EP0547796A1

EP0547796A1 - Solid chemicals for processing silver halide photographic light-sensitive material

Info

Publication number: EP0547796A1
Application number: EP92310912A
Authority: EP
Inventors: Ichiro C/O Konica Corporation Tsuchiya
Original assignee: Konica Minolta Inc
Current assignee: Konica Minolta Inc
Priority date: 1991-12-17
Filing date: 1992-11-30
Publication date: 1993-06-23

Abstract

Disclosed is a solid chemical for processing a silver halide photographic light-sensitive material which is prepared by pressing granules :

wherein said granules comprises a primary component of a photographic processing agent coated thereon a minute amount component of a photographic agent ranging from 5 to 10 % by weight of said primary component.

The solid chemical used in a solution for processing a sliver halide photographic light-sensitive material is capable of containing uniformly the microconstituent components therein and being stable in a storage stability.

Description

FIELD OF THE INVENTION

This invention relates to a solid chemical for silver halide photographic light sensitive material (hereinafter referred also to as a light sensitive material), which is stable and uniformly contains the microconstituent components therein.

BACKGROUND OF THE INVENTION

Silver halide photographic light sensitive materials are usually subject to a development process by making use of the following processing solutions, namely, a black-and-white developer, a fixer, a color developer, a bleacher, a bleach-fixer and a stabilizer, so that images can be obtained imagewise. Each processing solution used there is put into a plastic-made bottle, in the form of a single concentrated solution part or plural parts thereof and is then supplied to the users as a processing chemical kit, so that they can easily be handled. The users dissolve the processing kit in water so as to prepare a solution (as a starting or replenishing solution) and then use them.
In the recent photographic processing industry, there have rapidly increased the so-called 'Mini-Labs' which are small-scale photofinishing laboratories where a small-sized automatic processor is used. With the increase of the Mini-Labs establishments, the quantity of the plastic-made bottles for processing chemical use used therein have also rapidly been increased year by year.
Because the plastics are light in weight and strong in quality, they have been widely used not only for the bottles for photographic processing use, but also for the other purposes. The plastic outputs of the whole world have continuously been increased year by year and, in 1988, the yearly outputs thereof has reached over one hundred million tons. On the other hand, the plastic wastes have become seriously huge. In Japan, for example, about 40% of the outputs have been wasted yearly. When wasting the plastics in ocean, the oceanic life environments are spoiled. In Europe, the problems such as acid rain troubles are raised because the trash burning treatments are made at the imperfect gas exhaustion facilities. Therefore, many serious problems have been raised.
For the above-mentioned problems, every countermeasure should be required urgently. It is the present situations in Europe and America that the legislating movements for recycling plastics, for inhibiting plastics to be used or for making obligatory use of decomposable plastics have become active.
In the above-mentioned situation, it is not desirable at all to use a large quantity of plastic-made bottles for any photographic processing chemicals even in a part.
Accordingly, it may be considered to pulverize the concentrated solutions of photographic processing chemicals into powder. When this is the case, however, the following problems may be raised. For example, there raises a problem that the operators' health are anxious to be affected because there is a possibility that fine powder is scattered in the air when dissolving it and the operator may inhale the powder, or another problems that the scattered processing chemical components may mix in the other photographic processing solutions so that the latter solutions may be contaminated to produce a trouble. For solving the above-mentioned problems, the techniques for tableting a photographic processing chemical to be granular shaped mixtures have been proposed in, for example, Japanese Patent Publication Open to Public Inspection (hereinafter referred to as 'JP OPI Publication') Nos. 2-109042/1990, 2-109043/1990, 3-39735/1991 and 3-39739/1991. However, the following problems are still recurred, namely; the labor, safety and hygienic problems produced by scattering chemical powdery dusts; and the problems of chemical preparatory operability troubles such as those produced when a subject chemical is erroneously mixed as an impurity into the other processing solutions, when a caking phenomenon that is the precipitation-cohesion of a subject chemical to the bottom of a vessel produced in dissolution, and when a dissolution failure is produced by covering the other powder with their own wet coat. It is, therefore, the actual situation that the chemicals suitable for pulverization and granulation have still been limited.
Accordingly, JP OPI Publication No. 51-61837/1976 proposes a technique fortableting a processing chemical so as to utilize the advantages of the chemicals in a dry state.
However, these tablet type photographic processing chemicals are not comprised of one and single tablet, but are comprised of the separated tablets. Because of the separated tablets, in a color developer, for example, two parts, which are double as much as the single tablets, should be added by an additional device. Therefore, another serious problem is raised from the viewpoint of making an automatic processor be compact in size. These tablets have the following defects that any satisfactory characteristics cannot be obtained as a photographic processing tablet; a defect that the preservability of the tablets are deteriorated, for example, in the case of the tablets for color development use, the developing agents thereof are reacted to be so oxidized as to produce a tar-like insoluble products in the course of the preservation, or, in the case of a bleach-fixer or a tablet for fixing use, an insoluble matter such as sulfur or a sulfide is produced.
On the other hand, in a photographic process, an additive such as an antifoggant is ordinarily used. These additives are used in a minute amount (such as an amount of not more than 1 g/liter in general), so that a satisfactory effect can be displayed. Accordingly, the characteristics of a processing solution are greatly influenced by only varying a minute amount thereof added. It is, therefore, required to delicately control the com- poundings of the additives. In the conventional methods in which the above-mentioned powdered additives are added into the other photographic processing powder or granules, it has been difficult to control the amounts thereof added and it has therefore been unable to solve the above-mentioned problems.
The term, 'the solid chemicals of the invention for silver halide photographic light sensitive material use', means herein the granular type chemicals and the tablet type chemicals thereof. The granular type processing chemicals means a solid type chemical having a particle size within the range of not smaller than 100wm and 2000µm and desirably 300wm and 1000wm.
The term, a 'tablet', means herein those prepared by pressing the above-mentioned granules or powder so as to mold into a specific configuration.

OBJECTS OF THE INVENTION

It is an object of the invention to provide a solid chemical for silver halide photographic light sensitive material use, in which a minute amount of the components of the photographic processing chemical are contained uniformly in a tablet or granular type chemical.
Another object of the invention is to eliminate the use of any plastic-made bottles for a liquid type chemical, to prevent any bad influences of the powdered chemicals on human bodies and to solve the troubles produced in any photographic processes.

SUMMARY OF THE INVENTION

The above-mentioned objects of the invention can be achieved with a solid chemicals for light sensitive material use, which is prepared by uniformly adding a minute amount each of at least one or more kinds of the components of the photographic processing chemicals into at least one kind of the chemicals for photographic processing use.
The objects of the invention can be achieved with a solid chemicals prepared in the following method of preparing the solid chemicals. The primary processing chemicals thereof are each coated with a minute amount of a photographic processing chemical component by making use of a coating agent and the coated chemicals are then so compressed as to be tableted; or, the granules thereof prepared by making use of a binder are coated with a coating agent so that the solid chemicals for light sensitive material use can be prepared.
A preferred embodiment of the invention is, for example, a solid chemical prepared in the following method of preparing a solid chemical. The primary processing chemicals thereof are added with a minute amount of a photographic processing chemical in a proportion within the range of 5 to 10% (by weight) to the primary processing chemicals and they are mixed up uniformly, further, the mixture is added with the primary processing chemicals one after another and mixed up repeatedly so as to make the total amount. After they are granulated in a wet process and dried, the dried granules are compressed and then tableted; or, they are granulated by making use of a binder. Another preferred embodiment of the invention is, for example, a solid chemical for light sensitive material prepared in the following solid chemical preparation method. The primary processing chemicals thereof are added with a minute amount of a photographic processing chemical in a proportion within the range of 5 to 10% (by weight) to the primary processing chemicals and mixed up uniformly and the mixing- up thereof are repeatedly and the primary processing chemicals are added thereto one after another so as to make the total amount. After that, they are dry-increased in a dried state and the granules are prepared or the granules prepared in a dry process are compressed so as to be tableted.
The weight ratio of the minute amount of a photographic processing chemical to the primary processing chemical is from 1/20 to 1/5000, preferably from 1/20 to 1/1000 and more preferably, from 1/20 to 1/500.

BRIEF DESCRIPTION OF THE DRAWINGS

Fig. 1 is a schematic illustration showing an example of the automatic processors relating to the invention; and
Fig. 2 is a schematic illustration of an embodiment in which a solid chemical feeding condition is shown.
- 1 Color developing tank,
- 2 Bleaching tank,
- 3 Fixing tank,
- 4 Washing tank,
- 5 Stabilizing tank,
- 6 Drying tank,
- 7 Light sensitive material area detection sensor,
- 8 Solid chemical supply unit,
- 9 Liquid level detection sensor,
- 10 Replenishing water supply unit
- 11 Control section,
- 12 Electromagnetic valve,
- 13 Light sensitive material inlet,
- 14 Warm water for washing,
- 15 Replenishing water supply pipe,
- 16 Main processing tank,
- 17 Processing solution,
- 18 Circulation pump,
- 19 Thermostat heater,
- 20 Subtank,
- 20A Guide plate,
- 20B Top cover,
- 21 Filtration unit,
- 24 Solid chemical,
- 24A Solid chemical at top,
- 27 Communication pipe,
- 28 Processing rack,
- 29 Overflow outlet,
- 39 Filter,
- 91 supply tray body,
- 92 Piston sliding table,
- 94,99 Plunger,
- 94A, 99A Rack,
- 95, 97 Stepping motor,
- 96,98 Pinion

DETAILED DESCRIPTION OF THE INVENTION

The term, a'minute granular component' stated herein, means a component in an amount of not more than 1/50 of a total increased amount. For displaying the effects of the objects of the invention excellently, the minute granular components are to be within the range of 1/100 to 1/20000 and, preferably, 1/150 to 1/15000.
The processing chemicals of the invention for silver halide photographic light sensitive materials can be prepared in any ordinary methods such as those detailed in JP OPI Publication Nos. 51-61837/1976, 54-155038/1979 and 52-88025/1977, British Patent No. 1,213,808 and so forth.
The photographic minute amount components in the invention mean the additives well-known in the skilled in the art. They include, for example, a development accelerator, an antifoggant, a fluorescent whitening agent, an antistaining agent and an antisludging agent. The other photographically effective components include the ordinary photographic additives.
Now, the invention will be detailed.
The processing tablets of the invention for silver halide photographic light sensitive materials include, for example, a color developer, a black-and-white developer, a bleacher, a fixer, a bleach-fixer, a stabilizer and so forth.
When the processing tablets of the invention are used for a color developer, a p-phenylenediamine type compound having a water-soluble group may preferably be used, because the effects of the invention can be excellently displayed and few fog can be produced thereby.
The above-mentioned p-phenylenediamine type compounds each having a water-soluble group have not only the advantages that no contamination of any light sensitive materials can be produced and that no skin can be suffered by dermatitis even if it comes into contact with the skin, but also the objects of the invention can effectively be achieved particularly when making use of the processing tablets of the invention.
In the invention, when the color developers relating to the invention contain the compounds represented by the following Formulas [A] and [B], it can be one of the preferred embodiments of the invention, because not only the effects of the invention can be more displayed, but also the effect of reducing the fog produced in an unexposed area.

wherein R₁ and R₂ represent each an alkyl group, an aryl group, an R₃CO- group or a hydrogen atom, provided that R₁ and R₂ cannot represent each hydrogen atoms at the same time and that R₁ and R₂ are also allowed to form a ring.
In Formula [A], the substituted or non-substituted alkyl groups represented by R₁ and R₂ may be the same with each other and they include, preferably, an alkyl group having 1 to 3 carbon atoms. Further, these alkyl groups may have a carboxyl group, a phosphoric acid group, a sulfo group or a hydroxyl group. R₃ represents a substituted or non-substituted alkoxy group, a substituted or non-substituted alkyl group or a substituted or non-substituted aryl group. The rings which may be formed by R₁ and R₂ include, for example, a heterocyclic ring such as those of piperidine, pyridine, triazine or morpholine.

wherein R₁₁, R₁₂ and R₁₃ represent each a hydrogen atom, a substituted or non-substituted alkyl group, an aryl group or a heterocyclic group; R₁₄ represents a hydroxyl group, a hydroxyamino group, a substituted or non-substituted alkyl group, an aryl group, a hetercyclic group, an alkoxy group, an aryloxy group, a carbamoyl group or an amino group, provided that the heterocyclic groups have each a 5- or 6-membered ring, and they are each constituted of C, H, O, N, S and a halogen atom and they may also be either saturated or unsaturated; R₁₅ represents a divalent group selected from the group consisting of -CO-, -S0₂- and -C(=NH)-; and n is an integer of 0 or 1, provided that, when n is 0 in particular, R₁₄ represents a group selected from the group consisting of alkyl groups, aryl groups and heterocyclic groups, and that R₁₃ and R₁₄ are also allowed to form a heterocyclic ring.
The typical examples of the hydroxylamine type compounds represented by the above-given Formula [A] are given in, for example, U.S. Patent Nos. 3,287,125, 3,329,034 and 3,287,124. The particularly desirable exemplified compounds are typically include, for example, those of (A-1) through (A-39) given in JP Application No. 2-203169/1990, pp.36-38, (1) through (53) given in JP OPI Publication No. 3-33845/1991, pp.3-6, and (1) through (52) given in JP OPI Publication No. 3-63646/1991, PP-5-7.
Next, the typical examples of the compounds represented by Formula [B] include (B-1) through (B-33) given in JP Application No. 2-203169/1990, pp.40-43 and (1) through (56) given in JP OPI Publication No. 3-33846/1990, pp.4-6.
The compounds represented by Formulas [A] and [B] are ordinarily used in the forms of a free amine, a hydrochloric acid salt, a sulfuric acid salt, a p-toluenesulfinic acid salt, an oxalic acid salt and an acetic acid salt.
The hydroxylamine type compounds represented by the following Formula [A'] may also desirably be used as the preservatives for a color developer.
wherein L represents each a substituted or non-substituted alkylene group; A represents a carboxyl group, a sulfo group, a phosphono group, a phosphino group, a hydroxyl group, an alkyl-substitutable amino group, an ammonio group, a carbamoyl group or a sulfamoyl group; and R represents a hydrogen atom or a substituted or non-substituted alkyl group.
The typical examples of the compounds represented by Formula [A'] include (1) through (54) given in JP OPI Publication No. 3-184044/1991, the lower left column on P.4 to the lower right column on p.6. Among them, the following compounds (1) and (7) are desirably used.
The compounds represented by Formula [A'] can be prepared by making an alkylating reaction of any hydroxylamines available on the market. For example, they can be synthesized in the synthesizing processes detailed in, forexample, West German Patent No. 1,159,634, lnorganica Chemica Acta, 93,1984, pp.101~108, and so forth.
Those applicable as the preservatives include, for example, sugars.
Sugars (or carbohydrates) include a monosuccharide and a polysaccharide. Most of them are represented by the formula (C_nH_2nO_n). The above-mentioned monosaccharide is general term for the aldehydes or ketones of polyhydric alcohol, the reduction derivatives, oxidation derivatives and dehydration derivatives thereof and the widely ranged derivatives of amino sugar or thio sugar. The above-mentioned polysaccharides mean a product obtained by dehydrating and condensing two or more of the above-mentioned monosaccharides.
These sugars include, desirably, aldose having a reducible aldehyde group and the derivatives thereof and, more desirably among them, those corresponding to the monosaccharides.
In the invention, the typical examples of the monosaccharides applicable thereto will be given below. However, the invention shall not be limited thereto.

(1) erythritol,
(2) β-D-arabinose,
(3) β-L-arabinose,
(4) D-xylose,
(5) L-xylose,
(6) 2-deoxy-β-D-ribose,
(7) a-D-Iyxose,
(8) a-L-Iyxose,
(9) D-ribose,
(10) L-ribose,
(11) L-arabitol,
(12) D-arabitol,
(13) ribitol,
(14) β-D-altrose,
(15) β-L-altrose,
(16) β-D-allose,
(17) β-L-allose,
(18) a-D-galactose,
(19) β-D-galactose,
(20) a-L-galactose,
(21) a-D-quinovose,
(22) a-D-glucose,
(23) β-D-glucose,
(24) β-D-lactose,
(25) digitalose,
(26) digitoxose,
(27) cymarose,
(28) L-sorbose,
(29) D-tagatose,
(30) a-D-talose,
(31) 2-deoxy-D-glucose,
(32) a-D-fucose,
(33) a-L-fucose,
(34) a-D-mannose,
(35) L-mannose,
(36) a-L-rhamnose,
(37) D-inositol,
(38) myo-inositol,
(39) galactitol,
(40) d-quercitol,
(41) D-glucitol,
(42) D-mannitol,
(43) L-iduronic acid,
(44) galactaric acid,
(45) a-D-galacturonic acid,
(46) D-glucalic acid,
(47) β-D-glucuronic acid,
(48) D-gluconic acid,
(49) L-gluconic acid,
(50) 2-deoxy-D-gluconic acid,
(51) D-mannonic acid-6,3-lactone,
(52) methyl=¡3-D-galactopyranoside,
(53) methyl=a-D-galactopyranoside,
(54) methyl=a-D-glucopyranoside,
(55) methyl=¡3-D-glucopyranoside,
(56) methyl=a-D-furactofuranoside,
(57) methyl=a-D-mannopyranoside,
(58) methyl=¡3-D-mannopyranoside,
(59) N-acetyl-a-D-galactosamine,
(60) N-acetyl-a-D-glucosamine,
(61) N-acetyl-a-D-mannosamine,
(62) muramic acid,
(63) a-D-galactosamine,
(64) a-D-glucosamine,
(65) D-mannosamine,
(66) D-glycero-a-galacto-heptose,
(67) D-glycero-β-L-manno-heptose,
(68) D-manno-heptulose,
(69) D-altro-3-heptulose,
(70) D-glycero-D-galacto-heptitol,
(71) D-glycero-D-talo-heptitol,
(72) D-erythro-D-galacto-octitol

The above mentioned monosaccharides are widely present in a state of nature and, therefore, they can be readily available from the market. Further, the above-mentioned various derivatives can also readily be synthesized by making a reduction, oxidation or dehydration reaction.
The solid chemicals for color and black-and-white developments may necessarily be used with a buffer. The buffers applicable thereto include, for example, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate, sodium borate, potassium borate, sodium tetraborate (or boric acid), potassium tetraborate,, sodium o-hydroxybenzoate (or sodium salicylate), potassium o-hydroxybenzoate, sodium 5-sulfo-2-hydroxybenzoate (or sodium 5-sulfosalicylate) and potassium 5-sulfo-2-hydroxy benzoate (or potassium 5-sulfosalicylate).
If required, it is allowed to add a development accelerator including, for example, thioethertype compounds typified by those given in JP Examined Publication Nos. 37-16088/1962, 37-5987/1962, 38-7826/1963, 44-12380/1969 and 45-9019/1970 and U.S. Patent No. 3,813,247; p-phenylenediamine type compounds typified by those given in JP OPI Publication Nos. 52-49829/1977 and 50-15554/1975; quaternary ammonium salts typified by those given in JP Examined Publication No. 44-30074/1969 and JP OPI Publication Nos. 50-137726/1975, 56-156826/1981 and 52-43429/1977; the p-aminophenols given in U.S. Patent Nos. 2,610,122 and 4,119,462; amine type compounds such as those given in U.S. Patent Nos. 2,494,903, 3,128,182, 4,230.796 and 3,253,919, JP Examined Publication No. 41-11431/1966, U.S. Patent Nos. 2,482,546,2,596,926 and 3,582,346; polyalkylene oxides typified by those given in JP Examined Publication Nos. 37-16088/1962 and 42-25201/1967, U.S. Patent No. 3,128,183, JP Examined Publication Nos. 41-11431/1966 and 42-23883/1967 and U.S. Patent No. 3,532,501; and, besides the above, 1-phenyl-3-pyrazolidones, hydrazines, mesoionic type compounds, ionic type compounds and imidazoles.
For the purpose of preventing a fog production, color developers are also allowed to contain chlorine ion and bromine ion. In the invention, chlorine ions may be contained in a proportion within the range of, 1.0x10-² to 1.5x10^-1 mols per liter and, desirably, 3.5x10-² to 1.0x10^-1 mols per liter. When the concentration of the chlorine ions is higher than 1.5x10^-1 mols per liter, a high maximum density may not desirably be obtained, because the ions retard a development. When the concentration thereof is lower than 3.5x10-² mols per liter, the results may not become desirable, because stains may be produced and the photographic characteristics (including, particularly, a minimum density) may be varied seriously in the course of a continuous processing.
In the invention, a color developer contains bromide ions in an amount within the range of 3.0x10^-5 to 1.0x10-³ mols per liter, desirably, 5.Ox10-⁵ to 5x10-4 mols per liter and, more desirably, 1.Ox10-⁴ to 3.Ox10-⁴ mols per liter. When the bromide ion concentration is higher than 1.0x10^-3 mols per liter, the development is retarded and the maximum density and sensitivity are lowered. When the concentration thereof is lower than 3.0x10^-5 mols per liter, stains are produced and the photographic characteristics (including particularly the minimum density) are varied in the course of carrying out a continuous processing. Therefore, the results may not become desirable.
When bromide ions are added directly into a color developer, the chlorine ion supplying substances include, for example, sodium chloride, potassium chloride, ammonium chloride, nickel chloride, magnesium chloride, manganese chloride, calcium chloride and cadmium chloride. Among them, sodium chloride and potassium chloride may desirably be added thereto.
These substances may also be supplied in the form of the counter salts of a fluorescent whitening agent which is to be added into a color developer.
The bromine ion supplying substances include, for example, sodium bromide, potassium bromide, ammonium bromide, lithium bromide, calcium bromide, magnesium bromide, manganese bromide, nickel bromide, cadmium bromide, cerium bromide and thallium bromide. Among them, potassium bromide and sodium bromide may desirably be added thereto.
Besides the above-given chlorine ions and bromine ions, any one of the desired antifoggants may be added, if required, into the solid chemicals for color development use of the invention. The above-mentioned antifoggants applicable thereto include, for example, an alkali-metal halide such as potassium iodide and an organic antifoggant. The organic antifoggants include, typically, nitrogen-containing heterocyclic compound such as benzotriazole, 6-nitrobenzoimidazole, 5-nitroindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chlorobenzotriazole, 2-thiazolylbenzoimidazole, 2-thiazolylmethylbenzoimidazole, indazole, hydroxyazaindolidine and adenine.
From the viewpoint of the effects of the objects of the invention, it is desired to contain a triazinyl stilbene type fluorescent whitening agent in the solid chemicals for color development use of the invention. The above-mentioned fluorescent whitening agents include, desirably, the compounds represented by the following Formula [E].
Formula [E]
In the above-given formula, X₁, X₂, Y₁ and Y₂ represent each a hydroxyl group, a halogen atom such as those of chlorine and bromine, an alkyl group, an aryl group, a -N(R₂₁)(R₂₂) group,

or OR₂₅, in which R₂₁ and R₂₂ represent each a hydrogen atom, a substituted or non-substituted alkyl group or a substituted or non-substituted aryl group; R₂₃ and R₂₄ represent each a substituted or non-substituted alkylene group; R₂₅ represents a hydrogen atom, a substituted or non-substituted alkyl group or a substituted or non-substituted aryl group; and M represents a cation.
The details of the groups or the substituents thereof each given in Formula [E] are each synonymous with those given in JP Application No. 2-240400/1990, the 8th line from the bottom on p.62 to the 3rd line from the bottom on p.64. The concrete compounds may include, for example, E-1 through E-45 given in the same JP Application, pp.65-67.
The above-mentioned compounds can be synthesized in any well-known methods. The typical compounds will be exemplified below. Among them in particular, E-4, E-24, E-34, E-35, E-36, E-37 and E-41 may desirably be used. These compounds may be added in an amount within the range of, desirably, 0.2 to 10 g per 1000 ml of a color developer and, more desirably, 0.4 to 5 g.
In the invention, when a compound represented by the following Formula [F] is contained in a color developer relating to the invention, the solubility of a color developer tablet can be so improved as to be useful for preventing a crystal deposition.
Formula [F]

wherein R₄ represents a hydroxyalkyl group having 2 to 6 carbon atoms; R₅ and R₆ represent each a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a hydroxyalkyl group having 2 to 6 carbon atoms, a benzyl group or a formula of

in which n is an integer of 1 to 6; and X and Z represent each a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a hydroxyalkyl group having 2 to 6 carbon atoms.
The desirably concrete examples of the compounds represented by the above-given Formula [F] are as follows.
Ethanol amine, diethanol amine, triethanol amine, diisopropanol amine, 2-methylaminoethanol, 2-ethylaminoethanol, 2-dimethylaminoethanol, 2-diethylaminoethanol, 1-diethylamino-2-propanol, 3-diethylamino-1-propanol, 3-dimethylamino-1-propanol, isopropylaminoethanol, 3-amino-1-propanol, 2-amino-2-methyl-1,3-propanediol, ethylenediamine tetraisopropanol, benzyldiethanol amine, free amine of 2-amino-2-(hydroxymethyl)-1,3-propanediol, a borate, a hydrochloride and a phosphate. Among these compounds, ethanol amine, free amine of diethanolamine, a borate, a hydrochloride and a phosphate may desirably be used. In particular, free amine of ethanolamine, a borate, a hydrochloride and a phosphate may preferably be used.
In addition to the above, an auxiliary developing agent can also be used together with a developing agent. The known auxiliary developing agents include, for example, Metol, Phenidone, N,N-diethyl-p-aminophenol hydrochloride, N,N,N',N'-tetramethyl-p-phenylenediamine hydrochloride. They may be added usually in an amount within the range of, desirably, 0.01 to 1.0 g per liter.
Besides the above, a variety of additives such as an antistaining agent and an interlayer effect accelerator may be used.
From the viewpoint of effectively achieving the objects of the invention, it is desired to add a chelating agent represented by the following Formula [K] given in JP Application No. 2-240400/1990, the 9th line from the bottom of p.69 to p.75 and the exemplified compounds thereof K-1 through K-22, into a solid chemicals for color or black-and-white development use.
Formula [K]
Among the above-given chelating agents, K-2, K-9, K-12, K-13, K-17 and K-19 may desirably be used. In particular, the effects of the invention can be more displayed when adding K-2 and K-9 into a color developer.
These chelating agents may be added in an amount within the range of, desirably, 0.1 to 20 g per 1000 ml of a color or black-and-white developer used and, more desirably, 0.2 to 8 g.
Still further, the solid chemicals for color or black- and -white development use are allowed to contain each of anionic, cationic, amphoteric and nonionic surfactants. If required, it is also allowed to add a variety of surfactants such as alkylsulfonic acid, arylsulfonic acid, aliphatic carboxylic acid and aromatic carboxylic acid.
The binders applicable to the invention include, for example, hydroxypropyl cellulose, hydroxypropyl methylcellulose, polyvinyl pyrrolidone, starch, gelatin, pullulan, carboxymethyl cellulose, sodium carboxymethyl cellulose, polyvinyl alcohol and hydroxyethyl cellulose. Among them, hydroxy propyl cellulose, pullulan and starch are desirable applicable thereto and hydroxypropyl cellulose is most desirably applicable thereto.
The coating agents include, for example, hydroxypropyl cellulose, polyvinyl alcohol, pullulan, polyvinyl pyrrolidone and a water-dispersed product of poly(metha)acrylic acid and a poly(metha)acrylic acid ester. Among them, hydroxypropyl cellulose and hydroxypropylmethyl cellulose are desirably applicable thereto and hydroxypropyl cellulose is most desirably applicable thereto.
Silver halide photographic light sensitive materials are exposed to light and are then processed in the processing steps such as a developing step, a desilvering step, a washing step and a stabilizing step. A black-and-white developer or a color developer is used in the developing step; a bleacher, a bleach-fixer or a fixer, in the desilvering step; city water or ion-exchange water, in the washing step; and a stabilizer, in the stabilizing step; respectively. Each of the processing solutions is thermally controlled at a temperature within the range of, usually, 30 to 40°C and the subject light sensitive materials are dipped in and processed in the above-mentioned processing solutions.
The above-mentioned processing treatments are usually carried out through an automatic processor or the like and the subject light sensitive materials are transported one after another between the processing tanks in which the above-mentioned processing solutions are contained, respectively.
In the above-mentioned case, there adopts a system for supplying the replenishers to the corresponding processing solutions, for the purpose of keeping the activities of the processing solutions constant in the processing tanks, respectively.
To be more concrete, the processing treatments are carried out so as to keep supplying the replenishers timely from the replenishing tanks into the processing tanks, respectively.
In this case, there are two systems; in one system, the replenishers themselves reserved in the corresponding replenishing tanks are separately prepared and they are replenished into the corresponding replenishing tanks if occasion requires; and, in another system, the replenishers are prepared directly in the corresponding replenishing tanks.
The processing chemicals are supplied in the form of powder or condensed liquid and they are used after dissolving or diluting them with a specific amount of water.
For stabilizing the finished quality of a light sensitive material to be processed through an automatic processor, it is essential to control the rates of replenishments.
For controlling the rates of replenishments, it is essential to check up the periodical replenishing quantities. In the recent Mini-Labs, it has been actual that the periodical checking-up services are carried out by the manufacturers of the automatic processors about once a month when they have made the round of their assigned territories. Therefore, even if some replenishment should be clogged up, the replenishment has to be left as it is until they make the round.
The effects of the invention can be more excellently displayed when light sensitive materials are processed by making combination use of an automatic processor capable of solving the above-mentioned problems and a solid chemical of the invention.
Next, the above-mentioned automatic processor will be detailed below.
Fig. 1 is a schematic illustration of an example of the automatic processors relating to the invention, in which the control mechanism for a color negative film processing apparatus is briefly illustrated.
When a color negative film is inserted into light sensitive material inlet 13 and is then passed through light sensitive material area detection sensor 7, a specific area of the light sensitive material is detected. At this time, replenishing solid chemical supply units 8, replenishing water supply unit 10 and electromagnetic valves 12 are each operated upon receipt of a signal sent from control section 11, so that replenishing processing chemicals and replenishing water can each be replenished in the necessary amounts into processing tanks 1, 2, 3 and 5, respectively.
When an automatic processor is kept at a proper temperature for several hours, processing solutions 17 are evaporated from each of processing tanks 1 through 5. When the solutions are each lowered down to the specific levels, liquid level detection sensors 9 are operated and replenishing water supply unit 10 and electromagnetic valves 12 are then operated upon receipt of a signal from control section 11, so that replenishing water for compensating the evaporation can be supplied until the upper liquid level detection mechanisms of liquid level detection sensors 9 are operated. It is further desired that warm washing water 14, that is replenishing water supplied through replenishing water supply pipe 15, is to be made thermostatic together with replenishing water for preparing the solutions and replenishing water for compensating the evaporation. In reference to processing tanks 1, through 5, 1 is a color developing tank, 2 is a bleaching tank, 3 is a fixing tank, 4 is a washing tank and 5 is a stabilizing tank. And, further, 6 is a drying section.
Fig. 2 shows a schematic illustration of an embodiment of replenishing solid chemical supply units 8, in the case where the tablet-shaped, solid type replenishing processing chemicals are used.
When control section 11 is operated upon receipt of a signal from light sensitive material area detection sensor 7 and thereby stepping motor 95 for supplying solid type replenishing processing chemicals is then operated, driving pinion 96 directly coupling to the motor 95, which is engaged with rack 94A of extrusion plunger 94 for supplying the replenishing solid chemicals, such driving pinion 96 lifts up plunger 94 having the foregoing rack 94A by one step that is as same as a pitch length P of the thickness of a processing chemical, so that the uppermost solid chemical 24Acan be ready in the dropping position of supply tray 91. Therefore, one piece of processing chemicals 24 stored in supply tray 91 is completed to make it ready for dropping into filtration unit 21 provided to the inside of processing chemical supply tank (hereinafter called a subtank) which is a replenishing processing chemical dissolving section for each of processing tanks 1, 2, 3 and 5.
Solid chemical 24A ready at the uppermost position is slided laterally, by the forwarding movement of plunger 99 which horizontally reciprocates on the upper portion of piston sliding table 92, through a tunnel formed of guide plate 20A on the upper part of subtank 20 and top cover 20B, so that solid chemical 24A can be dropped on the liquid surface of filtration unit 21 of subtank 20. Plunger 99 is reciprocated by the foregoing stepping motor 97 started in motion by a demand signal, because rack 99A provided to a part of the foregoing plunger 99 is engaged with pinion 98 directly coupled to stepping motor 97. After dropping solid chemical 24A into subtank 20 by the forwarding movement of plunger 99, stepping motor 97 is reversely rotated so as to make plunger 99 backward to restore it to the original position and plunger 99 is then made ready for taking an action until the next signal is given. There may be some instances where a demand signal demands to supply plural solid chemicals. When this is the case, the above-mentioned operations are repeated several timed as specified. The replenishing processing chemicals 24 thus supplied are gradually dissolved and are then supplied by circulation pump 18 into main processing tanks 16 each of processing tanks 1, 2, 3 and 5. Further, when the whole or most part of the circulation flow of processing solution 17, which is being circulated between main processing tank 16 and subtank 20 by circulation pump 18, is so constituted as to pass directly through filtration unit 21 of subtank 20, the solubility of replenishing solid chemical 24 can be enhanced. In the drawings, 19 is a thermostatic heater, 27 is a communication pipe connecting between main processing tank 16 and subtank 20 each constituting each of processing tanks 1, 2, 3 and 5, 28 is a processing rack and 29 is an overflow outlet.
In the drawings, supply tray body 91 of solid chemical supply unit 8 is so constructed as to be covered by the vertical walls on four sides and to reciprocate plunger 94 in the vertical direction. As mentioned above, solid chemicals are protected in the supply tray in almost the sealed state and the uppermost solid chemical 24A is so extruded in almost the sealed state from the tunnel to subtank 20 as mentioned above. Therefore, the processing chemicals are neither contaminated by splashing any processing solutions nor affected by any evaporations.
The reciprocation speed of plunger 99 is properly controlled and the solid chemicals are fed to such a direction that the flat surfaces of the solid chemicals can be vertical as shown in Fig. 2. Therefore, the water scattering can extremely be reduced.
It is also more desirable to adopt the technique applied for another patent almost at the same time by the present patent applicants, wherein a floating cover and floating balls are arranged to the liquid surface to which the solid chemicals are fed on so as to serve as a cush ion to prevent any splashes utmost from scattering about.
Replenishing water for preparing solutions can be supplied in the following manner. When control section 11 is operated upon receipt of a signal from light sensitive material area detection sensor 7, the control section 11 demands to operate replenishing solid chemical supplying stepping motors 95 and 97, pinions 96 and 98 each driven by the above-mentioned motors, plunger 94 having rack 94Aand plunger 99 having rack 99Aeach linearly moved by the above-mentioned pinions, and, at the same time when supplying replenishing solid chemicals 24, replenishing water supply unit 10 and electromagnetic valves 12 are operated, so that replenishing water for preparing solutions can be supplied. The amounts of supplying the replenishing water for preparing solutions may be enough, provided that replenishing solid chemicals 24 can be dissolved. The amounts thereof can be controlled by inputting a operation time for both electromagnetic valves 12 and replenishing water supply unit 10 in advance to control section 11.
In the course of keeping an automatic processor thermally controlled or suspended in operation and if a liquid level is lowered by some evaporation of processing solutions 17 stored in processing tanks 1 through 5, liquid level detection sensors 9 detect the lowered liquid level and send a signal to control section 11 so as to operate electromagnetic valves 12 and replenishing water supply unit 10, so that replenishing water for compensating the evaporation can be supplied. When recovering a regular liquid level, liquid level detection sensors 9 detect the regular liquid level and send a signal to control section 11, so that electromagnetic valves 12 and replenishing water supply unit 10 are stopped in operation.

EXAMPLES

Some examples will be given below. However, the invention shall not be limited to the embodiments given in the examples.

Example 1

A solid type color development processing chemicals for color negative use was prepared in the following procedures.

Procedure (1)

Hydroxylamine sulfate of 150 g was milled in an air-jet fine mill, until the average particle size thereof could be 10 µ. Water of 10 ml was sprayed for about 7 minutes over to the resulting fine particles at room temperature in a fluidized bed spray granulator available on the market. After granulating them to have an average particle size of 150 µm, the resulting granules were dried up at an air temperature of 63°C for 8 minutes. Next, the granules were dried up in vacuum at 40°C for 90 minutes and the moisture of the granules was almost completely removed.

Procedure (2)

After milling 300 g of a developing agent CD-4, thatwas 4-amino-3-methyl-N-ethyl-N-β-hydroxylethyl-aniline sulfate, in an air-jet fine mill in the same manner as in Procedure (1), they were granulated. The amount of water sprayed was 10 ml. After granulating them, they were dried up at 60°C for 7 minutes. Next, the resulting granules were dried up in vacuum at 40°C for 90 minutes, so that the moisture of the resulting granules could be almost completely removed.

Procedure (3)

After uniformly mixing up 125 g of disodium 1-hydroxyethane-1,1-diphosphonate, 100 g of pentasodium diethylenetriamine pentaacetate, 175 g of sodium sulfite, 1540 g of potassium carbonate and 75 g of sodium hydrogen carbonate each in a mixer available on the market, the resulting uniform mixture was pulverized in an air-jet fine mill in the same manner as in Procedure (1). The resulting pulverized mixture was granulated by spraying the solution prepared by dissolving 40 g of sodium bromide in 150 ml of an aqueous 1% hydroxypropyl cellulose solution. After completing the granules, they were dried at 65°C for 15 minutes and the granules were then dried up in vacuum at 40°C for 90 minutes, so that the moisture thereof could be almost completely removed.

Procedure (4)

The granules prepared in the above-described procedures (1) through (3) were screened to obtain 500 g of the granular chemicals having a particle size within the range of 1000 µm to 300 µm, so that granular chemical sample 1 for color film development use could be prepared.

Procedure (5)

The granules prepared in Procedure (4) were tableted into those having a diameter of 30 mm and a weight of 10 g by applying a compression of 800 kg/cm² by making use of a tablet machine, so that 50 pieces of tablet type chemical sample 2 for color film development use could be prepared.

Procedure (6)

After uniformly mixing up 125 g of disodium 1-hydroxyethane-1,1-diphosphonate, 175 g of sodium sulfite, 154 g of potassium carbonate, 75 g of sodium hydrogen carbonate, 40 g of sodium bromide and 100 g of sodium diethylenetriamine pentaacetate each in a mixer available on the market, the resulting uniformed mixture was pulverized in an air-jet fine mill in the same manner as in Procedure (1). The resulting pulverized mixture was granulated. Then, the resulting granules were dried at 70°C for 10 minutes and the resulting granules were then dried up in vacuum at 40°C for 90 minutes, so that the moisture thereof were almost completely removed.

Procedure (7)

The granules granulated in the above-described procedures (1) and (2) were added to the granules granulated in the above-described procedure (5) and the mixture thereof were screened in the same manner as in Procedure (4) to obtain 500 g of the granules having a particle size within the range of 1000 µm to 300 µm so as to serve as a granular chemicals, so that granular sample 3 for color film development use could be prepared.

Procedure (8)

The granules granulated in the above-described procedures (1) and (2) were added to the granules granulated in the above-described procedure (6) and the mixture thereof were tableted by a tablet machine in the same manner as in the above-described Procedure (5), so that 50 pieces of tablet type sample 4 for color film development use could be prepared.

Experiment (1)

From the granular chemicals of Samples 1 and 3, 1 g each of them were sampled at random from 10 spots. The sodium bromide contents thereof were measured, and the contents thereof and the deviation values thereof were obtained. The results thereof will be given in Table 1 below.
It was proved from the above-given Table 1 that the deviation of the microconstituent contents in the invention was substantially smaller.

Experiment (2)

From the tableted chemicals of Samples 2 and 4, 10 tablets were sampled at random. The sodium bromide contents of each tablet were measured, and the contents thereof and the deviation values thereof were obtained. The results thereof will be given in Table 2 below.
It was proved from the above-given Table 2 that the deviation of the microconstituent contents in the invention was substantially smaller.

Example 2

Procedure 9

A mixture was made by-mixing up 150 g of hydroxylamine sulfate, 300 g of CD-4, 125 g of sodium 1-hydroxyethane-1,1-diphosphonate, 100 g of sodium diethylenetriamine pentaacetate, 175 g of sodium sulfite, 1540 g of potassium carbonate and 75 g of sodium hydrogen carbonate by making use of a mixer for 5 minutes. The resulting mixture was pulverized by an air-jet fine mill, until the average particle size thereof could be 10 µm.

Procedure 10

Sodium bromide of 40 g was pulverized by an air-jet mill, until the average particle size thereof could be 10 µm.

Procedure 11

The pulverized mixture of 360 g obtained in Procedure 9 was added to 40 g of sodium bromide finely pulverized in Procedure 10 and both of them were mixed up by a mixer for 10 minutes. Further, all the remaining pulverized mixture obtained in Procedure 9 were added thereto so as to be mixed up further for 10 minutes.

Procedure 12

The mixture prepared in Procedure 11 was sprayed with 120 ml of water by making use of a fluidized bed spray granulator, so that they could be granulated to have an average particle size of 800 µm. After that, the resulting granules were dried at 60°C for 20 minutes. Next, the resulting granules were dried up in vacuum at 40°C for 120 minutes, so that the moisture content of the granules could be almost completely removed.

Procedure 13

The granules obtained in the above-described Procedure 12 were screened so as to obtain 400 g of granules having a particle size within the range of 1000 f..lm to 300 µm and they were served as a granular chemical, so that granular chemical sample 5 for color film development use could be prepared.

Procedure 14

The granules prepared in Procedure (12) were tableted into those having a diameter of 30 mm and a weight of 10 g by applying a compression of 800 kg/cm² by making use of a tableting machine, so that 50 pieces of tablet type chemical sample 6 for color film development use could be prepared.

Procedure 15

A mixture was made by mixing up 150 g of hydroxylamine sulfate, 300 g of CD-4, 125 g of sodium 1-hydroxyethane-1,1-diphosphonate, 100 g of sodium diethylenetriamine acetate, 175 g of sodium sulfite, 1540 g of potassium carbonate, 75 g of sodium hydrogen carbonate and 40 g of sodium bromide by making use of a mixer for 5 minutes. The resulting mixture was pulverized by an air-jet fine mill, until the average particle size thereof could be 10 µm.

Procedure 16

The mixture prepared in Procedure 15 was sprayed with 135 ml of water by making use of a fluidized bed spray granulator, so that they could be granulated to have an average particle size of 800 µm. After that, the resulting granules were dried at 60°C for 20 minutes. Next, the resulting granules were dried up in vacuum at 40°C for 120 minutes, so that the moisture content of the granules could be almost completely removed.

Procedure 17

The granules obtained in the above-described Procedure 16 were screened so as to obtain 400 g of granules having a particle size within the range of 1000 µm to 300 µm and they were served as a granular chemical, so that granular chemical sample 7 for color film development use could be prepared.

Procedure 18

The granules prepared in Procedure (16) were tableted into those having a diameter of 30 mm and a weight of 10 g by applying a compression of 800 kg/cm² by making use of a tableting machine, so that 50 pieces of tablet type chemical sample 8 for color film development use could be prepared.

Experiment (3)

From the granular chemicals of Samples 5 and 7, 1 g each of them were sampled at random from 10 spots. The sodium bromide contents thereof were measured, and the contents thereof and the deviation values thereof were obtained. The results thereof will be given in Table 3 below.
It was proved from the above-given Table 3 that the deviation of the microconstituent contents in the invention was substantially smaller.

Experiment 4

From the tableted chemicals of Samples 6 and 8, 10 tablets were sampled at random. The sodium bromide contents of each tablet were measured, and the contents thereof and the deviation values thereof were obtained. The results thereof will be given in Table 4 below.
It was proved from the above-given Table 4 that the deviation of the microconstituent contents in the invention was substantially smaller.

Example 3

Procedure 19

The fine powder prepared in the same manner as in Procedure 11 was prepared to be a flake-shaped compressively formed product by making use of a roller compacting type dry granulator. After the resulting compressively formed products is roughly ground, they were graded so as to be granules having an average particle size of 700 µm. Further, the resulting granules were dried up in vacuum at 40°C for 60 minutes, so that the moisture of the granules could be almost completely removed.

Procedure 20

The granules obtained in the above-described Procedure 19 were screened so as to obtain 300 g of granules having a particle size within the range of 1000 f..lm to 300 µm and they were served as a granular chemical, so that granular chemical sample 9 for color film development use could be prepared.

Procedure 21

The granules prepared in Procedure (19) were tableted into those having a diameter of 30 mm and a weight of 10 g by applying a compression of 800 kg/cm² by making use of a tableting machine, so that 50 pieces of tablet type chemical sample 10 for color film development use could be prepared.

Procedure 22

The fine powder prepared in the same manner as in Procedure 15 was prepared to be a flake-shaped compressively formed product by making use of a roller compacting type dry granulator. After the resulting compressively formed products is roughly ground, they were graded so as to be granules having an average particle size of 700 µm. Further, the resulting granules were dried up in vacuum at 40°C for 60 minutes, so that the moisture of the granules could be almost completely removed.

Procedure 23

The granules obtained in the above-described Procedure 22 were screened so as to obtain 400 g of granules having a particle size within the range of 1000 µm to 300 µm and they were served as a granular chemical, so that granular chemical sample 11 for color film development use could be prepared.

Procedure 24

The granules prepared in Procedure 22 were tableted into those having a diameter of 30 mm and a weight of 10 g by applying a compression of 800 kg/cm² by making use of a tableting machine, so that 50 pieces of tablet type chemical sample 12 for color film development use could be prepared.

Experiment 5

From the granular chemicals of Samples 9 and 11, 1 g each of them were sampled at random from 10 spots. The sodium bromide contents thereof were measured, and the contents thereof and the deviation values thereof were obtained. The results thereof will be given in Table 5 below.
It was proved from the above-given Table 5 that the deviation of the microconstituent contents in the invention was substantially smaller.

Experiment 6

From the tableted chemicals of Samples 10 and 12, 10 tablets were sampled at random. The sodium bromide contents of each tablet were measured, and the contents thereof and the deviation values thereof were obtained. The results thereof will be given in Table 6 below.
It was proved from the above-given Table 5 that the deviation of the microconstituent contents in the invention was substantially smaller.

Example 4

Solidification of a bleach processing chemical

Procedure (25)

A granulation was made in the same manner as in Procedure 15 of Example 2 by making use of 90 g of ferric potassium 1,3-propylenediamine tetraacetate, 20 g of ferric sodium ethylenediamine tetraacetate, 2.5 g of sodium ethylenediamine tetraacetate and 2.5 g of sodium hydrogen carbonate. The sprayed amount of water was 27.5 ml, the drying temperature was 80°C and the time was 10 minutes, respectively.

Procedure (26)

A granulation was made in the same manner as in Procedures 15 and 16 by making use of 150 g of potassium bromide, 17.5 g of sodium nitrate and 14.5 g of maleic acid. The sprayed amount of water was 25 ml, the drying temperature was 77°C and the time was 10 minutes, respectively.

Procedure (27)

The solidification of the granules prepared in the above-described Procedures (25) and (26) were made in the same manner as in Procedure (18), so that 50 pieces of solid type bleach processing chemicals for color negative film use could be prepared in the same manner as in Procedure (18), except that the tablet weight was made to be 5.94 g when tableting them.

Example 5

Solidification of a fixing replenisher

Procedure (28)

The granulation was made in the same manner as in Procedure (3) by making use of 150 g of sodium thiosulfate, 10 g of sodium sulfite, 37.5 g of potassium thiocyanate, 1.0 g of sodium ethylenediamine tetraacetate and 1.0 g of sodium hydrogen carbonate. The sprayed amount of water was 12.0 ml, the drying temperature was 77°C and the time was 10 minutes, respectively.

Procedure (29)

The granules prepared in Procedure (28) were solidified in the same manner as in Procedure (18). By making use of the resulting solidified granules, 25 pieces of solid type replenishing fixer chemicals for color negative film use were prepared in the same manner as in Procedure (18), except that the amount of the solidified granules filled in a solid chemical tableting machine was 9.96 g.

Example 6

Solidification of a stabilizer replenishing chemical

Procedure (30)

The granulation was made in the same manner as in Procedure (15) by making use of 3.0 g of hexamethylene tetramine, 2.0 g of polyethylene glycol (having a molecular weight of 1540), 0.05 g of 1,2-benzisothiazolone-3-one, 0.12 g of polyvinyl pyrrolidone (having a polymerization degree of about 17) and 0.35 g of sodium hydrogen carbonate. While keeping the resulting granules be sprayed with 6 g of (P)-C₈H₁₇-C₆H₄-O-(CH₂CH₂0)₁₀H for about 20 minutes, the granulation was continued on. Next, the granules were dried at an air temperature of 65°C for 10 minutes and the dried granules were then dried up in vacuum at 40°C for 90 minutes.

Procedure (31)

The granules prepared in Procedure (30) were solidified in the same manner as in Procedure (18). By making use of the resulting solidified granules, 17 pieces of solid type replenishing stabilizer chemicals for color negative film use were prepared in the same manner as in Procedure (18), except that the amount of the solidified granules filled in a solid chemical tableting machine was 0.345 g.

Example 7

The running tests were tried in the following manner by making use of the automatic processors each shown in Figs. 1 and 2. As for the color developer, the tableted chemicals prepared in Procedure 5 described in Example 1 were used.
The following table shows the standard processing conditions applied to the automatic processors.
The stabilizing tanks were constructed in a cascade system in which a stabilizer was replenished to the third tank and the overflow was flowed in order into the second and then first tanks.
The processing solutions for the automatic processors were prepared in the following procedures.

a) Color developing tank solution (in 21.0 liters)

Into the color developing tank of an automatic processor, 15 liters of water warmed at 35°C were added and 85 pieces of solid type color development processing chemicals for color negative film use, which were prepared in the same manner as in Example 1, were put in and dissolved therein. Atthe same time when putting them in, they begin to be dissolved with producing bubbles faintly on the surfaces thereof and they were almost completely dissolved after lapsing 7 minutes 50 seconds, so that they could become transparent. Next, as a starter component, 21 pieces of the starters having the following chemical formula, which were solidified separately, were put in and were then completely dissolved. After completing the dissolution thereof, water was added up to the marked line of the tank, so that a tank solution could be prepared.
Color development starter for color negative use

b) Bleacher (in 5.0 liters)

Into the bleaching tank of the automatic processor, 3.0 liters of water warmed at 35°C and 250 pieces of solid type bleaching chemicals for color negative use, which were prepared in the procedures described in Example 4, were put in and were then dissolved. At the same time when putting them in, they begin to be dissolved with producing bubbles faintly on the surfaces thereof and they were almost completely dissolved after lapsing 10 minutes 30 seconds. Next, as a starter component, 5 pieces of the starters having the following chemical formula, which were solidified separately, were put in and were then completely dissolved. After completing the dissolution thereof, water was added up to the marked line of the tank, so that a tank solution could be prepared.
Bleaching starter for color negative use

c) Fixer (in 4.5 liters each for tanks 1 and 2)

Into the 1st and 2nd fixing tanks of the automatic processor, 3.0 liters each of water warmed at 35°C and 112 pieces of solid type fixing chemicals for color negative use, which were prepared in the procedures described in Example 5, were each put in and were then dissolved. At the same time when putting them in, they begin to be dissolved with producing bubbles faintly on the surfaces thereof and they were almost completely dissolved after lapsing 10 minutes 30 seconds. Next, water was added up to the marked line of the tank, so that a tank solution could be prepared.

d) Stabilizer (in 3.2 liters each for tanks 1 through 3)

Into fixing tanks 1 through 3 of the automatic processor, 3.0 liters each of water warmed at 35°C and 53 pieces of solid type stabilizing chemicals for color negative use, which were prepared in the procedures described in Example 6, were each put in and were then dissolved. At the same time when putting them in, they begin to be dissolved with producing bubbles faintly on the surfaces thereof and they were almost completely dissolved after lapsing 3 minutes 25 seconds. Next, water was added up to the marked line of the tank, so that a tank solution could be prepared. Next, while the automatic processor was being thermostatically controlled, 20 pieces each of the solid chemicals prepared in the same manner as in Example 1 were taken out of a polyethylene-made envelopes and were loaded on solid chemical supply unit 8 shown in Fig. 1.
By making use of the above-mentioned automatic processor, 20 rolls each of Konica Color Super DD100 films were processed every day and the stabilities of the processed characteristics for one month period were checked up and evaluated.
The same evaluation mentioned above was made under quite the same conditions, except that the same quantity of the tableted chemicals prepared in Procedures 15 through 18 of Example 2 was used for the purpose of comparison. Control slips CNK-4 of the top and every 20th roll of the films were processed and the stabilities of the processed characteristics thereof were evaluated by confirming the minimum and maximum transmission magenta densities thereof.
Table 8 shows the results of measuring the minimum and maximum transmission magenta densities.
From the results shown in Table 8, it can be proved that the processes in the inventive system are stable with few variation in both of the photographic characteristics and the compositions of the processing solutions, as compared to any conventional systems.
In Table 8, Dmin represents a minimum density; Dmax, a maximum density; and G, a green filter density; respectively.

Example 8

Solid type color development processing chemicals for color paper use were prepared in the following procedures.

Procedure (32)

The following compounds were mixed up together; 30.0 g of Cinopar SFP (manufactured by Ciba-Geigy AG), 25.0 g of diethylene triamine pentaacetic acid, 51.0 g of dimethoxyethylene hydroxylamine oxalate, 100.0 g of polyethylene glycol 6000, 120 g of CD-3 [1-(N-ethyl-N-methanesulfonamidoethyl)-3-methyl-p-phenylenediamine sesquisulfate.monohydrate, 300.0 g of sodium paratoluene sulfonate, 3.5 g of sodium sulfite, 330.0 g of potassium carbonate, and 80.0 g of potassium hydroxide. The resulting mixture was pulverized by an air-jet fine mill, until they could have an average particle size of 10 µm.

Procedure (33)

The microconstituent consisting of 0.5 g of potassium bromide and 0.1 g g of benzyl adenine was pulverized by an air-jet fine mill, until they could have an average particle size of 10 µm.

Procedure (34)

The finely pulverized matter of 5.4 g prepared in Procedure (32) were added to the mixture of 0.5 g of potassium bromide and 0.1 g of benzyl adenine prepared in Procedure (33) and they were uniformly mixed up for 10 minutes. Further, the finely pulverized matter prepared in Procedure (32) were added thereto little by little and then mixed together. After repeating the mixing them, all the finely pulverized matters prepared in Procedure (32) were finally mixed up.

Procedure (35)

The finely pulverized matter prepared in Procedure (34) was subjected to a roller compacting type dry granulator so as to prepare a flake-shaped compressed product and they were roughly grained. After that, the resulting rough grains were made to be the granules having an average grain size of 500 µm through a grading step. Further, the resulting graded granules were dried in vacuum at 40°C for 60 minutes and the moisture thereof was almost completely removed.

Procedure (36)

The granules obtained in the above-described Procedure (35) were screened so as to obtain 600 g of granules having a particle size within the range of 1000 µm to 300 µm and they were served as a granular chemical, so that granular chemical sample 13 could be prepared.

Procedure (37)

The granules prepared in Procedure (35) were tableted into those having a diameter of 30 mm and a weight of 9.32 g by applying a compression of 700 kg/cm² by making use of a tableting machine, so that 50 pieces of tablet type chemical sample 14 for color paper development use could be prepared.

Procedure (38)

Procedure (39)

The finely pulverized matter prepared in Procedure (38) was subjected to a roller compacting type dry granulator used in Procedure (38) so as to prepare a flake-shaped compressed product and they were roughly grained. After that, the resulting rough grains were made to be the granules having an average grain size of 500 µm through a grading step. Further, the resulting graded granules were dried in vacuum at 40°C for 60 minutes and the moisture thereof was almost completely removed.

Procedure (40)

The granules obtained in the above-described Procedure (39) were screened so as to obtain 600 g of granules having a particle size within the range of 1000 f..lm to 300 µm and they were served as a granular chemical, so that granular chemical sample 15 could be prepared.

Procedure (41)

The granules prepared in Procedure (39) were tableted into those having a diameter of 30 mm and a weight of 9.32 g by applying a compression of 700 kg/cm² by making use of a tableting machine, so that 50 pieces of tablet type chemical sample 16 for color paper development use could be prepared.

Experiment 7

From the granular chemicals of Samples 13 and 15, 1 g each of them were sampled at random from 10 spots. The sodium bromide and benzyl adenine contents thereof were each measured, and the contents thereof and the deviation values thereof were obtained. The results thereof will be given in Table 9 below.
From the contents of Table 9, it was proved that the microconstituent contents were deviated few in the invention.

Experiment 8

From the tableted chemicals of Samples 14 and 16, 10 tablets were sampled at random. The potassium bromide and benzyl adenine contents of each tablet were measured, and the deviation values of the contents thereof were obtained.
From the contents of Table 10, it was proved that the microconstituent contents were deviated few in the invention.

Procedure (42)

Solid chemical for bleach-fixing a color paper

The mixture of 1350 g of ferric ammonium ethylenediamine tetraacetate, 20.0 g of disodium ethylenediamine tetraacetate, 1550.0 g of ammonium thiosulfate and 400.0 g of sodium metabisulfate was made, and the mixture was then pulverized by an air-jet mill, until the pulverized grains could have an average of 10 µm.

Procedure (43)

The finely pulverized matter prepared in Procedure (42) was subjected to a roller compacting type dry granulator so as to prepare a flake-shaped compressed product and they were roughly grained. After that, the resulting rough grains were made to be the granules having an average grain size of 500 µm through a grading step. Further, the resulting graded granules were dried in vacuum at 40°C for 60 minutes and the moisture thereof was almost completely removed.

Procedure (44)

The granules prepared in Procedure (43) were tableted into those having a diameter of 30 mm and a weight of 9.0 g by applying a compression of 600 kg/cm² by making use of a tableting machine, so that 50 pieces of solid type chemicals for bleach-fixing color papers.

Procedure (45)

Solid chemical for stabilizing color papers

Ten (10.0) grams of potassium orthophenylphenoxide or phenolate, 100.0 g of Cinopar SFP (manufactured by Ciba-Geigy AG.), 200.0 g of sodium sulfite, 10 g of zinc chloride, 300.0 g of disodium 1-hydroxy ethylidene-1,1-diphosphonate and 150 g of disodium ethylenediamine tetraacetate were each subjected to Procedures (42), (43) and (44) in the same manner and those having a diameter of 15mm and a weight of 1.6 g were formed by applying a compression of 600 kg/cm², so that 50 pieces of solid chemicals for stabilizing color papers could be prepared.

Experiment 9

The running tests were tried in accordance with the following procedures by making use of an automatic processor, a Konica Color Paper QA Processor CL-PP718 modified by providing thereto with the control function, solid replenishing chemical supplying function and water supplying function each shown in Fig. 1.
Table 11 shows the standard processing conditions of the automatic processor.
The stabilizing tanks were constructed in a cascade system, in which a stabilizer was replenished to the third tank and the overflow was flowed in order into the second and then first tanks.
The processing solutions used in the automatic processor were prepared in the following procedures.

a) Color developing tank solution (in 23 liters)

Into a color developing tank of the automatic processor, 18 liters of water warmed at 35°C and 179 pieces of solid type development replenishing chemicals for color paper use, which were prepared in the same manner as in Example 8, were put in and were then dissolved. Next, as a starter component, 23 pieces of the starters having the following chemical formula, which were solidified separately, were put in and were then completely dissolved. After completing the dissolution thereof, water was added up to the marked line of the tank, so that a tank solution could be prepared.
Color development starter for color paper use

b) Bleach-fixer (in 23 liters)

Into a bleach-fixing tank of the automatic processor, 15 liters of water warmed at 35°C and 424 pieces of solid type bleach-fixing chemicals for color paper use, which were prepared in the same manner as in Procedures (42) through (44), were put in and were then dissolved. Next, as a starter component, 23 pieces of the starters having the following chemical formula, which were solidified separately, were put in and were then completely dissolved. After completing the dissolution thereof, water was added up to the marked line of the tank, so that a tank solution could be prepared.
Bleach-fixing starter for color paper use

c) Stabilizer (in 15 liters each on Tanks 1 through 3)

Into the first, second and third stabilizing tanks of the automatic processor, 12 liters each of water warmed at 35°C and 72 pieces each of solid type replenishing chemicals for stabilizing color papers were put in and then dissolved together. Next, water was added up to the marked lines of the tanks, so that a tank solution could be prepared. Further, the tablets were set in the solid chemical putting-in unit of the automatic processor. These replenishing tablets were put-in in the numbers necessary to meet the quantity of color paper to be processed, upon detecting the quantity thereof through a light sensitive material area detection sensor. At the same time, a replenishing water supply unit is operated to supply the calculated amounts of water into a color developing tank, a bleach-fixing tank and a stabilizing tank, respectively.
Konica Color Paper Type QA photographed thereon was set on the automatic processor and 15 m² of the color paper were then processed every day for one month, while printing thereon. The resulting stability of the processed characteristics for the month period was checked up and evaluated. Also, for the comparison purpose, replenishing solutions were each prepared and were then put in the conventional replenishing tanks, so as to evaluate the system in which the replenishments are made through bellows pumps, respectively.

Example 9

In the same manner as in Example 7, control slips CPK-2 of the top and every 30m² of the color papers were processed and the stabilities of the processed characteristics thereof were evaluated by confirming the resulting photographic densities.
Table 12 shows the results of the photographic density measurements obtained in Example 9.

Wherein, Dmin represents a minimum density; Dmax, a maximum density; and G, green filter density.
From the results shown in Table 12, it can be proved that the processes in the inventive system are few in variation of the photographic characteristics and more stable as compared to any conventional systems.

Claims

1. A solid chemical for processing a silver halide photographic light-sensitive material which is prepared by pressing granules:

2. The solid chemical of claim 1, wherein said granules are prepared by

(a) adding a solution of said minute amount component to said primary component;

(b) granulating said primary component; and

(c) drying said granulated primary component.

3. The solid chemical of claim 2, wherein a diameter of said granule is within the range of 100 to 2000 µm.

4. The solid chemical of claim 2, wherein a diameter of said granule is within the range of 300 to 1000 µm.

5. The solid chemical of claim 1, wherein said processing agent is a processing tablet and said process further comprises compressing dried granules and forming said tablet.

6. The solid chemical of claim 1, wherein the amount of said minute amount of a photographic processing agent is not less than 1/50 of said solid-chemical.

7. The solid chemical of claim 1, wherein the amount of said minute amount of a photographic processing agent is within the range of 1/100 to 1/20000 of said solid chemical.

8. The solid chemical of claim 1, wherein the amount of said minute amount of a photographic processing agent is within the range of 1/150 to 1/15000 of said solid chemical.

9. The solid chemical of claim 1, wherein said minute amount of a photographic processing agent is selected from the group consisting of a development accelerator, an antifoggant, a fluorescent whitening agent an anti staining agent and an antislugging agent.

10. The solid chemical of claim 1, wherein the primary component of said photographic processing agent is a color developing agent.

11. The solid chemical of claim 10, wherein said color developing agent comprising a compound represented by Formula A, Formula B and Formula A';

Formula A

Formula B

Formula A'

wherein R₁ and R₂ each represent a hydrogen atom, an alkyl group, an acyl group, or R₃CO- wherein R₃ represents an alkyl group, an alkoxyl group or an aryl group, R₁ and R₂ may combine with each other to form a ring; R₁₁, R₁₂ and R₁₃ each represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group; R₁₄ represents a hydroxyl group, a hydroxyamino group, an alkyl group, an aryl group, a heterocyclic group, an alkoxyl group, an aryloxy group, a carbamoyl group or an amino group, R₁₅ represents -CO-, -S0₂- or -C(=NH)-, n is an integer of 0 to 1, provided that when n is 0, R₁₃ and R₁₄ may form a heterocyclic ring together, L represents an alkylene group, A represents a carboxyl group, a sulfo group, a phosphono group, a phosphino group, a hydroxyl group, an amino group, an ammonium group, a carbamoyl group or a sulfamoyl group, R represents a hydrogen atom or an alkyl group.

12. The solid chemical of claim 10, wherein said color developing agent comprising a fluorescent whitening agent represented by Formula E:

Formula E

wherein X₁, X₂, Y₁ and Y₂ each represent a hydroxyl group, a halogen atom, an alkyl group, an aryl group, -N(R₂₁)(^R ₂₂),

or OR₂₅; R₂₁ and R₂₂ each represent a hydrogen atom, an alkyl group or an aryl group, R₂₃ and R₂₄ each represent an alkylene group, R₂₅ represents a hydrogen atom, an alkyl group or an aryl group, M represents a cation.

13. The solid chemical of claim 10, wherein said color developing agent comprises a compound represented by Formula K:

Formula K

wherein E represents an alkylene group, a cycloalkylene group, a phenylene group, a -R₅OR₅- group, a -R₅OR₅OR₅- group or a -R₅ZR₅- group, Z represents a N-R₅-A₅ group or a N-A₅ group, R_i,R₂, R₃, R₄ and R₅ each represent an alkylene group, A₁, A₂, A3, A4 and A₅ each represent a hydrogen atom, a hydroxyl group, a carboxyl group, a -P0₃(M)₂ group, M represents an alkaline metal.

14. A solid chemical for processing a silver halide photographic light-sensitive material which is prepared by pressing granules:

wherein said granules comprises a primary component of a photographic processing agent coated thereon a minute amount component of a photographic agent ranging from 5 to 10 % by weight of said primary component, wherein the amount of said minute amount component of a photographic agent is not less than 1/50 of said solid chemical.