JPH10274829A - Solid processing agent for silver halide photographic sensitive material, package of the same and method for putting the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a solid processing agent fit for an automatic processing machine and having improved preservability and stability by imparting convexity to at least one of plural faces of a compression-molded tablet. SOLUTION: This solid processing agent is a compression-molded tablet having plural faces including at least one convex face. The tablet may have any of the shapes of a spherical body, a cylindrical (columnar) body, a conical body, a square tubular (pillar) body, a pyramidal body, a cubic body, etc., if at least one of plural faces is convex. The pref. shape is the shape of the cylindrical or conical body and it is especially the shape of the cylindrical body from the viewpoint of effect and production. The tablet contains a compd. represented by the formula R-(O)x Sy Oz M [where R is an optionally substd. aliphatic group, an optionally substd. arom. group or an optionally substd. heterocyclic group, (x) is 0 or 1, (y) is 2 or 3, (z) is 2-8 and M is a cation].

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a solid processing agent for a silver halide photographic light-sensitive material (hereinafter also referred to as a "light-sensitive material"), and particularly to a solid which has excellent stability and is suitable for use in an automatic developing machine for a photographic material. The present invention relates to a processing agent, a package of a solid processing agent for a silver halide photographic light-sensitive material, and a charging method.

[0002]

2. Description of the Related Art A processing agent for a photosensitive material is supplied as a concentrated solution kit, and a method of diluting and adjusting the solution at the time of use is mainly used. The concentrated solution kit has the advantages that the solution preparation time is short without concern about the solubility and that the raw material can be used in the form of a solution so that it can be supplied at low cost. On the other hand, because it is a concentrated solution, it adheres to the skin, especially when it gets into the eyes,
High risk and safety issues. Further, since a strong plastic bottle must be used for the container, the weight is large and the volume is large, so that not only the load on the transportation cost is increased, but also the improvement in environmental protection is required.

Therefore, solidification of processing agents has been reviewed from the viewpoints of safety, small size, light weight and compactness, and processing agents in powder form and tablet form have been supplied. However, in the case of the powder form, there is a risk that the dissolving worker may inhale the dust, for example, when the dust flies when dissolving.

Further, it is known that components that interact with each other are stored and supplied in different parts in order to improve the storage stability of the processing agent. In some cases, the components are supplied after being packaged in different packaging materials. Therefore, the method of supplying each part is not preferable from the viewpoint of handling properties during use, misdissolution, dissolution by an automatic dissolution apparatus, and the like.

[0005] While rapid processing by automatic developing machines has become common, automatic developing machines provided with a dissolving device for solid processing agents have also been supplied, and it has been desired to improve the solubility of solid processing agents. In addition, while the method of charging the solid processing agent into the dissolution tank is also desired to be automated, good detachability from the packaging material is also required.

[0006] When the solid processing agent (ie, tablet) formed into a tablet by compression molding is released from the die after compression molding, a broken surface is formed in the tablet along the edge portion of the tablet upper surface, and the broken surface is formed. It is known that a failure called capping, which peels off in a hat shape from the upper side of the cross section, occurs. Furthermore, it is known that a tablet having a convex upper surface has a capping failure easily. Capping failure not only makes tablet production difficult, but also reduces the hardness of the tablet, etc., even if the capping failure does not occur during compression molding. It was a big problem.

[0007] In the processing step of the photosensitive material, the fixing agent used in the fixing step is composed of a thiosulfate as a main agent, a preservative, a hardener, a buffering agent and the like. In rapid processing of a photosensitive material, processing is performed with a fixing solution containing a hardener in an acidic solution to stop the development reaction, prevent scratches and reticulation (crepe wrinkles), and improve drying properties. It is known that salts are unstable and decompose in an acidic solution, and sulfur is separated out.

[0008] On the other hand, it is known that the decomposition of thiosulfate can be prevented by sulfite, but aluminum sulfite is deposited when aluminum salt used as a hardener is in direct contact. Therefore, a one-part solid fixing agent containing a thiosulfate and an acid agent, and an aluminum salt and a sulfite has a problem in storage stability due to precipitation, and it is difficult to produce a one-part fixed solid fixing agent.

Therefore, there has been a demand for the development of a one-part solid processing agent which has no capping failure and has good supply properties.

[0010]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a solid processing agent having improved storage stability and stability which is suitable for processing in an automatic developing machine, a flexible package of a solid processing agent for a photosensitive material, and charging. It is to provide a method.

[0011]

[Means for Solving the Problems]

1. A solid processing agent for a silver halide photographic light-sensitive material, which is a compression-molded tablet having a plurality of surfaces, wherein at least one of the plurality of surfaces is a convex curved surface.

2. 2. The solid processing agent for a silver halide photographic light-sensitive material according to 1, which comprises a compound represented by the following general formula (1).

[0013] Formula (1) _{R- (O) x S y O} z M [wherein, R is a substituted or unsubstituted aliphatic group, a substituted aromatic group, or a substituted unsubstituted, unsubstituted heterocyclic X represents 0
Or 1, y represents 2 or 3, z represents 2 to 8, and M represents a cation. 3. A solid processing agent for a silver halide photographic light-sensitive material, wherein the components in the tablet according to 1 or 2 are divided into at least two components.

A solid processing agent for a silver halide photographic light-sensitive material, wherein the tablet according to any one of 4.1 to 3 has a core and at least one shell layer covering the core.

[0015] 5. 5. The silver halide photographic light-sensitive material according to 4, wherein a tablet having a plurality of surfaces and at least one of the plurality of surfaces is a convex curved surface is used as a core, and at least one shell layer covering the core is provided. Solid processing agent for materials.

6. Solid processing for a silver halide photographic light-sensitive material, characterized in that an inert layer is provided in each layer between a layer containing a water-soluble aluminum salt and at least one layer containing a thiosulfate, and compression-molded. Agent.

[7] The solid processing for a silver halide photographic light-sensitive material according to any one of claims 1 to 6, wherein a tablet containing a water-soluble aluminum salt is used as a core and a shell layer containing at least one thiosulfate is provided. Agent.

A flexible solid processing agent for a silver halide photographic light-sensitive material, wherein a plurality of the solid processing agents according to any one of 8.1 to 7 are enclosed in a package having a plurality of pieces. Sex package.

9. 9. The flexible package according to 8, wherein the package has a plurality of pieces, wherein at least one of the plurality of pieces is opened and a plurality of tablets in the package are charged into a processing apparatus. How to add a solid processing agent for silver photographic materials.

Hereinafter, the present invention will be described in detail.

The solid processing agent for a light-sensitive material of the present invention is a compression-molded tablet having a plurality of surfaces, wherein at least one of the plurality of surfaces is a convex curved surface.

The shape of the tablet of the present invention may be a sphere, a cylinder (a cylinder), a cone, a prism (a prism), a pyramid if at least one of the plurality of surfaces is a convex curved surface as described above. A body, a cube, and the like may be in any shape, but a cylinder and a cone are preferred. In particular, a cylindrical body is preferable in terms of the effects of the present invention and production.

The size of the tablet of the present invention per tablet is 100 to 100,000 mm ³ in terms of handling.
And in production. More preferably, 250 to 1500
0 mm ³ , particularly preferably 500 to 10000 m
m is ^3.

In the present invention, when the shape of the tablet is cylindrical, the diameter of the circle of the cylindrical body is preferably 5 to 4
0 mm, and particularly preferably 10 to 30 mm. Further, the height (maximum thickness length) of the cylindrical body is preferably 1.5 to 18 mm, and particularly preferably 3 to 15 mm.

As a specific example of a tablet having at least one surface having a convex curved surface, the structural features will be described below based on the cross-sectional view of the tablet shown in FIG. 1, but the present invention is limited to FIG. Not something.

FIG. 1 is a sectional view of a tablet showing an example of the present invention.

FIG. 1A shows a cross section of a tablet usually called an R-side tablet. For example, in FIG.
When the diameter is 30 mm, R is a circumference having a radius of 34 mm, when the diameter is 21 mm, R is a circumference having a radius of 25 mm, and when the diameter is 9 mm, R is a circumference having a radius of 13 mm.

FIG. 1B shows a cross section of a tablet usually called a sugar-coated R-face tablet. For example, in FIG. 1B, when the diameter is 30 mm, R is a circumference having a radius of 28.5 mm,
When the diameter is 21 mm, R is a circumference having a radius of 19.5 mm, and when the diameter is 9 mm, R is a circumference having a radius of 7.5 mm.

FIG. 1 (C) shows a cross section of a tablet usually called a semi-flat tablet. For example, in FIG. 1 (C), when the diameter is 30 mm, R is a circumference having a radius of 7.5 mm, and H is 1 .2 mm. When the diameter is 21 mm, R is 5.2.
H is 0.84 mm, R is a circle having a radius of 2.2 mm when the diameter is 9 mm, and H is 0.36 mm.
Becomes FIG. 1 (D) shows a cross section of a tablet usually called a two-stage R-face tablet. For example, in FIG.
When 0 mm, R is a circumference having a radius of 31.5 mm, r is a circumference having a radius of 12 mm, H is 5 mm, and a diameter is 21 mm.
In the above, R is a circumference having a radius of 22.5 mm, r is a circumference having a radius of 8.4 mm, H is 3.5 mm and a diameter is 9 mm.
In this case, R is a circumference having a radius of 10.5 mm, r is a circumference having a radius of 3.6 mm, and H is 1.5 mm. FIG.
(E) represents the cross section of the tablet in which the band portion α of the tablet is a convex curved surface. For example, when the diameter is 30 mm and H is 10 mm, R is a circumference having a radius of 5 mm, and when the diameter is 21 mm and H is 7 mm, R is the radius. The circumference is 3.5 mm. In addition, R, r in each figure
Indicates the radius of curvature of the spherical surface. The above-mentioned diameter means the diameter of the circle of the cylindrical tablet.

1 (A) to 1 (D) have convex curved surfaces on the upper and lower sides of the tablet, respectively, but may have convex curved surfaces only on the upper side or only on the lower side. It may have a curved surface. In the tablet of FIG. 1 (E), the entire circumference has a convex curved surface, but only a specific part of the circumference may have a convex curved surface.

The solid processing agent of the present invention preferably contains the compound represented by the general formula (1). The content is preferably 0.01 to 3.0%, more preferably 0.1 to 2.5%, and still more preferably 0.5 to 2.0% of the total weight of the solid processing agent.

In the general formula (1), examples of the aliphatic group represented by R include an alkyl group, an alkenyl group, and an alkynyl group. Examples of the alkyl group include methyl, ethyl, i-propyl, butyl, and t. -Butyl, pentyl,
Each group includes cyclopentyl, hexyl, cyclohexyl, octyl, dodecyl and the like. These alkyl groups further include a halogen atom (for example, a halogen atom such as chlorine, bromine, and fluorine), and an alkoxy group (for example, methoxy, ethoxy, 1,1-dimethylethoxy, hexyloxy,
Groups such as dodecyloxy), aryloxy groups (such as phenoxy and naphthyloxy), aryl groups (such as phenyl and naphthyl), and alkoxycarbonyl groups (such as methoxycarbonyl, ethoxycarbonyl and butoxycarbonyl). Groups such as 2-ethylhexylcarbonyl), aryloxycarbonyl groups (such as phenoxycarbonyl and naphthyloxycarbonyl), alkenyl groups (such as vinyl and allyl) and heterocyclic groups (such as 2-pyridyl, 3-pyridyl,
4-pyridyl, morpholyl, piperidine, piperazil,
Pyrimidine, pyrazoline, furyl, etc.), alkynyl group (eg, propargyl group), amino group (eg, amino, N, N-dimethylamino, anilino, etc.),
It may be substituted by a cyano group or a sulfonamide group (for example, each group such as methylsulfonylamino, ethylsulfonylamino, butylsulfonylamino, octylsulfonylamino, and phenylsulfonylamino).

Examples of the alkenyl group include a vinyl group,
Examples include an allyl group and the like, and examples of the alkynyl group include a propargyl group.

Examples of the aromatic group represented by R include a phenyl group and a naphthyl group.

Examples of the heterocyclic group represented by R include a pyridyl group (each group such as 2-pyridyl, 3-pyridyl, 4-pyridyl), a thiazolyl group, an oxazolyl group, an imidazolyl group, a furyl group, a phenyl group, A pyrrolyl group, a pyrazinyl group, a pyrimidinyl group, a pyridazinyl group, a selenazolyl group, a sulfolanyl group, a pipedilinyl group, a pyrazolyl group,
And a tetrazolyl group.

The alkenyl group, alkynyl group, aromatic group and heterocyclic group are all the alkyl groups represented by R, the substituents of the alkyl groups, the groups shown as the substituted atoms, the groups and atoms similar to the atoms and the atoms. Can be replaced by

The cation represented by M is preferably a metal ion or an organic cation. Examples of the metal ion include a lithium ion, a sodium ion, and a potassium ion. Examples of the organic cation include an ammonium ion (each ion such as ammonium, tetramethylammonium, and tetrabutylammonium) and a phosphonium ion (eg, tetraphenylphosphonium). Ion), guanidyl ion and the like.

The compound represented by the general formula (1) improves lubricity at the time of compression molding by adding a solid processing agent when it is formed into a tablet by compression molding, but further reduces the friction coefficient of the tablet surface. It has been found that the friction coefficient can be specifically reduced as the contact area becomes smaller, especially when the contact area is small.

Specific examples of the compound represented by the general formula (1) are shown below, but the present invention is not limited thereto.

1-1 C ₂ H ₅ SO ₃ Na 1-2 CH ₃ (CH ₂ ) ₆ SO ₃ Na 1-3 CH ₃ (CH ₂ ) ₇ SO ₃ Na 1-4 CH ₃ (CH ₂ ) ₅ OSO _{3 Na 1-5 CH 3 (CH 2} ) 6 OSO 3 Na 1-6 CH 3 (CH 2) 7 OSO 3 Na 1-7 CH 3 O (CH 2) 2 SO 3 Na

[0041]

Embedded image

The components in the tablet of the present invention are divided into at least two components. As a method of compression molding by dividing the composition into at least two components, for example, a method in which two or more kinds of powders having different components are stacked in layers and compression molded as disclosed in JP-A-5-134362 is mentioned. Can be Such a tablet is generally called a multi-layer tablet, and the powder of different components is sequentially filled in a die of a tablet tableting machine (compression molding machine), and then compressed into a tablet or a powder of one component is compressed. There is a method in which granules are compressed into tablets each time they are filled. Specific examples of the tablet divided into at least two components of the present invention including this multilayer tablet are shown in FIGS.
However, the present invention is not limited to these. In FIG. 2 (F) to (K), the difference in pattern indicates the difference in component.

Further, the tablet of the present invention has a core / shell structure having a core (core) and at least one shell layer covering the core. Tablets having a core / shell structure are commonly referred to as dry-coated tablets.

Further, the tablet having a core / shell structure is preferably a tablet wherein the core has a plurality of surfaces and at least one of the plurality of surfaces is a convex curved surface.

A preferable range of the volume ratio between the core and the shell (core volume Vc / shell volume Vs) is 1/300 to 1
/1.5, more preferably 1/150 to 1/2, and particularly preferably 1/100 to 1/10.

Specific examples of these tablets having a core / shell structure are shown in FIGS. 3 (L) to 3 (R), but the present invention is not limited thereto. In addition, (L) of FIG.
In (R), the difference in pattern indicates the difference in components.

The shape of the tablet having no convex curved surface is shown in FIG.
(S) shows.

The tablet of the present invention is applied to a fixing agent and a developer.

A tablet obtained by applying a tablet as a fixing agent (hereinafter referred to as a fixing tablet) and a fixing solution obtained by dissolving the tablet will be described.

The fixing tablet of the present invention contains a water-soluble aluminum salt and a thiosulfate, and each layer is provided between a layer containing a water-soluble aluminum salt and at least one layer containing a thiosulfate. Tablet having an inert layer.

The substance constituting the inert layer includes, for example, water-soluble polymers. Specifically, water-soluble celluloses, water-soluble dextrins, water-soluble polyethylene glycols, water-soluble polyvinylpyrrolidones, water-soluble polyacrylamides and the like can be used.

Further, the fixing tablet of the present invention is a tablet having a core containing a water-soluble aluminum salt and a shell layer containing at least one thiosulfate.

Further, the tablet may be compression-molded by providing the above-mentioned inert layer on each of the core and the shell between a core containing at least a water-soluble aluminum salt and a shell containing at least a thiosulfate. preferable.

As the water-soluble aluminum salt, potassium alum,
Examples include ammonium alum, calcined alum, calcined ammonium alum, aluminum chloride, aluminum potassium chloride, and aluminum sulfate. Preferably, the following general formula (2)
Is preferably used.

Formula (2) Al ₂ (SO ₄ ) ₃ .nH ₂ O (n = 1 to 20) where n represents an average number, more preferably 4 to 18, and particularly preferably 6 to 12. . The average number of n means an average value when hydrate salts in which n differs are mixed.

The concentration of aluminum sulfate in the fixing solution in which the fixing tablet of the present invention is dissolved is 0.001 to 0.5 mol, preferably 0.005 to 0.5 mol per liter of the fixing solution.
0.3 mol, particularly 0.01 to 0.1 mol, is preferred.

The fixing tablet of the present invention preferably contains an organic acid or an organic acid salt, but preferably contains at least a layer and / or a core containing a water-soluble aluminum salt.

The organic acid preferably used in the fixing tablet of the present invention refers to an organic compound which exhibits acidity. The organic acid salt preferably used in the present invention is a water-soluble salt formed by reacting the organic acid with an alkali hydroxide or ammonium hydroxide.

Examples of the organic acid include carboxylic acids, sulfonic acids, sulfinic acids, phenols, enols, thiols, acid amides, oximes, sulfamides and the like. Acids and sulfinic acids are preferred, and carboxylic acids are particularly preferred.

Examples of the carboxylic acids include formic acid, acetic acid, benzoic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, maleic acid, tartaric acid, malic acid, fumaric acid,
Examples include phthalic acid, citric acid, aconitic acid and the like.

Further, examples of the organic acid salts include salts of the above-mentioned carboxylic acids. For example, sodium acetate, potassium citrate, lithium citrate, sodium citrate,
Ammonium citrate, lithium bitartrate, potassium bitartrate, potassium tartrate, sodium bitartrate,
Examples thereof include those represented by sodium tartrate, ammonium hydrogen tartrate, potassium ammonium tartrate, sodium potassium tartrate, sodium malate, ammonium malate, sodium succinate, ammonium succinate, and the like.

The thiosulfate contained in the fixing tablet of the present invention is specifically used as a salt of lithium, potassium, sodium and ammonium. Preferably, the thiosulfate is used as ammonium thiosulfate and sodium thiosulfate. A fixing solution having a high fixing speed can be obtained.

The fixing tablet of the present invention preferably contains a sulfite. As the sulfite, lithium, potassium, sodium, ammonium salts and the like are used, and preferably sodium sulfite. Also, metabisulfite is preferably used, and sodium metabisulfite is particularly preferable. The sulfite and / or metabisulfite of the tablet of the present invention is preferably contained in a layer or shell containing thiosulfate.

The fixing tablet of the present invention may contain an iodide salt or a thiocyanate as a fixing agent.

Further, a chelating agent may be contained. Examples thereof include aminopolycarboxylic acids such as nitrilotriacetic acid and ethylenediaminetetraacetic acid, and salts thereof.

Further, a surfactant may be contained. Examples thereof include anionic surfactants such as sulfated and sulfonated compounds, nonionic surfactants such as polyethylene glycol and ester, and amphoteric surfactants.

Further, a wetting agent may be contained. For example, alkanolamine, alkylene glycol and the like can be mentioned.

Further, a fixing accelerator may be contained. For example, thiourea derivatives, alcohols having a triple bond in the molecule, thioethers and the like can be mentioned.

The pH of the fixing solution obtained by dissolving the tablet of the present invention in water is preferably 3.8 or more, more preferably 4.
2 to 5.5.

Next, a tablet obtained by applying the tablet of the present invention to a developer (hereinafter referred to as a “developed tablet”) and a developer obtained by dissolving the developed tablet will be described.

The developing tablet of the present invention preferably contains, as a developing agent, reductones, particularly ascorbic acid and / or erythorbic acid (stereoisomer) and salts thereof.

Further, the following developing agents may be contained. Dihydroxybenzenes (for example, hydroquinone, chlorohydroquinone, bromohydroquinone, dichlorohydroquinone, isopropylhydroquinone,
Methylhydroquinone, 2,3-dichlorohydroquinone, methoxyhydroquinone, 2,5-dimethylhydroquinone, potassium hydroquinone monosulfonate, sodium hydroquinone monosulfonate, etc. 3-pyrazolidones (for example, 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, 1-p-tolyl-3-pyrazolidone, 1
-Phenyl-2-acetyl-4,4-dimethyl-3-pyrazolidone, 1- (2-benzothiazole) -3-pyrazolidone, 3-acetoxy-1-phenyl-3-pyrazolidone, etc., aminophenols (for example, o-aminophenol, p-aminophenol, N-methyl-o
-Aminophenol, N-methyl-p-aminophenol, 2,4-diaminophenol, etc.), 1-allyl-
3-aminopyrazolines (for example, 1- (p-hydroxyphenyl) -3-aminopyrazoline, 1- (p-methylaminophenyl) -3-aminopyrazoline, 1- (p
-Amino-m-methylphenyl) -3-aminopyrazoline, pyrazolones (eg, 4-aminopyrazolone), and the like, or a mixture thereof.

The developing tablet of the present invention preferably contains a sulfite and / or metabisulfite. Further, when the tablet is dissolved to form a developer, the amount of sulfite in the solution is 0.05 mol / L or more and less than 0.3 mol / L, and more preferably 0.1 mol / L or less.
It is preferably from 1 mol / liter to less than 0.3 mol / liter.

In addition, as a buffer (for example, carbonate, boric acid, borate, alkanolamine, etc.), an alkaline agent,
Dissolution aids (eg, polyethylene glycols and esters thereof), pH adjusters (eg, organic acids such as citric acid), sensitizers (eg, quaternary ammonium salts), development accelerators, hardeners (eg, Dialdehydes such as glutaraldehyde), a surfactant, and an azole organic antifoggant as an antifoggant (for example, indazole, imidazole, benzimidazole,
Triazole-based, benztriazole-based, tetrazole-based, thiadiazole-based), concealing agents sodium hexametaphosphate, calcium hexametaphosphate for concealing calcium ions mixed in tap water used in the treatment liquid,
A polyphosphate, ethylene triaminepentaacetic acid, or the like may be contained.

Further, a silver stain preventing agent, for example, JP-A-56-2
The compound described in No. 4347 can also be used.

Further, the p of the developing solution obtained from the developing tablet of the present invention is
H is preferably in the range of 10.5 or less, more preferably in the range of 9 to 10.0.

The developer obtained from the developing tablet of the present invention includes:
Amino compounds such as alkanolamines described in JP-A-56-106244 can be used.

In addition, the developer obtained from the developing tablet of the present invention includes F. A. Meson, "Photographic Processing Chemistry", Focal Press (1966), pp. 22-229, U.S. Pat.
3,015, 2,592,364, JP-A-48-48
No. 64933 may be used.

On the other hand, a carbonate having a buffering action is preferable as the alkaline agent. As carbonates, potassium carbonate,
Examples include sodium carbonate and lithium carbonate.

Further, the amount of carbonate in the developing solution is 0.3
It is preferably at least mol / l and less than 0.8 mol / l.

Next, the solidification of the processing agent for a silver halide photographic light-sensitive material will be described. In order to solidify the photographic processing agent, the photographic processing agent in the form of a concentrated liquid, a fine powder or a granular material and a water-soluble binder are kneaded and molded, or the water-soluble binder is added to the surface of the temporarily formed photographic processing agent. Any means can be adopted, such as forming a coating layer by spraying on the surface (Japanese Unexamined Patent Publication No.
No. 29136, 4-85535, 4-85536
Nos. 4-85533, 4-85534, 4-
172341).

As a preferred tablet production method, a solid processing agent component may be simply mixed and formed by a compression tableting step. However, a powdered solid processing agent is granulated in a granulation step and then obtained. A method in which granules are formed in a compression tableting step is more preferable.

As the granulation method, known methods such as tumbling granulation, extrusion granulation, compression granulation, crushing granulation, stirring granulation, fluidized bed granulation, and spray drying granulation can be used. The average particle size of the granules obtained in the granulation step is preferably from 100 to 800 μm in that the components are not made uniform, that is, so-called segregation does not easily occur during pressure compression (compression tableting). , More preferably 200 to 750 μm. Further, the particle size distribution is such that 60% or more of the granulated particles are ± 100 to 1
Those with a deviation of 50 μm are preferred. When the obtained granules are subjected to compression molding (compression tableting), a known compressor is used.
For example, a hydraulic press, a single-shot tableting machine, a rotary tableting machine, a briquetting machine, or the like can be used.

The tablet of the present invention having at least one of a plurality of surfaces having a convex curved surface can be obtained from the above-described compressor equipped with a punch and a die having a desired convex curved surface or a punch having a punch and a die having a desired convex curved surface. Tablets can be easily formed with a tablet machine.

The bulk density of the solid processing agent of the present invention is 0.4 g
/ Cm ^{3 to} 2.5 g / cm ³ , preferably 1.0 g / cm 3
Those having ^{3 to} 2.0 g / cm ³ are more preferable.

The solid processing agent of the present invention falls within the scope of the present invention in that only a part of a certain processing agent is tableted, but preferably all the components of the processing agent are tableted. .

In the tablet of the present invention, each component may be formed as a separate tablet and packaged in the same manner.

When the developer is solidified, all components such as a developing agent, an alkaline agent, a reducing agent, etc. are converted into a solid processing agent, and when compression-molded into a tablet, at least 3 or less, ie, 1 agent When two or more tablets are divided into tablets, these tablets are packaged in the same manner.

It is preferable that all the processing agents to be replenished into each processing tank according to the processing amount information are charged as solid processing agents.
When replenishing water is required, replenishing water is replenished based on the processing amount information or other replenishing water control information. In this case, the liquid to be replenished to the treatment tank can be only replenishing water. That is, when two or more types of processing tanks need replenishment, only one tank is required to store the replenishing liquid by sharing the replenishing water, and the size of the automatic developing machine can be reduced. The replenishing water tank may be provided outside or externally, or may be built in an automatic developing machine, and the built-in water tank is preferable in terms of space saving and the like.

The solid processing agent of the present invention is obtained by enclosing at least one of a plurality of pieces and a plurality of flexible packages into which a plurality of solid processing agents are charged.

A flexible package of the solid processing agent of the present invention and a method for charging the same will be described.

FIG. 5 illustrates a flexible package 1 according to the present invention in which at least one of a plurality of pieces is opened and a plurality of solid processing agents are charged.

The package 1 is composed of a moisture-proof bag 5 and an interior material 2 housed inside the moisture-proof bag, and the tablet type solid processing agent J having a convex curved surface of the present invention is housed therein.

FIG. 6 shows the interior material 2. The interior material has a substantially rectangular substrate 3 and portions 4 extending from three sides of the substrate, 41, 42, and 43, respectively [FIG. a)], the extending portion is bent in the same direction with respect to the substrate to form three surfaces each (FIG. 6 (b)).

FIG. 7 (a) shows an opening portion 7 provided in the back seal portion 6 of the moisture-proof bag, and FIG. 7 (b) cuts a part of the moisture-proof bag into a strip shape to open the opening portion 7. Indicates that the test was performed.

FIG. 8 is a perspective view showing an opened flexible package of the solid processing agent and the state of the solid processing agent J in the package.

Thereafter, the opened package is set and accommodated in a processing agent charging section of the automatic developing machine, and is inclined obliquely downward so as to face the opening from the opening, and is loaded so that the tablet slides down.

Since the contained tablet-type solid processing agent J has a water-absorbing property, the flexible package is required to have moisture-proof properties.

Therefore, the intermediate layer of the moisture-proof bag is provided with an Al layer of 3 to 20 μm, preferably 5 to 10 μm, and the outermost layer is preferably 10 to 40 μm in order to prevent the occurrence of pinholes during transportation and handling. Is 12-30 μm P
It has ET (polyethylene terephthalate) or nylon. The inside of the moisture-proof bag has a substantially rectangular substrate.
It has a portion 4 extending from the side, and these three sides are members that are bent with respect to the substrate, so that the flexible moisture-proof bag can be easily held and the tablet can be stored and taken out reliably. .

The flexible moisture-proof bag is desirably a gusset type from the viewpoints of tablet accommodating and opening properties, and ease of setting in an automatic developing machine.

Further, in order to surely open the moisture-proof bag and load the stored tablet into the automatic developing machine, the gusset-type moisture-proof bag can be opened in a strip shape from the back seal portion to the back seal portion. 7 is preferably provided.

The width of the band is 5 to 25 mm, preferably 8 to 25 mm.
20 mm is good. If the width is smaller than 5 mm, there is a risk of being cut off in the middle, and if it is larger than 25 mm, it becomes difficult to open.

Further, in order to ensure the opening of the band, the lateral tensile strength of the bag is 800 kg / m ² or less, preferably 600 kg / m ² or less, and the longitudinal tensile strength of the bag is ² kg / m ² or less.
000kg / m ² or more, preferably 2,500kg / m ²
As described above, by providing the uniaxially stretched PE (polyethylene) having a thickness of 20 to 80 μm in the intermediate layer of the moisture-proof bag, the band-like opening of the moisture-proof bag can be reliably performed. Furthermore, by using LDPE (low density polyethylene) or EVA (ethylene-vinyl acetate copolymer) having a thickness of 20 to 80 μm as the innermost layer, it is possible to perform a band-like opening with a stable sealing property and a small force. Become.

The member accommodated in the moisture-proof bag has a basis weight of 10
A paper material having a friction coefficient of 0.6 or less and a thickness of 20 to 200 μm laminated on at least one surface of the paper material having a friction coefficient of 0 to 600 g / m ² and a friction coefficient of 0.6 or less. The use of the composite material ensures that the tablets are fed into the automatic processor.

If the grammage is less than 100 g / m ² , the strength of the member becomes weak, causing deformation at the time of handling, which may make it impossible to set the member in an automatic developing machine.

On the other hand, if the basis weight is more than 600 g / m ^2, it is difficult to bend a portion extending from three sides of a substantially rectangular substrate and assemble it, which not only lowers the working efficiency but also increases the cost, which is not preferable.

When the interior material 2 is a paper material, the paper material absorbs moisture and affects the tablet, so that the water content of the member must be controlled. It is preferable to use a plastic having a static friction coefficient of 0.6 or less, since it is not necessary to consider moisture absorption, and the management in the production process becomes very easy.

Further, as shown in FIG.
By providing a plurality of rail-shaped projections 8 on the surface of the substantially square substrate 3, the contact area with the tablet-type solid processing agent can be reduced, and good tablet-injection properties can be obtained.

The width of the rail-shaped projection is 0.5 to 10 mm,
The height is desirably 0.1 to 4 mm.

FIGS. 8 and 9 show an example of the process of setting the flexible package of the solid processing agent into an automatic processor.

FIG. 8 shows a state in which the processing agent feeding section is pulled out of the automatic developing machine and a flexible package of solid processing agent of the developer and the fixing agent is to be prepared at the loading site. FIG. After the flexible package of the solid processing agent is loaded into the bag, a part of the moisture-proof bag is cut out in a strip shape from the opening portion 7 provided on the back seal portion 6 of the moisture-proof bag, and the bag is opened. By storing the tablet in the agent charging section 10, the package in which the tablet is stored is inclined obliquely so as to face downward from the opening and the tablet is loaded so as to slide down.

[0112]

【Example】

Example 1 Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited thereto.

<Preparation of solid fixing agent> [Granulated product (ZA)] In a commercially available bantam mill, 14580 g of ammonium thiosulfate / sodium thiosulfate (90/10 weight ratio) is ground to an average of 10 μm. To this fine powder, 550 g of sodium sulfite, 750 g of sodium metabisulfite, and 1220 g of pine flow were added, and the amount of water was added to 50 ml, and the mixture was stirred and granulated. The granulated product was dried at 50 ° C. with a fluidized bed dryer to remove water. It was removed to 1.0% (weight ratio) or less, and further sized with a sizing machine equipped with a 1.0 mm mesh to obtain a granulated product (ZA).

[Preparation of Fixing Tablets a, b, c] The granules (ZA) thus obtained were added to β-alanine 3000
g, sodium acetate 4330 g, and the compound No. 1 represented by the general formula (1) of the present invention. 1-3 is 1.5 of the total weight
%, And mixed for 5 minutes using a commercially available rotary mixer. The obtained mixture (KA) was adjusted to a filling amount of 10 g per tablet using a tableting machine modified from Tough Press Collect 1527HU manufactured by Kikusui Seisakusho Co., Ltd. to make the filling amount per tablet 10 g, and (S) in FIG. 1 (A), (B) and FIG. Compression tableting was performed using a punch and a die capable of forming a tablet having the shape shown in (1), thereby forming cylindrical fixing tablets a, b, and c each having a circular diameter of 30 mm.

[Granulated product (ZB)] 600 g of boric acid, 1480 g of aluminum sulfate octahydrate, 1100 g of succinic acid, and 300 g of tartaric acid are pulverized in a commercially available bantam mill to an average of 10 μm. D-Mannit 250 is added to these fine powders.
g, 50 g of D-Sorbit, and the added amount of water is 30 m.
and agitated granulation.
C. to remove water to 1.0% (weight ratio) or less,
The granulated product (ZB) was obtained by sizing with a sizing machine equipped with a 1.0 mm mesh.

[Preparation of Fixing Tablets d, e, f] Sodium acetate 750 was added to the granules (ZB) thus obtained.
g, and the compound N of the present invention represented by the general formula (1)
o. 1-3 was added to 1.5% of the total weight, and mixed for 5 minutes using a commercially available rotary mixer. The obtained mixture (KB) was mixed with Kikusui Seisakusho Co., Ltd. Tough Press Collect 1
Using a punch and a mill capable of forming tablets having the shape shown in FIGS. 1 (A), (B) and (S) in FIG. Compression tableting was performed to prepare cylindrical fixing tablets d, e, and f each having a circular diameter of 30 mm.

[Preparation of tablet flexible package] The obtained tablets a, b, c, d, e, and f were weighed with an interior material of 100 to 600.
g / m ² paper material and a single-sided laminated plastic film with a thickness of 20 to ²⁰⁰ μm was used.
Each of the flexible packaging materials of the shape shown in FIG.
The tablets were packed by 0 to prepare a flexible package of tablets.

The hardness and friction coefficient of the obtained tablet were measured.
Further, the solubility was evaluated.

<Evaluation of Hardness> Twenty tablet samples obtained by the above operation were each measured with a hardness measuring machine (TS-5 manufactured by Okada Seiko Co., Ltd.).
0N), the average value was taken as the hardness (strength) of the tablet sample, and the results are shown in Table 1.

<Evaluation of Coefficient of Friction> The coefficient of friction with respect to a cardboard having a water content of 5.5% was measured using a static friction coefficient measuring instrument HEIDEN.
-10 (manufactured by Shinto Kagaku Co., Ltd.). Table 1 shows the results.

<Evaluation of solubility>
Each tablet was stirred and dissolved in 300 cc of tap water at a constant temperature of 30 ° C. using a magnetic stirrer, and the time from when the tablets were introduced until all the tablets were completely dissolved was compared and evaluated. The results are shown in Table 1. Indicated. The dissolution time is an average value of five times of performing this operation five times.

<Evaluation of Injectability> 70 tablets of each of the tablet samples a to f were packaged in the flexible packaging material having the shape shown in FIGS. 5 to 7 to prepare a flexible package. . At this time, the total volume of the 70 tablets was 65% of the volume of the packaging material. Further, the kit opened as shown in FIG. 8 is set in the input section of the automatic developing machine of the type shown in FIGS. 8 and 9, and the input section is inclined at an inclination angle of 45 degrees so that all the tablets in the automatic developing machine are set. The time of dropping into the dissolution tank was measured. Each measurement was performed 10 times, and the average drop time required for all the tablets in the packaging material to fall was measured. Therefore, it indicates that the smaller the average time required for charging is, the better the charging performance is.

[0123]

[Table 1]

From Table 1, it can be seen that tablets a and b of the present invention correspond to comparative tablet c, and tablets d and v of the present invention correspond to comparative tablet f.
It can be seen that e has a high tablet hardness, a low coefficient of friction with respect to a cardboard having a water content of 5.5%, and is excellent in solubility. Further, it can be seen that the tablet of the present invention has better dosing properties than the comparative tablet.

The tablets having a convex curved surface shown in FIGS. 1A and 1B have a lower coefficient of friction than the tablets having no convex curved surface shown in FIG. It is understood that the method is suitable for a method of packaging a plurality of tablets in such a packaging material, setting the tablets in an automatic developing machine, and feeding the tablets. Further, it can be seen that the tablet of the present invention is suitable for processing in an automatic developing machine for rapidly processing a large amount of photosensitive material.

Example 2 [Preparation of Comparative Fixing Tablet g] The mixture (KA) and (KB) obtained in Example 1 were mixed at a weight ratio of 8.3: 1.7 by a rotary mixer for 5 minutes. The obtained mixture was adjusted to a filling amount of 10 g per tablet using a tableting machine modified from Tough Press Collect 1527HU manufactured by Kikusui Seisakusho Co., Ltd.
Compression tableting was performed using a punch capable of forming a tablet having a shape as shown in (S) to prepare a cylindrical comparative fixing tablet g having a diameter of 30 mm.

[Preparation of Fixing Tablet h] Subsequently, the mixture (K
A) and (KB) are not mixed, and the weight ratio is 8.3: 1.7.
Using a punch capable of forming a tablet having a sugar-coated R surface with a filling amount of 10 g per tablet using a multi-layer rotary tableting machine modified from Clean Press Collect 3L51K manufactured by Kikusui Seisakusho Co., Ltd. Then, compression tableting was performed to produce a cylindrical fixing tablet h having a circular diameter of 30 mm and a double structure as shown in FIG. 2 (F).

[Preparation of Fixing Tablet i] Next, the mixture (KA) of Example 1 was used as the lower layer (first layer) in a lower layer (first layer) using a multi-layer rotary tableting machine modified from Clean Press Collect 3L51K.
3 g and the upper layer (second layer) were each filled with 1.7 g of the above-mentioned mixture (KB), and an average molecular weight of polyethylene glycol 4000 (PEG 4000) was used as an inert substance between the first and second layers. Is compression-molded so as to be filled with 0.1 g, and has a sugar-coated R surface.
A cylindrical fixing tablet i having a circular diameter of 30 mm and a structure as shown in (G) was prepared.

[Preparation of Fixing Tablets j and k] Next, the mixture (KB) was mixed with Kikusui Seisakusho Co., Ltd. Tough Press Collect 15
A punch capable of forming tablets (tablet j and tablet k, respectively) as shown in FIGS. 1 (B) and 4 (S) with a filling amount of 1.7 g per tablet using a modified tableting machine of 27HU. Then, compression tableting was performed to prepare cylindrical fixing tablets j and k each having a circular diameter of 21 mm.

[Preparation of Fixing Tablets 1 and m] Subsequently, tablets j and k having a diameter of 21 mm were obtained by using a nucleated rotary tableting machine modified from Clean Press Collect 45DC manufactured by Kikusui Seisakusho Co., Ltd.
Was pressed into a die so that the mixture (KA) obtained in Example 1 became a shell, while being charged into a die so as to become a core. The mixture (KA) was filled so that the weight per tablet was 10 g, and a punch having a diameter of 30 mm was formed using a punch capable of forming a shape having a sugar-coated R surface, as shown in FIGS. 3 (O) and (L). Cylindrical core / shell fixing tablets 1 (core is tablet j) and m (core is tablet k) were prepared.

[Preparation of fixing tablets n and o] As an inert substance, polyethylene glycol average molecular weight 4000 (PEG
4000) was coated on the fixing tablets j and k with a coating machine (HCT-MINI, manufactured by Freund Corporation) to give 0.05 g per tablet to prepare fixing tablets n and o, respectively.

[Preparation of Fixing Tablets p and q] Subsequently, the coated tablets n and o having a diameter of 21 mm were used as cores by using a nucleated rotary tableting machine modified from Clean Press Collect 45DC manufactured by Kikusui Seisakusho Co., Ltd. While being charged into the mortar, compression tableting was performed so that the mixture (KA) obtained in Example 1 became a shell. The mixture (KA) was filled so that the weight per tablet became 10 g, and a punch having a diameter of 30 mm was formed using a punch capable of forming a tablet having a sugar-coated R surface, as shown in FIGS. 3 (P) and (M). Cylindrical core / shell fixing tablets p (core is tablet n) and q (core is tablet o) were prepared.

<Evaluation of Hardness> Twenty tablet samples obtained by the above operation were each measured with a hardness measuring machine (TS-5 manufactured by Okada Seiko Co., Ltd.).
0N), and the average value was taken as the hardness (strength) of the tablet sample. Table 2 shows the results.

<Evaluation of Storage Hardness of Tablets> Furthermore, 70 tablets of each tablet were placed in a flexible package shown in FIGS. A flexible package was prepared and stored at 50 ° C. for 30 days.
After 30 days, the tablet flexible package was opened and the strength was measured in the same manner as above. Table 2 shows the results.

<Evaluation of Solubility> Further, the tablets stored under exactly the same storage conditions as described above were evaluated for solubility in the same manner as in Example 1. Table 2 shows the results.

[0136]

[Table 2]

As shown in Table 2, the tablet of the present invention is excellent in hardness and preservability, has a high dissolution rate, and completely dissolves without storage even after storage.

[0138]

Industrial Applicability According to the present invention, a solid processing agent for a photosensitive material, which is excellent in hardness, storability and injectability, has a high dissolution rate, and is suitable for an automatic developing machine for rapidly processing a large amount of the photosensitive material, Of the flexible package and the charging method.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view at the center of a tablet showing an example of the tablet of the present invention.

FIG. 2 is a cross-sectional view of a tablet divided into two or more components at the center of the tablet, showing an example of the tablet of the present invention. Differences in patterns indicate differences in components.

FIG. 3 is a cross-sectional view at the center of a tablet having a core / shell structure, showing an example of the tablet of the present invention.

FIG. 4 is a sectional view of a tablet having no convex curved surface at the center of the tablet.

FIG. 5 is a perspective view showing a flexible package enclosing a plurality of solid processing agents of the present invention.

FIG. 6 is a perspective view of an interior material having a stretched and bent portion and an interior material having a projection on a substrate of a flexible package enclosing a plurality of solid processing agents of the present invention.

FIG. 7 is a perspective view of a flexible package enclosing a plurality of the solid processing agents of the present invention and a package having an opening portion opened.

FIG. 8 is a perspective view showing a flexible package in which a plurality of solid processing agents of the present invention are enclosed, and a state of a solid processing agent J in the package.

FIG. 9 is a perspective view showing a state in which a processing agent charging section of the automatic developing machine is ready for loading a package.

FIG. 10 is a perspective view showing a state immediately before the processing agent is put in a set of flexible packaging bodies enclosing a plurality of the solid processing agents of the present invention in the processing agent feeding section of the automatic developing machine.

[Explanation of symbols]

H Height of the spherical surface part R Radius of the spherical surface r Indicates the radius of the circle where the end of the spherical surface contacts the tip of the tablet band 1 Radial packaging body containing a plurality of solid processing agents 2 Interior material 3 Substrate 4 , 41, 42, 43 A part extending from the substrate 5 A bag-shaped member (moisture-proof bag) 6 A back seal part 7 An opening part 8 A rail-shaped convex part 9 An automatic developing machine 10 A processing agent input part J Tablet type solid processing agent

Claims (9)

[Claims] 1. A solid processing agent for a silver halide photographic light-sensitive material, which is a compression-molded tablet having a plurality of surfaces, wherein at least one of the plurality of surfaces is a convex curved surface. 2. The solid processing agent for a silver halide photographic light-sensitive material according to claim 1, comprising a compound represented by the following general formula (1). Formula (1) _{R- (O) x S y O} z M [wherein, R is a substituted, represents a non-substituted aliphatic group, an aromatic group or a heterocyclic group, x is 0 or 1, y is 2 Or 3, z is 2
-8 and M represent a cation. ] 3. A solid processing agent for a silver halide photographic light-sensitive material, wherein the components in the tablet according to claim 1 or 2 are divided into at least two components. 4. A solid processing agent for a silver halide photographic light-sensitive material, wherein the tablet according to any one of claims 1 to 3 has a core and at least one shell layer covering the core. 5. The tablet according to claim 4, wherein the core is a tablet having a plurality of surfaces and at least one of the plurality of surfaces is a convex curved surface, and at least one shell layer covering the core. A solid processing agent for a silver halide photographic light-sensitive material as described above. 6. A silver halide photograph wherein an inactive layer is provided between each of a layer containing a water-soluble aluminum salt and at least one layer containing a thiosulfate, and compression-molded. Solid processing agent for photosensitive materials. 7. The halogenated compound according to claim 1, wherein a tablet containing a water-soluble aluminum salt is used as a core, and at least one shell layer containing a thiosulfate is provided. Solid processing agent for silver photographic materials. 8. A solid processing agent for a silver halide photographic light-sensitive material, wherein a plurality of the solid processing agents according to claim 1 are enclosed in a package having a plurality of pieces. Flexible packaging. 9. The flexible package according to claim 8, comprising a plurality of pieces, wherein at least one of the plurality of pieces is opened and a plurality of tablets in the package are put into the processing device. A method for charging a solid processing agent for a silver halide photographic light-sensitive material, characterized by comprising: