Production method of granular agent and production method of tablet

Abstract

 A production method of a granular agent is disclosed. The method comprises steps of mixing powder and additive liquid by agitation and forming a granular agent, and surface tension of the additive liquid is no more than 60 dyn/cm.

Description

BACKGROUND OF THE INVENTION

[0001] The present invention relates to a production method of granular agent and a tablet, and specifically, in producing a granular agent and a tablet employing a wet-type agitation granulation method, relates to a production method which exhibits excellent continuous production stability for producing a granular or tablet-shaped solid processing agent with excellent storage stability and solubility for a silver halide photosensitive photographic material.

[0002] A silver halide photosensitive color photographic material (hereinafter referred to as photosensitive material or photographic material) is generally exposed, and is then processed employing steps such as color development, desilvering, stabilizing, etc. Furthermore, a black-and-white silver halide photosensitive photographic material is exposed and is then developed and fixed. For the development process, a black-and-white developer or a color developer is employed; for the desilvering process, a bleach or a bleach-fixer is employed; for a fixing process, a fixer is employed; for washing, tap water or deionized water is employed; for nonwater washing, a stabilizer bath is employed; and for a dye-stabilizing, a stabilizer is employed.

[0003] There have been certain problems in stability of producing of granular agent or tablet. For example, general producing method of granular agent in which water is added to powder as a solid component then they are mixed by agitation, requires drying process to remove water added during the producing process after the granulation. An apparatus is required for this purpose which makes the cost of production and time for drying is required which makes the processing time longer.

[0004] In case that the solid component is water-soluble, a lot of water is required because it is difficult to mix water with powder homogeneously when an amount of the water is small. When much amount of water is added, drying apparatus and longer drying time are required, which make the producing cost expensive. In the wet-type agitation granulation, friction heat generated by agitation raises the temperature of the granules themselves and melts them partially so that granulation is not stabilized due to adhesion of partly melted granules onto the walls and bottom of the granulation apparatus. In addition to the instability, the stirring blade is curved, and particularly, when the wet-type agitation granulation is continually carried out, this trend is very evident, In order to overcome this problem, it has been necessary during the production to carry out water washing or wiping between batches. Namely, a major problem exists so that the production is not stable, which increases costs. It is known that the granular replenishing agent and the tablet replenishing agent (hereinafter occasionally referred to as a solid processing agent) are markedly excellent in stability and ease of handling in the photoprocessing area. However there are problems in producing method of granular agent or tablet mentioned above. Furthermore, when a granular solid processing agent is compressed to prepare a tablet-shaped solid processing agent, certainly, in terms of the generation of a fine powder, it is superior to the granular solid processing agent, however, the problem in which solubility is greatly degraded. Still further, because water-soluble components make up at least 50 percent of a solid processing agent, an increase in cost results, during producing tablets, due to the impossibility of high speed and continual tableting caused by creaking of the pestle, adhesion to the pestle, etc.

SUMMARY OF THE INVENTION

[0005] Accordingly, a purpose of the present invention is to provide a production of a granular agent or tablet employing a wet-type agitation granulation method, which requires reduced amount of water markedly whereby drying time is reduced, an drying apparatus is made simple or deprived and producing cost can be reduced. The other purpose of the invention is to provide a production of a granular agent or tablet exhibiting an excellent in continuous production stability, and specifically to a production method which exhibits excellent stable continuous production for producing a granular or tablet-shaped agent with excellent storage stability as well as solubility for silver halide photosensitive photographic material.

[0006] The invention is described below.

[0007] A production method of a granular agent, comprising steps of

mixing powder and additive liquid by agitation and

forming a granular agent

wherein surface tension of the additive liquid is no more than 60 dyn/cm.

[0008] The amount of the water is preferably no more than 5 weight percent, and more preferably no more than 1 weight percent with reference to powder amount.

[0009] The preferable example of powder is a material for processing agent for a silver halide photosensitive photographic material.

[0010] In this case, the powder preferably comprises at least one of potassium carbonate, p-phenylenediamine derivatives, iron salts of polyaminocarboxylic acid, thiosulfates, hydroquinone and aluminum sulfates.

[0011] The additive liquid preferably comprises water and a surfactant.

[0012] A production method of a tablet wherein the granular agent produced by a method described above is made tabletted.

[0013] The preferable embodiment of the invention is described below.

1. A production method of a solid processing agent for a silver halide photosensitive photographic material, which is produced employing a wet-type agitation granulation, a production method of a solid processing agent for a silver halide photosensitive photographic material characterized in that the surface tension of added water employed during said wet-type agitation granulation is no more than 60 dyn/cm.
Namely, a major problem of the wet-type agitation granulation method, in order to achieve production stability, is how combining water can be added uniformly. When a photographic processing agent, composed mainly of water-soluble component, is granulated employing a wet-type method, after all, the absorption of added combining water by water-soluble components competes with its diffusion on the surface of the powder. When sufficient amount of water, necessary for the combination, is added, the added amount becomes more than the actually required amount, and as a result, granules having an excessive water content and those having a deficient water content are formed. Thus, granules are formed which are not stable in physical properties , and in addition, granules having a high water content form undissolved flour-like coagula. Further, excessive water is present on the interior wall of the wet-type agitation granulation apparatus, and when granulation is continued, the distribution of the water content ratio of the above-mentioned granules is broadened, and the granules adhere on the interior wall of a wet-type agitation granulation apparatus, and the solubility of the granules for water increases. Further, the viscosity of the granules increase to tend to generate friction heat. In order to overcome this, conventionally, it has been necessary to carry out water washing between granulation batches and subsequently drying. However, when the surface tension of added water is adjusted as specified above, according to the present invention, granulation is accomplished employing a minimal amount of added water while it is assumed that the diffusion of the added water on the surface of powder is more rapidly carried out than its absorption by the powder. Furthermore, excessive water does not adhere either on the interior wall of a type agitation granulation apparatus or on the stirrer blades to markedly improve the continuity of granule production and to make it unnecessary to carry out water washing between granulation batches and drying, while it is assumed that the distribution of the water content difference becomes smaller because the small amount of added water is well employed. Furthermore, a surprising effect is found such that the rate of dissolution of the solid processing agent prepared as described above becomes greater. Further, when employing the granules prepared as described above, surprising effects are found such that when a tablet-like processing agent is prepared under compression employing a rotary tableting apparatus, the adhesion to the pestle and the creaking noise of the pestle not only decrease but also during high speed tableting, the targeted hardness and abrasion degree are obtained and the dissolving time of the tablet-like solid processing agent is shortened.
When the amount of the above-mentioned added water was no more than 5 weight percent of the added solid amount, it was found that the effects of the present invention were further excellently achieved. Specifically, the continuity of wet-type granulation and granulation properties (decrease in the fine powder amount) were improved, and porous granules were formed to exhibit marked effects in shortening the dissolving time.

2. The production method of the solid processing agent for a silver halide photosensitive photographic material described in 1., characterized in that the amount of the above-mentioned added water is no more than 5 weight percent of the added solid amount.

3. The production method of a solid processing agent described in 1. or 2., characterized in that the above-mentioned solid processing agent comprises at least the compound described below:

potassium carbonate, p-phenylenediamine derivatives, iron salts of polyaminocarboxylic acid, hydroquinone, aluminum sulfates.

Namely, it was found that when the above-mentioned solid processing agent comprised at least the above-mentioned compound, the effects of the present invention were prominent.

4. The production method of a solid processing agent described in any one of 1., 2., and 3., characterized in that the amount of the above-mentioned added water is no more than 1 weight percent of the amount of the solid to which the water is added.
Namely, when the amount of added water was no more than 1 weight percent of the amount of the solid to which the water was added, it was found that a drying process which had been inevitably required for the wet-type agitation granulation was not required. Particularly, it was surprising that a tablet-like solid processing agent was able to be prepared without employing the drying process.

5. The production method of a solid processing agent described in any one of 1., 2., 3., and 4., characterized in that the above-mentioned solid processing agent is a granular agent.

6. The production method of a solid processing agent described in any one of 1., 2., 3., and 4., characterized in that the above-mentioned solid processing agent is a tablet agent.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT

[0014] The present invention will now be detailed below.

[0015] The solid processing agent of the present invention is produced via a wet-type agitation granulation process.

[0016] Granulation as described in the present invention will be explained below. The present invention can be applied to a majority of production method of granular agent or tablet, and it is preferably applied to those using water soluble solid composition. The invention is preferably applied to the case that all components of granular or tablet are soluble in water. For example, it is applied to a production method of solid-type processing agent for silver halide light sensitive material in granular or tablet shape, and a detergent in granular or tablet shape. The following description is based on the production method of processing solid agent for silver halide photographic material, which is preferable example of the invention. The processing solid agent is applied to a color photographic material or monochrome photographic material. The component is preferably soluble in an amount of not less than 0.005 g, more preferably 0.1 g in 100 g of water at 25 °C.

[0017] Granulation denotes an operation to prepare almost uniformly shaped and sized granules from powder, granular, and liquid materials. Granulation methods include those known in the art such as rotation granulation, extrusion granulation, compression granulation, kneading granulation, agitation granulation, fluid layer granulation, spray-dry granulation, etc. However, the method for the solid processing agent of the present invention is the agitation granulation method.

[0018] The agitation granulation method as described herein is a method utilizing aggregation properties of powder. Generally, miscibility is excellent. The method is such that liquid is added to powder materials placed in a fixed vessel and granulation is carried under agitation. In the agitation granulation method according to the present invention, at least a part of the granulation process is carried out in an atmosphere of 25 to 120 °C, and is preferably carried between 40 to 80 °C.

[0019] As a method to prepare an atmosphere of at least 25 °C, a method is preferred in which adjustment is carried out employing agitation heat generated by high speed agitation. However, a more preferred method is one in which a jacket is provided around a mixer vessel (hereinafter referred to as a pot) and the temperature is regulated by the circulation of water, oil, etc. adjusted to a specified temperature. Furthermore, a method may be employed in which a mixer vessel is tightly closed and the temperature may be regulated while varying the pressure in the vessel. The temperature of the interior of the mixer is preferably measured in a timed series employing a thermometer such as a thermocouple thermometer, etc. installed in the vessel.

[0020] On the other hand, liquid added to the agitation granulation process as described herein denotes water and organic solvents, and preferably, solutions prepared by dissolving a combining (or binding) agent in water or organic solvents.

[0021] The surface tension of the additive liquid is regulated to be not more than 60 dyn/cm, preferably 50 dyn/cm, more preferably 40 dyn·cm. The amount of the additive liquid is referably not more than 5 wt %, more preferably 3 wt%, particularly preferably 1 wt% based on 100 wt % powder.

[0022] The additive liquid is preferably composed of water and a surfactant. The surface tension may be adjusted by making use of mixture of water and organic solvent or organic solvent only. Various methods of measuring surface tention are known. The value described in this specification is measured by an automatic surface tension meter produced by Kyowa Kaimen Kagaku Co., Ltd.

[0023] The regulation method of the surface tension as described in the present invention will be described below.

[0024] The surface tension can be regulated employing so-called surface active agents. The more water-soluble a surface active agent is, the better it is.

[0025] As examples of preferred surface active agents in the present invention, the compounds (surface active agents) represented by general formulas (I) through (IV) are illustrated below. However, the present invention is not limited to these example.

[0026] The surfactants mentioned below may be employed in production of majority of granule agent or tablet of the invention and particularly are suitable for the production of solid processing agent for silver halide photographic light sensitive material.

[0027] The surfactants added to liquid additive are preferably those which do not make harmful effect to silver halide photographic light sensitive material in image quality or image stability when they are employed in the production of solid processing agent for silver halide light sensitive photographic material.

[0028] The compounds (surface active agents, fluorine series anionic surface active agents) represented by the general formula (I) will be described.

   wherein Rf represents a saturated or unsaturated alkyl group having at least one fluorine atom, and X represents sulfonamides shown below:

Y represents an alkylene oxide group and an alkylene group, and Rf' represents a saturated or unsaturated hydrocarbon group having at least one fluorine atom. Further, "A" represents hydrophilic group such as -SO₃M, -OSO₃M, -COOM, -OPO₃(M₁)(M₂), -PO₃(M₁)(M₂), etc.; M, M₁, and M₂ each represents H, Li, K, Na, or NH₄, and "m" represents an integer of 0 or 1, and "n" represents 0 or an integer of 1 to 10.

[0029] In the above-mentioned general formula (I), Rf represents a saturated or unsaturated alkyl group (for example, an alkyl group, an alkenyl group, an alkynyl group) which is preferably an alkyl group having from 4 to 12 carbon atoms, and is more preferably an alkyl group having from 6 to 9 carbon atoms. "A" is preferably -SO₃M, and M, M₁, and M₂ each is preferably Li, K, and Na, and is most preferably Li. "m" represents 0 or 1; "n" represents 0 or an integer of 1 to 10, and preferably "m" represents 0 and "n" represents 0.

[0030] The representative exemplified compounds represented by the general formula (I) are illustrated below, however, the present invention is not limited to these.

        C₈F₁₇SO₃K     I-1



        C₈F₁₇SO₃Li     I-2



        C₈F₁₇COONH₄     I-3



        C₈F₁₇COOK     I-4





        C₇F₁₅COONH₄     I-9

[0031] Of the above-mentioned compounds, particularly preferred compounds are (I-1), (I-2), and (I-4).

[0032] These compounds can be synthesized employing common methods and are available as commercial products.

[0033] Next, the compounds (surface active agents) represented by general formula (II) will be described.

   wherein R₁ represents an alkyl group or an alkenyl group; R₂ represents a hydrogen atom, an alkyl group or a hydroxyalkyl group; R₃ and R₄ each independently represents a hydrogen atom, a hydroxyl group, an alkyl group or -COOM₂ (M₂ represents a hydrogen atom or an alkali metal atom); X represents -CO- or -SO₂-; Y represents -O-, -S- or -CONR₅- (R₅ represents a hydrogen atom, an alkyl group or a hydroxyalkyl group); M₁ represents a hydrogen atom or an alkali metal atom; "l" represents 0 or 1; "m" represents an integer of 0 to 2; and "n" represents an integer of 1 to 3.

[0034] In the above-mentioned general formula (II), R₁ represents an alkyl group or an alkenyl group; R₂ represents a hydrogen atom, an alkyl group or a hydroxyalkyl group; R₃ and R₄ each independently represents a hydrogen atom, a hydroxyl group, an alkyl group or -COOM₂ (M₂ represents a hydrogen atom or an alkali metal atom); X represents -CO- or -SO₂-; Y represents -O-, -S- or -CONR₅- (R₅ represents a hydrogen atom, an alkyl group or a hydroxyalkyl group); M₁ represents a hydrogen atom or an alkali metal atom; "l" represents 0 or 1; "m" represents an integer of 0 to 2; and "n" represents an integer of 1 to 3.

[0035] R₁ is preferably a straight or branched alkyl group having from 5 to 20 carbon atoms or an alkenyl group, and R₂ is preferably a hydrogen atom, a straight or branched alkyl group having from 1 to 5 carbon atoms or a hydroxyalkyl group.

[0036] Next, specific examples of compounds represented by the general formula (II) are shown below.

        C₅H₁₁CONHC₂H₄COONa     II-1





        C₁₁H₂₃CONHC₂H₄COONa     II-4





        C₁₃H₂₇CONHC₂H₄COONa     II-6





        C₅H₁₁CONHCH₂COONa     II-8





        C₁₁H₂₃CONHCH₂COONa     II-10

[0037] In addition to the above-listed compounds, may be employed exemplified compounds described on pages 4 to 6 of Japanese Patent Publication Open to Public Inspection No. 62-56951.

[0038] The above-mentioned exemplified compounds are those known in the art, and are commercially available and may be obtained through an ordinary channel.

[0039] Next, compounds (surface active agents) represented by general formula (III) or (IV) will be explained.

[0040] R₁, R₂, R₃, R₄, and R₅ each represents an alkyl group, an aralkyl group, an alkenyl group, a styryl group, and cinnamyl group; l₁, l₂, l₃, l₄, and l₅ each represents an integer of 0 or 1, and n represents an integer of 2 to 100. However, when R₃ represents an alkyl group and l₃ represents 1, at least one of l₁, l₂, l₄, and l₅ is 1. When l₁, l₂, l₃, l₄, and l₅ each represents 0, responding R₁, R₂, R₃, R₄, and R₅ each represents a hydrogen atom.

[0041] In the above formula, the alkyl group represented by R₁, R₂, R₃, R₄, and R₅ has from 1 to 20 carbon atoms, and may be any of a chain and a ring. The chain groups include a straight chain and a branched chain, and specifically each of, for example, a methyl, ethyl, n-propyl, i-propyl, butyl, t-butyl, sec-butyl, amyl, hexyl, heptyl, octyl, nonyl, decyl, octadecyl group, etc. The aralkyl groups represented by R₁, R₂, R₃, R₄, and R₅ are those having from 7 to 20 carbon atoms and specifically include each of a benzyl, phenetyl, dibenzyl, 2-naphthylmethyl group, etc.

[0042] The alkenyl groups represented by R₁, R₂, R₃, R₄, and R₅ are those having from 3 to 20 carbon atoms and specifically, include each of, for example, an allyl, 4-hexenyl, 4-decenyl, octadecenyl group, etc.

[0043] An aromatic ring of an aralkyl group and a styryl group may have a substituent. Listed as the substituents can be, for example, an alkyl group (for example, each of a methyl, ethyl, propyl, t-amyl, nonyl group, etc.), an alkoxy group (for example, each group of methoxy, ethoxy, proxy, 2-ethoxyethoxy, etc.), an aryloxy group (for example, each of a phenoxy, p-tolyloxy, o-chlorophenoxy group, etc.). Specifically, are listed, for example, each group of p-methoxybenzyl, 2,4-dimethylbenzyl, p-phenoxyphenetyl, p-butylsyrene, etc.

   wherein R represents an alkyl group which may have from 4 to 25 carbon atoms and a straight or branched chain or represents:

   wherein R₁₁ and R₁₂ each represents an alkyl group having from 1 to 20 carbon atoms which may have a hydrogen atom or a substituent. "n" and "m" each represents 0 or an integer of 1 to 25 and represents no 0 at the same time. "A" and "B" each represents:

may be the same or different. However, n₁, m₁, and l₁ each represents 0, 1, 2, or 3, and m₁ in A and B represents no 0 at the same time and when n or m represents 0, m₁ represents no 0. D represents a hydrogen atom.

[0044] Exemplified compounds represented by the general formula (III) or (IV) are illustrated below.

[0045] Next, the compounds (surface active agents) represented by general formula (V) will be explained.

        R₁―O(̵R₂―O)̵_mX₁     General Formula (V)

   wherein R₁ represents a monovalent organic group; R₂ represents an ethylene group or a propylene group, and "m" represents an integer of 4 to 50. X₁ represents a hydrogen atom, -SO₃M or -PO₃M₂, wherein M represents a hydrogen atom, an alkali metal atom, or -NH₄.

[0046] Next, the compounds represented by the general formula (V) are further explained; R₁ in the above-mentioned general formula (V) represents a monovalent organic group, for example, an alkyl group having from 6 to 20 carbon atoms, preferably from 6 to 12 carbon atoms such as hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, etc. or represents an aryl group substituted with an alkyl group having from 3 to 20 carbon atoms, and the substituents, which are preferably an alkyl having from 2 to 12 carbon atoms, include propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, etc. The aryl groups include phenyl, tolyl, xynyl, buphenyl, naphthyl, etc., and preferably phenyl or tolyl. A position at which an alkyl group combines with an aryl group may be any of an ortho, meta, and para position. R₂ represents an ethylene group or a propylene group, and "m" represents an integer of 4 to 50. X₁ represents a hydrogen atom, -SO₃M or -PO₃M₂, in which M is a hydrogen atom, an alkali metal atom (Na, K, Li, etc.) or -NH₄.

[0047] Specifically exemplified compounds represented by the general formula (V) are illustrated below.

        C₁₂H₂₅O(C₂H₄O)₁₀H     V-1



        C₈H₁₇O(C₃H₆O)₁₅H     V-2



        C₉H₁₉O(C₂H₄O)₄SO₃Na     V-3



        C₁₀H₂₁O(C₂H₄O)₁₅PO₃Na₂     V-4

[0048] Next, the compounds (surface active agents) represented by general formula (VI) are described.

        R-(O)_xS_yO_zM     General Formula (VI)

   wherein R represents a substituted or unsubstituted aliphatic group, an aromatic group or a heterocyclic group; x represents 0 or 1; y represents 1 or 2; z represents an integer of 2 to 8; and M represents a cation.

[0049] In the general formula (VI), the aliphatic groups represented by R include an alkyl group, an alkenyl group, an alkynyl group, etc. and alkyl groups include, for example, each of a methyl, ethyl, i-propyl, butyl, t-butyl, pentyl, cyclopentyl, hexyl, cyclohexyl, octyl, dodecyl, group, etc. These alkyl groups may be further substituted with a halogen atom (for example, a halogen atom such as chlorine, bromine, fluorine, etc.), an alkoxy group (for example, each of a methoxy, ethoxy, 1,1-dimethylethoxy, hexyloxy, dodecyloxy, group, etc.), an aryloxy group (for example, each of a phenoxy, naphthyloxy, group, etc.), an aryl group (each of phenyl, naphthyl group, etc.), an alkoxycarbonyl group (for example, each of a methoxycarbonyl, ethoxycarbonyl, butoxycarbonyl, 2-ethylhexylcarbonyl group, etc.), an aryloxycarbonyl group (for example, each of a phenoxycarbonyl, naphthyloxycarbonyl group, etc.), an alkenyl group (for example, each of a vinyl, allyl group, etc.), a heterocyclic group (for example, each of a 2-pyridyl, 3-pyridyl, 4- pyridyl, morphoryl, piperidine, piperadyl, pyrimidine, pyrazoline, furyl group, etc.), an alkynyl group (for example, propargyl group, etc.), an amino group (for example, each of an amino, N,N-dimethylamino, anilino group, etc.), a cyano group, a sulfoamide group (for example, each of a methylsulfonylamino, ethylsulfonylamino, butylsulfonylamino, octylsulfonylamino, phenylsulfonylamino group, etc.).

[0050] Listed as alkenyl groups are, for example, a vinyl group, an allyl group, etc. Listed as alkynyl groups are, for example, propargyl group, etc.

[0051] Listed as the aromatic group represented by R, are, for example, a phenyl group, a naphthyl group, etc.

[0052] Listed as the heterocyclic group represented by R are, for example, a pyridyl group (each of a 2-pyridyl, 3- pyridyl, 4- pyridyl group, etc.), a thiazolyl group, an oxazolyl group, an imidazolyl group, a furyl group, a thienyl group, a pyrrolyl group, a pyrazinyl group, a pyrimidinyl group, a pyridazinyl group, a selenazolyl group, a sulforanyl group, a pipedirinyl group, a pyrazolyl group, a tetrazolyl group, etc.

[0053] Any of the above-mentioned alkenyl group, alkynyl group, aromatic group, and heterocyclic group can be substituted with the alkyl group represented by R, the substituent of the alkyl group, a group shown as a substituent atom, a group similar to an atom, and an atom.

[0054] Cations represented by M are preferably metal ions or organic cations. Listed as the metal ions are, for example, a lithium ion, a sodium ion, a potassium ion, etc., and listed as the organic cations are, for example, an ammonium ion (each ions of ammonium, tetramethylammonium, tetrabutylammonium, etc.), a phosphonium ion (for example, a tetraphenylphosphonium ion, etc.), a guanidyl ion.

[0055] The specific examples of compounds represented by the general formula (VI) are listed below, however the present invention is not limited to these.

        C₂H₅SO₃Na     VI-1



        CH₃(CH₂)₆SO₃Na     VI-2



        CH₃(CH₂)₇SO₃Na     VI-3



        CH₃(CH₂)₅OSO₃Na     VI-4



        CH₃(CH₂)₆OSO₃Na     VI-5



        CH₃(CH₂)₇OSO₃Na     VI-6



        CH₃O(CH₂)₂SO₃Na     VI-7





        CH₃(CH₂)₁₁SO₃Na     VI-13

[0056] In the solid processing agent of the present invention, the ratio of particles having a particle diameter (particle size) in the range of 0.1 mm to 1.5 mm is preferably at least 60 percent of the entire weight, is more preferably at least 70 percent, and most preferably at least 80%.

[0057] Known as methods to measure the particle size of powder particles are, for example, a sieving method, a microscopic method, a call counter method, a precipitation method, a centrifugal method, an air sieving method, a diffusion method, an adsorption method, etc., which are described, for example in Kawakita, Koishi, and Tanetani, "Funtai Kogaku (Powder Engineering)", Maki Shoten (published in 1973). The Particle diameter (particle size) as described in the present invention denotes a value measured by the sieving method and an average particle size of the size distribution obtained by the sieving method.

[0058] In the present invention, the specific volume of a granular solid processing agent is preferably between 0.7 and 2.8 cm³/g. The specific volume of no more than 0.7 cm³/g is not preferred because a long time is required for dissolution. The specific volume of not less than 2.8 cm³/g is not preferred because a fine powder tends to be generated during handling.

[0059] In the present invention, the number of rotations of the stirring blade are preferably between 50 and 5,000 rpm, is more preferably between 100 and 3,000 rpm, and is most preferably between 300 and 2,000. Low number of rotations requires more time until completion of mixing and is not preferred in terms of cost. On the contrary, a high number of rotations results in the formation of excessively hard granules for preparing a tablet-like solid processing agent, which makes it impossible to prepare the tablet-like solid processing agent having desired hardness and abrasion degree. The range of the present invention is appropriate in terms of cost and production efficiency and results in the formation of hardness and abrasion degree in the good range.

[0060] Color developing agents employed in the solid color developing agent in the present invention include p-phenylenediamine derivatives (hereinafter may be referred to as p-phenylenediamine series compounds), and specifically, p-phenylenediamine series compounds, having a water-soluble group, are preferably employed because the object of the present invention is optimally accomplished and a decrease in fog results.

[0061] The p-phenylenediamine series compounds having a water-soluble group result in minimum staining of a photosensitive material and minimum skin poisoning, compared to p-phenylenediamine series compounds having no water-soluble group such as N,N-diethyl-p-phenylenediamine, etc., and particularly, in combination with the color developing agent of the present invention, the object of the present invention can be more efficiently achieved.

[0062] Those having at least one of the above-mentioned water-soluble compound on the amino group or the benzene nucleus of p-phenylenediamine series compound are listed and specific water-soluble groups include preferably:

-(CH₂)_n-CH₂OH,

- (CH₂)_m-NHSO₂-(CH₂)_nCH₃

- (CH₂)_m-O-(CH₂)_n-CH₃

- (CH₂CH₂O)_nC_mH_2m+1 ("m" and "n" each represents an integer of 0 or more),

-COOH group, -SO₃H group.

[0063] Listed as specific exemplified compounds of the developing agents preferably employed in the present invention are (C-1) through (C-126) described on pages 26 to 31 of Japanese Patent Application No. 2-203169.

[0064] The above-mentioned color developing agents are usually employed in the form of salts such as chlorides, sulfates, p-toluenesulfoantes, etc.

[0065] Furthermore, the above-mentioned color developing agents may be employed individually or in combination of at least two of them, and further, if desired, may be employed in combination of black-and-white developing agents such as phenidone, 4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone or metol, etc.

[0066] Furthermore, in the present invention, the effects of the object of the present invention are preferably exhibited by comprising compounds represented by the general formulas (A) and (B) described below.

[0067] Namely, when converted to a solid processing agent, the effects are obtained in that the keeping quality of a tablet is improved compared to other compounds and in addition, the tablet strength is maintained, and further, advantages are obtained in which photographic functions are stable and minimum fog is formed in an unexposed area.

   wherein R₁ and R₂ each represent an alkyl group and an aryl group while both represent no hydrogen atom at the same time.

[0068] Or each of them represents a hydrogen atom, and the alkyl groups represented by R₁ and R₂ may be the same or different, and each alkyl group having from 1 to 3 carbon atoms is preferred. Furthermore, these alkyl groups may have a carboxylic acid group, a phosphoric acid group, a sulfonic acid group or a hydroxyl group.

[0069] R' represents an alkoxy group, an alkyl group or an aryl group. The alkyl groups and aryl groups of R₁, R₂, and R' include those having a substituent and R₁ and R₂ may combine with each other to from a ring and may form a heterocyclic ring such as, for example, piperidine, pyridine, triazine, morpholine.

   wherein R₁₁, R₁₂, and R₁₃ each represents a hydrogen atom, a substituted or unsubstituted alkyl group, aryl group, or a heterocyclic group, an alkoxy group, an aryloxy group, a carbamoyl group, and an amino group. The heterocyclic ring group is a 5- to 6-membered ring which is composed of C, H, O, N, S, and a halogen atom and may be saturated or unsaturated. R₁₅ represents a divalent group selected from -CO-, -SO₂- or

"n" is 0 or 1. Especially, when n is 0, R₁₄ represents a group selected from an alkyl group, an aryl group, and a heterocyclic group, and R₁₃ and R₁₄ may form a heterocyclic group in combination of these.

[0070] Specific examples of hydroxylamine series compounds represented by the above-mentioned general formula (A) are described in U.S. Patent Nos. 3,287,125, 3,293,034, and 3,287,124. However, listed as particularly preferred specific examples are (A-1) through (A-39) on pages 36 to 38 of Japanese Patent Application No. 2-203169, (1) through (53) on pages 3 to 6 of Japanese Patent Publication Open to Public Inspection No. 3-33845, and (1) through (52) on pages 5 to 7 of Japanese Patent Publication Open to Public Inspection No. 3-63646.

[0071] Next, listed as specific examples of compounds represented by the above-mentioned general formula (B) are (B-1) through (B-33) on pages 40 to 43 of Japanese Patent Application No. 2-203169 and (1) through (56) on pages 4 to 6 of Japanese Patent Publication Open to Public Inspection No. 3-33846.

[0072] Compounds represented by these general formula (A) or (B) is generally employed in the form free amines, hydrochlorides, sulfates, p-toluenesulfonates, oxalates, phosphates, acetates, etc.

[0073] In the color developing agent and black-and-white developing agent, the minimal amount of sulfites may be employed as a preservative. Listed as said sulfites are sodium sulfite, potassium sulfite, sodium bisulfite, potassium bisulfite.

[0074] In the color developing agent and black-and-white developer, it is required to employ buffers. Listed as the buffers can be sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, dipotassium phosphate, sodium borate, potassium borate, sodium tetraborate (boric acid), potassium tetraborate, sodium o-hydroxybenzoate (sodium salicylate), potassium o-hydroxybenzoate, sodium 5-sulfo-2- hydroxybenzoate (sodium 5-sulfosalicylilate), potassium 5- sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate).

[0075] Added as development accelerators can be, if desired, thioether series compounds described in Japanese Patent Publication Nos. 37-16088, 37-5987, 38-7826, 44-12380, 45-9019, U.S. Pat. No. 3,813,247, etc.; p-phenylenediamine series compounds described in Japanese Patent Publication Open to Public Inspection Nos. 52-49829 and 50-15554; quaternary ammonium salts described in Japanese Patent Publication Open to Public Inspection No. 50-137726, Japanese Patent Publication No. 44-30074, Japanese Patent Publication Open to Public Inspection Nos. 56-156826, 52-43429, etc.; p-aminophneols described in U.S. Pat. Nos. 2,610,122 and 4,119,462; amine series compounds described in U.S. Pat. Nos. 2,494,903, 3,128,182, 4,230,796, 3,253,919, Japanese Patent Publication No. 41-11431, U.S. Pat. Nos. 2,482,546, 2,596,926, 3,582,346, etc.; polyalkylene oxides described in Japanese Patent Publication Nos. 37-16088, 42-25201, U.S. Pat. No. 3,128,183, Japanese Patent Publication Nos. 41-11431, 42-23883, U.S. Pat. No. 3,532,501, etc.; and in addition, 1-phenyl-3-pyrazolidones, hydrozines, mesoionic compounds, ionic compounds, imidazoles, etc.

[0076] A color developing agent which substantially comprises no benzyl alcohol is preferred. "Substantially" as described herein is that the amount is preferably no more than 2.0 ml per liter in terms of the finished volume of the color developer, and is more preferably zero. Then substantially not added, more preferred results are obtained in such a way that during continual processing, less variation of photographic characteristics occurs and specifically, the increase in staining is less.

[0077] In order to minimize fog and the like, it is necessary that chlorine ions and bromine ions are present in the color developer solution in a processing tank. In the present invention, the chlorine ions are contained preferably in an amount of 1.0 × 10^-2 to 1.5 × 10^-1 mole/liter, and are more preferably in an amount of 4 × 10^-2 to 1 × 10^-2 mole/liter. The concentration of chlorine ions of no less than 1.5 × 10^-2 mole/liter is not preferred to obtain the maximum density quickly due to the retardation of development. Furthermore, the concentration below 1.0 × 10^-2 mole/liter is not preferred because variations in photographic properties (especially, minimum density) increases during continual processing. Accordingly, in the solid processing agent, it is necessary to adjust the concentration of the color developer solution in a processing tank to the above-mentioned concentration range.

[0078] In the present invention, the color developer solution in a processing tank preferably comprises bromine ions in an amount of 3.0 × 10^-3 to 1.0 × 10^-3 mole/liter, more preferably in an amount of 5.0 × 10^-3 to 5 × 10^-4 mole/liter and most preferably in an amount of 1 × 10^-4 to 3 × 10^-4 mole/liter. When bromine ion concentration exceeds 1.0 × 10^-3 mole/liter, development is retarded, and the maximum density and sensitivity decease, while the concentration of less than 3.0 × 10^-3 mole/liter is not preferred in the points of stain formation and variations of photographic properties (particularly minimum density) during continual processing. It is necessary to regulate, in the same manner as chlorine ions, the bromine concentration in the solid processing is regulated so as to be in the above-mentioned range.

[0079] When added directly to a color developing agent, listed as chlorine ion-supplying materials are sodium chloride, potassium chloride, ammonium chloride, nickel chloride, magnesium chloride, manganese chloride, calcium chloride, and cadmium chloride. Of these, sodium chloride and potassium chloride are preferred.

[0080] Furthermore, chlorine ions may be supplied to the color developing agent and the developing agent in the form of a paired salt of a fluorescent whitening agent. Listed as bromine ion-supplying materials are sodium bromide, potassium bromide, ammonium bromide, lithium bromide, calcium bromide, magnesium bromide, manganese bromide, nickel bromide, cadmium bromide, cilium bromide, and thallium bromide. Of these, potassium bromide and sodium bromide are preferred.

[0081] In the color developing agent and developing agent employed in the present invention, in addition to chlorine ions and bromine ions, optional antifoggants may be added, if desired. Employed as the antifoggants, are alkali metal halides such as potassium iodide, and organic antifoggants. Listed as organic antifoggants, are nitrogen-containing heterocyclic compounds as representative compounds such as, for example, benztriazole, 6-nitrobenzotriazole, 5-nitroisoindazole, 5- methylbenztriazole, 5-nitrobenztriazole, 5-chloro-benztriazole, 2-thiazolylbenzimidazole, 2-thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolizine, and adenine.

[0082] In terms of effects of the object of the present invention, triazinylstilbene series fluorescent whitening agents are preferably incorporated into the color developing agent and developing agent employed in the present invention. As such fluorescent whitening agents, those represented by the general formula (E) described below are preferred.

   wherein X₂, X₃, Y₁, and Y₂ each represents a hydroxyl group, a halogen atom such as chlorine, bromine, etc., an alkyl group, an aryl group;

or -OR_25' wherein R₂₁ and R₂₂ each represents a hydrogen atom, an alkyl group (including an substituted group), an aryl group (including an substituted group); R₂₃ and R₂₄ each represents an alkylene group (including a substituted group); R₂₅ represents a hydrogen atom, an alkyl group (including a substituted group), an aryl group (including a substituted group) or aryl group (including a substituted group), and M represents a cation.

[0083] Specific examples of compounds represented by general formula (E) are illustrated below.

[0084] The above-mentioned compounds can be synthesized employing methods known in the art. Of the above listed exemplified compounds, particularly, those preferably employed include E-4, E-24, E-34, E-35, E-36, E-37, and E-41. A solid processing agent is prepared so that the added amount of these compounds is preferably in the range of 0.2 to 10 g per liter of the color developer solution, and is more preferably in the range of 0.4 to 5 g.

[0085] Further, in the compositions of the color developing agent and the black-and-white developing agent employed in the present invention, compounds such as methylcellosolve, methanol, acetone, dimethylformamide, β-cyclodextrin, and in addition, compounds described in Japanese Patent Publication Nos. 47-33378 and 44-9509 can be employed in order to increase the solubility of the developing agent.

[0086] Further, auxiliary developing agents can be employed together with a developing agent. As these auxiliary developing agents, are known Metol, phenidone, N,N-diethyl-p-aminophenol hydrochloride, N,N,N,N'-tetramethyl-p-phenylenediamine hydrochloride, etc.

[0087] Furthermore, in addition, various additives such as antistaining agents, antisludging agents, interimage effect enhancing agents, etc. can be employed.

[0088] Further, it is preferred from the viewpoint to efficiently achieve the object of the present invention that in compositions of the color developing agent and black-and-white developing agent, chelating compounds represented by general formula (K) described from the 8th line from the bottom on page 63 to the third line from the bottom on page 64 in Japanese Patent Application No. 2-240400 and exemplified compounds K-1 through K-22 thereof are added.

[0089] Of these chelating agents, particularly, K-2, K-9, K-12, K-13, K-17, and K-19 are preferably employed, and particularly, K-2 and K-9 improve the effects of the present invention.

[0090] These chelating agents are added to a solid processing agent so that the added amount is preferably in the range of 0.1 to 20 g per liter of the color developer solution and the black-and-white developer solution, and is more preferably in the range of 0.2 to 8 g.

[0091] Further, each of anionic, cationic, amphoteric, and nonionic surface active agents may be incorporated into the above-mentioned color developing agent and solid processing agents for black-and-white development.

[0092] Furthermore, may be added various types of surface active agents such as alkylsulfonic acids, arylsulfonic acids, aliphatic carboxylic acids, aromatic carboxylic acids, if desired.

[0093] Bleaching agents preferably employed in the bleaching agents or bleach-fixing agents according to the present invention are organic acid ferric complex salts represented by general formula (C) described below:

   wherein A₁ through A₄ may be the same and different, and each represents -CH₂OH, -COOM or -PO₃M₁M₂. M, M₁, and M₂ each represent a hydrogen atom, an alkali metal or ammonium. X represents a substituted or unsubstituted alkylene group having from 3 to 6 carbon atoms.

[0094] Compounds represented by general formula (C) will be explained in detail below.

[0095] Further, in the formula, A₁ through A₄ are the same as those described from the 15th line from the top of page 12 to the 3rd line from the top of page 15 of Japanese Patent Application No. 1-260628. Therefore, detailed explanation is abbreviated.

[0096] The organic acid ferric complex salts exhibit high bleaching capability to result in a decrease in the necessary amount in tableting, to make it possible to prepare light and small tablets, and to further improve the keeping quality of tablets. Thus, those are preferably employed in the present invention.

[0097] Preferred examples of compounds represented by the above-mentioned general formula (C) are shown below.

[0098] As the ferric complex salts of these compounds (C-1) through (C-12), sodium salts, potassium salts, and ammonium salts of these ferric complex salts can be optionally employed. From the points of the effects of the present invention and solubility, these ferric salts are preferably employed.

[0099] Of the above-mentioned compound examples, in the present invention, (C-1), (C-3), (C-4), (C-5), and (C-9) are preferably employed, and particularly, (C-1) is preferably employed.

[0100] In the present invention, except for complex salts represented by the above-mentioned general formula (C) as a main bleaching agent, ferric complex salts described below can be employed in the bleaching agent or bleach-fixing agent.

(A'-1) ethylenediaminetetraacetic acid

(A'-2) trans-1,2-cyclohexanediaminetetraacetic acid

(A'-3) dihydroxyethylglycinic acid

(A'-4) ethylenediaminetetrakismethylenephosphonic acid

(A'-5) nitrilotrismethylenephosphonic acid

(A'-6) diethylenetriaminepentakismethylenephosphonic acid

(A'-7) diethylenetriaminepentaacetic acid

(A'-8) ethylenediaminediorthohydroxyphenylacetic acid

(A'-9) hydroxyethylethylenediaminetriacetic acid

(A'-10) ethylenediamonedipropionic acid

(A'-11) ethylenediaminediacetic acid

(A'-12) hydroxyethyliminodiacetic acid

(A'-13) nitrilotriacetic acid

(A'-14) nitrilotripropionic acid

(A'-15) triethylenetetraminehexaacetic acid

(A'-16) ethylenediaminetetrapropionic acid

(A'-17) β-alaninediacetic acid

[0101] The added amount of the above-mentioned organic acid ferric complex salts is preferably in the range of 0.01 to 2.0 moles per liter of the bleaching solution or bleach-fixing solution, and is more preferably in the range of 0.05 to 1.5 moles/l. Accordingly, the solid processing agent requires to be prepared so that the concentration of the organic acid ferric complex salts in the bleaching solution or bleach-fixing solution of a processing tank, should be in the above-mentioned range.

[0102] The rate of processing may be improved by incorporating at least either imidazoles and derivatives thereof, described in Japanese Patent Publication Open to Public Inspection No. 64-295258 or compounds represented by general formulas (I) through (IX) described in the same publication, into a bleaching agent, bleach-fixing agent, and fixing agent.

[0103] Except for the above-mentioned accelerators, similarly employed are compounds described on pages 51 to 115 in Japanese Patent Publication Open to Public Inspection No. 62-123459, on pages 22 to 25 in Japanese Patent Publication Open to Public Inspection No. 63-17445, and in Japanese Patent Publication Open to Public Inspection Nos. 53-95630 and 53-28426.

[0104] Into the bleaching agent or bleach-fixing agent, except for those described above, can be incorporated halides such as ammonium bromide, potassium bromide, and sodium bromide, various types of fluorescent whitening agents, antifoaming agents, and surface active agents.

[0105] Thiocyanates and thiosulfates are preferably employed as major fixing agents used in the fixing agent or bleach-fixing agent in the present invention. The content of thiocyanates is preferably at least 0.1 mole per liter of a fixing solution or bleach-fixing solution, when processing color negative film strips, is more preferably at least 0.5 mole per liter, and is most preferably at least 1.0 mole per liter. The content of thiosulfates is preferably at least 0.2 mole per liter of the fixing solution or bleach-fixing solution, however, when processing color negative film strips, it is more preferably at least 0.5 mole per liter. In the present invention, the object of the present invention is more effectively achieved by employing thiocyanate salts and thiosulfate salts in combination.

[0106] Into the fixing agent or bleach-fixing agent employed in the present invention, besides these main fixing agents, pH buffering agents composed of various salts can also be incorporated individually or in combination of two or more types. Further, a large amount of rehalogenating agents such as alkali halides or ammonium halides, such as, for example, potassium bromide, sodium bromide, sodium chloride, ammonium bromide, etc. is preferably incorporated. Further, compounds which are commonly known as those added to a fixing agent or bleach-fixing agent, such as alkylamines, polyethylene oxides, etc. can also be suitably added.

[0107] Compounds represented by general formula (FA) described below as well as exemplified compounds thereof described in Japanese Patent Publication Open to Public Inspection No. 64-295258 are preferably added to the fixing agent or bleach-fixing agent. By so doing, the effects of the present invention are optimally obtained, and in addition, another effect is obtained in which sludge is minimized, which forms in the processing solution having fixing capability during processing of small amounts of photosensitive materials over a long period.

[0108] The compounds represented by the general formula (FA) described in the above-mentioned patent specification can be synthesized employing the common methods as described in U.S. Pat. Nos. 3,335,161 and 3,260,718. Further, the compounds represented by the above-mentioned general formula (FA) may be employed individually or in combination of at least two types.

[0109] Further, when the added amount of these compounds represented by the general formula (FA) is in the range of 0.1 to 200 g per liter of the fixing solution or bleach-fixing solution, good results are obtained.

[0110] In the present invention, chelating agents, having a chelate stability constant of at least 8 for ferric ions, are preferably incorporated into the stabilizer. The chelate stability constant as described herein denotes a constant generally known from L.G. Sillen and A.E. Martell, "Stability Constants of Metal-ion Complexes", The Chemical Society, London (1964), S. Chaberek and A.E. Martell, "Organic Sequestering Agents", Wiley (1959), and the like.

[0111] Listed as chelating agents having a chelate stability constant of at least 8 for ferric ions are those described in Japanese Patent Application Nos. 2-234776 and 1-324507.

[0112] The employed amount of the above-mentioned chelating agents is preferably between 0.01 and 50 g per liter of the stabilizer and best results are obtained in the range of 0.05 to 20 g.

[0113] Further, as preferred compounds which are added to the stabilizer, ammonium compounds can be listed. These are supplied from various types of ammonium salts of inorganic compounds. The added amount of the ammonium compounds is preferably in the range of 0.001 to 1.0 mole per liter of the stabilizer, and is more preferably in the range of 0.002 to 2.0 moles.

[0114] Further, sulfites are preferably incorporated into the stabilizing agent.

[0115] Furthermore, metal salts are preferably incorporated into the stabilizer together with the above-mentioned chelating agent. Such metal salts include salts of metals such as Ba, Ca, Ce, Co, In, La, Mn, Ni, Bi, Pb, Sn, Zn, Ti, Zr, Mg, Al or Sr, and can be supplied as inorganic salts or water-soluble chelating agents such as halides, hydroxides, sulfates, carbonates, phosphates, acetates, etc. The employed amount is preferably in the range of 1 × 10^-4 to 1 × 10^-1 per liter of the stabilizer, and is more preferably in the range of 4 × 10^-4 to 2 × 10^-2 mole.

[0116] Further, added to the stabilizer can be organic acid salts (citric acid, acetic acid, succinic acid, oxalic acid, benzoic acid), and pH regulators (phosphates, borates, hydrochloric acid, sulfates). Further, in the present invention, antiseptics known in the art can be employed individually or in combination, in the range in which the effects of the present invention are not adversely affected.

[0117] Further, deionized water is preferably employed in the stabilizer. Further, in order to decrease a replenishment rate, an embodiment is preferred to achieve the present invention, employing a method in which a reverse osmosis membrane is employed, and a solution having a high salt concentration is returned to a fixing or bleach-fixing solution, or a forefront bath, while a solution having a low salt concentration is returned to the final bath of the stabilizer.

[0118] A developing agent which can be employed for the black-and-white developing tablet agent preferably comprises reductones, especially ascorbic acid and/or erythorbic acid (stereoisomer) and salts thereof.

[0119] Furthermore, developing agents described below may be incorporated: dihydroxybenzenes (for example, hydroquinone, chlorohydroquinone, bromohydroquinone, dichlorohydroquinone, isopropylhydroquinone, methylhydroquinone, 2,3-dichiorohydroquinone, methoxyhydroquinone, 2,5-dimethylhydroquinone, potassium hydroquinonemonosulfonate, sodium hydroquinonemonosulfonate, 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-diamino phenol, etc.), 1-allyl-3-amino pyrazolines (for example, 1-(p-hydroxyphenyl-3-aminopyrazoline, 1-(p-methylaminophenyl)-3-aminopyrazoline, 1-(p-amino-m-methylphenyl)-3-aminopyrazoline, etc.); pyazolones (for example, 4-amino pyrazolone), and the like, or mixtures thereof are listed.

[0120] A developing tablet agent preferably comprises sulfites and/or metabisulfites. Further, when the developing solution is prepared by dissolving the tablet, the amount of sulfites in the solution is at least 0.05 mole/liter and less than 0.3 mole/liter, and is preferably at least 0.1 mole/liter and less than 0.3 mole/liter.

[0121] In addition, may be incorporated buffering agents (for example, carbonates, boric acids, borates, alkanolamine, etc.), alkali agents, dissolving aids (polyethylene glycols, and esters thereof, etc.), pH regulators (for example, organic acids such as citric acid, etc.), sensitizers (for example, quaternary ammonium salts, etc.), development accelerators, hardeners (for example, dialdehyde such as glutaraldehyde, etc.) surface active agents, further, azole series organic antifoggants to minimize fog (for example, indazole series, imidazole series, benzimidazole series, triazole series, benztriazole series, tetrazole series, thiazole series), sequestering agents such as sodium hexametaphospahte, calcium hexametaphosphate, polyphosphates, diethylenetriaminepentaacetic acid, which sequesters calcium ions mixed in city water employed for preparing processing solutions, and the like. Further, silver stain preventing agents, for example, compounds described in Japanese Patent Publication Open to Public Inspection No. 56-24347 may be employed.

[0122] The pH of a developer solution prepared by the developing tablet agent is preferably in the range of no more than 10.5, and is more preferably in the range of 9 to 10.0.

[0123] In the developer solution prepared employing the developing tablet agent, amine compounds such as alkanolamine, etc. may be employed which are described in Japanese Patent Publication Open to Public Inspection No. 56-106244.

[0124] In addition to these, in the developer solution obtained by employing the developing tablet agent, may be employed those described on pages 22 to 229 of L.F.A. Meson, "Photographic Processing Chemistry" published by Focal (1966), U.S. Pat. Nos. 2,193,015 and 2,592,364, Japanese Patent Publication Open to Public Inspection No. 48-64933, etc.

[0125] On the other hand, as alkali agents, carbonates having a buffering action are preferred. Listed as carbonates are potassium carbonate, sodium carbonate, lithium carbonate, etc. Further, the amount of carbonates in a processing solution is preferably at least 0.3 mole/liter and less than 0.8 mole/liter.

[0126] Next, the fixing solution employed in the present invention will be described.

[0127] The fixing solution employed in the present invention is preferably prepared in such a manner that a solid processing agent is prepared and then is dissolved to prepare a processing solution. As fixing agents, thiosulfates are preferably employed as a main fixing agent. Thiosulfates are specifically employed as salts of lithium, potassium, sodium, and ammonium, and ammonium thiosulfate and sodium thiosulfate are preferably employed to obtain the fixing solution exhibiting a high rate of fixing.

[0128] In addition to these, as main fixing agents, iodides and thiocyanates may also be employed. The fixing solution employed in the present invention comprises sulfites. Employed as sulfites are solid lithium, potassium, sodium, and ammonium salts.

[0129] The fixing solution employed in the present invention may comprise water-soluble chromium salts or water-soluble aluminum salts. Listed as water-soluble chromium salts are chrome alum, etc., while listed as water-soluble aluminum salts can be aluminum sulfate, aluminum potassium chloride, aluminum chloride, etc.

[0130] The fixing solution employed in the present invention comprises acetic acid ions. Types of acetic acid ions are optional. The present invention can be applied to optional compounds which dissociate acetic acid ions, however, acetic acid, and lithium, potassium, sodium, ammonium salts, etc. of acetic acid are preferably employed, and specifically, sodium salts and ammonium salts are preferred.

[0131] Further, citric acid, tartaric acid, malic acid, succinic acid, phenylacetic acid and optical isomers thereof, etc. may be incorporated.

[0132] Listed as preferred salts are, for example, lithium, potassium, sodium, ammonium salts, etc., represented by, for example, potassium citrate, lithium citrate, sodium citrate, ammonium citrate, lithium hydrogentartarate, potassium hydrogentartarate, potassium tartarate, sodium hydrogentartarate, sodium tartarate, ammonium hydrogentartarate, potassium ammonium tartarate, potassium sodium tartarate, sodium maliate, ammonium maliate, sodium succinate, ammonium succinate, etc.

[0133] Of the above listed compounds, those which are more preferred include citric acid, isocitric acid, malic acid, phenylacetic acid and salts thereof. Listed as other acids are inorganic acids such as sulfuric acid, hydrochloric acid, nitric acid, and boric acid, and salts thereof, and organic acids such as formic acid, propionic acid, oxalic acid, malic acid, and salts thereof. However, are preferred acids such as boric acid, aminopolycarboxylic acids, etc. and salts thereof.

[0134] Listed as chelating agents are, for example, aminopolycarboxylic acids such as nitorilotriacetic acid, ethylenediaminetetraacetic acid, etc. and salts thereof.

[0135] Listed as surface active agents are, for example, anionic surface active agents such as sulfuric acid esterified compounds, sulfonated compounds, nonionic surface active agents such as polyethylene glycol series, ester series, etc., amphoteric surface active agents, and the like.

[0136] Listed as fixing accelerators are thiourea derivatives and alcohols having a triple bond in the molecule, thioether, etc.

[0137] A fixing solution has a pH of at least 3.8, and has preferably a pH of 4.2 to 5.5.

[0138] Further, the replenishment rate during processing according to the present invention is preferably no more than 20 ml/10 × 12 inch size for both developer solution and fixing solution in terms of a decrease in the waste amount, and is more preferably 15 ml/10 × 12 inch size.

[0139] The tablet solid processing composition (hereinafter referred to simply tablets) is obtained by compression-molding into a specific shape a solid processing composition comprising granules, and preferably by compression-molding into tablets a composision consisting of granules in that the invention is markedly effected. One kind of granules is preferably compression-molded, and two or more kinds of granules may be used in view of storage stability. When two or more kinds of granules are mixed before compression-molded or a lubricant is mixed, the mixture is preferably mixed for 5-10 minutes using an ordinary mixer. The lubricant is preferably a water soluble surfactant for a photographic processing tablet.

[0140] The solid processing tablet can be produced using compressors such as a hydraulic press machine, a single tableting machine, a rotary tableting machine and a briqueting machine. The rotary tableting machine is preferably used in view of mass production.

[0141] In a rotary tableting machine upper rod and lower rod are cylindrically arranged in a turn table. Granules are loaded by a hopper, compressed with the upper and lower rods and continuously tableted to prepare tablets. The process of compressing granules to tablets consist of a first process in which the upper and lower rods contact and apply pressure along a pressure roller, a second process in which the upper and lower rods move horizontally along the lowest end of the pressure roller and the uppermost end of the pressure roller and a third process in which compression is completed and tablets are removed. The time taken at the first process refers to kinetic compression time, and the time taken at the second process refers to compression dwell time. The sum of the both refers to total compression time. Then the rotation speed of the turn table is high, the dwell time is short, and pressure strain in an inner portion of the tablets is not sufficiently relaxed and tablet expansion may occur. The tableting pressure, dwell time and loading amount are determined according to physical properties to be given to granules or tablets. However, the present invention is preferably carried out by the following conditions in view of a problem such as capping or lamination.

	Preferable	Especially Preferable
Tableting Pressure	140-4300 kg/cm2	700-2100 kg/cm2
Compression Dwell Time	0.02-1.00 sec.	0.05-0.80 sec.

[0142] The shape of tablets may be in any form, but is preferably in cylindrical form in view of ease of producibility or processability. The diameter of the cylindrical tablet is optional according to the intended use, but preferably 10 to 35 mm.

[0143] In this manufacturing method of tablets it is preferable that the particles and/or granules have a moisture content of 0.05 to 3.0 wt%, not more than 10 wt% of the particles and/or granules are particles and/or granules having a diameter of 53 µm or less, the particles and/or granules have a bulk density of 0.4 to 0.95 g/cm³, or strength of the particles and/or granules is 100 to 400 g/mm².

[0144] The strength is represented by the following equation:

A

: a cross-sectional area (mm²) of granules

P

: a loading weight (g) at which the granules are broken

d

: a diameter of the granules (mm).

[0145] The present inventor has found that there is a difference in the expansion of tablets among tablets having the same hardness, the expansion can be controlled by a compression dwell time in manufacturing the tablets and tablets manufactured at a compression pressure of 400 to 4500kg/cm² markedly reduce the above expansion.

[0146] Tablets produced at a compression dwell time of less than 0.020 seconds and at a compression pressure within the range described above expand during storage, since pressure strain inside the tablets is not sufficiently relaxed. This is probably because the binding ability inside the tablets is reduced by the strain. Tablets produced at a compression dwell time exceeding 1.000 second are assumed to expand during storage on account of lowering of the strength, although the strain is assumed to be relaxed. It is surprising that determining a compression dwell time and a compression pressure in molding can overcome troubles due to the tablet expansion. Further, it has been proved that this has another great effect on prevention of defects, breakage and antiabrasion even in tablets which are not expanded to a lesser degree. It is surprising that this technique, preventing the expansion, removes the strain, enhances the binding ability and improves the strength and anti-abrasion property of the tablets.

[0147] The particles in the invention preferably refer to particles having a particle diameter of 53 to 2830 µm, or granules having a particle diameter of 53 to 2830 µm which are obtained by granulating powder, and have preferably a weight average particle diameter of 100 to 600 µm. The weight average particle diameter in the invention refers to one obtained by a screening method. The weight average particle diameter (D) is represented by the following:

wherein d represents a center value of sieve meshes according to JIS Standard and n represents a weight frequency of the particles. The powder refers to an aggregate of fine particle crystals.

[0148] The compression dwell time will be explained in the manufacturing method of the present invention.

[0149] In order to manufacture tablets of solid processing agent from granular or particle solid processing agent by means of compression, it is necessary to provide a process for changing an initial space in which the granular or particle solid processing agent exists into the same configuration as that of a predetermined tablet. In this case, the method can be arbitrarily selected.

[0150] For example, a compression device can be used which is equipped with upper and lower pounder-shaped members moving upward and downward so as to compress the solid processing agent in the vertical direction. As long as a compressing action can be exerted on the solid processing agent, one of the pounder-shaped members may be fixed. From the viewpoint of enhancement of workability, it is preferable that the compressing motion is carried out in the vertical direction. However, as long as particles of solid processing agent can be compressed into a predetermined form of tablet, the direction of compression is not specifically limited. It can be arbitrarily determined.

[0151] The compression dwell time described in the present invention is defined as follows:
When the particle solid processing agent is compressed by the method arbitrarily selected as described above, the compression dwell time is from (1) a moment at which the initial space has been just formed into a predetermined configuration of tablet (referred to as a setting space hereinafter), to (2) a moment at which the setting space is returned to the initial space. Then the compressing motion is further advanced passing through the moment (1), a space formed at the final end point of compression is referred to as a compression end point space. In this case, the compressing motion is returned from the compression end point space to the initial space through the setting space described above. In this case, it is possible to determine a moment at which the motion passes through the setting space to be the moment (2). It is also possible to determine a moment at which the motion has reached the setting space to be the moment (2).

[0152] A method of computing the compression dwell time will be explained below referring to a rotary tablet machine as an example.

[0153] Fig. 1 is a schematic illustration showing an overall arrangement of the rotary tablet machine. Particles and/or granules are supplied from the hopper 1 to the mortar 3 arranged on the turn table 2. When the turn table 2 rotates, particles and/or granules are pinched between the upper and the lower pounder in the mortar 3. Then, particles and/or granules are compressed and formed into tablets. Numeral 6 is an upper compression roller for pushing the upper pounder 4 downward, and numeral 7 is a lower compression roller for pushing the lower pounder 5 upward.

[0154] Fig. 2A, Fig. 2B and Fig. 2C show a process in which particles and/or granules are compressed and formed into tablets by the rotary tablet machine. Fig. 2A shows a condition in which the upper pounder 11 and the lower pounder 12 approach each other compress the grains and/or granules by the action of the upper and lower compression rollers 13, 14. Fig. 2B shows a condition in which the lowermost end of the upper compression roller 13 moves horizontally along the upper end of the upper pounder 11 and also the uppermost end of the lower compression roller 14 moves horizontally along the lower end of the lower pounder 12. Fig. C shows a condition in which the compression is completed. Numeral 10 is a turn table. Numeral 11a is a bottom surface of the upper pounder 11, and numeral 12a is a bottom surface of the lower pounder 12.

[0155] In the device shown in Figs. 2A through 2C, the compression dwell time is defined as a period of time from when the upper pounder comes into contact with the lowermost end of the upper compression roller and the lower pounder comes into contact with the uppermost end of the lower compression roller, to when the upper and lower pounders are separate from the upper and lower compression rollers. Therefore, the compression dwell time is the same as a period of time in which the turn table rotates by a distance equal to the diameter of the bottom surface of the upper or lower pounder.

[0156] Therefore, the following equation is established.

where de (cm) is a diameter of the bottom surface 11a or 12a of the pounder, R (cm) is a radius of the pitch circle of the mortar center, N (rpm) is a number of revolution of the turn table, and t (sec) is a compression dwell time.

[0157] In the invention, the particles preferably have a moisture content of 0.05 to 3.0 wt%. When the moisture content is over 3.0 wt%, lubricity is lowered, and in compression molded tablets are likely to adhere to the mortar and to be pulled in a direction opposite the compression direction, resulting in strain inside the tablets. The strain tends to cause capping immediately after tableting and to produce defects or breakage due to impact during storage, resulting in lowering of the effects of the invention. As is apparent from the above mentioned, moisture is necessary for tableting.

[0158] It is preferable in view of the effects of the invention that the content of particles having diameters of 53 µm or less in the particles of the invention is not more than 10 wt%. This is preferable for tablets with poor binding ability in preventing capping or lamination.

[0159] The particles preferably have a bulk density of 0.4 to 0.95 g/cm³ in that the invention is more markedly effected. Since the granules having a bulk density over 0.95 g/cm³ are difficult to be broken in compression-molding (tableting), the bulk density is preferably not more than 0.95 g/cm³ in view of the effects of the invention. Then the bulk density is less than 0.4 g/cm³, too bulky particles and/or granules are likely to fluctuate in loading amount in molding. The bulk density of not less than 0.4 g/cm³ can eliminate the fluctuation of the loading amount.

[0160] The granules preferably have a strength of 100 to 4000 g/mm² in that the invention is more markedly effected. Granules having a strength over 4000 g/mm² are difficult to be broken in compression-molding (tableting), and the strength is preferably not more than 4000 g/mm² in view of the effects of the invention. Then the strength is less than 100 g/mm², tablets are likely to produce defects or breakage, resulting in an increase of compression-molding failure. Therefore, the strength is preferably not less than 100 g/mm² in view of the effects of the invention. The strength of granules is represented by the following expression;

   wherein

, A represents a sectional area (mm²) of granules, P represents a loading weight (g) at which the granules are broken, and d represents diameter of the granules (mm). The reference of the strength is made to Yoshio Hiramatsu and Yukitoshi Seki, Nikkoshi, 81,1024(1965).

[0161] In the invention the above P and d were measured by GRANO, a particle hardness tester produced by Okada Seimitsu Kogyo Co., Ltd. The measurement were carried out at 25°C and at 45 %RH P is an arithmetical average value of 20 pieces of granules.

[0162] The particles preferably have a weight average particle diameter of 100 to 600µm in that the invention is more markedly effected. Granules having a strength over 4000 g/mm² are difficult to be broken in compression-molding (tableting) and the strength is preferably not more than 4000 g/mm² in view of the effects of the invention. When the weight average particle diameter is within the above range, physical properties are stable in continuous tableting and the tablets of the invention can be manufactured stably.

[0163] In the manufacturing method of the invention the photographic agent for compression-molding into tablets is preferably in the form of granules, since the granule form is high in the effects of the invention. The granules are broken in compression-molding to produce fresh surfaces having not been exposed to air and contribute to an increase of the binding ability.

[0164] As for the granulating processes for forming the granules, it is possible to use any of the well-known processes such as the processes of a rolling granulation, an extrusion granulation, a compression granulation, a cracking granulation, a stirring granulation and a fluidized-layer granulation. The granules are preferably produced to have a strength of 100 to 4000 g/mm² in view of the effects of the invention.

[0165] For example, the tablets of the invention preferably include a color developing composition, a black-and-white developing composition, a bleaching composition, a fixing composition, a bleach-fixing composition and a stabilizing composition.

[0166] In this manufacturing method it is preferable to mold at a compression pressure of 400 to 4500kg/cm² and at a compression dwell time of 0.020 to 1.000 second particles and/or granules containing at least one of the following compounds (a) through (e):

(a) a p-phenylene diamine color developing agent

(b) a hydroxylamine and/or its derivatives

(c) an alkali metal carbonate

(d) an amino polycarboxylic acid ferric complex and

(e) a thiosulfate.

[0167] In this manufacturing method it is preferable to repeat the molding compression twice or more. The pressure balance is preferably controled to satisfy the following formula;

, wherein 2 ≤ n ≤ 5.

[0168] It is preferable to mold tablets within 24 hours after completion of preparation of granulars to obtain good tablet characteristics in case of preparation of tablets of processing composition for silver halide photographic material.

EXAMPLES

[0169] The present invention will be detailed with reference to examples, however, the embodiments of the present invention are not limited to these.

Example 1

[0170] Based on the operations described below, a fixing agent employed for graphic art and industrial materials (hereinafter referred to as an industrial fixing agent) was prepared. However, the surface tension of added water was adjusted by varying the amount of sodium octanesulfonate as shown in Table 1.

Industrial Fixing Agent

(1) Preparation of Granule Agent A1

[0171] 

Group 1
Ammonium thiosulfate	113.43 kg
Sodium bisulfite	10.89 kg
Sodium sulfite	0.78 kg
Pine flow	7.0 kg

Group 2
Sodium sulfite anhydride	14.0 kg

Group 3
Sodium octanesulfonate	2.02 kg

Added water
Purified	14.0 kg
Sodium octanesulfonate	in an amount to obtain the surface tension of added water described in Table 1

〈〈Operation 1〉〉

[0172] Group 1 was placed in a Mitsui Henschel mixer FM-500J (manufactured by Mitsui Kinzoku Co.) and was subjected to preliminary mixing at 440 rpm for one minute.

〈〈Operation 2〉〉

[0173] Next, the resulting mixture was added with water over about 1.0 minute and kneaded at 440 rpm.

〈〈Operation 3〉〉

[0174] Next, Group 2 was added and mixed at 220 rpm for 30 seconds.

〈〈Operation 4〉〉

[0175] Further, Group 3 was added and mixed at 220 rpm for 30 seconds.

[0176] As described above, Granule Agent A1 was prepared. (2) Preparation of Granule Agent B1

Group 1
Succinic acid	39.6 kg
Tartaric acid	9.0 kg
Boric acid	18.0 kg
Sorbitol	3.45 kg
Mannitol	7.5 kg

Group 2
Desiccated aluminum sulfate	34.5 kg
Sodium sulfate anhydride	30.0 kg

Group 3
Sodiun octanesulfonate	2.16 kg

Group 4
PEG # 4000	2.25 kg

Added water
Purified	439.8 g
Sodium octanesulfonate	in an amount to obtain the surface tension of added water described in Table 1

〈〈Operation 1〉〉

[0177] Group 1 was placed in a Mitsui Henschel mixer FM-500J (manufactured by Mitsui Kinzoku Co.) and was subjected to preliminary mixing at 440 rpm for one minute.

〈〈Operation 2〉〉

[0178] Next, the resulting mixture was added with water over about 1.5 minutes and kneaded at 220 rpm.

〈〈Operation 3〉〉

[0179] Next, Group 2 was added and mixed at 220 rpm for 30 seconds.

〈〈Operation 4〉〉

[0180] Further, Group 3 was added and mixed at 220 rpm for 30 seconds.

〈〈Operation 5〉〉

[0181] Next, Group 4 was added and mixed at 220 rpm for 30 seconds.

[0182] As described above, Granule Agent B1 was prepared.

〈〈Number of Continual Batches〉〉

[0183] Employing the above-mentioned operations, granulation was carried out continually through 10 batches and evaluation was carried out on how many batches could be continually prepared without a need for washing between granulation batches.

〈〈Weight Ratio of Fine Powder with no more than 125 µm of Granule Agent〉〉

[0184] The weight ratio (fine powder ratio) of the prepared granule agent of no more than 125 µm was measured.

〈〈Dissolution Behavior and Dissolving Time〉〉

[0185] Granule Agent A1: 190 g was placed in an aluminum bag and tightly sealed.

[0186] Granule Agent B1: 48.82 g was placed in an aluminum bag and tightly sealed.

[0187] These Granule Agents were stored at a high temperature of 60 °C for 10 days, and were then unsealed. First, in the order of Granule Agent A1 and Granule Agent B1, they were dissolved in about 800 ml of water. During dissolution, the dissolution behavior was observed and dissolving time was measured.

Dissolution behavior

[0188] 

ⓞ: when unsealing the aluminum bag, no scattered powder was noted and dissolution was smooth

○: when unsealing the aluminum bag, a minimal amount of powder scattered. However, no mask is required to work with the tablet powder, dissolution was smooth

△: when unsealing the aluminum bag, a small amount of powder scattered, it is advisable to wear a mask during work with the tablets. A number of aggregated lumps were found. During dissolution, lumps remain at the bottom of the vessel, however, the product is commercially viable.

X: when unsealing the aluminum bag, powder scattered and it is advised to wear a mask. Problems with many lumps occurred.

X X: Then the number of "X" increases, the amount of scattered powder also increases. Also the number of lumps increases and dissolution time is extended.

[0189] Table 1 shows the above results.

Table 1

Granule Agent No.	Type of Granule Agent	Surface Tension of Added Water (dyn/cm)	Number of Continual Batches	Amount of Fine Powder with no more than 125 µm immediately after Granulation	Dissolution Behavior	Dissolving Time (minute)	Remarks
101	A1	70	1	60	XX	46	Comp.
102	A1	62	1	58	XX	43	Comp.
103	A1	60	7	25	C	18	Inv.
104	A1	58	7	22	C	18	Inv.
105	A1	45	7	20	B	12	Inv.
106	A1	35	10	10	A	8	Inv.
107	A1	25	10	5	A	8	Inv.
108	B1	70	1	68	XX	47	Comp.
109	B1	62	1	64	XX	46	Comp.
110	B1	60	7	25	C	21	Inv.
111	B1	58	7	24	C	21	Inv.
112	B1	45	7	23	B	15	Inv.
113	B1	35	10	15	A	10	Inv.
114	B1	25	10	10	A	10	Inv.

Comp.: Comparative,

Inv.: Present Invention

[0190] As can clearly be seen from Table 1, when the added water of the present invention is employed, it reveals that the amount of fine powder immediately after granulation, dissolution behavior after storage at high temperature, and dissolving time are markedly improved.

Example 2

[0191] Employing Granule Agent A1, Tablet A1 having a diameter of 30 mm and a weight of 10.5 g was prepared employing a Tough Press Collect 1527HU (tablet preparing apparatus, tableting apparatus) manufactured by Kikusui Seisakusho, while employing Granule Agent B1, Tablet B1 with the same diameter as A1 and a weight of 10.3 g was prepared in the same manner.

〈〈Evaluation Method〉〉

〈〈Behavior during Tableting〉〉

[0192] The behavior of adhesion to the pestle and creaking of the pestle was observed and "Behavior during Tableting" was evaluated as described below.

A: very good: neither adhesion to the pestle nor creaking of the pestle occurred

B: good: minimum adhesion to the pestle occurred, but no problem for commercial viability, no creaking of the pestle occurred

C: adhesion to the pestle occurred but no problem for commercial viability, but no creaking of the pestle occurred

X: adhesion to the pestle occurred to cause problems for commercial viability, and creaking of the pestle occurred somewhat

XX: as the number of "X" increases, adhesion to the pestle as well as creaking of the pestle increased.

〈〈Adhesion and Solubility after Storage〉〉

[0193] Further, samples were prepared in such a manner that 18 A1 tablets were placed in an aluminum bag, 5 B1 tablets were placed in another aluminum bag, and 18 A1 tablets together with 5 B1 tablets were placed in a third aluminum bag. These aluminum bags were tightly sealed and stored at 60 °c for 10 days. After storage, the aluminum bags were unsealed and the number of adhered tablets was noted. A1 Tablets and B1 Tablets were dissolved in about 80 ml of water in this order and dissolution behavior was observed. "Adhesion and Solubility after Storage" was evaluated as described below:

A: no adhesion and good solubility

B: slight adhesion and no problem with solubility

C: 2 to 5 clumps of adhered tablets were found but no problem was noted during dissolution

X: at least 10 clumps of adhered tables were found and a problem occurred in which tablets formed clumps at the bottom of the vessel

XX: an increase in the number of "X" indicates increased adhesion.

The above results are shown in Table 2.

Table 2

Tablet No.	Granule Agent Used			Behavior during Tableting	Adhesion and Solubility after Storage	Dissolving Time (minutes)	Re-marks
	No.	Type	Surface Tension of Added Water (dyn/cm)
201	101	A1	70	XX	X	54	Comp.
202	102	A1	62	XX	X	53	Comp.
203	103	A1	60	C	C	35	Inv.
204	104	A1	58	C	C	34	Inv.
205	105	A1	45	B	B	34	Inv.
206	106	A1	35	A	A	25	Inv.
207	107	A1	25	A	A	25	Inv.
208	108	B1	70	XX	X	55	Comp.
209	109	B1	62	XX	X	50	Comp.
210	110	B1	60	C	C	32	Inv.
211	111	B1	58	C	C	31	Inv.
212	112	B1	45	B	B	30	Inv.
213	113	B1	35	A	A	20	Inv.
214	114	B1	25	A	A	20	Inv.
215	101/108	A1/B1	70/70	-	XX	46	Comp.
216	102/108	A1/B1	62/62	-	XX	47	Comp.
217	103/110	A1/B1	60/60	-	C	30	Inv.
218	104/111	A1/B1	58/58	-	C	28	Inv.
219	105/112	A1/B1	45/45	-	B	26	Inv.
220	106/113	A1/B1	35/35	-	B	20	Inv.
221	107/114	A1/B1	25/25	-	A	19	Inv.

Comp.: Comparative,

Inv.: Present Invention

[0194] As can clearly be seen in Table 2, it is found that the present invention improves adhesion during tableting and adhesion after storage at high temperature, and solubility. Example 3 A developing agent for medical diagnostic materials was prepared as described below.

(1) Preparation of Developing Agent A2

[0195] 

Group 1
Glutaraldehyde sodium bisulfite	6063 g
Sodium bisulfite	15000 g
Erbit N (sodium isoerythorbate)	50000 g
Pyrazolidone-A (Phenidone)	4500 g
N-acetyl-penicillamine	100 g
Sorbitol (powder)	2500 g

Added water
Deionized water	in an amount to obtain the surface tension of the added water and a ratio to powder as described in Table 3
Sodium octanesulfonate	in an amount to obtain the surface tension of added water and a ratio to powder as described in Table 3
Sorbit L-70 (64 % aqueous solution)	5859 g

(Operation 1)

[0196] Group 1 was placed in a Speed Kneader NSK-750SJ Type manufactured by Okada Seiko Co., Ltd. and was subjected to preliminary mixing at 150 rpm for 3 minutes

(Operation 2)

[0197] The resulting mixture was added with added water over about 2 minutes 40 seconds at 150 rpm, and thereby kneaded.

(Operation 3)

[0198] Granulated granules were taken out and placed in a rotary fluid dryer, Slit Flow manufactured by Ohkawara Co., Ltd. and dried at 50 °C with dehydrated air so as to obtain a moisture content of no more than 1.0 percent.

(Operation 4)

[0199] Dried granules were uniformly sized employing a Speed Mill ND-75S equipped with a 1 mm filter.

[0200] The granules prepared as described above are denoted as Granule A2 of Developing Agent A2.

(2) Preparation of Developing Agent B2

[0201] 

Group 1
Potassium carbonate	64100 g
DTPA-5H	1436 g
MSPMT	316 g
D-mannitol	14340 g
Sorbitol (powder)	3667

Added water
Deionized water	in an amount to obtain the surface tension of added water and the ratio to powder as described in Table 3
Sodium octane sulfonate	in an amount to obtain the surface tension of added water and the ratio to powder as described in Table 3
Potassium iodide	50.1 g
B-4533	71.6 g

(Operation 1)

[0202] Group 1 was placed in a Speed Kneader NSK-750SJ Type manufactured by Okada Seiko Co., Ltd. and was subjected to preliminary mixing for 3 minutes at 150 rpm.

(Operation 2)

[0203] The resulting mixture was added with added water over about 2 minutes 40 seconds at 150 rpm, and thereby kneaded.

(Operation 3)

[0204] Granulated granules were taken out and were placed in a rotary fluid dryer, Slit Flow manufactured by Okawara Co., Ltd. and were dried at 50 °C with dry air so as to obtain a moisture content of no more than 1.0 percent.

(Operation 4)

[0205] Dried granules were uniformly sized employing a Speed Mill ND-75S equipped with a 1 mm filter.

[0206] The granules prepared as described above are denoted Granule B2 of Developing Agent B2.

〈〈Evaluation Method〉〉

〈〈Number of Continual Batches〉〉

[0207] The above-cited Operations were carried out continually through 10 batches and evaluation was carried out on how many batches could be continually prepared without a need for washing between granulation batches.

〈〈Weight Ratio of Fine Powder with no more than 125 µm Particles immediately after Granulation〉〉

[0208] The weight ratio of fine powder with no more than 125 µm particles immediately after granulation of a prepared granule agent was measured.

〈〈Dissolution Behavior〉〉

[0209] 190 g of Granule Agent A2 were placed in an aluminum bag and tightly sealed.

[0210] 48.82 g of Granule Agent B2 were placed in an aluminum bag and tightly sealed.

[0211] These Granule Agents were stored at the relatively high temperature of 60 °C for 10 days, and were then unsealed. In the order of Granule Agent A2 and Granule Agent B2, they were dissolved in about 800 ml of water. During dissolution, the dissolution behavior was observed and dissolving time was recorded.

Dissolution behavior

[0212] 

A: when unsealing the aluminum bag, no scattered powder was noted and dissolution was smooth

B: when unsealing the aluminum bag, a minimal amount of powder scattered. However, no mask is required to work with the tablet powder, dissolution was smooth

C: when unsealing the aluminum bag, a small amount of powder scattered, it is advisable to wear a mask during work with the tablets. A number of aggregated lumps were found. During dissolution, lumps remain at the bottom of the vessel, however, the product is commercially viable.

X: when unsealing the aluminum bag, powder scattered and it is advised to wear a mask. Problems with many lumps occurred.

XX: When the number of "X" increases, the amount of scattered powder also increases. Also the number of lumps increases and dissolution time is extended.

[0213] Table 3 shows the above results.

Table 3

Granule Agent No.	Type of Granule Agent	Surface Tension of Added Water (dyn/cm)	of Added Water to Powder (wt%)	Number of Continual Batches	Amount of Powder*	Dissolution Behavior	Dissolving Time (min.)	Remarks
301	A2	70	3	3	90	XX	59	Comp.
302	A2	70	5	2	80	XX	58	Comp.
303	A2	70	6	2	75	XX	58	Comp.
304	A2	70	10	1	55	X	54	Comp.
305	A2	62	3	1	58	XX	48	Comp.
306	A2	60	3	7	25	C	18	Inv.
307	A2	60	1.1	7	25	C	18	Inv.
308	A2	60	1	10	18	B	12	Inv.
309	A2	60	0.8	10	18	B	12	Inv.
310	A2	58	3	7	22	C	18	Inv.
311	A2	45	0.8	10	14	A	7	Inv.
312	A2	45	1.0	10	14	A	7	Inv.
313	A2	45	1.1	7	20	B	12	Inv.
314	A2	45	3	7	20	B	12	Inv.
315	A2	45	5	7	20	B	12	Inv.
316	A2	45	6	4	20	B	12	Inv.
317	A2	45	10	4	20	B	12	Inv.
318	A2	35	3	10	10	A	8	Inv.
319	A2	25	3	10	5	A	8	Inv.
320	B2	70	3	3	91	XX	62	Comp.
321	B2	70	5	2	88	XX	59	Comp.
322	B2	70	6	2	79	XX	54	Comp.
323	B2	70	10	2	60	X	53	Comp.
324	B2	62	3	1	64	XX	49	Comp.
325	B2	60	3	7	25	C	21	Inv.
326	B2	58	3	7	24	C	21	Inv.
327	B2	45	3	7	23	B	15	Inv.
328	B2	45	5	7	24	B	15	Inv.
329	B2	45	6	4	25	B	15	Inv.
330	B2	45	10	4	26	B	15	Inv.
331	B2	35	3	10	15	A	10	Inv.
332	B2	25	3	10	10	A	10	Inv.

Comp.: Comparative,

Inv.: Present Invention

Amount of Powder* : Amount of Powder with no more than 125 µm immediately after Granulation (wt%)

[0214] As can clearly be seen from Table 1, when the added water of the present invention is employed, it reveals that the amount of fine powder immediately after granulation, dissolution behavior after storage at high temperature, and dissolving time are markedly improved.

[0215] Furthermore, it is found that when the ratio of the added water to the powder is no more than 5 percent, continual granulation properties are excellently exhibited.

Example 4

[0216] Employing Granule Agent A2 prepared in Example 3, Tablet A2 having a diameter of 30 mm and a weight of 10.30 g was prepared employing a Tough Press Collect 1527HU manufactured by Kikusui Seisakusho, while employing Granule Agent B2, Tablet B2 with the same diameter as A2 but at a weight of 12.65 g was prepared in the same manner.

〈〈Evaluation Method〉〉

〈〈Behavior during Tableting〉〉

[0217] The behavior of adhesion to the pestle and pestle creaking of the pestle was observed and "Behavior during Tableting" was evaluated as described below.

A: very good: neither adhesion to the pestle nor creaking of the pestle occurred

B: minimum adhesion to the pestle occurred, but no problem for commercial viability; good: no creak of the pestle

C: adhesion to the pestle occurs but no problem for commercial viability, and no creaking of the pestle occurs

X: adhesion to the pestle occurred to cause problems for commercial viability, creaking of the pestle occurred somewhat

XX: as the number of "X" increases, adhesion to the pestle as well as creaking of the pestle increases.

〈〈Adhesion and Solubility after Storage〉〉

[0218] Further, samples were prepared in such a manner that 18 A2 tablets were placed in an aluminum bag, 5 B2 tablets were placed in another aluminum bag, and 18 A2 tablets together with 5 B2 tablets were placed in a third aluminum bag. These aluminum bags were tightly sealed and stored at 60 °c for 10 days. After storage, the aluminum bags were unsealed and the number of clumped tablets was noted. The A2 Tablets and the B2 Tablets were dissolved in about 80 ml of water in this order and dissolution behavior was observed. "Adhesion and Solubility after Storage" was evaluated on the basis described below:

A: no adhesion and good solubility

B: slight adhesion but no problem with solubility

C: 2 to 5 clumps of adhered tablets were noted but caused no problem during dissolution

X: at least 10 clumps of adhered tables were noted and problems occurred during dissolution in which tablets formed clumps at the bottom of the vessel

XX: an increase in the number of "X" indicates increased clumping. The above results are shown in Tables 4 and 5.

Table 4

Tablet No.	Granule Agent Used (drying*)			Ratio of Added Water to Powder (wt%)	Behavior during Tableting	Adhesion and Solubility after Storage	Dissolving Time (minutes)	Remarks
	No.	Type	Surface Tension of Added Water (dyn/cm)
401	301	A2	70	3	XX	X	66	Comp.
402	302	A2	70	5	XX	X	63	Comp.
403	303	A2	70	6	XX	X	62	Comp.
404	304	A2	70	10	XX	X	59	Comp.
405	305	A2	62	3	XX	X	55	Comp.
406	306	A2	60	3	C	C	23	Inv.
407	307	A2	60	1.1	C	C	23	Inv.
408	308	A2	60	1	B	B	16	Inv.
409	309	A2	60	0.8	B	B	16	Inv.
410	310	A2	58	3	C	C	20	Inv.
411	311	A2	45	0.8	A	A	12	Inv.
412	312	A2	45	1.0	A	A	12	Inv.
413	313	A2	45	1.1	B	B	18	Inv.
414	314	A2	45	3	B	B	18	Inv.
415	315	A2	45	5	B	B	18	Inv.
416	316	A2	45	6	C	C	22	Inv.
417	317	A2	45	10	C	C	22	Inv.
418	318	A2	35	3	A	A	15	Inv.
419	319	A2	25	3	A	A	15	Inv.
420	320	B2	70	3	XX	X	66	Comp.
421	321	B2	70	5	XX	X	63	Comp.
422	322	B2	70	6	XX	X	62	Comp.
423	323	B2	70	10	XX	X	59	Comp.
424	324	B2	62	3	XX	X	55	Comp.
425	325	B2	60	3	C	C	23	Inv.
426	326	B2	58	3	C	C	20	Inv.
427	327	B2	45	3	B	B	18	Inv.
428	328	B2	45	5	B	B	18	Inv.
429	329	B2	45	6	C	C	22	Inv.
430	330	B2	45	10	C	C	22	Inv.
431	331	B2	35	3	A	A	15	Inv.
432	332	B2	25	3	A	A	15	Inv.

Comp.: Comparative,

Inv.: Present Invention

*: Granule Agent is dried (moisture content of no more than 1.0 percent) after granulation.

Table 5

Tablet No.	Granule Agent Used (drying*)			Ratio of Added Water to Powder (wt%)	Behavior during Tableting	Adhesion and Solubility after Storage	Dissolving Time (minutes)	Remarks
	No.	Type	Surface Tension of Added Water (dyn/cm)
433	301/320	A2/B2	70/70	3	XX	X	68	Comp.
434	302/321	A2/B2	70/70	5	XX	X	65	Comp.
435	303/322	A2/B2	70/70	6	XX	X	64	Comp.
436	304/323	A2/B2	70/70	10	XX	X	60	Comp.
437	305/324	A2/B2	62/62	3	XX	X	59	Comp.
438	306/325	A2/B2	60/60	3	C	C	23	Inv.
439	310/326	A2/B2	58/58	3	C	C	20	Inv.
440	314/327	A2/B2	45/45	3	B	B	18	Inv.
441	315/328	A2/B2	45/45	5	B	B	18	Inv.
442	316/329	A2/B2	45/45	6	C	C	22	Inv.
443	317/330	A2/B2	45/45	10	C	C	22	Inv.
444	318/331	A2/B2	35/35	3	A	A	15	Inv.
445	319/332	A2/B2	25/25	3	A	A	15	Inv.

Comp.: Comparative,

Inv.: Present Invention

*: Granule Agent is dried (to a moisture content of no more than 1.0 percent) after granulation.

[0219] As can clearly be seen in Tables 4 and 5, the present invention exhibits preferable effects.

Example 5

[0220] A developing agent for color paper was prepared as described below.

(1) Preparation of Developing Agent A3

[0221] 

Group 1
Potassium carbonate	50.82 kg
Sodium sulfite	0.54 kg
DTPA-5Na	9.24 kg
PTS-Na	20.02 kg
DSEHA	12.47 kg
Tinopal SFP	4.62 kg
LiOH·H2O	5.39 kg
D-Mannitol	7.7 kg
PEG #4000	15.4 kg

Group 2
CD -3	22.33 kg

Group 3
Alanon AMP	1.49 kg

Added water
Deionized water	439.8 kg
Sodium octanesulfonate	in an amount to obtain the surface tension of added water described in Table 5

〈〈Operation 1〉〉

[0222] Group 1 was placed in a Mitsui Henschel mixer FM-500J (manufactured by Mitsui Kinzoku Co.) and was subjected to preliminary mixing at 220 rpm for about 30 seconds.

〈〈Operation 2〉〉

[0223] The resulting mixture had water added for about 1.5 minute and thereby kneaded at 220 rpm.

〈〈Operation 3〉〉

[0224] Group 2 was added and mixed at 220 rpm for 30 seconds.

〈〈Operation 4〉〉

[0225] Group 3 was added and mixed at 220 rpm for 30 seconds.

[0226] As described above, Developing Agent A3 and Granule Agent A3 were thus prepared.

〈〈Evaluation Method〉〉

〈〈Number of Continual Batches〉〉

[0227] The above-mentioned Operations were carried out continually through 10 batches and evaluation was carried out on how many batches could be continually prepared without a need of washing between granulation batches.

〈〈Weight Ratio of Fine Powder with no more than 125 µm immediately after Granulation〉〉

[0228] The weight ratio of fine powder with no more than 125 µm particles immediately after granulation of a prepared granule agent was measured.

〈〈Dissolution Behavior〉〉

[0229] Granule Agent A3 in the amount of 97.42 g was placed in an aluminum bag and tightly sealed.

[0230] This Granule Agent was stored at a relatively high temperature of 60 °C for 10 days, and was then unsealed. Granule Agent A3 was dissolved in about 800 ml of deionized water. During dissolution, the dissolution behavior was observed and dissolving time was noted.

Dissolution behavior

[0231] 

A: when unsealing the aluminum bag, no scattered powder was noted and dissolution was smooth

B: when unsealing the aluminum bag, a minimal amount of powder scattered. However, no mask is required to work with the tablet powder, dissolution was smooth

C: when unsealing the aluminum bag, a small amount of powder scattered, it is advisable to wear a mask during work with the tablets. A number of aggregated lumps were found. During dissolution, lumps remain at the bottom of the vessel, however, the product is commercially viable.

X: when unsealing the aluminum bag, powder scattered and it is advised to wear a mask. Problems with many lumps occurred.

XX: When the number of "X" increases, the amount of scattered powder also increases. Also the number of lumps increases and dissolution time is extended.

[0232] Table 6 shows the above results.

Table 6

Granule Agent No.	Type of Granule Agent	Surface Tension of Added Water (dyn/cm)	Number of Continual Batches	Amount of Powder with no more than 125 µm immediately after Granulation	Dissolution Behavior	Dissolving Time (minutes)	Remarks
501	A3	70	1	60	XX	50	Comp.
502	A3	62	1	58	XX	48	Comp.
503	A3	60	7	25	C	16	Inv.
504	A3	58	7	22	C	16	Inv.
505	A3	45	7	20	B	10	Inv.
506	A3	35	10	10	A	8	Inv.
507	A3	25	10	5	A	8	Inv.

Comp.: Comparative,

Inv.: Present Invention

[0233] As can clearly be seen in Tables 6, it is found that the present invention exhibits the preferable effects.

Example 6

[0234] Employing Granule Agent A3 prepared in Example 5, Tablet A3 having a diameter of 30 mm and a weight of 11.0 g was prepared employing a Tough Press Collect 1527HU manufactured by Kikusui Seisakusho.

〈〈Evaluation Method〉〉

〈〈Behavior during Tableting〉〉

[0235] The behavior of adhesion to pestle and creaking of the pestle was observed and "Behavior during Tableting" was evaluated as described below.

A: very good; neither adhesion to the pestle nor creaking of the pestle occurred

B: good: minimum adhesion to the pestle occurred, but no problem for commercial viability, no creaking of the pestle occurred

C: adhesion to the pestle occurred but not to cause problems for commercial viability, and also no creaking of the pestle occurred

X: adhesion to the pestle occurred to cause problems for commercial viability, creaking of the pestle occurred somewhat

XX: as the number of "X" increases, adhesion to the pestle, as well as creaking of the pestle, also increases.

〈〈Adhesion and Solubility after Storage〉〉

[0236] Further, 18 A3 tablets were placed in an aluminum bag, the aluminum bag was tightly sealed, and stored at 60 °C for 10 days. After storage, the aluminum bag was unsealed and the number of clumped tablets was noted. Tablets A3 were dissolved in about 80 ml of water, and at that time, dissolving time was recorded and dissolution behavior was observed. "Adhesion and Solubility after Storage" was evaluated as described below:

A: no adhesion and good solubility

B: slight adhesion and no problem with solubility

C: 2 to 5 clumps of adhered tablets were found but caused no problem during dissolution

X: at least 10 clumps of adhered tables were found and problems occurred in which tablets formed clumps at the bottom of the vessel

XX: an increase in the number of "X" indicates more sticking. The above results are shown in Table 2.

Table 7

Tablet No.	Granule Agent Used			Behavior during Tableting	Adhesion and Solubility after Storage	Dissolving time (min.)	Remarks
	No.	Type	Surface Tension of Added Water (dyn/cm)
601	501	A3	70	XX	X	54	Comp.
602	502	A3	62	XX	X	53	Comp.
603	503	A3	60	C	C	35	Inv.
604	504	A3	58	C	C	34	Inv.
605	505	A3	45	B	B	34	Inv.
606	506	A3	35	A	A	25	Inv.
607	507	A3	25	A	A	25	Inv.

Comp.: Comparative,

Inv.: Present Invention

[0237] As can clearly be seen in Table 7, it was found that the effects of tablet agents of the present invention favorably exhibited the desired effects.

[0238] In producing a granular agent or a tablet employing a wet-type agitation granulating system, the present invention made it possible to provide a production method which requires markedly reduced amount of water anwhereby drying time is reduced, simple drying apparatus can be applied or drying apparatus is deprived, and production cost can be reduced markedly, and exhibits excellent continuous production stability for producing a solid processing agent for a silver halide photosensitive photographic material, and specifically to provide a production method for a granular or tablet-like solid processing agent, which exhibits excellent high speed continuous production stability, particularly employing water soluble components.

[0239] Disclosed embodiment can be varied by a skilled person without departing from the spirit and scope of the invention.

Claims

1. A production method of a granular agent, comprising steps of

mixing powder and additive liquid by agitation and

forming a granular agent

wherein surface tension of the additive liquid is no more than 60 dyn/cm.

2. The production method of claim 1, wherein amount of the additive liquid is no more than 5 weight percent with reference to the powder amount.

3. The production method of claim 1, wherein amount of the additive liquid r is no more than 1 weight percent with reference to the powder amount.

4. The production method of claim 1, wherein the powder is a material for processing agent for a silver halide photosensitive photographic material.

5. The production method of claim 4, wherein the powder comprises at least one of potassium carbonate, p-phenylenediamine derivatives, iron salts of polyaminocarboxylic acid, thiosulfates, hydroquinone and aluminum sulfates.

6. The production method of claim 4, wherein the additive liquid comprises water and a surfactant.

7. A production method of a tablet wherein the granular agent produced by a method described in claim 1 is made tabletted.

Drawing