Granular or tablet-form color-developing composition

Abstract: A solid processing compositon for color-developing a silver halide color photographic material which is in the form of granules or a tablet, the solid processing composition containing an alkali agent and a compound represented by the following formula [P] and having a moisture content of 0.5 to 5.0% by weight, formula [P] HO-(A₁-O) ℓ1 -(A₂-O) ℓ2 -(A₃-O) ℓ3 -H where A₁, A₂ and A₃ independently represent an alkylene group.

Description: Field of the Invention The present invention relates to a granular processing composition and to a process for preparing a solid processing composition in the form of a tablet (hereinafter, granular and tablet forms are referred to simply as a solid processing composition as a general term) both for color-developing a silver halide color photographic light-sensitive material. Background of the Invention Recently, a method wherein photographic processing chemicals are solidified and added directly to a dissolving tank, or a method wherein processing agents are dissolved in water in advance and are used as a conventional working solution (a starter and a replenisher) as disclosed in Japanese Patent Publication Open to Public Inspection Nos. 119454/1993, 254853/1992 and 197090/1993 (hereinafter referred to as Japanese Patent O.P.I Publication) are under study, for the purpose of solving problems, such as legal restriction for transportation, a problem of handling, mixing of other processing agent caused by the bursting of a container caused by a shock in transportation and reduction of storage space at the user side, all are caused by the fact that photographic processing chemicals are liquid. In Japanese Patent O.P.I. Publication No. 61837/1976, on the other hand, there is disclosed a photographic processing tablet-form composition containing a carbonate and polyethyleneoxide and a method of manufacturing the same. This method, however, proved to have a new problem that the tablet absorbs moisture rapidly and swells because it is anhydrous, when it is subjected to aging storage, though it is dissolved easily in water. In Japanese Patent O.P.I. Publication No. 254853/1992, on the other hand, there is disclosed a photographic processing agent that is spray granulated polyethyleneoxide. Granules prepared in this method are mostly free from the problem of production of fine powder, but proved to have a new problem in that the solid processing composition sticks together (blocking phenomenon) when the processing agents are stored hermetically for a certain period of time. In Japanese Patent O.P.I. Publication No. 119450/1993, on the other hand, there is disclosed a tablet whose moisture content is controlled to 0.5 - 10.0 wt%. A tablet made by this method is greatly improved in residue rate of a color developing agent, in the state of a tablet immediately after it is dropped, and in the presence of insoluble material. Even in this method, however, there is a new problem in that the solid processing composition may swell or causes blocking. In Japanese Patent O.P.I. Publication Nos. 142708/1993, 197090/1993, 341468/1993 and 102628/1994, on the other hand, there are disclosed granules wherein a paraphenylenediamine (hereinafter referred to sometimes as p-phenylenediamine) type color developing agent, hydroxylamine derivative and alkali agent are respectively granulated, and average particle size of the granules is controlled within a specific range, or polyethylene glycol and a specific compound are contained. The tablet made through this method is remarkably improved, as compared with a conventional tablet, in dissolving property, residue rate of paraphenylenediamine type color developing agent, reduction of occurrence of insoluble material and strength as well as molding property of the tablet. However, it was proved to have a new problem. Summary of the Invention In view of the aforementioned problems, an object of the invention is to provide a granular processing composition and a process for preparing a tablet-form processing composition used for preparing a color-developing solution for a silver halide color photographic light-sensitive material capable of greatly reducing generation of fine powder caused by hygroscopic swelling of a solid processing composition. Another object of the invention is to provide a granular solid processing composition and a process for preparing a tablet-form processing composition used for colour-developing a silver halide colour photographic light-sensitive material wherein the problem of sticking together of the solid processing composition can be reduced greatly in aging storage of the processing compositions. The objects of the invention mentioned above can be attained by the following constitution: 1. A granular processing composition suitable for use in preparing a solution for colour-developing a silver halide colour photographic light-sensitive material containing an alkali agent which shows alkalinity of pH of 8 or more in an aqueous solution, wherein the composition comprises a compound represented by the following formula (P), having a moisture content of from 0.5 - 5.0 wt%. Formula (P) HO-A 1 -O) l1 -(A 2 -O) l2 -(A3-O) l3 -H In the formula, A 1 , A 2 and A 3 each represent a straight chained or branched alkylene group, which may be substituted, and these may be either the same as or different from each other, l 1 , l 2 and l 3 each represent from 0 to 500, wherein the sum of l 1 + l 2 + l 3 is at least 5, with the proviso that a granular solid processing composition prepared by mixing sodium p-toluene sulphonate, toluene sulphite, potassium hydroxide, polyethylene glycol (average molecular weight 6000), potassium carbonate and D-mannit while adding water, and drying the resulting granules at 40 °C for 12 hours, so that the moisture content is reduced to 1% or less is excluded. 2. The granular solid processing composition suitable for use in preparing a solution for colour-developing a silver halide colour photographic light-sensitive material described in Item 1 above, wherein the aforementioned alkali agent is a carbonate. 3. The granular solid processing composition described in Item 1 or Item 2 above, wherein the content of a compound represented by the Formula (P) for the total weight in the above-mentioned granular solid processing composition is from 1.0 to 30.0 wt%. 4. The granular solid processing composition described in Items 1-3 above, wherein the compound represented by the Formula (P) is polyethylene glycol. 5. The granular solid processing composition described in Item 4, wherein the average molecular weight of the polyethylene glycol is from 2000 to 20000. 6. The granular solid processing composition described in Items 1 - 5 above, wherein the granular solid processing composition is a mixture with a paraphenylenediamine type granule. 7. The granular solid processing composition described in Items 1 - 6 above, wherein 60 wt% or more of the granular solid processing compositions have a particle size within a range of from 149 to 1490 µm. 8. A tablet-shaped solid processing composition used for colour-developing a silver halide colour photographic light-sensitive material comprising at least one kind of alkali agent, and at least one compound represented by the Formula (P) mentioned above and having a moisture content of from 0.5 - 5.0 wt%. 9. The tablet-shaped solid processing composition described in Item 8 above, wherein the alkali agent is a carbonate. 10. The tablet-shaped solid processing composition in Items 8 or 9 above, wherein the content of a compound represented by the Formula (P) mentioned above for the total weight in the above-mentioned tablet-shaped solid processing composition is from 1.0 to 30.0 wt%. 11. The tablet-shaped solid processing composition in Items 8 to 10 above, wherein the compound represented by the Formula (P) is polyethylene glycol. 12. The tablet-shaped solid processing composition in Item 11, wherein the average molecular weight of the polyethylene glycol is from 2000 to 20000. 13. A process for preparing a solid processing composition in the form of a tablet having a moisture content of from 0.5 to 5 wt.%, which process comprises pressure-moulding a granular solid processing composition according to any of items 1 to 7 to form a tablet. 14. A process for preparing a solid processing composition in the form of a tablet having a moisture content of from 0.5 to 5 wt.%, which process comprises mixing a granulated p-phenylenediamine compound with a granular solid processing composition according to any of items 1 to 7 to form a mixture and compression-moulding the mixture to prepare the tablet. 15. The tablet-shaped solid processing composition described in Items 8 to 14 above, wherein the composition is obtained by compression-moulding solid processing compositions in which 60 wt% or more of the tablet-shaped solid processing compositions containing the alkali agent have a particle size within the range of from 149 to 1490 µm. Detailed explanation of the invention. The Inventors of the present invention have found out through experiments, the following facts with respect to an alkali agent-containing solid processing composition for colour-developing a silver halide colour photographic light-sensitive material. It was found that unless a compound represented by the Formula (P) is contained in the solid processing composition for colour-developing a silver halide colour photographic light-sensitive material containing alkali agents of the invention, the solid processing composition swells suddenly on moisture sorption, resulting in occurrence of fine powder. Even when a compound represented by Formula [P] is contained in the solid processing composition, unless the moisture content is controlled in the scaled up production, problems of instability may arise, resulting in generation of fine powder and causing blocking, although adequate performance as a solid processing composition was obtained in some cases. Further, in a test model of storage at high temperature for transportation, there was sometimes observed a problem of instability. After intensive studies on this point, the inventors found out that it is possible to provide a solid processing composition which is stable even in scaled up production if the moisture content of the solid processing composition is controlled to be within a range of from 0.5 to 5.0 wt%. When the moisture content (wt%) is less than 0.5 wt%, a solid processing composition will show no problem immediately after production, but in aging storage a solid processing composition retaining no moisture swells rapidly on absorption of moisture, resulting in production of fine powder. When the moisture content exceeds 5.0 wt%, the solid processing composition will stick together in storage at high temperature. The reason why the moisture content is measured is that the stability of solid processing composition at temperature is important for the following reasons, though stability in humidity is also important. When solid processing compositions are transported by sea after shipment, the temperature and humidity are not normally controlled during the transportation and an actual measured temperature of 45 - 50°C is observed. In this case, it is very difficult to control the temperature though the humidity can be controlled by moistureproofing agents or the like. After making studies on this point, it was found out that a solid processing composition extremely improved in temperature stability can be obtained even in the case of scaled up production, if the moisture content of the solid processing composition is controlled within a range of 0.5 - 5.0 wt%, provided that the moisture content (wt%) is calculated under the condition that all of the reduction in weight in heating at 80°C for 1 hour is regarded as moisture. A solid processing composition of the invention contains at least one alkali agent and at least one of the compounds represented by the Formula [P], and when this solid processing composition is granular, it is made through granulation after the alkali agent and the compound are mixed. Even when a part of granules contains alkali agent and another part of the granules contains only a compound represented by the Formula [P], such granules are also included in the invention. A tablet-form solid processing composition may be made either through compression molding after the powdery solid materials are mixed or through compression molding after the step of mixing and granulation. From the viewpoint of storage stability, a tablet-form solid processing composition made through compression molding after the step of granulation is preferable. The mixture in the invention is one made through mixing or compression molding after alkali agents and paraphenylenediamine compounds are respectively granulated separately, for example, an alkali agent, paraphenylenediamine type color developing agent and preserving agent (hydroxylamine and/or its derivative) are granulated respectively and then subjected to mixing and compression molding. As a method for manufacturing a granular solid processing composition, known methods such as rolling granulation, extrusion granulation, compression granulation, cracking granulation, stirring granulation, moving-bed granulation and spray drying granulation may be used, and from the viewpoint of granule strength of a granular processing composition, the method of stirring granulation is preferable. As a method for manufacturing a tablet-form solid processing composition, a method employing a well-known compressor may be used. For example, a hydraulic press, a single shot tablet-molding machine, a rotary tablet-molding machine and a briquetting machine may be used. Though a tablet-form solid processing composition can take any shape, a cylindrical one is preferable from the viewpoint of productivity and ease of handling. When the tablet-form solid processing composition is cylindrical in shape, a tablet whose ratio of its diameter to its thickness is within a range of 1.0 - 6.0 is preferable and a tablet with that ratio of 2.0 - 4.0 is more preferable from the viewpoint of prevention of occurrence of powder caused by vibration during transportation. While the diameter of a tablet can take any value, depending on the purpose of application, its range of 5 - 50 mm is preferable and that of 7 - 30 mm is more preferable from the viewpoint of productivity. In the invention, the moisture content of a solid processing composition which is within a range of 0.5 - 5.0 wt% is satisfactory, but from the viewpoint of effects of the invention, the range of 0.8 - 3.5 wt% is preferable. In addition, for controlling the moisture content to be within the range specified according to the invention, a method of granulating by the use of a solvent, namely the wet type granulating method is preferable. In the case of wet granulation, a solvent is added to raw powder materials for granulation, and the solvent used in this case includes a polar solvent such as alcohol, acetone, acetonitrile and water, or a mixture thereof. Water is preferred, as it is more explosion-proof. It is preferable that an added amount of the above-mentioned solvent to raw materials is 1 - 10 wt%, preferably 2 - 6 wt%. When the added amount is less than 1 wt%, granulation can not be conducted sufficiently, while when it exceeds 10 wt%, not only may drying time be extended, but also raw materials may deteriorate in the course of granulation and drying. Moisture content in the invention is a value based on all of the reduced weight, which is calculated as moisture after drying the material for one hour at 80°C by used of a commercially-available electronic moisture meter. Measurement is conducted, using a sample of about 10 g, under conditions of atmospheric pressure, temperature of 25 - 30°C and relative humidity of 40 - 45%. The moisture content of the invention may be calculated by using the following equation: Percent moisture content = (w 0 - w)/w 0 x 100 where w 0 and w are a weight of a material before and after being dried at 80°C for one hour, respectively. Particle size referred to herein is a value obtained by measuring particle sizes after sieving by the use of a sieve specified in the Japanese Industrial Standards. From the viewpoint of preventing fluctuation before and after the storage, it is preferable that 60 wt% or more of particles have a particle size within the range of 149 - 1490 µm. It is more preferable that 70 wt% or more of particles have the particle size within the range of 149 - 1490 µm. Next, compounds represented by Formula [P] will be explained concretely as follows: HO- (A 1 -O) ℓ1 -(A 2 -O) ℓ2 - (A 3 -O) ℓ3 -H In the formula, A 1 , A 2 and A 3 each represent a straight chained or branched alkylene group, which may be substituted and these may be either the same or different. As a substituent, there may be given a hydroxy group, a carboxy group, a sulfonyl group, an alkoxy group, a carbamoyl group and a sulfamoyl group. Preferably, A 1 , A 2 and A 3 are each an unsubstituted alkylene group. More preferably A 1 , A 2 and A 3 each are -CH 2 CH 2 - or -CH(CH 3 )-CH 2 -. ℓ 1 , ℓ 2 and ℓ 3 each represent from 0 to 500, provided that the total number thereof is equal to or larger than 5 (ℓ 1 + ℓ 2 + ℓ 3 ≧ 5). Among the foregoing, preferably, at least one of ℓ 1 , ℓ 2 and ℓ 3 is 15 or more and more preferably, at least one of ℓ 1 , ℓ 2 and ℓ 3 is 20 or more. When a compound represented by Formula [P] in the invention is a copolymer wherein two kinds of monomers A and B are copolymerized, those having configurations shown below are also included. -A-B-A-B-A-B-A-B-A-B- -A-A-B-A-B-B-A-A-A-B-A-A-B-B-A- -A-A-A-A-A-A-B-B-B-B-B-B-A-A-A-A-A- Among those copolymers a block polymer (nonionic polymer of a Pluronic type) of ethylene glycol and propylene glycol represented by the following Formula [P'] is preferred. Formula [P'] HO-(CH 2 CH 2 -O) ℓ4 -[CH(CH 3 )CH 2 -O] ℓ5 - (CH 2 CH 2 -O) ℓ6 -H In the formula, ℓ 4 , ℓ 5 and ℓ 6 are the same as ℓ 1 , ℓ 2 and ℓ 3 defined above in the aforementioned Formula [P]. In a compound represented by Formula [P'] in the invention, it is preferred that the content (wt%) of ethyleneoxide in the total molecular weight is 70 wt% or more, and it is especially preferred that the content is 80 wt% or more. Specific compounds represented by Formula [P] and Formula [P'] are further shown below. Compound, HO-(CH 2 -CH 2 -O)n"-H Average molecular weight P-1 300 P-2 600 P-3 1000 P-4 1500 P-5 2000 P-6 3000 P-7 4000 P-8 6000 P-9 10000 P-10 15000 P-11 20000 P-12 30000 Compound, HO-(CH 2 CH 2 -O)a'-[CH(CH 3 )-CH 2 -O]b'-(CH 2 CH 2-O )c'-H Content (wt%)of ethyleneoxide in the total molecular weight Average molecular weight P'-1 80 8350 P'-2 80 10800 P'-3 50 4600 P'-4 70 6500 P'-5 80 5000 P'-6 50 3500 P'-7 70 7850 P'-8 50 4150 Among compounds represented by Formula [P] and Formula [P'] in the invention, the most preferred is polyethylene glycol (hereinafter referred to sometimes as PEG). In the case of polyethylene glycols, those having an average molecular weight ranging from 2000 to 20000 are preferred, and especially preferred includes those having an average molecular weight ranging from 3000 to 15000. The average molecular weight in the invention is a molecular weight determined based on a hydroxyl value. It is preferable in terms of effects of the invention that a compound represented by the aforementioned Formula [P] is contained in an amount of from 1 to 30 wt% per unit weight of solid processing composition of the invention, and from 3 to 20 wt% is more preferable. Further, compounds represented by the Formula [P] may be used independently or in combination of two or more kinds. Next, an alkali agent will be explained as follows. An alkali agent as used herein is a compound which shows alkalinity of pH of 8 or more in an aqueous solution thereof. Preferable concrete examples include sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, , disodium phosphate, dipotassium phosphate, sodium borate, potassium borate, sodium tetraborate (borax), potassium tetraborate, sodium hydroxide, potassium hydroxide, and lithium hydroxide. From the moisture-proof viewpoint, sodium carbonate, potassium carbonate sodium bicarbonate, sodium borate and trisodium phosphate are preferable. Among them, a carbonate is especially preferable in the invention. As a p-phenylenediamine compound in the invention, those having a water-solubilizing group are used preferably because they offer the effects of the invention superbly and they cause less occurrence of fog. Compared with a paraphenylenediamine compound having no water-solubilizing group such as N,N-diethyl-p-phenylenediamine and others, a p-phenylenediamine compound having a water-solubilizing group not only has an advantage that a light-sensitive material is not contaminated thereby and a rash is not caused even when it sticks to the skin, but also attains efficiently an object of the invention when it is combined with a color developing solution of the invention. As the above-mentioned water-solubilizing group, those wherein an amino group or a benzene nucleus of p-phenylenediamine compound has at least one are preferred. Preferred water-solubilizing groups include the following: -(CH 2 ) n -CH 2 OH, -(CH 2 ) m -NHSO 2 -(CH 2 ) n CH 3 , -(CH 2 ) m -O-(CH 2 ) n -CH 3 , -(CH 2 CH 2 O) n C m H 2m+1 (m and n represent integers of not less than 0), -COOH group, and -SO 3 H Preferred examples of p-phenylenediamine compounds are set out below. It will be understood that the invention is not limited thereto. The aforementioned color developing agent is used usually in a form of a salt such as a hydrochloride, a sulfate and a p-toluenesulfonate salt. In the invention, more advantageous effects can be displayed when the color developing agent of the invention contains a compound represented by Formula [A] shown below. Namely, there are provided effects that when solidified, storage stability of a solid processing composition such as in the form of a granule or a tablet is improved compared with other compounds, and in addition, strength of the solid processing composition can be maintained. Further, it is stable in photographic performance and it causes less fog on the unexposed portion. In the formula, R 1 and R 2 independently represent a hydrogen atom and a substituted or unsubstituted alkyl group. With regard to the compound represented by the aforesaid Formula [A] of the invention, those represented further by the following Formula [A'] are preferable from the viewpoint of the invention. In the formula [A'], L represents a substituted or unsubstituted, straight-chained or branched alkylene group having from 1 to 10 carbons, preferably from 1 to 5. For example, methylene, ethylene, trimethylene and propylene are given, and as a substituent, a carboxyl group, a sulphone group, a phosphone group, a phosphinic acid agroup, a hydroxy group, a cyano group and an ammonio group which may be substituted by an alkyl group having from 1 to 5 carbon atoms are given. A represents a carboxyl group, a sulfone group, a phosphone group, a phosphinic acid residue, a hydroxy group, a cyano group, an alkoxy group, an amino group which may have an alkyl group having 1 to 5 carbon atoms, an ammonio group which may have an alkyl group having 1 to 5 carbon atoms, a carbamoyl group which may have an alkyl group having 1 to 5 carbon atoms, a sulfamoyl group which may have an alkyl group having 1 to 5 carbon atoms and a substituted or unsubstituted alkylsulfonyl group. Examples of A-L- include carboxymethyl, carboxyethyl, carboxypropyl, sulfoethyl, sulfopropyl, sulfobutyl, phosphonomethyl, phosphonoethyl, methoxyethyl, cyanoethyl and hydroxyethyl. R 3 represents a hydrogen atom, a substituted or unsubstituted, straight-chained or branched alkyl group having from 1 to 10 carbon atoms. The substituent includes a carboxyl group, a sulfo group, a phosphone group, a phosphonic acid residue, a hydroxy group, a cyano group, an alkoxy group, a carbamoyl group and an ammonio group which may have an alkyl group having 1 to about 5 carbon atoms, provided that L and R may combine to form a ring. These compounds are used as an isolated amine and also as a salt such as a hydrochloride, a sulfate, an oxalate, a p-toluenesulfonate, an alkali metal salt and an ammonium salt. The exemplified compound represented by Formula [A] of the invention will be given below, but is not limited thereto. R 1 R 2 A-1 -H -H A-2 -H -CH 3 A-3 -CH 3 -CH 3 A-4 -H -C 2 H 5 A-5 -CH 3 -C 2 H 5 A-6 -C 2 H 5 -C 2 H 5 A-7 -C 3 H 7 (n) -C 3 H 7 (n) A-8 -C 3 H 7 (i) -C 3 H 7 (i) A-9 -C 4 H 9 (n) -C 4 H 9 (n) A-10 -C 4 H 9 (i) -C 4 H 9 (i) A-11 -C 4 H 9 (t) -C 4 H 9 (t) A-12 -CH 3 -CH 2 CH 2 COOH A-13 -CH 3 -CH 2 CH 2 SO 3 H A-14 -CH 3 -CH 2 COOH A-15 -CH 3 -CH 2 CH 2 PO 3 H 2 A-16 -H -CH 2 CH 2 SO 3 H A-17 -CH 2 CH 2 COOH -CH 2 CH 2 COOH A-18 -CH 2 CH 2 SO 3 H -CH 2 CH 2 SO 3 H A-19 -CH 2 COOH -CH 2 COOH A-20 -CH 2 CH 2 PO 3 H 2 -CH 2 CH 2 PO 3 H 2 A-21 -CH 2 CH 2 OH -CH 2 CH 2 OH A-22 -CH 3 -CH 2 CH 2 CONH 2 A-23 -CH 2 CH 2 CONH 2 -CH 2 CH 2 CONH 2 A-24 -CH 3 -CH 2 CH 2 OCH 3 A-25 -CH 2 CH 2 OCH 3 -CH 2 CH 2 OCH 3 A-26 -CH 3 -CH 2 CH 2 OH A-27 -CH 2 CH(CH 3 )COOH -CH 2 CH(CH 3 )COOH A-28 -CH 2 CH 2 CN -CH 2 CH 2 CN Incidentally, compounds A-12 to A-20 and A-27 can be used in a form of an alkali metal salt (sodium salt, potassium salt or lithium salt). Preferable compounds among those mentioned above are the following compounds. It is preferable in terms of prevention of dispersion caused in production that a sulfite, a bisulfite or a metabisulfite is added to the solid processing composition of the invention. Specific examples of the aforementioned sulfite, bisulfite, metabisulfite include sodium sulfite, potassium sulfite, sodium bisulfite, potassium bisulfite, sodium metabisulfite and potassium metabisulfite. Preferable one includes sodium sulfite and potassium sulfite, and these compounds can be used in an arbitrary form of an anhydrous salt and hydrous salt. In the case of the hydrous salt, however, the one wherein water is not isolated at 50°C or less is especially preferable in terms of the effects of the invention. It is possible to add a halide to the solid processing composition of the invention from the viewpoint of prevention of fog. As a halide, there may be given potassium chloride, sodium chloride, potassium bromide, sodium bromide, potassium iodide and sodium iodide. The solid processing composition of the invention may contain a chelating agent represented by the following Formula [I]. In the formula, T 1 represents a hydrogen atom, a hydroxy group, a carboxy group, a sulfo group, a carbamoyl group, a phosphono group, a phosphone group, a sulfamoyl group, a substituted or unsubstituted alkyl group, an alkoxy group, an alkylsulfonamide group, an alkylthio group, an acylamino group, a hydroxamic acid group, a hydroxyalkyl group or W 1 represents a substituted or unsubstituted alkylene group, an arylene group, an alkenyl group, a cycloalkylene group, an aralkylene group or X represents -O-, -S-, a divalent heterocycle or R 11 through R 15 independently represent a hydrogen atom, a hydroxy group, a carboxy group, a sulfo group, a carbamoyl group, a phosphono group, a phosphone group, a sulfamoyl group, a sulfonamide group, an acylamino group and a hydroxam acid group, provided that at least one of R 11 through R 15 represents a carboxy group; L 11 through L 17 represent a substituted or unsubstituted alkylene group, arylene group, alkenyl group, cycloalkylene group or aralkylene group; and ℓ 11 through ℓ 17 independently represent an integer of 0 to 6, provided that ℓ 15 and ℓ 16 are not 0 concurrently. Exemplified compounds of the aforesaid chelating agent that improves the effects of the invention include (I-1) to (I-8), (I-12), (I-14) to (I-20), (I-22), (I-23) and (I-27). Among those, more preferred are (I-1), (I-2), (I-3), (I-5), (I-6), (I-12), (I-14), (I-15) or (I-17). These compounds can be used in a form of a free acid, sodium salt and potassium salt. Especially preferred is the sodium salt. The saccharides in the invention refer to monosaccharides or polysaccharides in which monosaccharides are combined with each other through a glycosid bond including a derivative thereof or a decomposition product thereof. Monosaccharides referred to herein include a polyhydroxy aldehyde, polyhydroxy ketone and their derivatives such as reduction derivatives, oxidation derivatives, deoxy-derivatives, aminoderivatives or thio-derivatives. Most of them are represented by the general formula C n' (H 2 O)m'. The monosaccharide used in the invention includes a compound derived from the saccharide skeleton represented by the above formula. Preferred is a sugar alcohol having a primary or secondary alcohol group to which an aldehyde or ketone group is reduced. Polysaccharides include celluloses, starches or glycogens. The celluloses include derivatives such as cellulose ethers in which all or a part of the hydroxy groups are etherified, and starches include various hydrolysis and decomposition compounds thereof, such as maltose or dextrins. Celluloses may be in an alkali salt form in view of solubility. Preferred polysaccharides are celluloses or dextrins, and dextrins are more preferably used. Examples of monosaccharides including derivatives thereof will be shown below. (Exemplified compounds) B-(1) glycelaldehyde B-(2) dihydroxyacetone (including a dimer) B-(3) D-erythrulose B-(4) L-erythrulose B-(5) D-threose B-(6) L-threose B-(7) D-ribose B-(8) L-ribose B-(9) D-arabinose B-(10) L-arabinose B-(11) D-xylose B-(12) L-xylose B-(13) D-lixose B-(14) L-lixose B-(15) D-xylulose B-(16) L-xylulose B-(17) D-ribulose B-(18) L-ribulose B-(19) 2-deoxy-D-ribose B-(20) D-allose B-(21) L-allose B-(22) D-altrose B-(23) L-altrose B-(24) D-glucose B-(25) L-glucose B-(26) D-mannose B-(27) L-mannose B-(28) D-gulose B-(29) L-gulose B-(30) D-idose B-(31) L-idose B-(32) D-galactose B-(33) L-galactose B-(34) D-talose B-(35) L-talose B-(36) D-quinobose B-(37) digitalose B-(38) Digitoxose B-(39) Cymalose B-(40) D-sorbose B-(41) L-sorbose B-(42) D-Tagatose B-(43) D-fucose B-(44) L-fucose B-(45) 2-deoxy-D-glucose B-(46) D-psicose B-(47) D-fructose B-(48) L-fructose B-(49) D-rhamnose B-(50) D-galactosamine B-(51) L-galactosamine B-(52) D-mannosamine B-(53) D-glycero-D-galactoheptose B-(54) D-glycero-D-mannoheptose B-(55) D-glycero-L-mannoheptose B-(56) D-glycero-D-guloheptose B-(57) D-glycero-D-idoheptose B-(58) D-glycero-L-glucoheptose B-(59) D-glycero-L-taloheptose B-(60) D-altroheptulose B-(61) D-mannoheptulose B-(62) D-altro-3-heptulose B-(63) D-glucuronic acid B-(64) L-glucuronic acid B-(65) N-acetyl-D-glucosamine B-(66) Glycerin B-(67) D-threitol B-(68) L-threitol B-(69) meso-Erithorit (produced by Mitsubishi Kasei Shokuhin Co. Ltd., Erythritol) B-(70) D-arabitol B-(71) L-arabitol B-(72) adnite B-(73) xylitol B-(74) D-sorbitol B-(75) L-sorbitol B-(76) D-mannitol B-(77) L-mannitol B-(78) D-iditol B-(79) L-iditol B-(80) D-talitol B-(81) L-talitol B-(82) dulcin B-(83) allodulcitol Of these compounds, B-(66) to (83) are preferably used, and B-(69) and B-(74) to (83) are more preferably used. Examples of polysaccharides and their decomposition products will be shown below: C-(1) Maltose C-(2) Cellobiose C-(3) trehalose C-(4) gentiobiose C-(5) isomaltose C-(6) lactose C-(7) raffinose C-(8) gentianose C-(9) stachyose C-(10) xylan C-(11) araban C-(12) Glycogen C-(13) dextran C-(14) inulin C-(15) levan C-(16) galactan C-(17) agalose C-(18) amylose C- (19) sucrose C-(20) agarobiose C-(21) Methylcellulose C-(22) Dimethylcellulose C-(23) Trimethylcellulose C-(24) Ethylcellulose C-(25) Diethylcellulose C-(26) Triethylcellulose C-(27) Carboxymethylcellulose C-(28) Carboxyethylcellulose C-(29) Aminoethylcellulose C-(30) Hydroxymethylcellulose C-(31) Hydroxyethylcellulose C-(32) Hydroxypropylcellulose C-(33) Hydroxypropylmethylcellulose C-(34) Hydroxypropylmethylcelluloseacetatesuccinate C-(35) carboxymethylhydroxyethylcellulose C-(36) α-dextrin C-(37) β-dextrin C-(38) γ-dextrin C-(39) δ-dextrin C-(40) ε-dextrin C-(41) α-limit-dextrin C-(42) β-limit-dextrin C-(43) Phospherylase limit dextrim C-(44) Soluble starch C-(45) Thin-boling starch C-(46) White dextrin C-(47) Yellow dextrin C-(48) British gumm C-(49) α-cyclodextrin C-(50) β-cyclodextrin C-(51) γ-cyclodextrin C-(52) Hydroxypropyl-α-cyclodextrin C-(53) Hydroxypropyl-β-cyclodextrin C-(54) Hydroxypropyl-γ-cyclodextrin C-(55) Maltodextrin Of these compounds, C-(21) to (55) are preferably used, and compounds, C-(36) to (55) are more preferably used. The weight average molecular weight of dextrins used in the composition of the invention may be any, but it is preferably 10 to 10000. Saccharides exist widely in the nature, and are commercially available. The derivatives can be readily prepared by reduction, oxidation or dehydration reactions. Starch compounds available on the market include Pineflow, Pine-dex series, Max 100, Glistar P, TK-16, MPD, H-PDX and Stuco-dex produced by Matsutani Kagaku Co., Ltd. or Oil Q series produced by Nihon Yushi Co., Ltd. Examples The invention will be explained in detail as follows, referring to examples to which the invention is not limited. Example 1 Alkali agent (Compound described on Table 1) 13000 g Compound represented by Formula [P], as described in Table 1 2000 g Compounds stated above each were crushed by a commercially-available hammer mill to the particle size of 149 µm or less. The resulting crushed compounds were mixed sufficiently by a commercially-available stirring granulating machine, and then water was added thereto for granulation. The granules thus obtained were dried by a commercially-available moving-bed dryer, while controlling the temperature of hot air to be at 50 - 65°C in the course of drying. In the course of drying and after drying, the granules were subjected to grain-dressing by a commercially-available granulating machine, with the use of a 1.5 mm-mesh screen. An added amount of water and drying time both for the granulation were adjusted appropriately so that the moisture content described in Table 1 may be obtained. In the manner stated above, granule samples (1-1) to (1-26) were prepared. Experiment (1-1) The granular samples (1-1) to (1-26) thus prepared were vibrated for one minute by a micro-type electromagnetic vibration screening machine (Model M-100) by the use of a screen with 100 µm-mesh. After fine powder is removed completely, samples weighing 50 g on the screen were put in an opened laboratory dish to prepare two of each of the various samples, which were stored for three hours in the environmental chamber where the temperature was 25°C and relative humidity was 45%. After the storage, the granular samples were screened again by the screen with 100 µm-mesh under the above-mentioned conditions, to test the occurrence of powder after storage. Following criteria were used for evaluation. o ○ o ○ : None of the two samples passed through the screen. o ○: Only one sample passed through the screen, and occurrence of fine powder was observed. However, an amount of fine powder was very small and it did not fly up, causing no problem. ○: Both samples passed through the screen. However, an amount of fine powder was very small and it did not fly up, causing no problem. ×: Both samples passed through the screen, and occurrence of fine powder was caused and its flying up was observed. Experiment (1-2) From each of granular samples (1-1) to (1-26) prepared, samples each weighing 100 g were picked up and sealed by aluminum packaging material individually. These were stored for 30 days under the following conditions by use of a small-sized environmental testing machine. Blocking properties of the granular samples after the storage were evaluated. The results of the evaluation are shown on Table 1. The following criteria were used for evaluation. o ○ o ○ : Two samples did not show any occurrence of blocking. o ○ : Only one sample showed blocking, but the blocking was only partial and was quickly restored by fine vibration. ○: Both samples showed blocking, but the blocking was only partial, and was quickly restored by fine vibration. ×: Both samples showed blocking taking place on about a half of the total of each sample, and the blocking was not restored by fine vibration. Samples ranked X, when they are supplied at a constant amount, cause dispersion, which is a problem. Temperature change conditions Temperature was changed to be 60°C → 20°C → 60°C in a cycle of 16 hours. Incidentally, the condition for the temperature to rise and fall was 5°C/1 hour. Sample No. Alkali agent Compounds represented by Formula [P] Moisture content (wt%) Occurrence of fine powder Blocking Remarks 1-1 Potassium carbonate PEG Average molecular weight 300 2.0 ○ ○ Inv. 1-2 Potassium carbonate PEG Average molecular weight 600 2.0 ○ ○ Inv. 1-3 Potassium carbonate PEG Average molecular weight 1500 2.0 ○ ○ Inv. 1-4 Potassium carbonate PEG Average molecular weight 2000 2.0 ○ o ○ Inv. 1-5 Potassium carbonate PEG Average molecular weight 3000 2.0 o ○ o ○ o ○ o ○ Inv. 1-6 Potassium carbonate PEG Average molecular weight 6000 2.0 o ○ o ○ o ○ o ○ Inv. 1-7 Potassium carbonate PEG Average molecular weight 10000 2.0 o ○ o ○ o ○ o ○ Inv. 1-8 Potassium carbonate PEG Average molecular weight 15000 2.0 o ○ o ○ o ○ o ○ Inv. 1-9 Potassium carbonate PEG Average molecular weight 20000 2.0 o ○ o ○ o ○ Inv. 1-10 Potassium carbonate PEG Average molecular weight 30000 2.0 ○ o ○ o ○ Inv. 1-11 Potassium carbonate Pluronic A 2.0 ○ o ○ o ○ Inv. 1-12 Potassium carbonate Pluronic B 2.0 ○ o ○ Inv. 1-13 Potassium carbonate Pluronic C 2.0 ○ o ○ o ○ Inv. 1-14 Sodium carbonate PEG Average molecular weight 6000 2.0 o ○o ○ o ○ o ○ Inv. 1-15 Trisodium phosphate PEG Average molecular weight 6000 2.0 ○ o ○ o ○ Inv. 1-16 Potassium carbonate PEG Average molecular weight 6000 0.3 × o ○ o ○ Comp. 1-17 Potassium carbonate PEG Average molecular weight 6000 0.5 ○ o ○ o ○ Inv. 1-18 Potassium carbonate PEG Average molecular weight 6000 0.8 o ○ o ○ o ○ Inv. 1-19 Potassium carbonate PEG Average molecular weight 6000 1.0 o ○ o ○ o ○ o ○ Inv. 1-20 Potassium carbonate PEG Average molecular weight 6000 1.5 o ○ o ○ o ○ o ○ Inv. 1-21 Potassium carbonate PEG Average molecular weight 6000 3.0 o ○ o ○ o ○ Inv. 1-22 Potassium carbonate PEG Average molecular weight 6000 3.5 o ○ o ○ Inv. 1-23 Potassium carbonate PEG Average molecular weight 6000 4.0 o ○ ○ Inv. 1-24 Potassium carbonate PEG Average molecular weight 6000 5.0 o ○ ○ Inv. 1-25 Potassium carbonate PEG Average molecular weight 6000 6.0 o ○ × Comp. 1-26 Potassium carbonate - 2.0 × o ○ Comp. As is apparent from Table 1, it is understood that when a compound represented by Formula [P] and an alkali agent are contained in a granular solid processing composition of the invention and the moisture content is controlled to be 0.5 - 5.0 wt%, it is possible to provide a granular solid processing composition wherein occurrence of fine powder after moisture absorption and blocking tendency in hermetical storage are greatly reduced. Effects of the invention were remarkably exhibited when an alkali agent is a carbonate and a compound represented by Formula [P] is polyethyleneglycol having an average molecular weight of from 2000 to 20000. Although a moisture content of from 0.5 wt% to 5.0 wt% is satisfactory according to the invention, it was found that particularly favorable effects may be obtained when the moisture content is within the range of from 0.8 to 3.5 wt%. Example 2 Operation (2-1) Potassium carbonate 10000 g Sodium sulfite 1400 g Pentasodium diethylenetriaminepentaacetate 600 g Polyethyleneglycol #6000 (made by Nihon Yushi Co., Ltd.) added amount in Table 2 Sodium paratoluenesulfonate 2000 g D-mannitol 1000 g Each of the above-mentioned compounds was crushed and granulated in the same manner as in Example 1. In this case, the amount of water added was 4 wt% of the total weight used for granulation, and granules thus obtained were dried until the moisture content was from 1.5 to 2.0 wt%. The resulting granules were subjected to grain-dressing in a similar manner to Example 1. The samples thus obtained were defined to be granular samples (2-1) to (2-11). Operation (2-2) Potassium carbonate 7000 g Sodium sulfite 100 g Pentasodium diethylenetriaminepentaacetate 700 g Polyethyleneglycol #4000 (made by Nihon Yushi Co., Ltd.) added amount in Table 2 D-mannitol 1200 g Sodium paratoluenesulfonate 3000 g Lithium hydroxide monohydrate 800 g Granular samples (2-12) - (2-22) were prepared from the above-mentioned compounds through the same manner as in Operation (2-1). Experiment (2-1) Evaluation was made for the samples in the same manner as in Experiments (1-1) and (1-2). Table 2 shows the results of the experiments. Sample No. Added amount (wt%) of compound represented by Formula [P] per composition Occurrence of fine powder Blocking Remarks 2-1 0 × o ○ Comparative 2-2 0.5 ○ o ○ Invention 2-3 1.0 o ○ o ○ Invention 2-4 3.0 o ○ o ○ o ○ Invention 2-5 5.0 o ○ o ○ o ○ o ○ Invention 2-6 10.0 o ○ o ○ o ○ o ○ Invention 2-7 15.0 o ○ o ○ o ○ o ○ Invention 2-8 20.0 o ○ o ○ o ○ o ○ Invention 2-9 25.0 o ○ o ○ o ○ Invention 2-10 30.0 o ○ o ○ o ○ Invention 2-11 35.0 o ○ o ○ ○ Invention 2-12 0 × o ○ Comparative 2-13 0.5 ○ o ○ Invention 2-14 1.0 o ○ o ○ Invention 2-15 3.0 o ○ o ○ o ○ Invention 2-16 5.0 o ○ o ○ o ○ o ○ Invention 2-17 10.0 o ○ o ○ o ○ o ○ Invention 2-18 15.0 o ○ o ○ o ○ o ○ Invention 2-19 20.0 o ○ o ○ o ○ o ○ Invention 2-20 25.0 o ○ o ○ o ○ Invention 2-21 30.0 o ○ o ○ o ○ Invention 2-22 35.0 o ○ o ○ ○ Invention As is apparent from Table 2, addition of polyethyleneglycol in an amount of from 1.0 to 30 wt% per unit weight to the granular solid processing composition of the invention is preferable in terms of the effects of the invention, and an addition amount of 3.0 - 20.0 wt% is more preferable. Example 3 Operation (3-1) 4-amino-3-methyl-N-ethyl-β-(hydroxy)ethyl-aniline sulfate granule (CD-4) (produced by Konica Chemical Co., Ltd.) 1700 g The above-mentioned granules were subjected to grain size-dressing by a grain size-selecting machine, and classified by the use of a screen to control them within a range of particle size from 149 to 1490 µm. This was defined to be Granule (A). Operation (3-2) 4-amino-3-methyl-N-ethyl-N-[-β-(methane-sulphoneamide)ethyl]aniline 3/2 sulfate monohydrate granules (CD-3) (produced by Konica Chemical Co., Ltd.) 3000 g The above-mentioned compounds were sieved and classified in the same manner as in Operation (3-1), and this was denoted as Granule (B). Operation (3-3) Hydroxylamine sulfate 1000 g Potassium bromide 100 g Disodium pyrocatechol-3,5-disulfonic acid monohydrate 50 g Pineflow (maltodextrin) 100 g The above compounds were crushed by a commercially-available hammer mill to a particle size of 149 µm or less. These crushed compounds were mixed sufficiently by a commercially-available stirring and granulating machine, and then water was added thereto for granulation. An amount of water added in this case was 3 wt% of the total weight of the crushed compounds. These granules were dried by a commercially-available moving-bed dryer until the moisture content (at 80°C) was from 1.5 to 2.0 wt% while controlling the temperature of hot air for drying at from 50 to 60°C. The granules were size-selected by a commercially-available grain size-dressing machine during the course of drying and after drying, and then classified by the use of a screen to control the particle size of the granules within a range of from 149 to 1490 µm. These granules were defined to be Granule (C). Operation (3-4) Bis(sulphoethyl)hydroxylamine disodiumsalt 1000 g Tinopal SFP (produced by Ciba Geigy Co., Ltd.) 3000 g Sodium paratoluenesulfonate 500 g D-mannitol 500 g The above-mentioned compounds were crushed, granulated, dried and size-selected under the same conditions as in Operation (3-3), and then were fractionated. These granules were defined to be Granule (D). Operation (3-5) Potassium carbonate 10000 g Sodium sulfite 1400 g Pentasodium diethylenetriaminepentaacetate 600 g Polyethyleneglycol #6000 (produced by Nihon Yushi Co., Ltd.) 1300 g Sodium paratoluenesulfonate 2000 g D-mannitol 2000 g The above-mentioned compounds were crushed, granulated, dried and size-selected under the same conditions as in Operation (2-1). In this case, the screen for size-selecting was changed and the compounds were classified by the use of a screen so that the particle size was controlled to that shown on Table 3. These granules were defined to be Granule (E). Operation (3-6) Potassium carbonate 7000 g Sodium sulfite 100 g Pentasodium diethylenetriaminepentaacetate 700 g Polyethyleneglycol #4000 (produced by Nihon Yushi Co., Ltd.) 1000 g D-mannitol 2000 g Paratoluenesulfonicacid sodium salt 3000 g Lithium hydroxide monohydrate 800 g The above-mentioned compounds were crushed, granulated, dried, size-selected and classified in the same manner as in Operation (3-5) so that the particle size was controlled to that shown on Table 3. These granules were defined to be Granule (F). Experiment (3-1) The mixture of granules described on Table 3 was put in a commercially-available cross-rotary mixing machine for sufficient mixing. After that, 1 kg of the mixture was picked up to be stored under the same conditions as in Experiment (1-1). Granular samples (3-1) to (3-12) from the mixture mentioned above each weighing 10 g were picked up 10 times for determination of the paraphenylenediamine compound to evaluate the fluctuation thereof. The aforementioned granular samples after being stored were mixed again by the mixing machine. The samples after mixing each weighing 10 g were picked up 10 times to test for fluctuation of solid processing composition through determination of the paraphenylenediamine compound. Evaluation criteria o ○ o ○ : All samples are within a fluctuation range of ±3%. o ○: All samples are within a range of ±5%. ○: Not less than 7 pcs are within a range of ±5% and the rest are within a range of ±10%. ×: Not less than 5 pcs are within a range of ±5% and some of the rest exceed ±10%. However, when some of them exceed ±10%, processing is adversely affected, which is not allowed. Experiment (3-2) Some 20 g of the mixture prepared by mixing combined granules at the rate described on Table 3 was picked up and put in an opened laboratory dish, then stored for 60 minutes under the conditions of temperature at 25°C and relative humidity at 45%. After that, the granular samples (3-1) - (3-12) after being stored were sealed with aluminum packaging materials and stored for 30 days in a small-sized environmental testing equipment having the same condition of temperature change as in Experiment (1-2). The granular samples after being stored were subjected to evaluation of coloring. Evaluation criteria o ○ o ○ : Blackened portion was not observed. ○: Tiny blackened portions were observed partially at several locations, each being in a shape of a spot. ×: Most portions were blackened. Table 3 shows the results of the evaluation. Sample No. Granules Moisture content (%) Fluctuation Coloring Remarks Fresh sample Stored sample 3-1 (A) (C) (E) 50 2.0 ○ ○ ○ Inv. 3-2 (A) (C) (E) 60 2.0 ○ ○ o ○ Inv. 3-3 (A) (C) (E) 70 2.0 o ○ o ○ o ○ Inv. 3-4 (A) (C) (E) 80 2.0 o ○ o ○ o ○ o ○ o ○ Inv. 3-5 (A) (C) (E) 80 0.3 o ○ o ○ × × Comp. 3-6 (A) (C) (E) 80 6.0 o ○ o ○ × × Comp. 3-7 (B) (D) (F) 50 2.0 ○ ○ ○ Inv. 3-8 (B) (D) (F) 60 2.0 ○ ○ o ○ Inv. 3-9 (B) (D) (F) 70 2.0 o ○ o ○ o ○ Inv. 3-10 (B) (D) (F) 80 2.0 o ○ o ○ o ○ o ○ o ○ Inv. 3-11 (B) (D) (F) 80 0.3 o ○ o ○ × × Comp. 3-12 (B) (D) (F) 80 6.0 o ○ o ○ × × Comp. As is apparent from Table 3, when a paraphenylenediamine compound is mixed with the granular solid processing composition of the invention, it is possible to provide a granular solid processing composition wherein coloring and composition fluctuation after storage are greatly reduced. Further, it is understood that when 70 wt% or more of the solid processing composition is accounted for by granules having a particle size of from 149 to 1490 µm, the fluctuation before storage can also be reduced. Example 4 Preparation of tablet-form solid processing composition samples Operation (4-1) Granular samples were prepared in the same manner as in Example 1. To the granular solid processing composition thus prepared, sodium myristoyl-N-methyl-β-alanine crushed to a particle size of 100 µm or less was added in an amount of 0.5 wt% of the total weight of the solid processing composition, and then they were mixed for 3 minutes by a commercially-available cross-rotary mixing machine. The mixed granules were subjected to continuous tablet-molding on the modified rotary tableting machine, Clean Pressed Correct 18K made by Kikusui Manufacturing Co., Ltd. Tablets were prepared under conditions that a diameter of a tablet was 15 mm, weight of a tablet was 1.5 g and pressure for compression was 1400 kg/cm 2 (Samples 4-1 to 4-26). Operation (4-2) Alkali agent (compound described on Table 5) 13000 g The compounds were each crushed to a particle size of 149 µm or less by a commercially-available hammer mill. These crushed compounds were granulated in a commercially-available stirring and granulating machine by adding water thereto. The granules thus obtained were dried by a commercially-available moving-bed drying machine while controlling the temperature of hot air for drying to be at from 50 to 65°C. The granules were size-selected by a commercially-available size-selecting machine by the use of a 1.5 mm screen during the course of drying and after drying. Further, the amount of water added for granulation and the drying time were adjusted appropriately so that the moisture content shown on Table 5 was obtained. 2000 g of a compound (described on Table 5) represented by Formula [P] and crushed to a particle size of 149 µm or less was added to the granules mentioned above, and they were mixed for 10 minutes in a commercially-available cross-rotary mixing machine. Then, sodium myristoyl-N-methyl-β alanine crushed to a particle size of 100 µm or less was added to the above-mentioned mixture in an amount of 0.5 wt% of the total weight of the solid processing composition, and mixing was further conducted for 3 minutes. The mixture was subjected to continuous tablet-molding in the same manner as in Operation (4-1). Thus, tablet-shaped Samples (4-27) to (4-37) were prepared. In the manner mentioned above, tablet-shaped Sample (4-1) to (4-37) were prepared. Experiment (4-1) The tablet-shaped samples thus prepared were put in an open laboratory dish so that two each for respective samples were prepared. They were stored for 3 hours in an environmental chamber where temperature and relative humidity were maintained at 25°C and 45% respectively. Each sample after storage was vibrated for 1 minute by a micro-type electromagnetic vibrator (Model M-100) with a screen with 100 µm-mesh, and occurrence of fine powder after storage was tested. Evaluation conditions for the above test were the same as those in Experiment (1-1). Experiment (4-2) Two each of the respective tablet-form samples thus prepared were superposed and packed in the same manner as in Experiment (1-2), and they were stored. The above-mentioned tablet-form samples after storage was evaluated with respect to stickiness thereof. Tables 4 and 5 show the results of the evaluation. Evaluation criteria o ○ o ○ : Sticking was not observed at all. o ○ : When lifting tablets, sticking between tablets was slightly felt, but no sticking was observed, ○: When lifting tablets, sticking between tablets took place. However, they were easily separated by slight vibration. ×: There occurred sticking between tablets which were not separated by slight vibration. Sample No. Granular sample used Alkali agents Compounds represented by Formula [P] Moisture content (wt%) Occurrence of fine powder Sticking Remarks 4-1 1-1 Potassium carbonate PEG Average molecular weight 300 2.0 ○ ○ Inv. 4-2 1-2 Potassium carbonate PEG Average molecular weight 600 2.0 ○ ○ Inv. 4-3 1-3 Potassium carbonate PEG Average molecular weight 1500 2.0 ○ ○ Inv. 4-4 1-4 Potassium carbonate PEG Average molecular weight 2000 2.0 ○ o ○ Inv. 4-5 1-5 Potassium carbonate PEG Average molecular weight 3000 2.0 o ○ o ○ o ○ o ○ Inv. 4-6 1-6 Potassium carbonate PEG Average molecular weight 6000 2.0 o ○ o ○ o ○ o ○ Inv. 4-7 1-7 Potassium carbonate PEG Average molecular weight 10000 2.0 o ○ o ○ o ○ o ○ Inv. 4-8 1-8 Potassium carbonate PEG Average molecular weight 15000 2.0 o ○ o ○ o ○ o ○ Inv 4-9 1-9 Potassium carbonate PEG Average molecular weight 20000 2.0 o ○ o ○ o ○ Inv. 4-10 1-10 Potassium carbonate PEG Average molecular weight 30000 2.0 ○ o ○ o ○ Inv. 4-11 1-11 Potassium carbonate Pluronic A 2.0 ○ o ○ o ○ Inv. 4-12 1-12 Potassium carbonate Pluronic B 2.0 ○ o ○ Inv. 4-13 1-13 Potassium carbonate Pluronic C 2.0 ○ o ○ o ○ Inv. 4-14 1-14 Sodium carbonate PEG Average molecular weight 6000 2.0 o ○ o ○ o ○ o ○ Inv. 4-15 1-15 Trisodium-phosphate PEG Average molecular weight 6000 2.0 ○ o ○ o ○ Inv. 4-16 1-16 Potassium carbonate PEG Average molecular weight 6000 0.3 × o ○ o ○ Comp. 4-17 1-17 Potassium carbonate weight PEG Average molecular 6000 0.5 ○ o ○ o ○ Inv. 4-18 1-18 Potassium carbonate weight 6000 PEG Average molecular PEG Average 0.8 o ○ o ○ o ○ Inv. 4-19 1-19 Potassium carbonate molecular weight 6000 1.0 o ○ o ○ o ○ o ○ Inv. 4-20 1-20 Potassium carbonate PEG Average molecular weight 6000 1.5 o ○ o ○ o ○ o ○ Inv. 4-21 1-21 Potassium carbonate PEG Average molecular weight 6000 3.0 o ○ o ○ o ○ Inv. 4-22 1-22 Potassium carbonate PEG Average molecular weight 6000 3.5 o ○ o ○ Inv. 4-23 1-23 Potassium carbonate PEG Average molecular weight 6000 4.0 o ○ ○ Inv. 4-24 1-24 Potassium carbonate PBG Average molecular weight 6000 5.0 o ○ ○ Inv 4-25 1-25 Potassium carbonate PBG Average molecular weight 6000 6.0 o ○ × Comp. 4-26 1-26 Potassium carbonate - 2.0 × o ○ Comp. Sample No. Granular sample used Alkali agents Compounds represented by Formula [P] Moisture content (wt%) Occurrence of fine powder Sticking Remarks 4-27 - Potassium carbonate PEG Average molecular weight 6000 0.3 × o ○ Comp 4-28 - Potassium carbonate PEG Average molecular weight 6000 0.5 ○ o ○ Inv. 4-29 - Potassium carbonate PEG Average molecular weight 6000 0.8 ○ o ○ Inv. 4-30 - Potassium carbonate PEG Average molecular weight 6000 1.0 o ○ o ○ Inv. 4-31 - Potassium carbonate PEG Average molecular weight 6000 1.5 o ○ o ○ Inv. 4-32 - Potassium carbonate PEG Average molecular weight 6000 2.0 o ○ o ○ Inv. 4-33 - Potassium carbonate PEG Average molecular weight 6000 3.0 o ○ o ○ Inv. 4-34 - Potassium carbonate PEG Average molecular weight 6000 3.5 ○ ○ Inv. 4-35 - Potassium carbonate PEG Average molecular weight 6000 4.0 ○ ○ Inv. 4-36 - Potassium carbonate PEG Average molecular weight 6000 5.0 ○ ○ Inv. 4-37 - Potassium carbonate PEG Average molecular weight 6000 6.0 × × Comp. Inv.: Invention Comp.: Comparative As is apparent from Tables 4 and 5, it is understood that when a compound represented by Formula [P] and an alkali agent are contained in a tablet-form solid processing composition of the invention and the moisture content is controlled to be from 0.5 to 5.0 wt%, it is possible to provide a tablet- solid processing composition wherein occurrence of fine powder after moisture absorption and sticking of tablet-form solid processing compositions in hermetical storage are greatly reduced. In addition, it is understood that more effects of the invention are displayed by tablet-form samples prepared by mixing an alkali agent and a compound represented by Formula [P] and using the granular samples. Further, when an alkali agent is a carbonate and a compound represented by Formula [P] is polyethyleneglycol having an average molecular weight of from 2000 to 20000, more effects of the invention are exhibited. The moisture content that is within 0.5 to 5.0 wt% is satisfactory, but when it is within 0.8 to 3.5 wt%, more effects of the invention can be exhibited. Example 5 Preparation of tablet-shaped solid processing composition Operation (5-1) Granular samples were prepared in the same manner as in Example 2. From the granular samples, tablet-form Samples (5-1) to (5-22) were prepared in the same manner as in Example 4. Samples were prepared under the condition that the diameter of a tablet was 20 mm, the weight of a tablet was 2.6 g and the pressure for compression was 1400 kg/cm 2 . Experiment (5-1) In the same manner as in Experiments (4-1) and (4-2), samples were evaluated with respect to occurrence of fine powder and sticking, provided that the method and criteria of the evaluation were the same as those in Example 4. Table 6 shows the results of the evaluation. Sample No. Granular sample used Added amount (wt%) of compound represented by Formula [P] Occurrence of fine powder Sticking Remarks 5-1 2-1 0 × o ○ Comparative 5-2 2-2 0.5 ○ o ○ Invention 5-3 2-3 1.0 o ○ o ○ Invention 5-4 2-4 3.0 o ○ o ○ o ○ Invention 5-5 2-5 5.0 o ○ o ○ o ○ o ○ Invention 5-6 2-6 10.0 o ○ o ○ o ○ o ○ Invention 5-7 2-7 15.0 o ○ o ○ o ○ o ○ Invention 5-8 2-8 20.0 o ○ o ○ o ○ o ○ Invention 5-9 2-9 25.0 o ○ o ○ o ○ Invention 5-10 2-10 30.0 o ○ o ○ o ○ Invention 5-11 2-11 35.0 o ○ o ○ ○ Invention 5-12 2-12 0 × o ○ Comparative 5-13 2-13 0.5 ○ o ○ Invention 5-14 2-14 1.0 o ○ o ○ Invention 5-15 2-15 3.0 o ○ o ○ o ○ Invention 5-16 2-16 5.0 o ○ o ○ o ○ o ○ Invention 5-17 2-17 10.0 o ○ o ○ o ○ o ○ Invention 5-18 2-18 15.0 o ○ o ○ o ○ o ○ Invention 5-19 2-19 20.0 o ○ o ○ o ○ o ○ Invention 5-20 2-20 25.0 o ○ o ○ o ○ Invention 5-21 2-21 30.0 o ○ o ○ o ○ Invention 5-22 2-22 35.0 o ○ o ○ ○ Invention As is apparent from Table 6, it is preferable in terms of effects of the invention that polyethyleneglycol is added in an amount of from 1.0 to 30 wt% per unit weight, preferably form 3.0 to 20.0 wt%. Example 6 Operation (6-1) Granules (A), (C) and (E) were prepared in the same manner as in Example 3. Granules (A), (C) and (E) were mixed for 10 minutes by a commercially-available cross-rotary mixing machine, then sodium myristoyl-N-metyl-β-alanine was added thereto in an amount of 0.5 wt% of the total weight of the mixture to be mixed for another 3 minutes, and thereby tablet-form samples (6-1) to (6-6) were prepared in the same manner as in Example 4. In the conditions for preparation in this case, the diameter of a tablet was 30 mm, the weight of a tablet was 12.0 g and the pressure for compression was 1400 kg/cm 2 . Operation (6-2) Granules (B), (D) and (F) were subjected to mixing and compression-molding under the same conditions for preparation as in Operation (6-1), and thereby tablet-shaped samples (6-7) to (6-12) were prepared. Experiment (6-1) In the same manner as in Experiment (3-2), the tablet-shaped solid processing composition was evaluated with respect to coloring thereof. Table 7 shows the results of the evaluation. Experiment (6-2) From an average value (average of 10 pcs) of compression breaking strength of the prepared tablet-form solid processing composition before storage (S 0 ) and that after the storage (S) under the same conditions as in Experiment (6-1), the rate of reduction on storage was calculated ((S 0 -S)/S 0 ×100). The results thereof are shown on Table 7, wherein those showing a reduction of 10% or more are not acceptable because they are broken by shock. Sample No. Granular sample used Coloring Reduction of compression breaking strength (%) Remarks 6-1 3-1 ○ 5.3 Invention 6-2 3-2 o ○ 5.8 Invention 6-3 3-3 o ○ 2.7 Invention 6-4 3-4 o ○ 0.9 Invention 6-5 3-5 × 25.3 Comparative 6-6 3-6 × 4.2 Comparative 6-7 3-7 ○ 5.6 Invention 6-8 3-8 o ○ 4.9 Invention 6-9 3-9 o ○ 2.4 Invention 6-10 3-10 o ○ 1.1 Invention 6-11 3-11 × 24.8 Comparative 6-12 3-12 × 3.8 Comparative As is apparent from Table 7, when a tablet-form solid processing composition of the invention is mixed with a paraphenylenediamine compound, it is possible to provide a table-form solid processing composition improved in coloring. It is further understood that when 70 wt% or more of the processing composition is accounted for by a particle size within the range of from 149 to 1490 µm, hardness reduction after storage can also be greatly reduced.

Claims: A granular solid processing composition suitable for use in preparing a colour-developer solution for a silver halide colour photographic material, wherein the solid processing composition comprises an alkali agent which shows alkalinity of pH of 8 or more in an aqueous solution and a compound represented by the following formula [P] and having a moisture content of from 0.5 to 5% by weight, the moisture content being a value based on all of the reduced weight of the composition after drying the composition for one hour at 80°C, formula [P] HO-(A 1 -O) ℓ1 -(A 2 -O) ℓ2 -(A 3 -O) ℓ3 -H wherein A 1 , A 2 and A 3 independently represent an optionally substituted, straight chain or branched alkylene group; l 1 , l 2 and l 3 are independently from 0 to 500, and the sum of l 1 , l 2 and l 3 is at least 5, with the proviso that a granular solid processing composition prepared by mixing sodium p-toluene sulphonate, toluene sulphite, potassium hydroxide, polyethylene glycol (average molecular weight 6000), potassium carbonate and D-mannit while adding water, and drying the resulting granules at 40 °C for 12 hours, so that the moisture content is reduced to 1% or less is excluded. A granular solid processing composition according to claim 1, wherein the alkali agent is a carbonate. A granular solid processing composition according to claims 1 or 2, wherein the compound represented by formula [P] is present in an amount of from 1.0 to 30.0% by weight. A granular solid processing composition according to claim 3, wherein the compound represented by formula [P] is polyethylene glycol. A granular solid processing composition according to claim 4, wherein the polyethylene glycol has an average molecular weight of from 2000 to 20000. A granular solid processing composition according to any preceding claim, wherein the solid processing composition is mixed with a granulated p-phenylenediamine compound to form a mixture. A granular solid processing composition according to any preceding claim, wherein at least 60% by weight of the solid processing composition has a particle size of from 149 to 1490 µm. A process for preparing a solid processing composition in the form of a tablet having a moisture content of from 0.5 to 5 wt.%, which process comprises pressure-moulding a granular solid processing composition according to any of claims 1 to 7 to form a tablet. A process for preparing a solid processing composition in the form of a tablet having a moisture content of from 0.5 to 5 wt.%, which process comprises mixing a granulated p-phenylenediamine compound with a granular solid processing composition according to any of claims 1 to 7 to form a mixture and compression-moulding the mixture to prepare the tablet.

Inventors: DEGUCHI TAKASHI, TSUCHIYA ICHIRO, DEGUCHI, TAKASHI, TSUCHIYA, ICHIRO
Applicants: KONISHIROKU PHOTO IND, KONICA CORPORATION
Application year: 1995
Main classification: G03C5
IPC codes: G03C7, G03C5