JPH09127657A - Solid photographic treating agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To prevent powdering of a treating agent and to obtain good solubility by forming a powdery photographic chemicals into a briquet of a specified size and shape. SOLUTION: This solid photographic treating agent contains such a briquest that is produced from at least one kind of source material powder by using a roll pocket and that has a thick part and a flange part in the center part in the thickness direction of the peripheral part. The max. thickness t(mm) of the briquet is 2.0-10.0mm and the minor axial length a(mm) of the principal plane of the briquet satisfies t/a=0.50 to 0.90. The are photographic chemicals which are especially preferable to be formed into a briquet are dihydroxybenzenes such as hydroquyinone which are used as the component of a developer. This kinds of photographic chemical easily causes capping or squeaking when the chemicals are formed into a tablet, and therefore, it has low productivity. However, when the chemicals are formed into the shape and size above described, high productivity is obtd. and the chemical can be produced at a low cost. Moreover, the chemicals thus formed has high solubility and high strength and is hardly broken.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a solid photographic processing agent used in processing a silver halide photographic light-sensitive material (hereinafter also referred to as "light-sensitive material" or "sensitive material").

[0002]

2. Description of the Related Art A silver halide black-and-white photographic light-sensitive material is subjected to processes such as black-and-white development, fixing and washing with water after exposure, and a processing solution such as a black-and-white developing solution, a fixing solution and a washing solution is used. On the other hand, a silver halide color photographic light-sensitive material is subjected to processes such as color development, desilvering, washing with water, and stabilization after exposure, and a color developing (color) developing solution, a bleaching solution, a bleach-fixing solution, a fixing solution, and a washing solution. And a processing solution such as a stabilizing solution.

[0003] These treatment liquids are prepared using various chemicals, and most of the chemicals at this time are in a solid state.

[0004] In addition, these processing liquids
The preparation may be required by the user, but in such a case, in general, in consideration of an inexperienced user, the solution is delivered to the user in the form of a concentrated solution requiring only a dilution operation. However, in such a liquid state, there are many problems in terms of transportation such as liquid leakage, and recently, solid-state treating agents have been reviewed again.

As such a solid photographic processing agent, a powdery one is mentioned first. However, powder processing agents have problems such as scattering, adhesion, and remaining of the powder.

[0006] In order to solve such a problem, it has been proposed to use tablets or the like. However, with such a type of treating agent, there are problems such as pulverization due to friction between tablets and reduction in solubility. Become.

Japanese Patent Application Laid-Open No. 5-127 discloses a method for preventing the powdering due to such fine powdering and improving the solubility.
No. 322, “Compression molding pressure 400-3000 in the production of processing tablets containing powdered or granular drug.
A method for producing a tablet for color-sensitive material processing, which is solidified at kg / cm ² . And "a tablet formed by the above method." However, as a means for carrying out the compression molding method, a tableting machine (a modified version of Tough Press Collect 1527HU manufactured by Kikusui Seisakusho) is only shown in the examples. When a drug for a sensitive material is molded by using such a tableting machine, there is a problem in that the yield rate is low, because failures such as capping and squeaking easily occur during tableting. In order to avoid this, a step of granulating before tableting can be added as described in this publication, but in any case, the productivity becomes low.

Further, JP-A-6-313949 discloses, "A solid processing agent for a silver halide photographic light-sensitive material, wherein a processing tablet obtained by compressing powder or granules has a friability of 5% or less. Is disclosed. That is, the crushability of a tablet obtained by tableting powder or granules is defined by the friability. Specific means for achieving a friability of 5% or less include the range of tableting pressure, the use of a binder, and the coating of the tablet surface. The problems of tableting are as described above. On the other hand, if a binder or coating material is used, even if it is water-soluble, the concentration will increase due to repeated use of the processing liquid, adversely affecting photographic properties, and insoluble matter will adhere to the photosensitive material. Occurs. Further, even if the binder and the covering material are substances which are harmless to the developing process, they may have a harmful effect on the fixing process, and the photographic property may be deteriorated by bringing the developing solution into the fixing solution. . Therefore, this technique has drawbacks in both productivity and photographic quality.

Further, Japanese Patent Laid-Open No. 7-5642 (EP
0611986A1), "Solid processing agents for silver halide photographic light-sensitive materials, wherein the mechanical strength Z of the tablet for processing a color light-sensitive material obtained by compressing powder or granules is 0.3 to 3.5. However, mechanical strength Z = (breaking strength in the direction perpendicular to the pressure applied during molding kg) / (length of the main axis of the tablet m
m)] ”is disclosed.

In this product, the range of mechanical strength is limited to the tableting product of the processing agent for the color sensitive material, but essentially, there are problems in tableting in the same manner as described above. is there. Further, it is also described that after granulation and tableting, as shown in the examples of the above-mentioned publication, a granulation aid such as polyethylene glycol is added during granulation, similar to the above. However, there is a concern that such additives may adversely affect photographic properties.

[0011]

The object of the present invention is that it can be applied to all photographic chemicals, the raw material powder can be used as it is without any processing such as granulation and coating, and a binder for solidification, etc. No need for additives, no deterioration in photographic properties due to these additives, no deterioration in quality, high yield, excellent productivity, excellent solubility, crushing during transportation and handling, and bulk It is an object of the present invention to provide a solid photographic processing agent containing a molded product which has a high density, is small in the size of the container, does not easily powder during handling, and is advantageous in the handling work environment.

[0012]

This object is achieved by the following constitutions (1) to (8). (1) Includes a briquette having a thick portion obtained by briquetting at least one raw material powder using a roll pocket and a brim portion at a peripheral portion in the thickness direction central portion, and the maximum thickness of the briquette. t (mm) is 2.0 mm to 10.0
mm, and t / a is 0.50 to 0.90 when the minor axis length of the main surface of the briquette is a (mm). (2) When the thickness of the flange is t '(mm), t' / t
Is 0.10 to 0.40, the solid photographic processing agent according to (1) above. (3) The above-mentioned (1) or (2) in which two or more layers are formed by filling the briquette into a container in layers and further filling other components of a treatment liquid containing the raw material powder of the briquette into layers. Solid photographic processing agent. (4) The solid photographic processing agent according to any one of (1) to (3) above, wherein the raw material powder of the briquette is dihydroxybenzenes. (5) A sheet-like molded product obtained by compacting at least one raw material powder, and having a compressive strength [wherein the compressive strength is a flat plate compressed in the same direction as the molding compression direction] Is the value obtained by dividing the load at the time of fracture by the cross-sectional area of the molded product, and the unit is kgf / mm ² . ] Is 0.1
kgf / mm ² solid photographic processing agent which is a ~50kgf / mm ^2. (6) The solid photographic processing agent according to (5) above, which is obtained by crushing the molded product into granules having an average major axis length of 10 mm or less. (7) The solid photographic process according to (6) above, wherein the granules are packed into a container in layers, and further the other components of the processing liquid containing the raw material powder of the granules as a component are packed in layers to form two or more layers. Agent. (8) The solid photographic processing agent according to any one of (5) to (7) above, wherein the raw material powder of the molded product or granule is thiosulfate.

[0013]

In the present invention, since the powdery photographic chemicals are formed into briquettes of a predetermined shape and a predetermined size, it is possible to prevent fine powder formation and to improve the solubility. Further, since it is not necessary to add a binder or an additive for molding, a high quality photograph can be obtained without adversely affecting the photographic property. Particularly, photographic chemicals that are preferably made into briquettes include dihydroxybenzenes such as hydroquinone, which is a developer component. With such photographic chemicals, capping, squeaking, etc. are likely to occur when tableting,
Although the productivity is low, the treating agent molded into the shape and size of the present invention has high productivity and can be provided at low cost. In addition, it is highly soluble, has high strength against impact during handling and transportation, and does not easily crush, so the working environment for handling is good.

Further, when the developer components are packed in layers in a container, the briquettes are less likely to be crushed by vibration, so that diffusion of powder raw materials between layers is less likely to occur in the container packed in layers, and vibration and after storage Little deterioration in photographic property. Therefore, for example, it is unlikely that hydroquinone and an alkaline component come into contact with each other and deteriorate.

Further, in the present invention, the powdery photographic chemical is compacted into a sheet-shaped molded product having a predetermined compressive strength, so that it is possible to prevent pulverization and to improve the solubility. be able to. Further, since it is not necessary to add a binder or an additive for molding, there is no adverse effect on photographic properties. After compacting, the sheet-shaped molded product may be used as it is, or may be further sized by using a crusher into granules having an average major axis length of 10 mm or less. This is preferable in terms of solubility. In addition, when it is filled in a container, it is preferable because it has a high bulk density and can be reduced in volume, and since it is difficult to move in the container, it is also good for preventing crushing during transportation. Particularly preferred photographic chemicals to be compacted are thiosulfates such as ammonium thiosulfate (ATS) and sodium thiosulfate, which are fixing solution components. Such photographic chemicals are prone to malfunctions such as capping and squeaking when tableted, resulting in low productivity.
The molding by the compacting of the present invention has high productivity. In addition, it is highly soluble, has high strength against impact during handling and transportation, and is not easily crushed, so the working environment for handling is good. Thiosulfates such as ATS have poor solubility, and for example, hydroquinone is easily dissolved by the presence of alkali, whereas thiosulfates have no factor for improving the solubility. Therefore, the molded product obtained by compacting is easily dissolved, which is advantageous.

[0016]

[Specific Configuration] Hereinafter, a specific configuration of the present invention will be described in detail.

The solid photographic processing agent of the present invention comprises at least 1
A sheet-shaped molded product containing a raw material powder of various photographic chemicals in a briquette of a predetermined shape and a predetermined size, or having a predetermined compressive strength by compacting, preferably granules obtained by crushing the molded product. Including.

First, the briquette will be described.

The briquette in the present invention is obtained by briquetting using, for example, lens type, almond type or pillow type roll pockets, and as shown in FIG. 1, the briquette thus obtained is It has a thick portion and a flange portion at the center in the thickness direction of the peripheral portion. FIG. 1 shows a perspective view of a briquette, a plan view from the briquette main surface side, and a side view from the thickness direction side. According to FIG. 1, the briquette of the present invention has a maximum thickness t.
(Mm) is 2.0 mm to 10.0 mm, and when the minor axis length of the briquette main surface is a (mm), t / a is 0.50 to 0.
90.

By controlling the shape and size of the briquette as described above, it is difficult to crush, the yield is increased, the powder is less likely to be powdered, and the solubility is sufficient. On the other hand, when the thickness exceeds 10.0 mm, the solubility decreases and 2.
If it is less than 0 mm, it becomes difficult to mold and the molding yield decreases. Further, when t / a exceeds 0.90, the hardness is lowered, and it is apt to be crushed by impact, difficult to mold, and the yield is lowered. Also, when t / a is less than 0.50, the strength against impact becomes small, and the powder is liable to be shattered and the working environment deteriorates.

As shown in FIG. 1, the minor axis length a (mm) means the diameter of the circle in the case of the lens type, and therefore, the major surface is the circle in the case of the almond type and the pillow type. Since it is almost elliptical, it means the minor axis of the ellipse.

The collar length L (mm) is 0.1 to 4.0 mm.
And the major axis b of the almond type and pillow type
(Mm) is 3.0 to 25.0 mm.

The above length and thickness can be determined by measuring with a vernier caliper or the like by appropriately using a magnifying glass or the like.

Furthermore, the thickness t '(m
m) preferably has t '/ t of 0.10 to 0.40. By controlling this ratio within this range, the strength is improved. On the other hand, when this ratio is large, the strength of the briquette itself is small and it is easy to crush by impact, and when it is small, the strength of the brim portion is weak and the briquettes are easily crushed and crushed easily.

The above t and a can be realized by adjusting the shape and size of the roll pocket. In this case, the pressure between the rolls is 0.5ton / cm ² ~
A range of 5 ton / cm ² is preferred. If it is smaller than this, the hardness tends to be small, and it is easily crushed too much by the impact of transportation or handling, and when it is put into a developing machine, it is liable to be shattered and the working environment tends to be deteriorated. If it is too large, it is too hard and the solubility tends to decrease.

Further, t'can be controlled from the relationship with the depth of the roll pocket by adjusting the minimum roll gap S (FIG. 2).

Regarding briquetting, for example, "Granulation Handbook" (edited by Japan Powder Industrial Technology Association, Ohmsha,
p216, 1991).

As the photographic chemicals which are preferably made into briquettes, dihydroxybenzenes such as hydroquinone,
There are phenylenediamines, aminophenols, sulfites and the like, and among them, dihydroxybenzenes such as hydroquinone are preferable. With these photographic chemicals, capping and squeaking easily occur when tablets are used,
The briquette increases the profitability.

In the present invention, the photographic chemicals made into briquettes as described above are used by being packed in a container in layers.
Usually, this photographic chemical is used in a multi-layer filled photographic processing agent having a layer structure of two or more layers together with a component layer composed of other components of a processing liquid as a component. With such a photographic processing agent, briquettes are less likely to be broken by vibration. Therefore, the diffusion of the powder raw material between the layers is unlikely to occur, and the deterioration of the photographic chemicals can be prevented. For example, in a photographic processing agent for a developing solution, it is unlikely that hydroquinone and an alkaline component are deteriorated due to contact with each other, so that there is no quality deterioration due to transportation and storage of the photographic processing agent, and good photographic properties can be obtained. .

Next, a molded product obtained by compacting will be described.

In the present invention, the compression strength of the sheet-shaped molded product obtained by compacting is 0.1 kgf / mm ² to
It is 50 kgf / mm ² . With such a compressive strength, the solubility becomes good and the strength of the molded article becomes sufficient. On the other hand, when the compressive strength exceeds 50 kgf / mm ² , the molded product becomes too hard and the dissolution rate becomes slow. On the other hand, 0.1 kg
If it is less than f / mm ² , the strength of the molded product will be low, it will be easily crushed during handling and transportation, and powder will easily fall into the developing machine and the working environment will deteriorate.

The compacting may be performed by using a roller compactor, and the roller compactor may be a biaxial horizontal roll type or a biaxial vertical roll type.

Here, the compressive strength is a value (kgf / mm ² ) obtained by dividing the load when the molded flat plate sample is subjected to a compression test with a flat plate in the same direction as the molding compression direction and is broken by the cross sectional area of the sample.

The thickness of the sheet-shaped molded product thus obtained is 1.0 to 10.0 mm.

In order to obtain the above compression strength, the compression pressure of the roller compactor is preferably 0.1 ton / cm to 5 ton / cm with respect to the effective roll width.

After the roller compacting, the sheet-shaped molded product may be used as it is, or may be further sized by using a crusher into granules having an average major axis length of 10 mm or less. This is preferable in terms of solubility. Filling in a container is preferable because it has a high bulk density and can be reduced in volume, and it is also suitable for preventing crushing during transportation because it is difficult to move in the container. On the other hand, if the average major axis length exceeds 10 mm, the solubility tends to be poor.

As a disintegrator for making granules, a coarse crusher, a fine crusher and a sizing machine are used. As the crusher, there are a single-axis pin rotor type breaker, a nye floater type breaker, a two-axis rough breaker, and the like. Examples of fine granulators and granulators include uniaxial pin rotor type fish mills, rotary fine granulators, frebits and grooved double roll type roll granulators.

The size of the granules in the above is the average major axis length 1
It is preferably 0 mm or less, more preferably about 1 to 8 mm.

Granules are usually plate-shaped, and the major axis length means the maximum length of the surface corresponding to the compression molding surface. When the surface is circular, the diameter of the circle is oval, and when it is elliptical. The major axis of the ellipse, the long side of the rectangle, etc.

The photographic chemicals which are preferably formed into a sheet-shaped molded product by compacting are thiosulfates such as sodium thiosulfate and ammonium thiosulfate (ATS), sulfites, bisulfites, polyhydroxy such as dihydroxybenzenes. There are benzenes, phenylenediamines, aminophenols and the like, and among them, thiosulfates such as sodium thiosulfate and ammonium thiosulfate (ATS) are preferable. These photographic chemicals are prone to malfunctions such as capping and squeaking when they are tableted, and have low productivity, but the molding by the roller compacting of the present invention has high productivity. In addition, it has high solubility, high strength against impact during handling and transportation, and is difficult to crush.

In the present invention, the photographic chemicals formed into a sheet by compacting are filled in a container for use. In particular, it is preferable that the crushed and granulated product is used as a so-called multi-layer filling type photographic processing agent,
It is preferable to use it by filling the container in layers. Even if it is a sheet-shaped molded product, it can be used as a multi-layer filled photographic processing agent by controlling its size.

The container used in the present invention may be either a bottle, a bag or the like, but in particular, the main body of the bottle container is a bellows body (for example, it is described as a liquid container in JP-A-6-301189). It is preferable to use a bottle that has been used. Such a bottle-shaped container is easy to handle after use, including disposal. As the bottle material, a flexible plastic material such as low density polyethylene, high density polyethylene, polyethylene terephthalate, polypropylene, or a laminated composite material of polyethylene / polyamide / polyethylene is preferable. Further, it is preferable that the bottle-shaped container is sealed with a seal and a cap after filling the drug. Although the size of the bottle depends on the amount of the photographic processing agent to be filled, a bottle having a volume of about 200 ml to 5 liters is usually used. The thickness of the plastic material is about 100 to 700 μm.

The material of the bag container may be a laminated material of Al and the above plastic material.

The solid photographic processing agent of the present invention can be used for preparing various processing solutions for silver halide photographic light-sensitive materials. In particular, briquettes are dihydroxybenzenes such as hydroquinone which is a developing agent for black and white developing solutions. Since it is preferably applied, it is preferable to use this as a multi-layer filling type solid photographic processing agent for preparing a developer for a black and white sensitive material, which is filled in layers. On the other hand, the molded product by compacting and the granules obtained from this molded product are
It is preferably applied to thiosulfates such as sodium thiosulfate and ammonium thiosulfate, which are fixing agents for the fixing solution.

First, a developing solution and a fixing solution for a silver halide black-and-white photographic light-sensitive material which is preferably prepared by using the solid photographic processing agent of the present invention will be described.

The developing agent used in the developer for black and white light-sensitive material is not particularly limited, but preferably contains dihydroxybenzenes and ascorbic acid derivatives, and in view of developing ability, dihydroxybenzenes and ascorbic acid. A combination of the derivative and 1-phenyl-3-pyrazolidone or a combination of the dihydroxybenzene or ascorbic acid derivative and p-aminophenol is preferable.

Examples of the dihydroxybenzene developing agent include hydroquinone, chlorohydroquinone, isopropylhydroquinone and methylhydroquinone, and hydroquinones are particularly preferable. Ascorbic acid derivative developing agents include ascorbic acid, isoascorbic acid and salts thereof.

The developing agents for 1-phenyl-3-pyrazolidone or its derivatives include 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone and 1-phenyl-4-methyl-4. -Hydroxymethyl-3-pyrazolidone and the like. Examples of the p-aminophenol-based developing agent used in the present invention include N-methyl-p-aminophenol, p-aminophenol and N-
(Β-hydroxyethyl) -p-aminophenol, N
Although there are-(4-hydroxyphenyl) glycine and the like, N-methyl-p-aminophenol is preferable among them.

The dihydroxybenzene type developing agent and the ascorbic acid type developing agent are usually preferably used in an amount of 0.05 to 0.8 mol / liter. When a combination of dihydroxybenzenes and the like and 1-phenyl-3-pyrazolidones or p-aminophenols is used, the former is 0.05 to 0.5 mol / liter and the latter is 0.06 mol / liter or less. It is preferably used in an amount.

A preservative is preferably added to the developer. As the preservative, it is preferable to use a sulfite salt such as sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite, and formaldehyde sodium bisulfite. This sulfite is preferably used in an amount of 0.20 mol / liter or more, particularly 0.3 mol / liter or more, but if added in an excessively large amount, it precipitates in the developer and causes liquid contamination, so the upper limit is 1.2 mol. It is desirable to set it to / liter.

The developing solution has a pH of 9 to 13, especially 9.
It is preferably set to 5-12. Therefore, an alkaline agent for setting the pH is added to the developer. As such an alkaline agent, a hydroxide is preferable, and specifically, an alkali hydroxide such as sodium hydroxide, potassium hydroxide or lithium hydroxide is preferable. Among them, widely used sodium hydroxide is preferable. Furthermore, it is preferable to add a pH buffer. Examples of the buffer include carbonates such as potassium carbonate and sodium carbonate, bicarbonates such as sodium bicarbonate and potassium bicarbonate, sulfites such as sodium sulfite, potassium sulfite and ammonium sulfite, sodium bisulfite and potassium bisulfite. Bisulfite and the like are preferable. Of these, potassium carbonate, sodium carbonate, sodium sulfite and the like are preferable. Further, as a buffering agent, boric acid described in JP-A-62-186259, saccharides (for example, saccharose), oximes (for example, acetoxime) and phenols (for example, 5-for example, described in JP-A-60-93433). Sulfosalicylic acid), tertiary phosphate (for example, sodium salt, potassium salt) and the like may be added.

Additives other than those mentioned above include development inhibitors such as sodium bromide and potassium bromide; organic solvents such as ethylene glycol, diethylene glycol, triethylene glycol and dimethylformamide;
Development promoters such as alkanolamines such as diethanolamine and triethanolamine, imidazole or derivatives thereof; mercapto compounds such as 1-phenyl-5-mercaptotetrazole, indazole compounds such as 5-nitroindazole, and benzotriazole compounds. It may be included as an inhibitor or a black pepper inhibitor, and may further contain a toning agent, a surfactant, an antifoaming agent, a water softener, a hardener, etc., if necessary. Further, a compound described in JP-A-62-212651 can be used as a development unevenness preventing agent, and a compound described in JP-A-61-267759 can be used as a dissolution aid.

The fixing agent contained in the fixing solution for black and white light-sensitive material is not particularly limited, but ammonium thiosulfate, sodium thiosulfate, ammonium sodium thiosulfate and / or a mixture thereof is preferably used.
The amount of these fixing agents used can be changed as appropriate, and the concentration in the fixing solution is generally 0.7 to about 3.0 mol / liter.

The fixing solution may contain a water-soluble aluminum salt which acts as a hardening agent, and is not particularly limited, but examples thereof include aluminum chloride, aluminum sulfate, potassium alum, sodium alum, and ammonium alum. There are inorganic aluminum salts such as banana, aluminum nitrate and aluminum chlorate, and organic aluminum salts such as aluminum lactate. It is preferable that these are contained at an aluminum ion concentration of 0.01 to 0.15 mol / liter in the used liquid.

Gluonic acid, 5-sulfosalicylic acid, iminodiacetic acid, tartaric acid, citric acid, malic acid, glucoheptanoic acid, boric acid and / or derivatives thereof may be used in combination in the fixing solution as an aluminum stabilizer. It is preferable that the liquid used is 0.001 to 0.45 mol / liter, more preferably 0.004 to 0.4 mol / liter.

In addition, if desired, a compound capable of stabilizing aluminum and softening water (for example, gluconic acid, iminodiacetic acid, 5-sulfosalicylic acid, glucoheptanic acid and derivatives thereof, malic acid, tartaric acid, citric acid, Oxalic acid, maleic acid, glycolic acid, benzoic acid, salicylic acid, tyrone, ascorbic acid, glutaric acid, aspartic acid, glycine, cystine, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, 1,3-propanediaminetetraacetic acid, nitrilotriacetic acid, Sugars, lactic acid, boric acid, etc.), preservatives (eg sulfite, bisulfite, etc.),
pH buffering agents (eg, acetic acid, sodium acetate, sodium carbonate, sodium hydrogen carbonate, phosphoric acid, succinic acid, adipic acid, etc.), pH adjusting agents (eg, sodium hydroxide, ammonia, sulfuric acid, etc.), JP-A-62-1 78551
The compounds described in the above publication, surfactants, wetting agents, fixing accelerators and the like can be included. Examples of the surfactant include anionic surfactants such as sulfates and sulfone oxides, polyethylene surfactants, JP-A-57-684.
The amphoteric surfactants described in JP-A-0 can be mentioned, and known defoaming agents can also be used. Examples of the wetting agent include alkanolamine and alkylene glycol.
Examples of the fixing accelerator include Japanese Patent Publication No. 45-35754.
No. 58-122535, No. 58-122.
536, a thiourea derivative described in Japanese Patent No. 536, 536, an alcohol having a triple bond in the molecule, a thioether compound described in U.S. Pat. No. 4,126,459, JP-A-64-4739,
A mercapto compound described in JP-A-1-4739, JP-A-1-159645 and JP-A-3-101728, a mesoionic compound described in JP-A-4-170539, and ammonium thiocyanate may be included.

The pH of the fixing solution is 4.0 or more, and particularly 4.7 to.
It is preferably set to 5.1.

Known processing conditions may be used, and development is preferably carried out for 40 seconds or less, preferably for 6 to 35 seconds and at a temperature of 25 to 50 ° C., preferably 30 to 40 ° C. The replenishing amount of the developing solution is preferably about 100 to 500 ml per 1 m ^{2 of the} light-sensitive material. The fixing time is 40 seconds or less, preferably 6 to 35 seconds and 25 to 25 seconds.
It is preferable to carry out at a temperature of 50 ° C., preferably 30 to 40 ° C. Fixer replenishment rate is 80 to 600 per 1 m ² of sensitive material
It is preferably about ml. After development and fixing, washing and stabilization are performed. The treatment time and temperature may be 40 seconds or less, usually 10 to 30 seconds, and 0 to 50 ° C. Further, the replenishment amount may be 3 liters or less per 1 m ^{2 of the} light-sensitive material, and the replenishment amount may be 0, that is, washing with water.

The molded product obtained by compacting and the granules obtained therefrom may be used for preparing a fixing solution for a color light-sensitive material, and are particularly effective when a thiosulfate is used as a fixing agent. As for the composition of the fixing solution for color light-sensitive materials, the fixing agents used in the fixing solution are known fixing agents, that is, thiosulfates such as sodium thiosulfate and ammonium thiosulfate; sodium thiocyanate, ammonium thiocyanate and the like. Thiocyanate: a thioether compound such as ethylenebisthioglycolic acid, 3,6-dithia-1,8-octanediol, and a water-soluble silver halide solubilizer such as thioureas, and one or two of these may be used. The above can be mixed and used. Preference is given to using thiosulfates, especially ammonium thiosulfates. The amount of the fixing agent per liter is 0.3 to
2 mol is preferred.

The fixing solution preferably contains a sulfite ion-releasing compound such as sulfite, bisulfite, and metabisulfite as a preservative. These compounds are preferably contained in an amount of about 0.02 to 0.05 mol / liter in terms of sulfite ion, and more preferably 0.04 to 0.40 mol / liter. As a preservative, ascorbic acid, a carbonyl bisulfite addition product, a carbonyl compound, or the like may be added.

In addition, a buffer, a fluorescent whitening agent, and
A chelating agent, a defoaming agent, an antifungal agent and the like may be added as necessary. In the fixer, the preferable pH range is 3 to
9, and more preferably 4-8.

In addition, various processing solutions such as a color developing solution are used for processing the color light-sensitive material. For details of these processing solutions and processing, refer to the description of JP-A-6-301189. be able to.

The light-sensitive material is usually processed using an automatic processor. The black-and-white photographic light-sensitive material may be a general black-and-white photographic light-sensitive material, particularly a photographic material for a laser light source, a light-sensitive material for printing, a direct medical X-ray photosensitive material, a medical indirect X-ray photosensitive material. , CRT image recording light-sensitive materials, microfilms, and general photographic light-sensitive materials. The color photographic light-sensitive material includes a color negative film, a color negative paper, a color reversal paper, an auto positive paper, a color reversal film, a negative film for movies, a positive film for movies.

[0064]

The present invention will be specifically described below with reference to examples.

Example 1 The developer has the following composition in which the amount of each component is 10 liters. Composition Hydroquinone 400 g Potassium bromide 30 g Potassium metabisulfite 808 g Diethylenetriamine pentaacetic acid 20 g 2-Mercaptobenzimidazole-5-sodium sulfonate 3 g 5-Methylbenzotriazole 1.6 g Potassium hydroxide 400 g Potassium carbonate 615 g

Of the above components, hydroquinone was molded into briquettes of various shapes shown in Table 1 (see FIG. 1) using a briquetting machine (Pharmapactor L200 / 50P manufactured by Hosokawa Micron Corp.). The resulting briquette samples were evaluated for compressive strength, pulverization degree after vibration test, solubility and yield. The results are shown in Table 2.

Further, hydroquinone (HQ) was added to a rotary tableting machine (Tough Press Collect 1257H manufactured by Kikusui Co., Ltd.).
Using (U), tablets were formed into a cylindrical shape (height 5 mm) under the conditions of a diameter of 8 mm and a molding pressure of 1000 kg / cm ² . The evaluation results of this sample are shown in Table 2.

The sizes of the briquette and the tablet were measured visually or with a caliper using a magnifying glass.

The evaluation method is as follows. <Evaluation method> Compressive strength: A flat plate compression test was performed using a compression tester in an atmosphere of 23 ° C. and 50% RH. The compression speed was 5 mm / min, and the compression direction was the same as the compression during molding. Strength is breaking load
The value obtained by dividing kgf by the cross-sectional area mm ² of the sample was used.

Degree of pulverization: A sample was put in a 100 ml polybin up to a height of 1 cm from the mouth, covered with a lid, set in a vibration tester, and vertically oscillated for 30 minutes at an amplitude of 1 cm and a frequency of 300 cpm. The sample was sieved through a 300 μm mesh to determine the weight percentage of the powder passing through.

Solubility: 200 g of a sample was put into a 5 liter dissolution tank containing water at 5 ° C. and stirred, and the time until dissolution was examined. ◯ for 30 minutes or less, Δ for more than 30 minutes to 60 minutes. And those exceeding 60 minutes were marked with x.

Proportion: The ratio of briquettes or tablets obtained by treating 25 kg of powder raw material was obtained.

[0073]

[Table 1]

[0074]

[Table 2]

Example 2 Each of the hydroquinone briquette and the tableted product obtained in Example 1 was used to form a polyethylene bottle container (container body: bellows, average wall thickness: 500 μm, container volume: 1 liter). As shown in 3, the composition was laminated and filled with other components. Use a vibration tester to measure this with the container.
After oscillating at a frequency of 300 cpm for 5 hours, 60 ℃ 80%
It was aged for 2 weeks under RH environment. The developing solution obtained by dissolving this was evaluated for photographic properties. Immediately after the filling, each photographic property obtained by dissolving the vibrated product was evaluated. The results are shown in Table 4.

The bottom layer is sodium hydroxide pellets (average particle size 7 mm) and potassium carbonate powder (average particle size 500).
The second layer is potassium bromide (average particle size 600 μm), potassium metabisulfite (average particle size 30 μm).
0 μm), diethylenetriamine pentaacetic acid (average particle size 10
0 μm), sodium 2-mercaptobenzimidazole-5-sulfonate (average particle size 200 μm) and 5-
A mixed layer of methylbenzotriazole (average particle size: 150 μm) was formed.

The photographic properties were examined for sensitivity and contrast (γ) as follows.

The components shown in Table 3 were dissolved in water to obtain 10 liters of a working solution. This used solution was diluted 2 times and tested.

Using sensitizing material LS-A manufactured by Fuji Photo Film Co., Ltd., it was exposed to xenon flash light having an emission time of 10 ^-5 sec through an interference filter having a peak at 488 nm and a step wedge, and then exposed at 35 ° C. After developing for 30 seconds, fixing
It was washed with water and dried. The sensitivity is shown by the relative value of the reciprocal of the exposure amount giving 1.5, and the relative sensitivity when treating agent No. 9 is 100.

As an index (γ) representing the contrast of an image, a point of fog + density 0.3 to a point of fog + density 3.0 of the characteristic curve is connected by a straight line, and the slope of this straight line is expressed as a γ value. That is, γ = (3.0-0.3) / [lo
g (exposure amount giving a density of 3.0) -log (density of 0.3
Exposure amount) which gives a higher γ value, indicating that the photographic characteristics have higher contrast.

[0081]

[Table 3]

[0082]

[Table 4]

From Table 4, it can be seen that the samples of the present invention, which are less crushed by vibration, are prevented from diffusing during storage, so that deterioration of photographic performance due to storage is suppressed.

Example 3 The fixer has the following composition in which the amount of each component is 1 liter.

Composition Ammonium thiosulfate 150.0 g Ammonium alum 26.0 g Sodium bisulfite 20.0 g Sodium acetate 2.0 g Tartaric acid 2.0 g

Of the above components, ammonium thiosulfate was used to obtain a thickness of 3 using a roller compactor (roll diameter 200 mm, roll width 60 mm) at roll pressures shown in Table 5.
It was molded into a sheet of mm and further crushed by a crusher so that the average major axis length was about 5 mm.

The resulting granule sample (3 mm thick × 5 mm × 5 mm size) was evaluated for compressive strength, pulverization degree after vibration test, solubility and yield.

Further, ammonium thiosulfate (ATS)
A Kikusui rotary tablet press (Tough Press Collect 1
257 HU) diameter 8 mm, molding pressure 1000 kg / m
Tableted into a cylindrical shape (height 5 mm) under the condition of ² . The evaluation results of this sample are shown in Table 5.

The sizes of the granules and tableted products were measured visually or with a caliper using a loupe.

The evaluation method is as follows. <Evaluation method> Compressive strength: A flat plate compression test was performed using a compression tester in an atmosphere of 23 ° C. and 50% RH. The compression speed was 5 mm / min, the compression direction was the same as the compression at the time of roller compaction, and the molded product sample before crushing was performed. Strength is breaking load kgf
The value obtained by dividing the cross-sectional area of the sample by mm ² was used.

Degree of pulverization: A granule sample of 100 mm was put into a polybin up to a height of 1 cm from the mouth, covered with a lid, and set in a vibration tester. The amplitude was 1 cm in the vertical direction and the frequency was 300 cpm at 30
Shake for a minute. The sample was sieved through a 300 μm mesh to determine the weight percentage of the powder passing through.

Solubility: 600 g of the granule sample was put into a 5 liter dissolution tank containing water at 5 ° C., stirred and the time until dissolution was examined.
Minutes were marked with Δ, and those exceeding 60 minutes were marked with x.

Proportion: The proportion of molded granules or tablets obtained by treating 25 kg of powder raw material was determined.

[0094]

[Table 5]

[0095]

According to the present invention, it is possible to obtain a solid photographic processing agent which is less likely to be crushed by vibration and has a good working environment including a molded product which does not easily powder. It is possible to provide a solid photographic processing agent containing a molded product having high yield, high productivity and high solubility. In particular, when the briquette according to the present invention is used in a layered mixture of the developer components, it is difficult to crush against vibration, so that in addition to the above effects, diffusion of powder raw material due to vibration hardly occurs between layers, and further storage is possible. In this case, the deterioration of the photographic property is less likely to occur because the deterioration is small.

[Brief description of the drawings]

FIG. 1 is an explanatory diagram for explaining the shape and size of a briquette.

FIG. 2 is an explanatory diagram of a roll used for manufacturing a briquette.

Claims (8)

[Claims] 1. A briquette having a thick portion obtained by briquetting at least one raw material powder using a roll pocket and a brim portion at a peripheral portion in the thickness direction central portion, the briquette of Maximum thickness t (mm) is from 2.0 mm
10.0 mm, the minor axis length of the briquette main surface is a (mm)
Is a solid photographic processing agent having t / a of 0.50 to 0.90. 2. The solid photographic processing agent according to claim 1, wherein t '/ t is 0.10 to 0.40 when the thickness of the collar portion is t' (mm). 3. The briquette is packed into a container in a layered form, and further the other components of the treatment liquid containing the raw material powder of the briquette as a component are packed into a layered form to form two or more layers. Solid photographic processing agent. 4. The solid photographic processing agent according to claim 1, wherein the raw material powder of the briquette is dihydroxybenzenes. 5. A sheet-shaped molded product obtained by compacting at least one raw material powder, wherein the molded product has a compressive strength [where the compressive strength is a flat plate compressed in the same direction as the molding compression direction]. It is a value obtained by dividing the load when the molded product is broken by the cross-sectional area of the molded product, and the unit is kgf / mm ² . ]
Is 0.1 kgf / mm ^{2 to} 50 kgf / mm ² solid photographic processing agent. 6. The molded product is crushed to obtain an average major axis length of 10
The solid photographic processing agent according to claim 5, which is a granule having a size of not more than mm. 7. The solid photograph according to claim 6, wherein the granules are packed into a container in layers and further other components of a treatment liquid containing the raw material powder of the granules are packed into layers to form two or more layers. Processing agent. 8. The solid photographic processing agent according to claim 5, wherein the raw material powder of the molded product or granule is thiosulfate.