EP0964303A1 - Verfahren zur Herstellung eines granulierten Mittels und Verfahren zur Herstellung einer Tablette - Google Patents

Verfahren zur Herstellung eines granulierten Mittels und Verfahren zur Herstellung einer Tablette Download PDF

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Publication number
EP0964303A1
EP0964303A1 EP99111249A EP99111249A EP0964303A1 EP 0964303 A1 EP0964303 A1 EP 0964303A1 EP 99111249 A EP99111249 A EP 99111249A EP 99111249 A EP99111249 A EP 99111249A EP 0964303 A1 EP0964303 A1 EP 0964303A1
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Prior art keywords
group
agent
tablet
water
powder
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EP99111249A
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English (en)
French (fr)
Inventor
Hiroshi Yoshimoto
Kouki Kawashima
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Konica Minolta Inc
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Konica Minolta Inc
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
    • G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
    • G03C5/264—Supplying of photographic processing chemicals; Preparation or packaging thereof
    • G03C5/265—Supplying of photographic processing chemicals; Preparation or packaging thereof of powders, granulates, tablets

Definitions

  • 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.
  • 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.
  • a black-and-white developer or a color developer is employed;
  • a bleach or a bleach-fixer is employed;
  • 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.
  • 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.
  • drying apparatus and longer drying time are required, which make the producing cost expensive.
  • 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.
  • 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.
  • a production method of a granular agent comprising steps of
  • 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.
  • the preferable example of powder is a material for processing agent for a silver halide photosensitive photographic material.
  • the powder preferably comprises at least one of potassium carbonate, p-phenylenediamine derivatives, iron salts of polyaminocarboxylic acid, thiosulfates, hydroquinone and aluminum sulfates.
  • the additive liquid preferably comprises water and a surfactant.
  • the solid processing agent of the present invention is produced via a wet-type agitation granulation process.
  • 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.
  • 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.
  • 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.
  • the method for the solid processing agent of the present invention is the agitation granulation method.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the surface tension can be regulated employing so-called surface active agents.
  • surface active agents The more water-soluble a surface active agent is, the better it is.
  • 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.
  • 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.
  • Rf represents a saturated or unsaturated alkyl group having at least one fluorine atom
  • X represents sulfonamides shown below:
  • Y represents an alkylene oxide group and an alkylene group
  • Rf' represents a saturated or unsaturated hydrocarbon group having at least one fluorine atom.
  • A represents hydrophilic group such as -SO 3 M, -OSO 3 M, -COOM, -OPO 3 (M 1 )(M 2 ), -PO 3 (M 1 )(M 2 ), etc.; M, M 1 , and M 2 each represents H, Li, K, Na, or NH 4 , and "m” represents an integer of 0 or 1, and “n” represents 0 or an integer of 1 to 10.
  • 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 -SO 3 M, and M, M 1 , and M 2 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.
  • particularly preferred compounds are (I-1), (I-2), and (I-4).
  • R 1 represents an alkyl group or an alkenyl group
  • R 2 represents a hydrogen atom, an alkyl group or a hydroxyalkyl group
  • R 3 and R 4 each independently represents a hydrogen atom, a hydroxyl group, an alkyl group or -COOM 2
  • M 2 represents a hydrogen atom or an alkali metal atom
  • X represents -CO- or -SO 2 -
  • Y represents -O-, -S- or -CONR 5 -
  • R 5 represents a hydrogen atom, an alkyl group or a hydroxyalkyl group
  • M 1 represents a hydrogen atom or an alkali metal atom
  • "l” represents 0 or 1
  • "m” represents an integer of 0 to 2
  • n represents an integer of 1 to 3.
  • R 1 represents an alkyl group or an alkenyl group
  • R 2 represents a hydrogen atom, an alkyl group or a hydroxyalkyl group
  • R 3 and R 4 each independently represents a hydrogen atom, a hydroxyl group, an alkyl group or -COOM 2
  • M 2 represents a hydrogen atom or an alkali metal atom
  • X represents -CO- or -SO 2 -
  • Y represents -O-, -S- or -CONR 5 -
  • R 5 represents a hydrogen atom, an alkyl group or a hydroxyalkyl group
  • M 1 represents a hydrogen atom or an alkali metal atom
  • "l” represents 0 or 1
  • "m” represents an integer of 0 to 2
  • "n” represents an integer of 1 to 3.
  • R 1 is preferably a straight or branched alkyl group having from 5 to 20 carbon atoms or an alkenyl group
  • R 2 is preferably a hydrogen atom, a straight or branched alkyl group having from 1 to 5 carbon atoms or a hydroxyalkyl group.
  • R 1 , R 2 , R 3 , R 4 , and R 5 each represents an alkyl group, an aralkyl group, an alkenyl group, a styryl group, and cinnamyl group; l 1 , l 2 , l 3 , l 4 , and l 5 each represents an integer of 0 or 1, and n represents an integer of 2 to 100. However, when R 3 represents an alkyl group and l 3 represents 1, at least one of l 1 , l 2 , l 4 , and l 5 is 1. When l 1 , l 2 , l 3 , l 4 , and l 5 each represents 0, responding R 1 , R 2 , R 3 , R 4 , and R 5 each represents a hydrogen atom.
  • the alkyl group represented by R 1 , R 2 , R 3 , R 4 , and R 5 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 R 1 , R 2 , R 3 , R 4 , and R 5 are those having from 7 to 20 carbon atoms and specifically include each of a benzyl, phenetyl, dibenzyl, 2-naphthylmethyl group, etc.
  • the alkenyl groups represented by R 1 , R 2 , R 3 , R 4 , and R 5 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.
  • An aromatic ring of an aralkyl group and a styryl group may have a substituent.
  • 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.).
  • R represents an alkyl group which may have from 4 to 25 carbon atoms and a straight or branched chain or represents: wherein R 11 and R 12 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, n 1 , m 1 , and l 1 each represents 0, 1, 2, or 3, and m 1 in A and B represents no 0 at the same time and when n or m represents 0, m 1 represents no 0.
  • D represents a hydrogen atom.
  • R 1 ⁇ O(R 2 ⁇ O) m X 1 wherein R 1 represents a monovalent organic group; R 2 represents an ethylene group or a propylene group, and "m" represents an integer of 4 to 50.
  • X 1 represents a hydrogen atom, -SO 3 M or -PO 3 M 2 , wherein M represents a hydrogen atom, an alkali metal atom, or -NH 4 .
  • R 1 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.
  • 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.
  • R 2 represents an ethylene group or a propylene group, and "m" represents an integer of 4 to 50.
  • X 1 represents a hydrogen atom, -SO 3 M or -PO 3 M 2 , in which M is a hydrogen atom, an alkali metal atom (Na, K, Li, etc.) or -NH 4 .
  • R-(O) x S y O z M 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.
  • 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.
  • 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
  • alkenyl groups are, for example, a vinyl group, an allyl group, etc.
  • alkynyl groups are, for example, propargyl group, etc.
  • aromatic group represented by R are, for example, a phenyl group, a naphthyl group, etc.
  • 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.
  • a pyridyl group each of a 2-pyridyl, 3- pyridyl, 4- pyridyl group, etc.
  • a thiazolyl group an oxazolyl group, an imidazolyl group
  • 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.
  • Cations represented by M are preferably metal ions or organic cations.
  • the metal ions are, for example, a lithium ion, a sodium ion, a potassium ion, etc.
  • 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.
  • 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%.
  • a sieving method 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.
  • 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.
  • the specific volume of a granular solid processing agent is preferably between 0.7 and 2.8 cm 3 /g.
  • the specific volume of no more than 0.7 cm 3 /g is not preferred because a long time is required for dissolution.
  • the specific volume of not less than 2.8 cm 3 /g is not preferred because a fine powder tends to be generated during handling.
  • 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.
  • 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.
  • 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.
  • 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.
  • the above-mentioned color developing agents are usually employed in the form of salts such as chlorides, sulfates, p-toluenesulfoantes, etc.
  • 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.
  • 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.
  • R 1 and R 2 each represent an alkyl group and an aryl group while both represent no hydrogen atom at the same time.
  • each of them represents a hydrogen atom
  • the alkyl groups represented by R 1 and R 2 may be the same or different, and each alkyl group having from 1 to 3 carbon atoms is preferred.
  • these alkyl groups may have a carboxylic acid group, a phosphoric acid group, a sulfonic acid group or a hydroxyl group.
  • R' represents an alkoxy group, an alkyl group or an aryl group.
  • the alkyl groups and aryl groups of R 1 , R 2 , and R' include those having a substituent and R 1 and R 2 may combine with each other to from a ring and may form a heterocyclic ring such as, for example, piperidine, pyridine, triazine, morpholine.
  • R 11 , R 12 , and R 13 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.
  • R 15 represents a divalent group selected from -CO-, -SO 2 - or "n" is 0 or 1. Especially, when n is 0, R 14 represents a group selected from an alkyl group, an aryl group, and a heterocyclic group, and R 13 and R 14 may form a heterocyclic group in combination of these.
  • 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.
  • the minimal amount of sulfites may be employed as a preservative.
  • sulfites sodium sulfite, potassium sulfite, sodium bisulfite, potassium bisulfite.
  • 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).
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • chlorine ion-supplying materials 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.
  • 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.
  • 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.
  • antifoggants may be added, if desired.
  • alkali metal halides such as potassium iodide, and organic antifoggants.
  • 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.
  • triazinylstilbene series fluorescent whitening agents are preferably incorporated into the color developing agent and developing agent employed in the present invention.
  • fluorescent whitening agents those represented by the general formula (E) described below are preferred.
  • X 2 , X 3 , Y 1 , and Y 2 each represents a hydroxyl group, a halogen atom such as chlorine, bromine, etc., an alkyl group, an aryl group; or -OR 25' wherein R 21 and R 22 each represents a hydrogen atom, an alkyl group (including an substituted group), an aryl group (including an substituted group); R 23 and R 24 each represents an alkylene group (including a substituted group); R 25 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.
  • 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.
  • 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, ⁇ -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.
  • auxiliary developing agents can be employed together with a developing agent.
  • auxiliary developing agents are known Metol, phenidone, N,N-diethyl-p-aminophenol hydrochloride, N,N,N,N'-tetramethyl-p-phenylenediamine hydrochloride, etc.
  • additives such as antistaining agents, antisludging agents, interimage effect enhancing agents, etc. can be employed.
  • 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.
  • 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.
  • 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.
  • 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.
  • surface active agents such as alkylsulfonic acids, arylsulfonic acids, aliphatic carboxylic acids, aromatic carboxylic acids, if desired.
  • 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 A 1 through A 4 may be the same and different, and each represents -CH 2 OH, -COOM or -PO 3 M 1 M 2 .
  • M, M 1 , and M 2 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.
  • a 1 through A 4 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.
  • 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.
  • those are preferably employed in the present invention.
  • 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.
  • (C-1), (C-3), (C-4), (C-5), and (C-9) are preferably employed, and particularly, (C-1) is preferably employed.
  • ferric complex salts described below can be employed in the bleaching agent or bleach-fixing agent.
  • 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.
  • 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.
  • halides such as ammonium bromide, potassium bromide, and sodium bromide, various types of fluorescent whitening agents, antifoaming agents, and surface active agents.
  • 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.
  • the object of the present invention is more effectively achieved by employing thiocyanate salts and thiosulfate salts in combination.
  • pH buffering agents composed of various salts can also be incorporated individually or in combination of two or more types.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • sulfites are preferably incorporated into the stabilizing agent.
  • 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.
  • organic acid salts citric acid, acetic acid, succinic acid, oxalic acid, benzoic acid
  • pH regulators phosphates, borates, hydrochloric acid, sulfates
  • deionized water is preferably employed in the stabilizer.
  • 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.
  • 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.
  • 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
  • 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.
  • buffering agents for example, carbonates, boric acids, borates, alkanolamine, etc.
  • alkali agents for example, 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
  • 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
  • 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.
  • amine compounds such as alkanolamine, etc. may be employed which are described in Japanese Patent Publication Open to Public Inspection No. 56-106244.
  • carbonates having a buffering action are preferred.
  • carbonates are potassium carbonate, sodium carbonate, lithium carbonate, etc.
  • the amount of carbonates in a processing solution is preferably at least 0.3 mole/liter and less than 0.8 mole/liter.
  • 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.
  • 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.
  • the fixing solution employed in the present invention comprises sulfites.
  • sulfites are solid lithium, potassium, sodium, and ammonium salts.
  • the fixing solution employed in the present invention may comprise water-soluble chromium salts or water-soluble aluminum salts.
  • water-soluble chromium salts are chrome alum, etc.
  • water-soluble aluminum salts can be aluminum sulfate, aluminum potassium chloride, aluminum chloride, etc.
  • 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.
  • citric acid tartaric acid, malic acid, succinic acid, phenylacetic acid and optical isomers thereof, etc. may be incorporated.
  • lithium, potassium, sodium, ammonium 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.
  • 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.
  • citric acid isocitric acid
  • malic acid phenylacetic acid and salts thereof.
  • inorganic acids such as sulfuric acid, hydrochloric acid, nitric acid, and boric acid, and salts thereof
  • organic acids such as formic acid, propionic acid, oxalic acid, malic acid, and salts thereof.
  • acids such as boric acid, aminopolycarboxylic acids, etc. and salts thereof.
  • chelating agents are, for example, aminopolycarboxylic acids such as nitorilotriacetic acid, ethylenediaminetetraacetic acid, etc. and salts thereof.
  • 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.
  • fixing accelerators are thiourea derivatives and alcohols having a triple bond in the molecule, thioether, etc.
  • a fixing solution has a pH of at least 3.8, and has preferably a pH of 4.2 to 5.5.
  • 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.
  • 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.
  • the lubricant is preferably a water soluble surfactant for a photographic processing tablet.
  • 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.
  • 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
  • the time taken at the second process refers to compression dwell time. The sum of the both refers to total compression time.
  • 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.
  • 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/cm 2 700-2100 kg/cm 2 Compression Dwell Time 0.02-1.00 sec. 0.05-0.80 sec.
  • 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.
  • 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 ⁇ m or less, the particles and/or granules have a bulk density of 0.4 to 0.95 g/cm 3 , or strength of the particles and/or granules is 100 to 400 g/mm 2 .
  • 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/cm 2 markedly reduce the above expansion.
  • the particles in the invention preferably refer to particles having a particle diameter of 53 to 2830 ⁇ m, or granules having a particle diameter of 53 to 2830 ⁇ m which are obtained by granulating powder, and have preferably a weight average particle diameter of 100 to 600 ⁇ m.
  • the weight average particle diameter in the invention refers to one obtained by a screening method.
  • the powder refers to an aggregate of fine particle crystals.
  • the compression dwell time will be explained in the manufacturing method of the present invention.
  • 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.
  • 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.
  • the direction of compression is not specifically limited. It can be arbitrarily determined.
  • 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).
  • a method of computing the compression dwell time will be explained below referring to a rotary tablet machine as an example.
  • 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.
  • 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
  • numeral 7 is a lower compression roller for pushing the lower pounder 5 upward.
  • 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
  • numeral 12a is a bottom surface of the lower pounder 12.
  • 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.
  • de 2 ⁇ RNt 60
  • 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
  • t (sec) is a compression dwell time.
  • the particles preferably have a moisture content of 0.05 to 3.0 wt%.
  • 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.
  • moisture is necessary for tableting.
  • the content of particles having diameters of 53 ⁇ m 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.
  • the particles preferably have a bulk density of 0.4 to 0.95 g/cm 3 in that the invention is more markedly effected. Since the granules having a bulk density over 0.95 g/cm 3 are difficult to be broken in compression-molding (tableting), the bulk density is preferably not more than 0.95 g/cm 3 in view of the effects of the invention. Then the bulk density is less than 0.4 g/cm 3 , 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/cm 3 can eliminate the fluctuation of the loading amount.
  • the granules preferably have a strength of 100 to 4000 g/mm 2 in that the invention is more markedly effected.
  • Granules having a strength over 4000 g/mm 2 are difficult to be broken in compression-molding (tableting), and the strength is preferably not more than 4000 g/mm 2 in view of the effects of the invention. Then the strength is less than 100 g/mm 2 , 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/mm 2 in view of the effects of the invention.
  • the reference of the strength is made to Yoshio Hiramatsu and Yukitoshi Seki, Nikkoshi, 81,1024(1965).
  • 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.
  • the particles preferably have a weight average particle diameter of 100 to 600 ⁇ m in that the invention is more markedly effected.
  • Granules having a strength over 4000 g/mm 2 are difficult to be broken in compression-molding (tableting) and the strength is preferably not more than 4000 g/mm 2 in view of the effects of the invention.
  • 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.
  • 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.
  • 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/mm 2 in view of the effects of the invention.
  • 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.
  • the pressure balance is preferably controled to satisfy the following formula; 0.5 ⁇ (compression pressure in kg/cm 2 at n-1 th time compression)/(compression pressure in kg/cm 2 at n th time compression) ⁇ 1.5 , wherein 2 ⁇ n ⁇ 5.
  • an industrial fixing agent employed for graphic art and industrial materials
  • the surface tension of added water was adjusted by varying the amount of sodium octanesulfonate as shown in Table 1.
  • 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.
  • Group 2 was added and mixed at 220 rpm for 30 seconds.
  • Group 3 was added and mixed at 220 rpm for 30 seconds.
  • 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
  • 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.
  • Group 2 was added and mixed at 220 rpm for 30 seconds.
  • Group 3 was added and mixed at 220 rpm for 30 seconds.
  • Group 4 was added and mixed at 220 rpm for 30 seconds.
  • Granule Agent B1 was prepared.
  • the weight ratio (fine powder ratio) of the prepared granule agent of no more than 125 ⁇ m was measured.
  • Granule Agent A1 190 g was placed in an aluminum bag and tightly sealed.
  • Granule Agent B1 48.82 g was placed in an aluminum bag and tightly sealed.
  • 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.
  • 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.
  • 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:
  • Example 3 A developing agent for medical diagnostic materials was prepared as described below.
  • 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
  • the resulting mixture was added with added water over about 2 minutes 40 seconds at 150 rpm, and thereby kneaded.
  • 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.
  • Dried granules were uniformly sized employing a Speed Mill ND-75S equipped with a 1 mm filter.
  • Granule A2 of Developing Agent A2 The granules prepared as described above are denoted as Granule A2 of Developing Agent A2.
  • 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.
  • the resulting mixture was added with added water over about 2 minutes 40 seconds at 150 rpm, and thereby kneaded.
  • 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.
  • Dried granules were uniformly sized employing a Speed Mill ND-75S equipped with a 1 mm filter.
  • the weight ratio of fine powder with no more than 125 ⁇ m particles immediately after granulation of a prepared granule agent was measured.
  • Granule Agent A2 190 g of Granule Agent A2 were placed in an aluminum bag and tightly sealed.
  • 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.
  • 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.
  • 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 developing agent for color paper was prepared as described below.
  • 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.
  • the resulting mixture had water added for about 1.5 minute and thereby kneaded at 220 rpm.
  • Group 2 was added and mixed at 220 rpm for 30 seconds.
  • Group 3 was added and mixed at 220 rpm for 30 seconds.
  • the weight ratio of fine powder with no more than 125 ⁇ m particles immediately after granulation of a prepared granule agent was measured.
  • Granule Agent A3 in the amount of 97.42 g was placed in an aluminum bag and tightly sealed.
  • 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.
  • 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.

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EP99111249A 1998-06-12 1999-06-09 Verfahren zur Herstellung eines granulierten Mittels und Verfahren zur Herstellung einer Tablette Withdrawn EP0964303A1 (de)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7727501B2 (en) 2003-08-11 2010-06-01 The Mosaic Company Compacted granular potassium chloride, and method and apparatus for production of same

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3265679A (en) * 1963-09-19 1966-08-09 Pennsalt Chemicals Corp Chemical product and method for its manufacture
US3981732A (en) * 1971-08-19 1976-09-21 Fuji Photo Film Co., Ltd. Granular p-phenylenediamine color developing agent
US4241137A (en) * 1977-11-22 1980-12-23 Daikin Kogyo Co., Ltd. Process for preparing polytetrafluoroethylene granular powder
EP0678782A1 (de) * 1994-04-19 1995-10-25 Konica Corporation Feste Verarbeitungszusammensetzung, Herstellungsverfahren für photographische, lichtempfindliche Silberhalogenidmaterialien
EP0691571A1 (de) * 1994-06-14 1996-01-10 Konica Corporation Entwicklungsgranulat oder -tablette für photographische lichtempfindliche Silberhalogenidmaterialien und Verfahren zu dessen Herstellung
EP0794213A2 (de) * 1996-03-05 1997-09-10 Dupont-Mitsui Fluorochemicals Co., Ltd. Verfahren zum Granulieren von Polytetrafluoräthylenpulver

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3265679A (en) * 1963-09-19 1966-08-09 Pennsalt Chemicals Corp Chemical product and method for its manufacture
US3981732A (en) * 1971-08-19 1976-09-21 Fuji Photo Film Co., Ltd. Granular p-phenylenediamine color developing agent
US4241137A (en) * 1977-11-22 1980-12-23 Daikin Kogyo Co., Ltd. Process for preparing polytetrafluoroethylene granular powder
EP0678782A1 (de) * 1994-04-19 1995-10-25 Konica Corporation Feste Verarbeitungszusammensetzung, Herstellungsverfahren für photographische, lichtempfindliche Silberhalogenidmaterialien
EP0691571A1 (de) * 1994-06-14 1996-01-10 Konica Corporation Entwicklungsgranulat oder -tablette für photographische lichtempfindliche Silberhalogenidmaterialien und Verfahren zu dessen Herstellung
EP0794213A2 (de) * 1996-03-05 1997-09-10 Dupont-Mitsui Fluorochemicals Co., Ltd. Verfahren zum Granulieren von Polytetrafluoräthylenpulver

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7727501B2 (en) 2003-08-11 2010-06-01 The Mosaic Company Compacted granular potassium chloride, and method and apparatus for production of same

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