the amount of powder remaining in the waste packaging material after preparation are required. Alternatively, considering the durability against breakage of granulated material due to vibration during transportation, the spherical equivalent particle size is 0.5 mm to 50 m in the case of granules.
The thickness is preferably about m, preferably about 1 mm to 15 mm, and the shape thereof is cylindrical, spherical, cubic, rectangular parallelepiped, or the like, and more preferably spherical or cylindrical.

Also in the case of tablets, a diameter of about 2 mm to 5 cm is preferable although it also depends on 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.

Examples of the polyhydroginebenzenes used in the present invention include dihydroxybenzenes (for example, hydroquinone, chlorohydroquinone, promohydroquinone, isopropylhydroquinone, methylhydroquinone, 2,3-dichlorohydroquinone, 2,5-dimethylhydroquinone, Hydroquinone potassium monosulfonate,
Hydroquinone sodium monosulfonate, etc.), pyrogallol, 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-dihydroxymethyl
-3-pyrazolidone), aminophenols (for example, o-aminophenol, p-aminophenol, N-methyl-o-aminophenol, N-methyl-p-aminophenol, 2,4-diaminophenol, etc.), 1-aryl-3-aminopyrazolines (eg, 1- (p-hydroxyphenyl) -3-aminopyrazoline, 1- (p-amino-m-methylphenyl) -3-aminopyrazoline, etc.) or There are mixtures of these.

Examples of color developing agents include primary aromatic amino developers such as phenylenediamines (eg, 4-amino-N, N-diethylaniline, 3-methyl-4-amino-N, N).
-Diethylaniline, 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, etc.) and the like.

The combination of a dihydroxybenzene chain and 1-phenyl-3-pyrazolidones is most preferable for the developing agent used in the black-and-white developing solution used in the present invention because good performance can be easily obtained. Of course, in addition to this, a p-aminophenol-based developing agent may be contained.

[0024] In addition, LFA Mason Photographic Proce
226-229 of ssing Chemistry (Focal Press, 1966)
Pages, those described in JP-A-48-64933 and the like can be used. It is preferable that these developing agents are usually used in an amount of 0.01 to 1.2 mol / liter.

As the preservative of sulfite used in the present invention, sodium sulfite, potassium sulfite, lithium sulfite,
Examples include ammonium sulfite, sodium bisulfite, potassium metabisulfite, and formaldehyde sodium bisulfite. The sulfite content is preferably 0.2 mol / l or more, more preferably 0.4 mol / l or more. The upper limit is preferably 2.5 mol / l.

The pH of the developer used in the present invention is preferably in the range of 9 to 13. More preferably, the pH is in the range of 10 to 12. The alkaline agent used for setting the pH includes a pH adjusting agent such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium triphosphate and potassium triphosphate.

JP-A-61-28708 (borate), JP-A-60
-93439 (eg saccharose, acetoxime, 5-
Sulfur salicylic acid), phosphates, carbonates and other buffering agents may be used.

As additives used in addition to the above components, development inhibitors such as sodium bromide, potassium bromide, potassium iodide: ethylene glycol, diethylene glycol, triethylene glycol, dimethylformamide, methyl cellosolve, hexylene glycol, Organic solvents such as ethinol and methanol: 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzimidazole
Mercapto-based compounds such as sodium 5-sulfonate, 5
-Indazole-based compounds such as nitroindazole, may contain an antifoggant such as benztriazole-based compounds such as 5-methylbenztriazole, and if necessary, toning agents, surfactants, defoaming agents, water softeners, JP-A-56
The amino compound described in No. 106244 may be included.

In the present invention, a silver stain preventing agent is added to the developer,
For example, the compounds described in JP-A-56-24347 can be used. Amino compounds such as alkanolamines described in JP-A-56-106244 can be used in the developer of the present invention.

Further, the amino compounds described in JP-A-56-106244 can be further contained.

Specific examples of the water-soluble aluminum compound used in the present invention are preferably aluminum halides, phosphates, sulfates and carbonates. Further, it may be a double salt such as potassium alum and sodium alum. The addition amount of aluminum ions is preferably 1.0 × 10 ^{-2 to} 0.5 × 10 ^-1 mol / liter.

The p of the fixing solution prepared from the fixing agent of the present invention
H is 3.8 to 6.0, preferably 4.2 to 5.5.

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,
It is used by being dissolved, and more preferably, by being supplied as an ammonium salt and used by being dissolved, a fixing solution having a high fixing speed 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 used by dissolving them in an aqueous solvent, and 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.

As the fixing agent, various acids other than 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, and JP-A-57-6840. Amphoteric surfactants described in "Fixing Solution for Photographs" and the like.

Examples of the wetting agent include alkanolamine and alkylene glycol.

As the fixing accelerator, for example, JP-B-45-357
No. 54, JP-B-58-122535 and JP-A-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 such as sulfuric acid, boric acid, aminopolycarboxylic acids and salts are preferred. The preferable addition amount of the additive is 0.5 to 20 g / l.

In the developer and / or the fixing agent of the present invention, the polyhydroxybenzenes and the aluminum compound preferably have an average particle size of 10 to 200 μm, more preferably 10 to 200 μm. And a solid processing agent granulated and molded using an aluminum compound.

The silver halide photographic light-sensitive material to which the developer and / or fixing agent of the present invention can be applied can be manufactured by a method known in the art.

The above light-sensitive material is a medical or industrial photographic material,
Photosensitive materials for photoengraving, microphotographic materials, X-ray photographic materials, micro-reversal photographic materials, computer typesetting films, papers, negative photographic materials for general photography, black-and-white photographic materials such as photographic papers, preferably photosensitive materials for photoengraving. And more preferably JP-A-52-18317, JP-A-53-95618, and JP-A-58-173.
A photographic light-sensitive material containing a hydrazine derivative as described in Nos. 737 and 58-106493.

[0050]

EXAMPLES Hereinafter, the effects of the present invention will be specifically illustrated by examples.

Example 1 (Preparation of Fixing Agent) Solid fixing agents F1 to F12 shown in Table 1 below.
Was prepared. The average particle size of each material was prepared by crushing the material with a crusher or crushing with an air jet mill.

For F1 to F6, each material is mixed for each ABC part, and polyethylene / Al / having a polyethylene inner surface is used.
A moisture-proof container each with a paper structure
Samples were filled by filling C and B in this order. F7 ~ F12
For each of A, B and C parts, add 12% of the total amount of water to make a granular solid with an average particle size of 5 mm by the fluidized bed agitation granulation method, and after drying, mix each part and The same samples as above were sealed in one moisture-proof container to prepare samples.

[0053]

[Table 1]

(Evaluation of Fixing Agent) Fixing Agent Samples F1 to F
12 as it is and as a substitute evaluation assuming long-term storage
After storing at 50 ° C for 1 day, the mixture was poured into water at room temperature with stirring, and the time until complete dissolution was visually evaluated. The evaluation results are shown in Table 2.

[0055]

[Table 2]

From the results shown in Table 2, it is clear that the solid fixing agent of the present invention has good solubility and little deterioration in solubility during storage. In addition, the solid fixing agent of the present invention is smaller in both volume and weight than a concentrated solution fixing agent using the same raw material formulation, and it is obvious that it is advantageous in transportation and storage. Further, in the present invention, F8 to F11 do not cause adhesion of the fixing agent to the packaging material container after use, and cause no problem when the packaging material container is discarded.

Example 2 (Preparation of photosensitive material for evaluation) (Synthesis of latex Lx) 0.125 kg of gelatin in 40 l of water
And liquid temperature of ammonium persulfate 0.05Kg, liquid temperature 80 ℃
While stirring under a nitrogen atmosphere, a mixture of (a) n-butyl acrylate 4.51 kg, (a) styrene 5.49 kg, and (c) acrylic acid 0.1 kg was added over 1 hour, and then 1.5
After stirring for 1.25 hours, gelatin 1.25 kg and ammonium persulfate 0.00
After adding 5 Kg and stirring for 1.5 hours, after completion of the reaction, steam distillation was carried out for another 1 hour to remove residual monomers, and after cooling to room temperature, the pH was adjusted to 6.0 using ammonia. The obtained latex liquid was adjusted to 50.5 Kg with water.

As described above, the average particle size is 0.25 μm and the Tg is
A monodisperse latex at about 0 ° C. was obtained.

(Preparation of Emulsion A) A silver sulfate solution and a solution prepared by adding a rhodium hexachloride complex to an aqueous solution of sodium chloride and potassium bromide so as to have a concentration of 8 × 10 ^-5 mol / Agmol were flow-controlled in the gelatin solution. While simultaneously adding and desalting, a cubic crystal, monodisperse, silver chlorobromide emulsion having a grain size of 0.13 μm and containing 1 mol% of silver bromide was obtained.

This emulsion was subjected to sulfur sensitization by a conventional method, 6-methyl-4-hydroxy-1,3,3a, 7-tetrazaindene was added as a stabilizer, and then the following additives were added to coat the emulsion. Liquid E
-1 to 14 are prepared, and then emulsion protective layer coating solution P-0, backing layer coating solution B-0, backing protective layer coating solution BP-0.
Was prepared with the following composition.

(Preparation of Emulsion Coating Solutions E-1 to 14) Compound (a) 1 mg / m ² NaOH (0.5N) Adjusted to pH 5.6 Compound (b) 40 mg / m ² Compound (c) 30 mg / m ² savonin (20%) 0.5cc / m ² sodium dodecylbenzenesulfonate 20mg / m ² 5-methylbenzotriazole 10mg / m ² compound (d) 2mg / m ² compound (e) 10mg / m ² compound (f) 6mg / m ² Latex Lx Amount shown in Table 1 Styrene-maleic acid copolymerizable polymer (thickener) 90 mg / m ²

[0062]

[Chemical 1]

[0063]

[Chemical 2]

(Emulsion protective layer coating solution P-0) Gelatin 0.5 g / m ² compound (g) (1%) 25 cc / m ² compound (h) 120 mg / m ² Spherical monodisperse silica (8 μ) 20 mg / m ² 〃 (3μ) 10mg / m ² compound (i) adjusted to 100 mg / ^{m 2} citric acid pH 6.0 (backing layer coating solution B-0) gelatin 1.0 g / m ² compound (j) 100mg / m ² compound (k ) 18 mg / m ² compound (l) 100 mg / m ² savonine (20%) 0.6 cc / m ² latex (m) 300 mg / m ² 5-nitroindazole 20 mg / m ² styrene-maleic acid copolymerizable polymer (thickening Agent) 45 mg / m ² glyoxal 4 mg / m ² compound (o) (backing protective layer coating liquid BP-0) gelatin 0.5 g / m ² compound (g) (1%) ² cc / m ² spherical polymethylmethacrylate (4 μ) 25 mg / m ² sodium chloride 70 mg / m ² glyoxal 22 mg / m ² compound (n) 10 mg / m ²

[0065]

[Chemical 3]

[0066]

[Chemical 4]

[0067]

[Chemical 5]

Each of the coating solutions prepared as described above was applied on a polyethylene terephthalate base having a thickness of 100 μ and subjected to 10 W / (m ² · mi) as shown in JP-A-59-19941.
After the corona discharge was applied in n), it was applied with the following composition using a roll-fit coating pan and an air knife. In addition, it is dried at 90 ℃ and the overall heat transfer coefficient is 25 Kcal (m ² · h
r · ° C.) parallel flow drying conditions for 30 seconds, followed by 140 ° C. for 90 seconds. The film thickness of this layer after drying was 1 μ, and the surface resistivity of this layer was 1 × 10 ⁸ Ω at 23 ° C. and 55%.

[0069]

[Chemical 6]

Ammonium sulfate 0.5 g / l Polyethylene oxide compound (average molecular weight 600) 6 g / l Curing agent 12 g / l

[0071]

[Chemical 7]

On this base, first, the emulsion layer side and emulsion protective layer side in this order from the side closer to the support as the emulsion surface side were simultaneously coated in multiple layers by the slide hopper system while maintaining the temperature at 35 ° C. while adding a hardener solution, and set with cold air. After passing through the zone (5 ° C.), the backing layer and the backing protective layer were coated by the slide hopper while adding the hardening agent, and set with cold air (5 ° C.). The coating liquid showed sufficient setting properties when passing through each set zone. Subsequently, both sides were simultaneously dried in the drying zone under the following drying conditions.
After coating both sides of the backing, it was conveyed until it was wound up with a roller and without contact with anything else. At this time, the coating speed was 100 m / min.

(Drying conditions) After setting, the product was dried with a dry air at 30 ° C. until the weight ratio of H ₂ O / gelatin reached 800%, and then 800 to 20.
0% was dried with 35 ° C (30%) dry air, and the air was blown as it was, and after 30 seconds from the time when the surface temperature reached 34 ° C (which is considered as the end of drying), it was dried with 48 ° C 16% air for 1 minute. . At this time,
Drying time is 50 seconds from the start of drying to 800% of H ₂ O / Gel, 800
% -200% is 35 seconds, and 200% -drying is 5 seconds.

This photosensitive material was wound up at 23 ° C. and 15% and then cut under the same environment.

(Preparation of Developer) Solid developers D1 to FD12 shown in Table 3 below were prepared. The average particle size of each material was prepared by crushing the material with a crusher or crushing with an air jet mill.

For D1 to D6, the respective materials were mixed for each A and B parts, and the A and B parts were respectively placed in a moisture-proof container having a polyethylene / Al / paper structure having a polyethylene inner surface from the top, A and B, respectively. The sample was filled and sealed in the order of.
D7 to D12 are the total amount of material for A and B parts respectively.
Add 12% water and average particle size 3 by fluidized bed agitation granulation method
A mm-sized granular solid was prepared, dried, and then each part was mixed and enclosed in one moisture-proof container as described above to obtain a sample.

[0077]

[Table 3]

(Evaluation of Developer) Developer Samples D1 to D
12 as it is and as a substitute evaluation assuming long-term storage
After storing at 50 ° C for 1 day, the mixture was poured into water at room temperature with stirring, and the time until complete dissolution was visually evaluated.

Further, the film for evaluation was subjected to wedge exposure,
With the developer and fixer CFL-871 (manufactured by Konica [Co.]), the processing time was 28 [deg.] C. and 30 seconds with an automatic processor GR-27 (manufactured by Konica [Co.]) to obtain a density of 3.5. The reciprocal was taken as the sensitivity. The results are shown in Table 4.

[0080]

[Table 4]

From the results shown in Table 4, it is clear that the solid developer of the present invention has good solubility and little deterioration in sensitivity during storage. In addition, the solid fixing agent of the present invention is smaller in both volume and weight than a concentrated solution fixing agent using the same raw material formulation, and it is obvious that it is advantageous in transportation and storage. Further, among the present invention, D8 to D11 did not cause adhesion of the fixing agent to the packaging material container after use, and did not cause a problem when the packaging material container is discarded.

[0082]

According to the present invention, it is possible to provide a solid processing agent which is easy to transport and store, has good solubility, is free from deterioration of solubility and photographic performance during storage, and is excellent in environmental suitability. I was able to.

Claims (2)

[Claims] 1. A black-and-white photographic developer containing polyhydroxybenzenes, wherein at least the polyhydroxybenzenes among the raw materials of the developer are used by adjusting the average particle size to 10 to 500 μm in advance. A solid black and white photographic developer characterized by. 2. A black-and-white photographic fixing agent containing a water-soluble aluminum compound, wherein the fixing agent contains at least the aluminum compound among the raw materials in advance with an average particle size of 10 to 50.
A solid black-and-white photographic fixing agent characterized by being used after being adjusted to 0 μm.